Sulfur Removal and Recovery (1975)

Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.
fw001
Sulfur Removal and Recovery

from Industrial Processes
In Sulfur Removal and Recovery; Pfeiffer, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1975.
Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.fw001
Sulfur Removal and Recovery

from Industrial Processes
J o h n B . Pfeiffer, Editor
A symposium sponsored by the Division of Industrial and Engineering Chemistry at the 167th Meeting of the American Chemical Society, Los Angeles, Calif., A p r i l 4 - 5 , 1974.
ADVANCES IN CHEMISTRY SERIES
139
AMERICAN
CHEMICAL D. C.
SOCIETY 1975
WASHINGTON,
Library of Congress CIP Data

Sulfur removal and recovery from industrial processes. (Advances i n chemistry series; 139 I S S N 0 0 6 5 - 2 3 9 3 ) Includes bibliographical references and index. 1. gresses. I. Pfeiffer, John B . , 1946ical Society. Division of Chemistry. QD1.A355 11557 II. American ChemIndustrial and Engineering SulphurCongresses. 2. DesulphurationCon-
III. Series: Advances i n chemistry series; 139. no. 139 [ T P 2 4 5 . S 9 ] 540'.8s [661'.1] 7 5 ADCSAJ 139 1-221
I S B N 0-8412-0217-6
Copyright 1975 American Chemical Society A l l Rights Reserved PRINTED IN THE UNITED STATES OF AMERICA
Advances in Chemistry Series

R o b e r t F. G o u l d , Editor
Advisory Board
Kenneth B. Bischoff Edith M . Flanigen Jesse C. H . Hwa Phillip C. Kearney Egon Matijevi Nina I. McClelland Thomas J. Murphy John B. Pfeiffer Joseph V. Rodricks
FOREWORD
A D V A N C E S
I N
C H E M I S T R Y
SERIES
w a s f o u n d e d i n 1 9 4 9 b y the and
A m e r i c a n C h e m i c a l S o c i e t y as a n outlet f o r s y m p o s i a
collections of d a t a i n s p e c i a l areas of t o p i c a l interest t h a t c o u l d n o t b e a c c o m m o d a t e d i n t h e Society's journals. It p r o v i d e s a m e d i u m for s y m p o s i a t h a t w o u l d o t h e r w i s e b e fragmented, t h e i r papers d i s t r i b u t e d a m o n g several journals or not p u b l i s h e d at a l l . P a p e r s are refereed c r i t i c a l l y a c c o r d i n g to A C S e d i t o r i a l standards a n d receive the c a r e f u l a t t e n t i o n a n d p r o c essing c h a r a c t e r i s t i c of A C S p u b l i c a t i o n s . in
A D V A N C E S I N C H E M I S T R Y SERIES
Papers published
are o r i g i n a l c o n t r i b u t i o n s may
not p u b l i s h e d elsewhere i n w h o l e or m a j o r p a r t a n d i n c l u d e reports of r e s e a r c h as w e l l as r e v i e w s since s y m p o s i a e m b r a c e b o t h types of p r e s e n t a t i o n .
PREFACE
t h e last s e v e r a l years, m u c h of the w o r k i n s u l f u r o x i d e e m i s s i o n * * c o n t r o l has b e e n a i m e d at emissions f r o m p o w e r p l a n t stacks. HowThe of ever, there are m a n y other s t a t i o n a r y sources of s u l f u r emissions i n c l u d i n g n o n - f e r r o u s smelters, s u l f u r i c a c i d p l a n t s , a n d p e t r o l e u m refineries. p a p e r s i n this c o l l e c t i o n are c o n c e r n e d s u l f u r - b e a r i n g off-gases. w i t h these " o t h e r " sources
T h i s v o l u m e is i n t e n d e d to b e a c o n s o l i d a t e d
reference source f o r those i n t e r e s t e d i n t h e latest s u l f u r r e c o v e r y m e t h o d s . A f t e r M r . Semrau's i n t r o d u c t o r y c h a p t e r f o l l o w f o u r p a p e r s w h i c h present a l t e r n a t i v e t e c h n i q u e s try. P r e s e n t l y , the only for r e c o v e r i n g s u l f u r d i o x i d e f r o m available recovery the
Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.pr001
m o r e c o n c e n t r a t e d smelter gas streams i n the n o n - f e r r o u s s m e l t i n g i n d u s commercially techniques of the produce s u l f u r i c a c i d or l i q u i d sulfur dioxide. However, two
discussions present d e v e l o p m e n t s s u l f u r values as e l e m e n t a l s u l f u r .
i n n e w processes for r e c o v e r y of the
T h e next f o u r papers concentrate o n a n o t h e r e m i s s i o n source, h y d r o g e n sulfide f r o m C l a u s units. T h e C l a u s process has b e e n u s e d for s e v e r a l years to r e m o v e h y d r o g e n sulfide f r o m p e t r o l e u m r e f i n e r y w a s t e gases. H o w e v e r , c u r r e n t e n v i r o n m e n t a l concerns r e q u i r e a m o r e efficient r e c o v e r y of the s u l f u r values. S o m e of the n e w t e c h n o l o g y to i m p r o v e C l a u s p l a n t efficiencies is d i s c u s s e d i n these chapters. T h e r e m a i n d e r of the b o o k deals w i t h s c r u b b i n g processes, t h e m o s t p u b l i c i z e d of the c o n t r o l m e t h o d s . ents are proposed and their discussed.
JOHN B. PFEIFFER
Process flowsheets for s e v e r a l a b s o r b in emission control are
applications
Allied Chemical Corp. Morristown, N.J. October, 1974
ix
1
Controlling the Industrial Process Sources of Sulfur Oxides
KONRAD SEMRAU
Stanford Research Institute, Menlo Park, Calif. 94025
Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001
Industrial process or "noncombustion" sources of sulfur oxides emission are frequently more significant locally than fossil fuel combustion sources. The most important process sources are: primary copper, lead, and zinc smelters; Claus sulfur plants; sulfuric acid plants; coke plants; iron ore sintering and pelletizing plants; regenerators of fluid catalytic cracking units; and sulfite pulp mills. In the future, Claus sulfur plants will become still more important sources because of growing hydrodesulfurization of increasingly sour petroleum stocks and because of future coal desulfurization to produce clean solid, liquid, and gaseous fuels. Control of sulfur oxides emissions from the industrial process sources is closely related to the technologies of the sources themselves, and changes in the process technologies may greatly improve the effectiveness and economy of emission control.
T o u r i n g the past decade, the principal concern with control of sulfur L /
oxides emissions has been focused on flue gases from fuel combus-
tion, primarily the flue gases from power plants. F u e l combustion accounts for about three quarters of the estimated total sulfur oxide emissions in the United States. However, the emissions from industrial processes are frequently more significant than is indicated by their contribution (about one fifth) to the total emission. Whereas many of the combustion sources are individually small and widely dispersed, industrial operations are often relatively large and concentrated sources and may cause severe local pollution problems. Copper, zinc, and lead smelters, in particular, have a long and notorious history as pollution sources. It is only in recent years that individual power plants have become large enough that their sulfur oxide emissions smelters. 1 In Sulfur Removal and Recovery; Pfeiffer, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1975. compare with those from
S U L F U R
R E M O V A L
A N D R E C O V E R Y
T h e i n d u s t r i a l processes present b o t h s p e c i a l p r o b l e m s a n d s p e c i a l o p p o r t u n i t i e s t h a t are n o t e n c o u n t e r e d w i t h f u e l c o m b u s t i o n gases. In most cases, s u l f u r d i o x i d e concentrations i n t h e waste gases a r e h i g h e r t h a n i n c o m b u s t i o n gases, a n d there are greater o p p o r t u n i t i e s to r e c o v e r t h e s u l f u r d i o x i d e i n u s e f u l forms. T h e processes d e s i g n e d t o treat c o m b u s t i o n gases are n o t a l w a y s w e l l a d a p t e d to t r e a t i n g process F i n a l l y , changes i n t h e i n d u s t r i a l processes f r e q u e n t l y present gases. oppor-
tunities f o r m o r e e c o n o m i c a l c o n t r o l a n d r e c o v e r y of t h e sulfur d i o x i d e . Emission Sources T w o sets o f s u l f u r o x i d e e m i s s i o n estimates f o r t h e U n i t e d States, d r a w n f r o m E n v i r o n m e n t a l P r o t e c t i o n A g e n c y sources ( I , 2, 3) are p r e Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 sented i n T a b l e s I a n d I I . T h e source categories i n t h e t w o tables are n o t consistent n o r a r e t h e estimates o f t h e total e m i s s i o n , e v e n a l l o w i n g f o r a 3-yr difference i n the base p e r i o d s . I t is also o b v i o u s t h a t c e r t a i n sources h a v e n o t b e e n a c c o u n t e d f o r i n t h e c o m p i l a t i o n s . N e v e r t h e l e s s , t h e estimates d o i d e n t i f y most o f the i n d u s t r i a l sources a n d i n d i c a t e t h e i r r e l a t i v e m a g n i t u d e s . T h e d i s t r i b u t i o n s o f sources i n other nations a r e s i m i l a r t o those i n t h e U n i t e d States i n a n u m b e r o f r e p o r t e d instances Table I. (4).
Estimated SO^ Emissions i n the United States (1970) SO Emission > tons/yr)
a 6
Source
Category
Per cent of Total 2.88 76.42 0.22 1.37 2.52 1.37 1.02 0.01 10.30 2.72 0.29 0.29 0.58 100.00%
Transportation F u e l c o m b u s t i o n i n s t a t i o n a r y sources I n d u s t r i a l process losses P u l p and paper C a l c i u m carbide Sulfuric acid plants C l a u s sulfur plants Coking P e t r o l e u m refining F l u i d catalytic cracking Thermal catalytic cracking Nonferrous metals Copper Z i n c a n d lead I r o n ore s i n t e r i n g a n d p e l l e t i z i n g S o l i d wastes d i s p o s a l Agricultural burning Miscellaneous C o a l refuse b u r n i n g Total
a k
1.0 26.5 0.077 0.002 0.474 0.875 0.474 0.354 0.005 3.57 0.9
?
0.1 0.1 0.2 34.68
From Rf. 1. except as noted. Ref. 2.
1.
SE M R A U Table II. Source
Industrial
Process Sources
Estimated SO* Emissions in the United States (1973) Category SOx Emission" (10* tons/yr) 1.15 28.15 7.77 4.45 0.57 4.40 0.54 0.83 0.44 0.19 48.50 Per cent of Total 2.37 58.04 16.02 9.18 1.18 9.07 1.11 1.71 0.91 0.39 100.00%
M o b i l e sources S t a t i o n a r y c o m b u s t i o n sources Steamelectric power I n d u s t r i a l boilers Metals P r i m a r y copper smelters P r i m a r y lead a n d zinc smelters Fuels industries P e t r o l e u m refineries N a t u r a l gas Chemicals Sulfuric acid Coking A c c i d e n t a l fires Total
a
From Ref. 8.
T h e s m e l t i n g of c o p p e r , l e a d , a n d z i n c f r o m sulfide ores is s e c o n d o n l y to f u e l c o m b u s t i o n U n i t e d States. as a source of s u l f u r o x i d e emissions i n the P e t r o l e u m refineries s t a n d i n t h i r d p l a c e i n T a b l e I I . emissions o f h i g h - s u l f u r fuels i n boilers o r process
H o w e v e r , i t seems c l e a r t h a t t h e greater p a r t of t h e refinery comes f r o m t h e c o m b u s t i o n heaters.
F r o m a process s t a n d p o i n t t h e y s h o u l d b e classified as o r i g i n a t -
i n g f r o m t h e category of stationary c o m b u s t i o n sources; this appears to h a v e b e e n d o n e i n T a b l e I . T h e s t r i c t l y process sources i n refineries consist p r i m a r i l y o f C l a u s s u l f u r p l a n t t a i l gases a n d t h e regenerators o f catalytic cracking units. T h e t a i l gases o f C l a u s s u l f u r plants a r e a p p a r e n t l y t h e s e c o n d largest process source after nonferrous smelters. T h e C l a u s plants convert h y d r o g e n sulfide, w h i c h is m o s t l y d e r i v e d f r o m p e t r o l e u m r e f i n i n g o r t h e treatment o f n a t u r a l gas. M o s t o f t h e largest C l a u s p l a n t s i n t h e U n i t e d States a n d C a n a d a are i n s t a l l e d at n a t u r a l gas-treating plants (2). I t is i r o n i c that a l t h o u g h n a t u r a l gas is o u r cleanest fossil f u e l , its p r e p a r a t i o n for u s e is sometimes a major source of s u l f u r o x i d e p o l l u t i o n . I n F r a n c e , the C l a u s plants at t h e L a c q n a t u r a l gas p l a n t w e r e e s t i m a t e d to y i e l d 10% o f t h e t o t a l s u l f u r o x i d e e m i s s i o n i n t h e n a t i o n f o r 1970 (4) a n d T h e emissions from C l a u s plants c a n b e e x p e c t e d to present a n from the M i d d l e East a n d h a v e b e e n a serious source o f p o l l u t i o n a n d a g r i c u l t u r a l d a m a g e ( 5 ) . i n c r e a s i n g l y serious p o t e n t i a l p r o b l e m i n t h e f u t u r e as p e t r o l e u m r e f i n eries operate o n i n c r e a s i n g l y sour crudes elsewhere ( S N G ) a n d l i q u i d fuels f r o m c o a l . a n d as plants a r e b u i l t to d e s u l f u r i z e substitute n a t u r a l gas
S U L F U R
R E M O V A L
A N D
R E C O V E R Y
S u l f u r i c a c i d plants c o n t i n u e to be s u b s t a n t i a l sources of s u l f u r o x i d e emissions. emissions sludge T h e emissions estimates p r e s e n t e d by-product i n Tables I and II preThe gases, the acid from smelter u m a b l y refer o n l y to emissions f r o m plants p r o d u c i n g f r o m s u l f u r - b u r n i n g a c i d plants. classified w i t h
a c i d , a n d other s u c h sources are p r o b a b l y
emissions f r o m the a p p r o p r i a t e industries. R e l a t i v e l y l i t t l e d i r e c t i n f o r m a t i o n has b e e n p u b l i s h e d o n the s u l f u r o x i d e emissions f r o m stantial. fluid catalytic cracking ( F C C ) unit regenerators (6, 7 ) , a l t h o u g h the estimate i n T a b l e I indicates that the t o t a l is s u b T h e s u l f u r r e m a i n i n g i n the coke d e p o s i t e d o n the catalyst is r e l a t e d to the s u l f u r content of t h e p e t r o l e u m feedstock. T h e s u l f u r o x i d e content of t h e regenerator flue gases f r o m units t r e a t i n g r e l a t i v e l y l o w s u l f u r feedstocks is r e p o r t e d to b e several h u n d r e d p p m . Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 E a s t e r n feedstocks m a y y i e l d flue gases c o n t a i n i n g 1 % dioxide. I n t h e steel i n d u s t r y the m o s t c o m m o n source of s u l f u r o x i d e e m i s sions is the b u r n i n g of c o k e o v e n gas that has n o t b e e n H o w e v e r , emissions f r o m i r o n ore sinter plants are r e c e i v i n g desulfurized. considerable However, the a u t h o r has b e e n i n f o r m e d p r i v a t e l y that units t r e a t i n g h i g h - s u l f u r M i d d l e or m o r e of sulfur
a t t e n t i o n i n G e r m a n y a n d J a p a n , i f not y e t i n the U n i t e d States. P e l l e t i z i n g plants are another p o t e n t i a l l y significant source. I n G e r m a n y , sinter plants are e s t i m a t e d to be responsible for a b o u t 6 % oxide emission (8). local of the t o t a l s u l f u r
T h e p a p e r p u l p i n g i n d u s t r y is r e p o r t e d l y not, i n t o t a l , a v e r y l a r g e e m i t t e r of s u l f u r oxides, a l t h o u g h i n d i v i d u a l plants m a y present problems. whereas sulfite m i l l s are m o r e i m p o r t a n t as emitters of s u l f u r the c h e m i c a l r e c o v e r y cycles use b a s i c c h e m i s t r y that c o u l d waste gases of other types of sources. F r o m t h e s t a n d p o i n t of s u l f u r r e c o v e r y , emphasized the recent experience has r e processes t h a t permit that d e s i r a b i l i t y , i n most cases, of K r a f t mills emit more malodorous reduced sulfur compounds, dioxide. well be
T h e p u l p i n g processes ( p a r t i c u l a r l y sulfite) are most i n t e r e s t i n g because a p p l i e d to r e c o v e r y of s u l f u r d i o x i d e a n d s u l f u r f r o m the flue a n d process
r e c o v e r y of e l e m e n t a l sulfur. S u l f u r i c a c i d is the u s e f u l b y - p r o d u c t
is u s u a l l y most r e a d i l y a n d e c o n o m i c a l l y p r o d u c e d f r o m s u l f u r d i o x i d e , b u t i t cannot b e e c o n o m i c a l l y s h i p p e d for l o n g distances or be e c o n o m i c a l l y a n d safely stored for l o n g periods. long distances or stored indefinitely problems. Nonferrous Smelters E l e m e n t a l s u l f u r c a n be s h i p p e d with minimal environmental
A large p a r t of t h e p e r t i n e n t l i t e r a t u r e to 1970 o n c o n t r o l of s u l f u r oxides f r o m c o p p e r , l e a d , a n d z i n c smelters was r e v i e w e d b y the a u t h o r
1.
SE M R A U
Industrial
Process Sources
i n t w o p r e v i o u s papers (9, 10).
T h e o u t p u t of r e l a t e d p u b l i c a t i o n s has and have first appeared devlop-
g r e a t l y i n c r e a s e d since. T h e major n e w d e v e l o p m e n t s i n smelter e m i s s i o n c o n t r o l h a v e b e e n r e l a t e d to process changes outside t h e U n i t e d States. I n the U n i t e d States itself, c o n t r o l
ments h a v e consisted m a i n l y of a d o p t i n g or a d a p t i n g systems or t e c h n i q u e s p i o n e e r e d a b r o a d . T h e c a p a b i l i t y for a h i g h degree of c o n t r o l b y l e a d a n d z i n c smelters is a c k n o w l e d g e d {11, 12), b u t w i t h respect to c o p p e r smelters, c o n t i n u i n g disputes center o n the a v a i l a b i l i t y of c o n t r o l methods for d i l u t e gases f r o m r e v e r b e r a t o r y furnaces a n d t h e a l l e g e d i m p r a c t i c a l i t y of attaining 9 0 % or greater c o n t r o l of emissions from c o m p l e t e smelters ( I I , 13, 14). I n a s m u c h as b o t h objectives h a v e b e e n regarded
a t t a i n e d at c o p p e r smelters a b r o a d a n d are n o w b e i n g a p p r o a c h e d i n some installations i n the U n i t e d States, the disputes m u s t b e Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 as m o r e p o l i t i c a l t h a n t e c h n i c a l i n o r i g i n . Control Methods for Smelter Gases. T h e favored control method
for smelter gases continues to b e the m a n u f a c t u r e of s u l f u r i c a c i d b y t h e contact process, either d i r e c t l y or after p r e l i m i n a r y c o n c e n t r a t i o n of t h e s u l f u r d i o x i d e i n w e a k gases b y some c y c l i c a b s o r p t i o n process. as there is a use for the a c i d , this is u n q u e s t i o n a b l y the most As long economical
m e t h o d a v a i l a b l e . C o n s u m p t i o n of s u l f u r i c a c i d for l e a c h i n g of l o w - g r a d e a n d o x i d e - t y p e c o p p e r ores has i n c r e a s e d greatly. H o w e v e r , i t w i l l u l t i m a t e l y b e necessary to recover p a r t of the s u l f u r d i o x i d e i n s o m e other f o r m , p r e f e r a b l y as e l e m e n t a l sulfur. T h e A l l i e d C h e m i c a l C o r p . r e d u c t i o n process has b e e n a p p l i e d c o m m e r c i a l l y a n d o n a large scale to p y r r h o t i t e roaster gases c o n t a i n i n g a b o u t 1 2 % s u l f u r d i o x i d e (15, 16). p r e l i m i n a r y c o n c e n t r a t i o n step is i n d i c a t e d (9, 10). Application to r i c h e r gases w i l l b e m o r e e c o n o m i c a l , a n d for leaner gases, use of a T h e A l l i e d C h e m i c a l process uses n a t u r a l gas as the r e d u c t a n t , w h i c h is u n d e s i r a b l e i n the face of the d i m i n i s h i n g supplies a n d i n c r e a s i n g costs of n a t u r a l gas. H o w e v e r , there is no o b v i o u s reason w h y the process A n o t h e r process u s i n g o i l or p u l v e r i z e d (17). sulfur cannot b e o p e r a t e d o n a p r o d u c e r gas g e n e r a t e d f r o m c o a l , as w a s d o n e earlier w i t h other processes ( 1 0 ) . c o a l as the r e d u c t a n t has b e e n d e v e l o p e d b y O u t o k u m p u O y for use i n c o n j u n c t i o n w i t h the O u t o k u m p u flash s m e l t i n g process The use of cyclic absorption processes for concentrating
d i o x i d e f r o m smelter gases is s t i l l v e r y l i m i t e d . If a n d w h e n s u l f u r d i o x i d e r e d u c t i o n is p r a c t i c e d , c o n c e n t r a t i o n processes m u s t b e u s e d m o r e extens i v e l y unless m e t a l l u r g i c a l processes are u s e d that d e l i v e r r i c h e r off-gases, p r o b a b l y w i t h s u l f u r d i o x i d e concentrations not l o w e r t h a n 2025%. A s a r c o D M A a b s o r p t i o n process (9, f e e d to s u l f u r i c a c i d p l a n t s . 10) is c o m i n g i n t o r e n e w e d The use,
p a r t l y to p r o d u c e l i q u i d s u l f u r d i o x i d e a n d p a r t l y to p r o v i d e e n r i c h e d
S U L F U R
R E M O V A L
A N D
R E C O V E R Y
A t the T a c o m a smelter, t h e D M A process is b e i n g u s e d o n c o p p e r c o n v e r t e r gas ( I S ) . A t the A j o smelter, i t is also to be u s e d to treat T h e D M A process is n o t r e a l l y c o p p e r r e v e r b e r a t o r y f u r n a c e gases ( 1 9 ) .
w e l l s u i t e d to treat gases as d i l u t e as those f r o m r e v e r b e r a t o r y furnaces. It is m o r e e c o n o m i c for use o n c o n v e r t e r gases, o r p r e f e r a b l y , s t i l l r i c h e r gases ( 9 ) . A t the R o n n s k a r w o r k s of B o l i d e n A B i n S w e d e n , w h i c h i n c l u d e b o t h a c o p p e r a n d a l e a d smelter, a c y c l i c process u s i n g w a t e r as the absorbent concentrates s u l f u r d i o x i d e b o t h to p r o d u c e l i q u i d s u l f u r d i o x i d e a n d f o r f e e d to a c i d plants (20,21). T h e process is r e p o r t e d to g i v e a n a b s o r p t i o n s u l f u r d i o x i d e . W a t e r is efficiency of a b o u t 9 8 % o n gas c o n t a i n i n g 2 %
n o t n o r m a l l y a f a v o r a b l e solvent for s u c h a n a p p l i c a t i o n b u t c a n b e u s e d Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 i n this case b e c a u s e i t is a v a i l a b l e at a l o w t e m p e r a t u r e , less t h a n 5 C f o r most of t h e year. Recovery of s u l f u r d i o x i d e f r o m t h e by applying complete (20). smelter is to b e i n c r e a s e d f r o m 90 to 9 5 % water-cooled
c o l l e c t i n g hoods a n d waste heat boilers to a l l the c o p p e r converters The Cominco process,
w h i c h uses a s o l u t i o n of a m m o n i a as the sulfur dioxide)
absorbent, has b e e n t r e a t i n g d i l u t e gases ( a b o u t 1 % (10, 22).
f r o m l e a d ore s i n t e r i n g m a c h i n e s o n a l a r g e scale for m o r e t h a n 30 y r T h e gases m u s t be c l e a n e d a n d c o n d i t i o n e d b e f o r e e n t e r i n g T h e r e a f t e r , the o r i g i n a l source of t h e gases is i m m a t e r i a l , the absorber.
a n d the process c o u l d b e u s e d to treat gases f r o m c o p p e r r e v e r b e r a t o r y furnaces, a l t h o u g h i t has not a c t u a l l y b e e n so u s e d . A b s o r p t i o n processes for s u l f u r d i o x i d e t h a t use a m m o n i a as the absorbent h a v e b e e n w i d e l y s t u d i e d a n d a p p l i e d c o m m e r c i a l l y i n processes s u c h as p u l p a n d p a p e r m a n u f a c t u r e (23, 24). T h e p r i n c i p a l variations appear i n the recovery sulfur cycles f o l l o w i n g the a b s o r p t i o n step. I n the C o m i n c o process, the spent absorbent is a c i d i f i e d w i t h s u l f u r i c a c i d to release c o n c e n t r a t e d d i o x i d e a n d to f o r m a m m o n i u m sulfate as a b y - p r o d u c t . c o n j u n c t i o n w i t h a s u l f u r i c a c i d p l a n t is g e n e r a l l y necessary. Operation in W h e r e i t is This power
d e s i r a b l e to conserve a m m o n i a a n d r e d u c e a m m o n i u m sulfate p r o d u c t i o n , the s u l f u r d i o x i d e c a n be s t e a m - s t r i p p e d f r o m the r i c h solvent. process v a r i a t i o n w a s once u s e d for a p e r i o d b y C o m i n c o (10) p l a n t gases ( 2 5 ) . r e c e n t l y b e e n i n v e s t i g a t e d b y Electricit de F r a n c e for use o n m o n i a a b s o r p t i o n process c a n be o p e r a t e d a n d has
I f i t is d e s i r e d to use a t h r o w a w a y process, t h e a m as a d o u b l e - a l k a l i system. This (26,
T r e a t i n g the spent absorbent w i t h l i m e p r e c i p i t a t e s c a l c i u m sulfate a n d sulfite a n d releases a m m o n i a for r e t u r n to the a b s o r p t i o n system. 1930's (26) 27). a n d has b e e n r e c e n t l y r e v i v e d i n F r a n c e a n d J a p a n (28). p r o c e d u r e w a s u s e d i n p a r t i n the G u g g e n h e i m process s t u d i e d i n t h e T h e same a m m o n i a r e c o v e r y process is also u s e d i n the A r b i t e r
process for l e a c h i n g c o p p e r ores
1.
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Industrial
Process Sources
O t h e r a b s o r p t i o n processes u s i n g s o l u b l e bases, s u c h as s o d i u m , o r adaptations of the contact s u l f u r i c a c i d process (29, a v a i l a b l e for t r e a t i n g d i l u t e smelter gases. t h a n the a m m o n i a - b a s e processes. T h e O n a h a m a smelter i n J a p a n illustrates the degree of control techniques fitted (31, 32). emission c o n t r o l a t t a i n a b l e at a c o n v e n t i o n a l c o p p e r smelter, u s i n g c o n v e n t i o n a l T h e converters are e q u i p p e d w i t h t i g h t l y hoods a n d w a s t e heat b o i l e r s , w h i c h m i n i m i z e s a i r i n f i l t r a t i o n a n d conver30) are p o t e n t i a l l y H o w e v e r , there is no reason
to expect that a n y of t h e m s h o u l d be a p p r e c i a b l y , i f at a l l , less expensive
raises the average s u l f u r d i o x i d e c o n c e n t r a t i o n i n the gas to 1 1 % b e f o r e it enters a n e w d o u b l e - c o n t a c t s u l f u r i c a c i d p l a n t . T h e average s i o n efficiency is 9 9 . 8 % . Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 treat the converter gases. T h e gases f r o m the r e v e r b e r a t o r y f u r n a c e are T h e s u l f u r d i o x i d e c o n c e n t r a t i o n i n the r e v e r -
t r e a t e d i n the r e b u i l t single-contact s u l f u r i c a c i d p l a n t o r i g i n a l l y u s e d to b e r a t o r y f u r n a c e gas has b e e n i n c r e a s e d b y m i n i m i z i n g air i n f i l t r a t i o n a n d b y u s i n g oxygen. T h e f u r n a c e is fitted w i t h o x y g e n - f u e l roof b u r n e r s s i m i l a r to those u s e d i n o p e n - h e a r t h steel furnaces. to m a k e t h e a c i d p l a n t autogenous f u e l - f i r e d heater. (10), T h e sulfur dioxide T h i s is too l o w c o n c e n t r a t i o n i n t h e gas e n t e r i n g the a c i d p l a n t is 2 . 5 % . T h e c o n v e r s i o n efficiency is 9 6 . 9 % .
so the gas is p r e h e a t e d i n a T h e gas c l e a n i n g
a n d c o n d i t i o n i n g system for t h e r e v e r b e r a t o r y f u r n a c e gas uses r e f r i g e r a t i o n for d e h u m i d i f i c a t i o n so that c o n c e n t r a t e d a c i d is p r o d u c e d even f r o m the d i l u t e gas. E v e n m i n o r r e s i d u a l emissions f r o m the O n a h a m a smelter are treated. T h e t a i l gases f r o m the a c i d plants are s c r u b b e d w i t h caustic soda to r e d u c e the final s u l f u r d i o x i d e c o n c e n t r a t i o n to a b o u t 20 p p m . T h e c o n v e r t e r b u i l d i n g is enclosed to p r e v e n t escape to the atmosphere of u n t r e a t e d gases that leak f r o m the furnaces. b e f o r e release. L e a k i n g gases are c o l l e c t e d as close to the sources as possible a n d are s c r u b b e d i n a l i m e r o c k t o w e r V i r t u a l l y a l l of the s u l f u r d i o x i d e f r o m t h e smelter is (32). reportedly contained
A f t e r the system d e s c r i b e d a b o v e was d e v i s e d , the O n a h a m a smelter was e x p a n d e d , a n d a c o m m e r c i a l magnesia-base a b s o r p t i o n system d e v e l o p e d b y the c o m p a n y w a s a p p l i e d to the r e v e r b e r a t o r y f u r n a c e gases (27). As described (27), the process is essentially the same as the of C h e m i c o - B a s i c process (33) added carbon. acid plant. H i g h degrees of s u l f u r oxides e m i s s i o n c o n t r o l are r e p o r t e d at the n e w e r Japanese c o p p e r smelters, w h e t h e r t h e y use c o n v e n t i o n a l or a d v a n c e d s m e l t i n g processes (31). A l l the p l a n t s u s i n g r e v e r b e r a t o r y or a l t h o u g h e q u i p m e n t details are not r e p o r t e d .
T h e m a g n e s i u m sulfite is d e c o m p o s e d i n a r o t a r y k i l n i n t h e presence the r i c h k i l n gas stream ( 1 3 - 1 5 % sulfur dioxide)
T h e m a g n e s i a is r e t u r n e d to the a b s o r p t i o n process, a n d is sent to a s u l f u r i c
8 flash
S U L F U R
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s m e l t i n g furnaces r e p o r t r e c o v e r y of at least 9 0 %
of the s u l f u r .
O f three plants u s i n g flash smelters, K o s a k a reports a s u l f u r r e c o v e r y of 9 5 % and T o y o and Saganoseki report 9 6 % . A s i l l u s t r a t e d b y the O n a h a m a smelter, it is essential to m i n i m i z e the v o l u m e of the off-gases f r o m a source. T h e c a p i t a l a n d o p e r a t i n g costs of a c o n t r o l system are d e t e r m i n e d p r i m a r i l y b y t h e v o l u m e of gas that m u s t b e t r e a t e d (9, 10). T h e g r o w i n g a p p l i c a t i o n of e m i s s i o n controls has l e d r e c e n t l y to m u c h m o r e active d e v e l o p m e n t of methods a n d e q u i p m e n t f o r c a p t u r e a n d c o o l i n g of waste gases as w e l l as heat r e c o v e r y f r o m t h e m (34,35). Smelting Processes. (36) Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 T h e experience of the T r a i l l e a d - z i n c smelter has d e m o n s t r a t e d t h a t h i g h a n d the O n a h a m a c o p p e r smelter (32)
degrees of e m i s s i o n c o n t r o l c a n b e a t t a i n e d e v e n at c o n v e n t i o n a l smelters t h a t e m i t w e a k gas streams. N e v e r t h e l e s s , the r e l a t i v e costs of c o n t r o l l i n g s u c h e m i s s i o n sources are necessarily h i g h . Costs c a n b e r a d i c a l l y r e d u c e d o n l y t h r o u g h process changes t h a t r e d u c e off-gas v o l u m e s a n d increase s u l f u r d i o x i d e concentrations ( 9 , 37). It is p a r t i c u l a r l y d e s i r a b l e to p r o d u c e off-gases r i c h e n o u g h to b e f e d d i r e c t l y to a s u l f u r d i o x i d e r e d u c t i o n p l a n t w i t h o u t u s i n g a p r e l i m i n a r y c o n c e n t r a t i o n process. T h e n e e d for process modifications or changes does not arise o n l y o r e v e n p r i m a r i l y f r o m a i r p o l l u t i o n c o n t r o l considerations, e v e n t h o u g h these m a y affect the t i m i n g . T h e p r i m a r y c o p p e r , l e a d , a n d z i n c s m e l t i n g i n d u s t r y i n the U n i t e d States is l a r g e l y obsolete. A n u m b e r of z i n c a n d l e a d smelters w e r e r e c e n t l y closed p r i m a r i l y because the installations were no longer economically competitive abandoned ones. (38) w i t h the m o r e modern smelters o p e r a t i n g a b r o a d . N e w or r e n o v a t e d smelters are r e p l a c i n g the A l t h o u g h means are a v a i l a b l e for c o n t r o l l i n g the b u l k of the e m i s sions f r o m the c o n v e n t i o n a l l e a d a n d z i n c smelters, n e w processes b e i n g d e v e l o p e d offer greater e c o n o m y as w e l l as better emission c o n t r o l ( 9 , 1 0 ) . C o m i n c o L t d . r e c e n t l y a n n o u n c e d the d e v e l o p m e n t of a n e w process to r e p l a c e the c o n v e n t i o n a l l e a d s m e l t i n g process w i t h its s i n t e r i n g p l a n t s a n d blast furnaces (39). has a p p e a r e d i n 41). This techa A great d e a l of n e w c o p p e r s m e l t i n g t e c h n o l o g y r e c e n t years, b u t m o s t l y outside the U n i t e d States (40,
n o l o g y is b e i n g a d o p t e d i n the U n i t e d States o n l y v e r y s l o w l y a n d w i t h s e e m i n g r e l u c t a n c e , p o s s i b l y b e c a u s e the cost of s m e l t i n g has b e e n r e c e n t l y (42). r e l a t i v e l y s m a l l p a r t of t h e t o t a l cost of c o p p e r p r o d u c t i o n a t least u n t i l T h e l i m i t s of cost r e d u c t i o n elsewhere are n o w b e i n g a p The p r o a c h e d , h o w e v e r , a n d the expense of s m e l t i n g is b e i n g i n c r e a s e d b y s u l f u r oxides c o n t r o l a n d the s h a r p l y i n c r e a s e d cost of f u e l ( 42, 43 ). characteristics, has a v e r y h i g h f u e l c o n s u m p t i o n . r e v e r b e r a t o r y s m e l t i n g f u r n a c e , b e c a u s e of its p o o r heat a n d mass transfer T h e l a r g e v o l u m e of
1.
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Industrial
Process Sources
c o m b u s t i o n gases g e n e r a t e d n o t o n l y is a source of heat loss, b u t d i l u t e s the s u l f u r d i o x i d e p r o d u c e d a n d increases the gas c l e a n i n g p r o b l e m that exists e v e n w i t h o u t s u l f u r o x i d e c o n t r o l . C u r r e n t l y , t h e shortages of n a t u r a l gas a n d f u e l o i l are l e a d i n g the c o p p e r smelters to c o n s i d e r c o n v e r s i o n to c o a l firing (44). S u c h c o n v e r s i o n is itself e x p e c t e d to b e a costly a n d a n d the I n c o o x y g e n to r e d u c e fuel time-consuming operation. T h e O u t o k u m p u flash s m e l t i n g process (35, 45) flash s m e l t i n g process (46) were originally developed
r e q u i r e m e n t s , b u t t h e y h a v e i n c i d e n t a l l y l e d to other process efficiencies a n d to m o r e effective a n d e c o n o m i c a l p o l l u t i o n c o n t r o l . T h e I n c o process is autogenous autogenous, Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 a n d p r o d u c e s a gas s t r e a m c o n t a i n i n g a b o u t 8 0 % but produces off-gases containing about 10-14% sulfur sulfur d i o x i d e . T h e o r i g i n a l f o r m of t h e O u t o k u m p u process is n o t c o m p l e t e l y d i o x i d e , d e p e n d i n g o n the s u l f u r content of the ore concentrate t r e a t e d . M o r e r e c e n t l y , the a i r has b e e n e n r i c h e d w i t h o x y g e n to m a k e the process c o m p l e t e l y autogenous, r e d u c i n g the gas v o l u m e a n d i n c r e a s i n g t h e s u l f u r d i o x i d e c o n c e n t r a t i o n to 17 or 1 8 % (45). O u t o k u m p u has also d e v e l o p e d an associated process for r e d u c i n g t h e s u l f u r d i o x i d e to e l e m e n t a l s u l f u r w i t h c o a l o r o i l . T h i s process is n o w g o i n g into c o m m e r c i a l a p p l i c a t i o n (17). T h e O u t o k u m p u flash s m e l t i n g process is w i d e l y u s e d t h r o u g h o u t (18). a n d has n o w r e p l a c e d the r e v e r b e r a t o r y f u r n a c e i n t w o T h e volume of the w o r l d , b u t the first u n i t i n the U n i t e d States w i l l b e i n the n e w T y r o n e smelter a b r o a d (40, 47) T h e e l e c t r i c s m e l t i n g f u r n a c e has a l r e a d y h a d a l o n g h i s t o r y of use U . S . c o p p e r smelters, C o p p e r h i l l a n d I n s p i r a t i o n (18).
off-gas f r o m a n e l e c t r i c f u r n a c e is d e t e r m i n e d b y the tightness of the f u r n a c e enclosure, a n d i t is p r a c t i c a l to restrict a i r i n l e a k a g e sufficiently to p r o d u c e a gas r i c h e n o u g h for f e e d to a s u l f u r i c a c i d p l a n t (47). the I n s p i r a t i o n smelter, a n average s u l f u r d i o x i d e c o n c e n t r a t i o n of is a n t i c i p a t e d (48). f u r n a c e , a n d the t h e r m a l efficiency is h i g h (47, p o w e r p l a n t , i f t h a t is the source of p o w e r . 49). At 4-8%
H e a t transfer a n d c o n t r o l are g o o d i n the e l e c t r i c H o w e v e r , electric
s m e l t i n g i n d i r e c t l y partakes of the t h e r m a l inefficiency of t h e t h e r m a l H e n c e , it m a y n o t be as g e n e r a l l y f a v o r a b l e as autogenous flash s m e l t i n g . T h e c o n v e n t i o n a l c o n v e r t i n g process, w i t h its b a t c h o p e r a t i o n , i n h e r ently involves lem fluctuations i n the v o l u m e a n d s u l f u r d i o x i d e c o n c e n t r a t i o n The probof the off-gases a n d thus c o m p l i c a t e s s u l f u r r e c o v e r y (42, 50). heat boilers a n d b y u s i n g o x y g e n i n c o n v e r t i n g ( 9 ) . the converter Smith (45).
has b e e n p a r t i a l l y a l l e v i a t e d b y u s i n g i m p r o v e d hoods a n d w a s t e T h e flash smelter
p r o d u c e s a r i c h e r matte, w h i c h reduces the w o r k that m u s t b e d o n e b y N e w types of converters are a p p e a r i n g that offer The I n s p i r a t i o n smelter is b e i n g fitted with better facilities for gas c o n t a i n m e n t t h a n does the c o n v e n t i o n a l P i e r c e converter (49).
10
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H o b o k e n s i p h o n converters, the first u s e d i n the U n i t e d States s m e l t i n g a n d c o n v e r t i n g (51). f o r autogenous concentrate
(48).
T h e t o p - b l o w n r o t a r y converter, u s i n g o x y g e n , has b e e n a p p l i e d to n i c k e l It is a p p l i c a b l e to c o p p e r s m e l t i n g , b o t h s m e l t i n g a n d for m a t t e c o n v e r s i o n (49, flow 52). of off-gas that is r e a d i l y (49).
Tests h a v e i n d i c a t e d t h a t the average s u l f u r d i o x i d e concentrations i n the off-gases c a n b e as h i g h as 2 5 - 5 0 % v e r t i n g steps c a n y i e l d a single, steady processed for s u l f u r r e c o v e r y . scale (44, 53, 54), I d e a l l y , a c o n t i n o u s process i n c o r p o r a t i n g b o t h s m e l t i n g a n d c o n T h r e e s u c h processes, the W O R C R A , the
M i t s u b i s h i , a n d the N o r a n d a , h a v e b e e n tested o n a s e m i c o m m e r c i a l a n d a f u l l - s c a l e c o m m e r c i a l p l a n t of the N o r a n d a process is u n d e r c o n s t r u c t i o n ( 55 ). A l l the processes p r o d u c e gas streams r i c h e n o u g h for f e e d to a s u l f u r i c a c i d p l a n t , a n d the use of o x y g e n c a n Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 p r o d u c e s t i l l r i c h e r gases. W i d e a p p l i c a t i o n of a n y of these processes a w a i t s c o m p l e t i o n of c o m m e r c i a l d e v e l o p m e n t . A n o t h e r a p p r o a c h to c o p p e r s m e l t i n g ( o x i d e s m e l t i n g ) , a l r e a d y i n use a b r o a d , is b e i n g i n c o r p o r a t e d i n t o a n e w smelter i n A r i z o n a b y H e c l a M i n i n g C o . (18). T h e sulfide ore is to b e roasted to sulfate i n a fluid b e d will be roaster ( 56 ) a n d the r i c h off-gas f e d to a s u l f u r i c a c i d p l a n t . T h e s u l f u r i c a c i d w i l l b e u s e d to l e a c h t h e c a l c i n e d ore, a n d t h e c o p p e r r e c o v e r e d b y e l e c t r o w i n n i n g . A r e l a t e d c o m m e r c i a l process, the B r i x l e g g E l e c t r o - S m e l t i n g Process, e m p l o y s d e a d r o a s t i n g of the c o p p e r ore, f o l l o w e d b y p y r o m e t a l l u r g i c a l r e d u c t i o n of the oxide c a l c i n e w i t h c a r b o n i n an electric furnace (57). A m o n g the v a r i o u s h y d r o m e t a l l u r g i c a l processes f o r c o p p e r r e c o v e r y , those i n c o r p o r a t i n g a c o n t r o l l e d o x i d a t i o n of the sulfide ore to e l e m e n t a l s u l f u r are of p a r t i c u l a r interest (9, 58). r e d u c t i o n of s u l f u r d i o x i d e . Sulfuric Acid Plants contact T h e y a v o i d the p r o d u c t i o n of p o s s i b l y u n n e e d e d s u l f u r i c a c i d or t h e costly c o l l e c t i o n a n d subsequent
T h e means for r e d u c i n g the s u l f u r d i o x i d e emissions f r o m s u l f u r i c a c i d plants are a l r e a d y r e l a t i v e l y w e l l d e v e l o p e d .
A n y sulfur
d i o x i d e r e c o v e r e d as s u c h c a n b e r e c y c l e d to the a c i d p l a n t for c o n v e r s i o n to a c i d . T h e most p o p u l a r a p p r o a c h , at least i n n e w p l a n t s , appears to b e the d o u b l e - c o n t a c t process (59, 60) b a s i c contact process itself. w h i c h is s i m p l y a n extension of the no (10). I n s u l f u r - b u r n i n g p l a n t s , this presents
serious p r o b l e m s , b u t w h e r e the a c i d p l a n t is o p e r a t i n g o n a r e l a t i v e l y d i l u t e process gas, i t m a y n o t b e p o s s i b l e to operate a u t o g e n o u s l y a u x i l i a r y h e a t m u s t b e s u p p l i e d (61). I n t h e latter instance, the d o u b l e - c o n t a c t process c a n s t i l l b e u s e d , b u t S o m e forms of the d o u b l e - c o n t a c t process are r e p o r t e d c a p a b l e of o p e r a t i n g a u t o g e n o u s l y w i t h s u l f u r d i -
1.
S E M R A U
Industrial
Process Sources (62).
11 Applications now being made
o x i d e concentrations as l o w as 5 % gas c o l l e c t i o n systems. The conversion efficiencies of
to smelter gases are assisted b y measures to l i m i t infiltration of a i r i n t o double-contact systems reportedly 62).
r a n g e f r o m 9 9 . 5 % to as h i g h as 9 9 . 9 % , w i t h exit sulfur d i o x i d e c o n c e n trations r a n g i n g f r o m a b o u t 500 p p m to as l o w as 100 p p m (60, These conditions obviously depend system d e s i g n factors. E x i s t i n g single-contact a c i d p l a n t s c a n also b e c o n v e r t e d to d o u b l e contact plants (63). I n s u c h cases, h o w e v e r , u s i n g a d d - o n scrubber systems is a n a l t e r n a t i v e , a n d s e v e r a l s u c h systems h a v e b e e n u s e d c o m m e r c i a l l y . T h e C o m i n c o a m m o n i a a b s o r p t i o n process has b e e n u s e d for m a n y years (22, Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 64). T h e L u r g i S u l f a c i d process (65) and WellmanThe Mitsu(27, L o r d process ( 6 6 ) 67, 68), h a v e h a d m o r e recent a n d l i m i t e d use. o n the i n i t i a l gas c o n d i t i o n s a n d
b i s h i - J E C C O process has also b e e n a p p l i e d to a c i d p l a n t t a i l gases U n i t e d States.
b u t t h e g y p s u m b y - p r o d u c t w o u l d b e essentially a waste i n the
I n J a p a n , o p e n - c y c l e s c r u b b i n g of w a s t e gases w i t h s o d i u m h y d r o x i d e or c a r b o n a t e solutions has b e e n p o p u l a r f o r t r e a t i n g gas streams ( i n c l u d i n g s u l f u r i c a c i d p l a n t t a i l gases ) that c o n t a i n r e l a t i v e l y s m a l l t o t a l q u a n t i ties of s u l f u r d i o x i d e (27). A b s o r b e n t r e g e n e r a t i o n has b e e n u n n e c e s s a r y because the s o d i u m sulfite or sulfate c o u l d b e s o l d to k r a f t p u l p m i l l s . T h e U n i o n C a r b i d e P u r a s i v S is a fixed-bed a d s o r p t i o n process u s i n g a m o l e c u l a r sieve adsorbent. o p e r a t e d i n sequence; It removes s u l f u r d i o x i d e f r o m the c l e a n , d r y t a i l gases of contact s u l f u r i c a c i d p l a n t s . T w o or m o r e adsorbers are the l o a d e d b e d is r e g e n e r a t e d b y a s t r e a m of h e a t e d a i r that desorbs the s u l f u r d i o x i d e a n d t h e n is f e d to t h e i n l e t of the s u l f u r i c a c i d p l a n t . T h e first c o m m e r c i a l p l a n t of this t y p e is n o w o p e r a t i n g o n t h e t a i l gases of a single-contact a c i d p l a n t t h a t processes a m i x t u r e of spent a l k y l a t i o n a c i d a n d h y d r o g e n sulfide f r o m a r e f i n e r y (69, 70). I t is r e p o r t e d to r e d u c e the exit sulfur d i o x i d e c o n c e n t r a t i o n (69). f r o m a b o u t 4000 p p m ( a v e r a g e ) to 1 5 - 2 5 p p m
Claus Sulfur
Plants
T h e h y d r o g e n sulfide present i n n a t u r a l gas, S N G , t o w n gas, a n d synthesis gas m u s t b e r e m o v e d for the sake of p r o d u c t gas quality. H e n c e , t e c h n o l o g y for r e m o v i n g h y d r o g e n sulfide f r o m gases has b e e n e x t e n s i v e l y d e v e l o p e d a n d is itself t h e subject of a v o l u m i n o u s literature (71, 72). F r o m t h e s t a n d p o i n t of e c o n o m i c r e c o v e r y of sulfur, the c h e m F o r t h e most p a r t , these processes are n o t w i t h i n the istry of h y d r o g e n sulfide is s u b s t a n t i a l l y m o r e t r a c t a b l e t h a n that of sulfur dioxide. chosen scope of the present p a p e r .
12
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O n c e r e c o v e r e d f r o m gas streams, h y d r o g e n sulfide m u s t g e n e r a l l y b e c o n v e r t e d e i t h e r to s u l f u r i c a c i d or, m o r e c o m m o n l y , to e l e m e n t a l sulfur. T h e C l a u s process is the s t a n d a r d one for c o n v e r t i n g h y d r o g e n A few a b s o r p t i o n processes, s u c h as the sulfide to e l e m e n t a l s u l f u r .
S t r e t f o r d (71, 72, 7 3 ) , t h a t also o x i d i z e t h e a b s o r b e d h y d r o g e n sulfide to e l e m e n t a l s u l f u r are u s e d p r i m a r i l y to treat gas streams c o n t a i n i n g o n l y r e l a t i v e l y l o w concentrations of h y d r o g e n sulfide. T h e c o n v e r s i o n of h y d r o g e n sulfide to e l e m e n t a l s u l f u r i n the C l a u s process is l i m i t e d b y a c o m b i n a t i o n of e q u i l i b r i u m a n d k i n e t i c factors. O v e r the past d e c a d e , t h e pressures of a i r p o l l u t i o n c o n t r o l r e q u i r e m e n t s h a v e r e s u l t e d i n m a j o r i m p r o v e m e n t s i n the d e s i g n a n d o p e r a t i o n of C l a u s p l a n t s , w i t h consequent increases i n c o n v e r s i o n a n d r e d u c t i o n of s u l f u r oxides emissions ( 74-79 ). N e v e r t h e l e s s , emissions s t i l l c o m m o n l y e x c e e d Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 the p e r m i s s i b l e l i m i t s c o m i n g into force b o t h i n the U n i t e d States a n d a b r o a d . S u l f u r d i o x i d e r e d u c t i o n plants present s i m i l a r p r o b l e m s . A p a r t f r o m the i n i t i a l f u r n a c e or reactor, t h e y are essentially C l a u s p l a n t s . T h e effluent streams f r o m C l a u s p l a n t s c o n t a i n u n r e a c t e d h y d r o g e n sulfide a n d s u l f u r d i o x i d e a n d e l e m e n t a l s u l f u r present as v a p o r a n d m i s t (77). (77). They commonly also c o n t a i n c a r b o n y l sulfide a n d carbon d i s u l f i d e f o r m e d b y reactions w i t h h y d r o c a r b o n s present i n t h e f e e d gas I t is u s u a l l y r e q u i r e d that t h e t a i l gas b e i n c i n e r a t e d , e v e n t h o u g h not otherwise t r e a t e d , to c o n v e r t t h e h y d r o g e n sulfide, c a r b o n y l sulfide, a n d c a r b o n d i s u l f i d e to the less toxic a n d m a l o d o r o u s s u l f u r d i o x i d e . S i n c e t h e c o n v e r s i o n l i m i t e v e n i n i m p r o v e d C l a u s p l a n t s is not r e a d i l y r a i s e d a b o v e a b o u t 9 7 % , the emphasis i n emission c o n t r o l has n o w passed to u s i n g t a i l gas-treating p l a n t s to attain o v e r a l l c o n v e r s i o n efficiencies of 9 9 % or m o r e . T h e e c o n o m i c s of c o n t r o l at C l a u s p l a n t s sulfur a r e p r o b a b l y m o r e f a v o r a b l e t h a n i n a n y other case r e q u i r i n g c o n t r o l of d i l u t e gas streams (i.e., those c o n t a i n i n g less t h a n about 2 - 3 % d i o x i d e ). T h e r e are three p r i n c i p a l approaches to t a i l gas t r e a t m e n t : 1. C o n t i n u a t i o n of the C l a u s r e a c t i o n at l o w e r e d temperatures, o n a s o l i d catalyst or i n a l i q u i d m e d i u m . 2. C a t a l y t i c hydrognation of the s u l f u r d i o x i d e , c a r b o n y l sulfide, a n d c a r b o n d i s u l f i d e i n t h e t a i l gas to r e f o r m h y d r o g e n sulfide, w h i c h is subsequently recovered b y absorption. 3. I n c i n e r a t i o n of the t a i l gas a n d c o n v e r s i o n of a l l s u l f u r c o m p o u n d s to s u l f u r d i o x i d e , f o l l o w e d b y one of the s u l f u r d i o x i d e c o n t r o l systems. T h e first class of systems is i l l u s t r a t e d b y the S u l f r e e n (80, 81, a n d I F P (83, 84) processes. takes p l a c e o n t h e c a r b o n or a l u m i n a catalyst i n a fixed-bed 82) I n the S u l f r e e n process the C l a u s r e a c t i o n reactor. A t
the r e d u c e d t e m p e r a t u r e , the c o n v e r s i o n e q u i l i b r i u m is i m p r o v e d , b u t the s u l f u r is r e t a i n e d o n t h e catalyst as a l i q u i d a n d m u s t b e r e m o v e d b y
1.
S E M R A U
Industrial
Process Sources cycle.
13 I n the I F P process the C l a u s (typically a polyalkylene efficiencies
h o t inert gas i n a r e g e n e r a t i o n glycol)
r e a c t i o n takes p l a c e i n a h i g h - b o i l i n g solvent not affected.
c o n t a i n i n g a catalyst. C a r b o n y l sulfide a n d c a r b o n d i s u l f i d e are T h e p r o d u c t s u l f u r is d r a w n off as a l i q u i d . T h e so that n e i t h e r
of the S u l f r e e n a n d I F P processes are about 7 5 - 9 0 % , trations r e a c h e d w i t h some of the other processes.
process is e c o n o m i c a l l y s u i t a b l e for a t t a i n i n g the v e r y l o w exit c o n c e n T h e s e c o n d class of systems is i l l u s t r a t e d b y the B e a v o n ( 73, 85 ) a n d S h e l l S C O T (86) processes. I n each process a c o b a l t m o l y b d a t e catalyst p r o m o t e s hydrognation of the s u l f u r d i o x i d e a n d e l e m e n t a l s u l f u r to h y d r o g e n sulfide. It also catalyzes the h y d r o l y s i s of the c a r b o n y l sulfide a n d c a r b o n disulfide to h y d r o g e n sulfide. T h e gas stream is t h e n c o o l e d , the w a t e r v a p o r is c o n d e n s e d out, a n d t h e h y d r o g e n sulfide is r e c o v e r e d . Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 I n the B e a v o n process, the h y d r o g e n sulfide is a b s o r b e d a n d o x i d i z e d to e l e m e n t a l s u l f u r b y the S t r e t f o r d process. I n the S C O T process, the absorbent h y d r o g e n sulfide is c o n c e n t r a t e d b y a b s o r p t i o n i n a n a l k a n o l a m i n e s o l u t i o n , a n d t h e c o n c e n t r a t e d h y d r o g e n sulfide s t r i p p e d f r o m the is r e c y c l e d to the C l a u s u n i t . technologies. concentrations The B o t h the B e a v o n a n d S C O T processes gives m u c h l o w e r exit
consist of c o m b i n a t i o n s of p r e v i o u s l y u s e d a n d essentially c o n v e n t i o n a l S t r e t f o r d system r e p o r t e d l y of h y d r o g e n sulfide t h a n does a l k a n o l a m i n e scrubbing,
b u t is c h e m i c a l l y a n d m e c h a n i c a l l y m u c h m o r e c o m p l e x . T h e t h i r d class of c o n t r o l systems m a y use a n y of t h e s u l f u r d i o x i d e c o n t r o l systems; a m o n g those u s e d c o m m e r c i a l l y are the H a l d o r T o p s o e (5, 8 0 ) , W e l l m a n - L o r d (27, 67), a n d C h i y o d a (27, 67, 87) systems. The circumstances are g e n e r a l l y h i g h l y f a v o r a b l e for r e c o v e r y processes that p r o d u c e a stream of c o n c e n t r a t e d sulfur d i o x i d e , since this c a n be r e c y c l e d to the C l a u s p l a n t . T h e a p p l i c a t i o n of processes that p r o d u c e s u l furic acid or s o l i d wastes of will be dictated recovery only by peculiar local a abcircumstances. O n e subclass sulfur dioxide processes incorporates the l i q u i d - p h a s e v a r i a t i o n of the C l a u s r e a c t i o n for r e g e n e r a t i n g are the Stauffer A q u a c l a u s process (88),
sorbent a n d d i r e c t l y p r o d u c i n g e l e m e n t a l s u l f u r . Processes of this t y p e w h i c h w a s d e v e l o p e d specifically (89). for C l a u s p l a n t t a i l gases, a n d the B u r e a u of M i n e s C i t r a t e process
I n e a c h , the absorbent is t h e s o d i u m salt of a stable, n o n v o l a t i l e w e a k a c i d , w h i c h forms a basic s o l u t i o n b y h y d r o l y s i s . T h e a n i o n of the a c i d buffers the s o l u t i o n as a c i d is f o r m e d b y the a b s o r p t i o n of s u l f u r d i o x i d e . T h e spent absorbent, w h i c h consists of a s o l u t i o n of s o d i u m sulfite a n d bisulfite a n d of the w e a k a c i d , is c o n t a c t e d d i r e c t l y w t i h h y d r o g e n sulfide. T h e h y d r o g e n sulfide reacts w i t h the sulfite a n d b i s u l f i t e to y i e l d elem e n t a l s u l f u r , a n d the regenerated basic salt s o l u t i o n is r e c i r c u l a t e d t o the a b s o r p t i o n step.
14
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I n the B u r e a u of M i n e s process the absorbent is s o d i u m c i t r a t e ; that u s e d i n the A q u a c l a u s process has b e e n i d e n t i f i e d as s o d i u m (90). phosphate A s is c o m m o n i n s i m i l a r processes, some of the s u l f u r d i o x i d e is C o n s e q u e n t l y , i t is necessary to
o x i d i z e d to sulfate, w h i c h is n o t r e a d i l y regenerated, a n d t h i o s u l f a t e a n d p o l y t h i o n a t e s are also f o r m e d (88, 89). d r a w off p u r g e streams of the absorbents, recover t h e citrate a n d p h o s p h a t e for reuse, a n d d i s c a r d t h e sulfate a n d thionates. Losses of citrate a n d p h o s p h a t e i n this o p e r a t i o n c a n g r e a t l y affect the e c o n o m i c s of the processes. I F P has d e v e l o p e d a n a m m o n i a a b s o r p t i o n process (91) t h a t is The p a r a l l e l to the C i t r a t e a n d A q u a c l a u s processes i n s o m e respects.
s u l f u r d i o x i d e is a b s o r b e d i n a m m o n i a s o l u t i o n i n a g e n e r a l l y c o n v e n t i o n a l Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 m a n n e r . T h e spent absorbent c o n t a i n i n g a m m o n i u m sulfite a n d bisulfite is d e c o m p o s e d b y h e a t i n g i n a n evaporator, a n d the r e s u l t i n g a m m o n i a , s u l f u r d i o x i d e , a n d w a t e r v a p o r are sent to a n I F P l i q u i d - p h a s e C l a u s reactor (83) i n t o w h i c h h y d r o g e n sulfide is also injected. T h e h y d r o g e n sulfide a n d s u l f u r d i o x i d e react to f o r m e l e m e n t a l s u l f u r , a n d the a m m o n i a , w h i c h is not affected, passes t h r o u g h the reactor a n d is r e c y c l e d to the absorber. T h e n o n v o l a t i l e sulfate a n d thionates f r o m t h e sulfite 91). T h e sulfur dioxide from e v a p o r a t o r pass to a sulfate r e d u c t i o n reactor w h e r e t h e y are r e d u c e d to s u l f u r d i o x i d e w i t h h y d r o g e n sulfide (27, I t has b e e n suggested (80, 88) this o p e r a t i o n also is sent to the I F P reactor. t h a t the A q u a c l a u s or C i t r a t e process m i g h t be s u b s t i t u t e d for the c o n v e n t i o n a l C l a u s p l a n t to c o n v e r t a l l t h e h y d r o g e n sulfide to e l e m e n t a l sulfur. O n e m a j o r factor d e t e r m i n i n g the p r a c t i c a l i t y of this a p p r o a c h is t h e p r o b l e m of s e p a r a t i n g the sulfate a n d thionates f r o m t h e p h o s p h a t e o r citrate. A secondary process system to r e c o v e r s o d i u m a n d s u l f u r f r o m the p u r g e d absorbent w i l l b e a v i r t u a l necessity at a n y l a r g e i n s t a l l a t i o n . T h e c a p i t a l cost of a C l a u s s u l f u r p l a n t s t r o n g l y depends t o t a l gas flow (77), flow d e t e r m i n e d p r i m a r i l y b y the gas flow. o n the
a n d the costs for a t a i l g a s - t r e a t i n g system w i l l b e C o n s e q u e n t l y , r e d u c i n g the gas A major,
c a n s i g n i f i c a n t l y r e d u c e b o t h c a p i t a l a n d o p e r a t i n g costs.
i f not the largest, p a r t of the gas i n the C l a u s system is n i t r o g e n w h i c h is i n t r o d u c e d i n the a i r u s e d to c o m b u s t the h y d r o g e n sulfide, a n d i n t o the t a i l gas w h e n t h e latter is i n c i n e r a t e d (72, b u s t i o n (72, 77). 77). T h e gas v o l u m e c o u l d b e g r e a t l y r e d u c e d b y u s i n g o x y g e n i n s t e a d of a i r to s u p p o r t the c o m T h e cost savings f r o m t h e use of o x y g e n w o u l d p r o b a b l y not b e sufficient to j u s t i f y c o n s t r u c t i n g a n o x y g e n p l a n t solely t o s u p p l y the C l a u s p l a n t , b u t i f a n o x y g e n p l a n t w e r e r e q u i r e d f o r other purposes a n y w a y , p r o v i d i n g i n c r e m e n t a l c a p a c i t y to s u p p l y t h e C l a u s
1.
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p l a n t as w e l l m i g h t h a v e m e r i t . I n p e t r o l e u m refineries p r o d u c i n g i n t e r m e d i a t e - B t u f u e l gas f r o m o i l or i n S N G p l a n t s , s u c h o x y g e n p l a n t s w i l l g e n e r a l l y be r e q u i r e d .
Petroleum
Refineries
P e t r o l e u m refineries, a l o n g w i t h n a t u r a l gas p r o c e s s i n g p l a n t s , are p r o b a b l y the best situated s u l f u r oxides sources w i t h respect to e m i s s i o n c o n t r o l . T h e a v a i l a b i l i t y of h y d r o g e n sulfide a l l o w s r e a d y processing r e c o v e r e d s u l f u r d i o x i d e to e l e m e n t a l s u l f u r for d i s p o s a l . I n U . S . refineries at least, the largest source of s u l f u r o x i d e emissions is u n d o u b t e d l y the b u r n i n g of h i g h - s u l f u r fuels, i n c l u d i n g sour refinery Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 gases, r e s i d u a l o i l , h e a v y refinery residues, a n d p e t r o l e u m coke. D u r i n g refinery upsets, the flaring of large amounts of u n t r e a t e d refinery gas m a y also result i n h i g h s h o r t - t e r m s u l f u r oxide e m i s s i o n rates. T h e pressure of air p o l l u t i o n c o n t r o l regulations is r e s u l t i n g i n g e n e r a l treatment of r e finery gases. H y d r o g e n sulfide is b e i n g r e m o v e d b y w e l l established Desulfurt e c h n o l o g y a n d c o n v e r t e d to e l e m e n t a l s u l f u r i n C l a u s p l a n t s . of
i z e d r e s i d u a l o i l m i g h t be u s e d , w h e r e a v a i l a b l e , to r e p l a c e t h e l i q u i d fuels, b u t it has b e e n c o m m o n p r a c t i c e for refineries to c o n s u m e t h e i r lowest g r a d e residues i n t h e i r o w n operations. F l u e gas s c r u b b i n g systems m i g h t be u s e d to c o n t r o l the s u l f u r d i o x i d e e m i t t e d f r o m b u r n i n g of s u c h fuels. T h i s is b e i n g d o n e to a l i m i t e d extent i n J a p a n (27). However, an (92). a l t e r n a t i v e a p p r o a c h is to gasify the residues to p r o d u c e a l o w - B t u f u e l gas, u s i n g a process s u c h as the S h e l l G a s i f i c a t i o n Process, ( S G P ) T h i s w o u l d p e r m i t r e c o v e r y of the s u l f u r as h y d r o g e n sulfide, u s i n g the same processes e m p l o y e d to treat the refinery gases. T h e S h e l l G a s i f i c a t i o n Process has b e e n a p p l i e d o n a f a i r l y large c o m m e r c i a l scale T h e s u l f u r oxide emissions f r o m the regenerators of fluid (93). catalytic (7).
c r a c k i n g units m a y b e c o n t r o l l e d either b y h y d r o t r e a t i n g the f e e d to the c a t a l y t i c c r a c k e r or b y s c r u b b i n g the flue gas f r o m t h e regenerator t i o n to emission r e d u c t i o n a n d is a l r e a d y i n use (7, 94, 95). t h e regenerator flue gas has b e e n p r o p o s e d (7, 96), tions a p p e a r to be i n service. I t is r e p o r t e d (97) H y d r o t r e a t i n g the feedstock presents several process advantages i n a d d i Scrubbing b u t no s u c h i n s u l a that t h e first k n o w n
w e t s c r u b b e r i n s t a l l a t i o n for regenerator flue gas w i l l go i n t o service at the E x x o n refinery at B a y t o w n , T e x . T h e scrubber w i l l remove sulfur It appears that the m a i n d u t y d i o x i d e as w e l l as collect catalyst fines, r e p l a c i n g the c o n v e n t i o n a l electrostatic p r e c i p i t a t o r for the latter d u t y . of t h e s c r u b b e r w i l l be p a r t i c u l a t e c o l l e c t i o n .
16 Steel Mills
S U L F U R
R E M O V A L
A N D
R E C O V E R Y
T h e c o k e o v e n gas p r o d u c e d a n d u s e d i n i n t e g r a t e d steel m i l l s has very commonly not b e e n d e s u l f u r i z e d except w h e r e the combustion gases c a m e i n contact w i t h m o l t e n m e t a l . C o n s e q u e n t l y , the c o m b u s t i o n of coke o v e n gas has b e e n one of the p r i n c i p a l sources of sulfur d i o x i d e emissions f r o m steel m i l l s , e v e n t h o u g h a d e q u a t e t e c h n o l o g y for c o n t r o l has l o n g b e e n a v a i l a b l e . O c c a s i o n a l l y , the h y d r o g e n sulfide i n the gas has b e e n c o n c e n t r a t e d b y a n a b s o r p t i o n process a n d c o n v e r t e d to s u l f u r i c a c i d i n a contact p l a n t or to e l e m e n t a l s u l f u r i n a C l a u s p l a n t . l a t i o n of m o r e s u c h systems b o t h i n the U n i t e d States a n d a b r o a d (27, B e c a u s e c o k e o v e n gas does n o t c o n t a i n e x t r e m e l y h i g h Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 b y processes s u c h as the S t r e t f o r d (73, 85) or T a k a h a x (27, sulfide concentrations of h y d r o g e n sulfide, i t c a n b e effectively 72), The 98). i n c r e a s i n g l y stringent a i r p o l l u t i o n c o n t r o l regulations are f o r c i n g i n s t a l hydrogen treated which
b o t h a b s o r b the h y d r o g e n sulfide a n d o x i d i z e it to e l e m e n t a l sulfur. A b o u t h a l f the s u l f u r oxides emission f r o m steel p l a n t s originates i n s i n t e r i n g p l a n t s (99), w i t h m u c h h i g h e r p r o p o r t i o n s at some m i l l s (100). T h e q u a n t i t y , of course, d e p e n d s o n t h e s u l f u r content of the ore b e i n g s i n t e r e d , a n d t h e s i t u a t i o n w i l l be s i m i l a r at p e l l e t p l a n t s , w h i c h are g e n e r a l l y l o c a t e d at the mines r a t h e r t h a n at the steel m i l l s . I n the U n i t e d States, c o n c e r n w i t h sinter p l a n t p o l l u t i o n has b e e n f o c u s e d l a r g e l y o n p a r t i c u l a t e matter, b u t i n G e r m a n y a n d J a p a n the s u l f u r oxides emission is of serious concern. I t is l i k e l y t h a t at some sinter plants, fluoride emissions are a c t u a l l y a m o r e serious p o l l u t i o n p r o b l e m t h a n s u l f u r oxide emission. F l u o r i d e emissions f r o m sinter plants are r e c e i v i n g i n c r e a s i n g l y serious attention i n G e r m a n y a n d the N e t h e r l a n d s . I n J a p a n , s c r u b b i n g systems are b e i n g a p p l i e d to sinter p l a n t s to c o n t r o l s u l f u r d i o x i d e a n d s h o u l d also be v e r y effective hydrogen fluoride. K a w a s a k i Steel C o r p . has tested scale
3
in removing and will now
Mitsubishi-JECCO (27)
l i m e s c r u b b i n g process o n a d e m o n s t r a t i o n i n s t a l l a full-scale system, h a n d l i n g 750,000 m N i p p o n K o k a n has d e v e l o p e d
gas/hr, on a new sintering double-
p l a n t that m a y b e t h e largest i n the w o r l d ( 100). a n d tested a n a m m o n i a - b a s e a l k a l i s c r u b b i n g process for sinter plants (27). t h e fluoride that is p r o b a b l y present. T h e concentrations of s u l f u r d i o x i d e i n sinter p l a n t gases are v a r i o u s l y r e p o r t e d to range f r o m a b o u t 0.02 to 1.5 v o l % (8,68,101). fluorides There to the would appears to be n o w a y to increase the s u l f u r d i o x i d e concentrations levels s u i t a b l e for e c o n o m i c recovery, a n d t h e presence of b e a h i n d r a n c e i n a n y case. H o w e v e r , it m a y b e feasible to r e d u c e B o t h i n this system a n d
the M i t s u b i s h i process, l i m e w i l l p r e c i p i t a t e the s u l f u r oxides as w e l l as
1.
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waste gas v o l u m e b y a p p l y i n g t h e t e c h n i q u e s of u p d r a f t s i n t e r i n g a n d gas r e c i r c u l a t i o n that h a v e b e e n u s e d i n the nonferrous s m e l t i n g i n d u s t r y .
Pulp
Mills I n t h e p u l p i n g i n d u s t r y , s u l f u r oxides emissions represent loss of
p u l p i n g c h e m i c a l , b u t t h e e c o n o m i c loss is a p p a r e n t l y n o t r e g a r d e d as v e r y serious, at least i n this p e r i o d of r e l a t i v e l y a b u n d a n t a n d c h e a p sulfur. I n c u r r e n t p r a c t i c e , m u c h s u l f u r is e v i d e n t l y lost to b e c o m e either a w a t e r o r a i r p o l l u t a n t (16, 53, 102), but pollution control regulations are f o r c i n g i n c r e a s e d r e c o v e r y a n d r e c y c l i n g of s u l f u r a n d other p u l p i n g c h e m i c a l s . T h e n e e d to increase heat r e c o v e r y a n d use s h o u l d also i n f l u Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 ence e m i s s i o n controls. I n t h e k r a f t process, the most serious a i r p o l l u t a n t s are h y d r o g e n sulfide a n d other r e d u c e d s u l f u r c o m p o u n d s (103). E v e n though their mass emissions m a y n o t b e h i g h , t h e i r extreme malodorousness constitutes the major p r o b l e m . T h e emissions of s u l f u r d i o x i d e f r o m k r a f t r e c o v e r y furnaces m a y range f r o m s m a l l to s u b s t a n t i a l , d e p e n d i n g o n t h e c o m p o sition of t h e b l a c k l i q u o r a n d o n t h e o p e r a t i n g c o n d i t i o n s i n the f u r n a c e (104-109). S e v e r a l recent studies h a v e t r e a t e d factors i n f l u e n c i n g t h e s u l f u r d i o x i d e e m i s s i o n (104, 106, 107, 108). T h e s u l f u r d i o x i d e i n k r a f t r e c o v e r y f u r n a c e gases c a n b e r e a d i l y s c r u b b e d w i t h s o d i u m c a r b o n a t e to p r o d u c e s o d i u m sulfite or sulfate as m a k e u p f o r c o o k i n g l i q u o r p r e p a r a t i o n . T h e absorbent l i q u o r c a n b e u s e d i n the s c r u b b e r units that collect p a r t of t h e s o d i u m carbonate a n d sulfate p a r t i c u l a t e s t h a t escape c o l l e c t i o n b y t h e electrostatic p r e c i p i t a t o r . P a r t i c u l a r l y i n S w e d e n , s u c h afterscrubbers are sometimes u s e d also to r e c o v e r l o w l e v e l heat (110), cover s u l f u r d i o x i d e as w e l l (111). sulfur dioxide from kraft recovery common i n Japan (27). a n d t h e y c o u l d b e e x t e n d e d to r e T h e use of afterscrubbers to c o l l e c t f u r n a c e gases a p p e a r to be f a i r l y
S u l f u r d i o x i d e e m i s s i o n is a m u c h m o r e serious p r o b l e m i n sulfite m i l l s . T h e s u l f u r d i o x i d e m a y b e e m i t t e d i n t h e t a i l gases f r o m a b s o r p t i o n towers u s e d to p r e p a r e c o o k i n g l i q u o r , i n b l o w p i t gases, i n digester r e l i e f gases, a n d i n v e n t i n g n o n c o n d e n s i b l e s l i q u o r evaporators (102, 103, 112). f r o m m u l t i p l e - e f f e c t spent (113). Vent T a i l gas s c r u b b e r s a r e sometimes
a p p l i e d to r e d u c e t h e emissions f r o m a b s o r p t i o n towers c o n t a i n e d (102, 103, 112).
gases m a y also b e sent to the absorbers to r e c o v e r the s u l f u r d i o x i d e B l o w p i t gases c a n b e s c r u b b e d w i t h w a t e r A l t h o u g h this p r o to r e c o v e r b o t h s u l f u r d i o x i d e a n d heat (6, 114). u n i v e r s a l l y p r a c t i c e d i n t h e U n i t e d States e v e n n o w .
c e d u r e is r e p o r t e d to b e e c o n o m i c a l l y f a v o r a b l e , i t is a p p a r e n t l y n o t
18
S U L F U R
R E M O V A L
A N D
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T h e r e q u i r e m e n t s for w a t e r p o l l u t i o n c o n t r o l h a v e b e e n f o r c i n g a shift to c o n c e n t r a t i n g spent sulfite p u l p i n g l i q u o r b y e v a p o r a t i o n , f o l l o w e d b y incineration w i t h heat recovery a b l e f o r r e c y c l e to the p u l p i n g process. (102). When calcium-base l i q u o r is b u r n e d , t h e s u l f u r emerges as c a l c i u m sulfate a n d is n o t a v a i l T h e flue gas f r o m s u c h furnaces s u l f u r d i o x i d e , a n d i n one i n S w e d e n is r e p o r t e d to c o n t a i n 0.20.3% (115). W h e n a m m o n i a - b a s e sulfite l i q u o r is b u r n e d , t h e s u l f u r is released as sulfur dioxide. H o w e v e r , i t has n o t b e e n t h e p r a c t i c e to r e c o v e r t h e developed systems Nevertheless, recovery (116). 121). s u l f u r d i o x i d e f o r re-use, a l t h o u g h a b s o r p t i o n systems w e r e for t h e p u r p o s e (23, 24, 102, 103, 112). Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 are n o w g o i n g i n t o service w i t h a m m o n i a - b a s e m i l l s
S w e d i s h m i l l a B a h c o w e t limestone s c r u b b e r is u s e d to treat t h e gases
M o s t of sulfite m i l l s u s i n g a s u l f u r d i o x i d e r e c o v e r y c y c l e h a v e u s e d the w e l l e s t a b l i s h e d magnesia-base process (117, 118, 119, 120, W h e n the magnesia-base spent l i q u o r is b u r n e d , or m a g n e s i u m sulfite a n d sulfate are s m e l t e d i n t h e presence of excess c a r b o n , t h e s u l f u r goes off as s u l f u r d i o x i d e , a n d t h e m a g n e s i u m r e m a i n s as t h e oxide. temperatures. and other I n the c a l c i u m system, t h e e q u i v a l e n t reactions t a k e p l a c e o n l y at m u c h h i g h e r E x p e r i e n c e w i t h t h e magnesia-base p u l p i n g process w a s (33) sulfur dioxide u n d o u b t e d l y t h e i n s p i r a t i o n f o r d e v e l o p m e n t of the C h e m i c o - B a s i c s i m i l a r processes u s i n g m a g n e s i a i n c y c l i c r e c o v e r y systems. T h e s o d i u m - b a s e sulfite systems present experience w i t h s u l f u r r e c o v e r y processes t h a t m a y h a v e w i d e a p p l i c a t i o n outside t h e p a p e r p u l p industry. T h e b a s i c c h e m i s t r y i n v o l v e d is h i s t o r i c a l l y v e r y o l d (122). E s s e n t i a l l y , f o u r steps u n d e r l i e t h e v a r i o u s processes: 1. T h e spent s o d i u m - b a s e sulfite l i q u o r is b u r n e d u n d e r r e d u c i n g c o n d i t i o n s , as i n the k r a f t process, y i e l d i n g a smelt of s o d i u m sulfide. 2. T h e s o d i u m sulfide is t r e a t e d w i t h steam a n d c a r b o n d i o x i d e . S o d i u m c a r b o n a t e is f o r m e d , a n d h y d r o g e n sulfide is d r i v e n off. 3. T h e s o d i u m c a r b o n a t e is u s e d to absorb s u l f u r d i o x i d e , p r o d u c i n g f r e s h s o d i u m sulfite or b i s u l f i t e f o r use as c o o k i n g l i q u o r . 4. T h e h y d r o g e n sulfide is b u r n e d to p r o v i d e t h e s u l f u r d i o x i d e f o r c o o k i n g l i q u o r p r o d u c t i o n , o r i n some processes, i t is sent to a C l a u s p l a n t f o r c o n v e r s i o n to e l e m e n t a l s u l f u r . A m o n g t h e v a r i o u s p u l p i n g c h e m i c a l r e c o v e r y systems a r e t h e S t o r a (123), S i v o l a (124), a n d T a m p e l l a (125) processes, w h i c h h a v e been d e m o n s t r a t e d c o m m e r c i a l l y . T h e first of t h e process steps g i v e n a b o v e c a n b e a c c o m p l i s h e d w i t h s o d i u m sulfate o r sulfite b y s m e l t i n g u n d e r r e d u c i n g c o n d i t i o n s , w h i c h is t h e oldest m e t h o d f o r p r o d u c i n g s o d i u m sulfide (126).
1.
SE M R A U
Industrial
Process Sources
19
T h e process c o m p o s e d of t h e a b o v e sequence of steps c a n b e u s e d t o recover e l e m e n t a l s u l f u r f r o m s u l f u r d i o x i d e - b e a r i n g gases, u s i n g s o d i u m c a r b o n a t e as t h e p r i m a r y absorbent. A l t e r n a t i v e l y , i t c a n b e u s e d to recover s u l f u r a n d s o d i u m c a r b o n a t e f r o m t h e s o d i u m sulfate f o r m e d i n the c y c l i c a b s o r p t i o n processes, s u c h as the W e l l m a n - L o r d , t h a t a r e u s e d for c o n c e n t r a t i n g s u l f u r d i o x i d e f r o m d i l u t e gas streams (10). A purge s t r e a m o f t h e absorbent m u s t b e w i t h d r a w n to p r e v e n t b u i l d u p of excessive sulfate. D i s p o s a l of the s o d i u m sulfate as s u c h w i l l p r o b a b l y b e c o m e difficult i f the s o d i u m - b a s e a b s o r p t i o n processes are u s e d o n a l a r g e N i t t e t u C h e m i c a l E n g i n e e r i n g has scale f o r s u l f u r d i o x i d e r e c o v e r y .
d e v e l o p e d a process u s i n g t h e same b a s i c c h e m i s t r y to d e a l s p e c i f i c a l l y w i t h t h e sulfate b u i l d u p i n s o d i u m - b a s e absorbents u s e d to d e s u l f u r i z e c o k e o v e n gas Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001 Literature (127).
Cited
1. Cavender, J. H . , Kircher, D. S., Hoffman, A. J., "Nationwide Air Pollutant Emission Trends1940-1970," E P A Publ. No. AP-115 (Jan. 1973). 2. Beers, W . D., "Characterization of Claus Plant Emissions," Processes Research, Inc., E P A Report EPA-R2-73-188, Apr. 1973, NTIS: PB-220376. 3. Environmental Protection Agency, "Cost of Clean Air1973," U.S. Senate Document No. 93-40, U.S. Government Printing Office, Washington, D.C. (1972). 4. Economic Commission for Europe, "Desulfurization of Fuels and Combustion Gases," Report on the Proceedings of the Seminar, Geneva (Nov. 16-20, 1970), United Nations, . Y., 1971. 5. Bailleul, M . R., Bapseres, . ., Guyot, G . L., in "Sulfur and S O Developments," pp. 119-122, A I C h E , 1971. 6. Lea, N . S., Christoferson, E . A., Chem. Eng. Progr. (1965) 61(11), 89. 7. Wollaston, E . G., Forsythe, W . L . , Vasalos, I. ., Oil Gas J. (1971) 69(31), 64. 8. Brocke, W., VDI-Berichte (1970) 149, 98. 9. Semrau, . T., J. Metals (1971) 23(3), 41. 10. Semrau, K. T., J. Air Pollut. Contr. Ass. (1971) 21, 185. 11. U.S. Bur. Mines, Inform. Cir. 8571 (1971). 12. Gibson, F. W., Chem. Eng. (1969) 76(26), 66. 13. Mining Eng. (1973) 25, 19. 14. Smelter Control Research Association, "The Removal of Sulphur Dioxide from Copper Reverberatory Furnace Gas by Wet-Limestone Scrubbing," New York (1973). 15. Hunter, W . D., Jr., Power (1973) 117(9), 63. 16. Hunter, W . D., Jr., Michener, A. W., Eng. Mining J. (1973) 174(6), 117. 17. Malmstrom, R., Tuominen, T . , Advan. Extract. Metallurgy Refining, Paper 20, Institution of Mining and Metallurgy, London, Oct. 1971. 18. Beal, J. V., Mining Eng. (1973) 25(4), 35. 19. Mining Eng. (1972) 24(4), 27. 20. Petersson, S. ., in "Environmental Control," C. Rampacek, ed., pp. 3-18, The Metallurgical Society of A I M E , 1972. 21. Petersson, S., Kem. Tidskr. (1970) 1, 34. 22. King, R. ., Ind. Eng. Chem. (1950) 42, 2241. 23. Clement, J. L . , Sage, W . L . , Tappi (1969) 52(8), 1449.
2
20
SULFUR REMOVAL AND RECOVERY
24. Palmrose, G. V., Hull, J. H . , Tappi (1952) 35, 193. 25. Mascarello, J., Auclair, J., Hamelin, R., Pelecier, C., Proc. Amer. Power Conf. (1969) 31, 439. 26. Dean, R. S., U.S. Bur. Mines, Rep. Invest. 3339 (May 1937). 27. Ando, J., "Recent Developments in Desulfurization of Fuel Oil and Waste Gas in Japan1973," E P A Rept. No. EPA-R2-73-229, May 1973, NTIS: PB-221-439. 28. Eng. Mining J. (1973) 174(2), 74. 29. Guyot, G., Chim. Ind., Genie Chim. (1969) 101, 31. 30. Ibid., 101, 813. 31. Eng. Mining J. (1971) 172(11), 69. 32. Ibid., 173(8), 69. 33. Shah, I. S., Chem. Eng. Progr. (1971) 67, 51. 34. Kakaria, V. K., Turner, A . L . , Teter, . K., in "Environmental Control," C. Rampacek, ed., pp. 89-102,The Metallurgical Society of A I M E , 1972. 35. Mealey, M . , Eng. Mining J. (1972) 173(6), 130. 36. Donovan, J. R., Stuber, P. J., Chem. Eng. (1970) 77(26), 47. 36. McMeekin, G . R., Can. Inst. Mining Met. Bull. (1973) 66(738), 51. 37. Semrau, K. T., Eng. Mining J. (1971) 172, 115. 38. Eng. Mining J. (1972) 173(2), 69. 39. Wall Street J. (Aug. 20, 1973) 7. 40. Treilhard, D . G., Chem. Eng. (1973) 80(9), P-Z. 41. White, L . , Chem. Eng. (1973) 80(9), A A - C C . 42. Milliken, C. L . , J. Metals (1970) 22(8), 51. 43. Kellogg, H . H . , Latin Amer. Conf. Mining Metallurgy, Santiago, Chile, Aug. 26-Sept. 1, 1973. 44. Pay Dirt (Bisbee, Ariz.) (1974) 415, 15. 45. Lutjen, G . P., Dayton, S. H . , Tinsley, C. R., Eng. Mining J. (1973) 174(11), 73. 46. Merla, S., Young, C. E . , Matousek, J. W., in "Environmental Control," C. Rampacek, ed., pp. 19-35, The Metallurgical Society of A I M E , 1972. 47. Persson, J. A., Treilhard, D . G., J. Metals (1973) 25, (1), 34. 48. Rodolff, D . W., Marble, E . R., Jr., J. Metals (1972) 24(7), 14. 49. Queneau, P. E., J. Metals (1973) 25, 15. 50. Holderreed, F . L . , Mining Eng. (1971) 23(9), 45. 51. Guccione, E . , Eng. Mining J. (1973) 174(12), 81. 52. Daniele, R. ., Jaquay, L . H . , " T B R C A New Smelting Technique," A I M E - T M S Paper A72-101 (1972). 53. Eng. Mining J. (1972) 173(8), 66. 54. Reynolds, J. O., Phillips, K. J., Fitzgerald, D. E . , Worner, . K., in " E n vironmental Control," C. Rampacek, ed., pp. 67-85, The Metallurgical Society of A I M E , 1972. 55. Themelis, N . J., McKerrow, G . C., Tarassoff, P., Hallett, G . D.,J.Metals (1972) 24(4), 25. 56. MacAskill, D., Eng. Mining J. (1973) 174(7), 82. 57. Kettner, P., Maelzer, C. ., Schwartz, W . H . , in "Environmental Control," C. Rampacek, ed., pp. 37-63, The Metallurgical Society of A I M E , 1972. 58. Eng. Mining J. (1973) 174(12), 33. 59. Remirez, R., Chem. Eng. (1969) 76(2), 80. 60. Tucker, W . G., Burleigh, J. R., Chem. Eng. Progr. (1971) 67(5), 57. 61. Furkert, H . , Chem. Eng. (1969) 76, (1), 70. 62. Browder, T . J., Chem. Eng. Progr. (1971) 67(5), 45. 63. Connor, J. M., Chemico World (1969) 4(5), 4. 64. Kronseder, J. G., Chem. Eng. Progr. (1968) 64(11), 71.
1.
SEMRAU
Industrial Process Sources
21
65. Scheidel, C. F., Annu. AIChE Meetg., 61st, Los Angeles, Dec. 1-5, 1968, preprint No. 6E. 66. Davis, J. C., Chem. Eng. (1971) 78(27), 43. 67. Elder, H . W., Princiotta, F . T., Hollinden, G. ., Gage, S. J., "Sulfur Oxide Control TechnologyVisits in Japan, August 1972," U.S. Government Interagency Report, Muscle Shoals, Ala. (Oct. 30, 1972). 68. Uno, T., Atsukawa, M., Muramatsu, K., Proc. 2nd Intern. Lime/Limestone Wet-Scrubbing Symp., E P A Publ. No. APTD-1161 (1972), pp. 833-49. 69. Collins, J. J., Fornoff, L . L . , Manchanda, K. D., Miller, W . C., Lovell, D. C., Annu. A I C h E Meetg, Philadelphia, Paper No. 24d, Nov. 15, 1973. 70. Collins, J. J., Fornoff, L . L . , Miller, W . C., Lovell, D. C., APCA Annu. Meetg, 66th, Chicago, June 24-28, 1973. 71. Goar, B. G., Oil Gas J. (1971) 69(28), 75; 69(29), 84. 72. Hyne, J. B., Oil Gas J. (1972) 70(35), 64. 73. Beavon, D. K., Vaell, R. P., Proc. Div. Refining, API (1972) 52, 267. 74. Barry, C.B., Oil Gas J. (1970) 68(19), 63. 75. Barry, C. B., Hydrocarbon Process. (1972) 51(4), 102. 76. Berlie, . M., 4th ]oint Chem. Eng. Conf., AIChE Can. Soc. Chem. Eng., Paper 19e, Vancouver, Canada, Sept. 9-12, 1973. 77. Bryant, H. S., Oil Gas J. (1973) 71(13), 70. 78. Palm, J. W., Hydrocarbon Process. (1972) 51, (3), 105. 79. Pearson, M . J., Hydrocarbon Process. (1973) 52, (2), 81. 80. Farrar, G. L . , Oil Gas J. (1970) 68(42), 72. 81. Krill, H . , Storp, K., Chem. Eng. (1973) 80(17), 84. 82. Storp, K., Air Pollut. Control Ass., Annu. Meetg., 65th, A P C A paper 72-83, Miami Beach, June 18-22, 1972. 83. Barthel, Y., Bistri, Y., Deschamps, ., Renault, P., Simadoux, J. C., Dutriau, R., Hydrocarbon Process. (1971) 50(5), 89. 84. Hirai, M . , Odello, R., Shimamura, H., Chem. Eng. (1972) 79(8), 78. 85. Beavon, D. K., Chem. Eng. (1971) 78(28), 71. 86. Naber, J. E., Wesselingh, J. ., Groenendaal, W., Chem. Eng. Progr. (1973) 69(12), 29. 87. Idemura, H . , Chem. Econ. Eng. Rev. (1972) 4(12), 23. 88. Hayford, J. S., Van Brocklin, L . P., Kuck, . ., Chem. Eng. Progr. (1973) 69(12), 54. 89. Rosenbaum, J. B., McKinney, W . ., Beard, H . R., Crocker, L . , Nissen, W. L . , U.S. Bur. Mines Rep. Invest. (1973) 7774. 90. Chem. Eng. (1974) 81(3), 64. 91. Busson, C., Dazael, C., Franckowiak, S., Odello, R., Oil Gas J. (1973) 71(32), 67. 92. Elec. World (1973) 179(3), 30. 93. Oil Gas J. (1973) 71(32), 61. 94. Hemler, C. L . , Vermillion, W . L . , Oil Gas J. (1973) 71(45), 88, 91. 95. Hildebrand, R. E., Huling, G. P., Ondish, G . F., Oil Gas J. (1973) 71(50), 112. 96. Finneran, J. A., Murphy, J. R., Whittington, E. L . , Oil Gas J. (1974) 72(2), 52. 97. Chem. Eng. (1973) 80(21), 79. 98. J. Metals (1973) 25, (1), 4. 99. Iron Steel Eng. (1974) 51, (1), D16. 100. J. Metals (1973) 25(8), 4. 101. Nakai, Y., Yokogawa, T., Chem. Econ. Eng. Rev. (1970) 2(5), 44. 102. Canty, C., Perry, F . G . , Jr., Woodland, L . R., Tappi (1973) 56(9), 52. 103. Hendrickson, E. R., Roberson, J. E., Koobler, J. B., "Control of Atmospheric Emissions in the Wood Pulping Industry," Vol. I-III, Final Report, APCA Contract No. C P A 22-69-18 (Mar. 15, 1970).
22
SULFUR REMOVAL AND RECOVERY
104. Borg, A., Teder, A., Warnqvist, B., Tappi (1974) 57(1), 126. 105. Gommi, J. V., Tappi (1972) 55, 1094. 106. Lang, C. J., DeHaas, G. G . , Gommi, J. V . , Nelson, W., Tappi (1973) 56, 107. 108. 108. 109. 110. 111. 112. 113. 114. 115. 116. 117. 118. 119. 120. 121. 122. 123. 124. 125. 126. 127. Lo Cicero, P. M . , Sjolseth, D . E., Tappi (1973) 56, 76. Walther, J. E., Amberg, H . R., Tappi (1972) 55, 1185. Price, F . C., Chem. Eng. (1973) 80(9), RR. Winklepleck, R. G., Suda, S., Tappi (1973) 56, (6), 73. Vegeby, ., Pulp Pap. Mag. Can. (1968) 69(9), 68. Croon, I., Pap. Trade J. (1973) 157(26), 27. E P A / N C A S I , "Atmospheric Emissions From the Pulp and Paper Manufacturing Industry," Publ. No. EPA-450/1-73-002, Environmental Protection Agency, Research Triangle Park, N . C . (Sept. 1973). Aho, W . O. Tappi (1969) 52, 620. Moody, D . M . , Tappi (1969) 52, 448. Foss, E., Pap. Trade J. (1973) 157(26), 28. Frantisak, F . , Air J. (Peabody Galion) (Fall 1973) 8. Clement, J. L . , Tappi (1966) 49(8), 127A. Hanway, J. E., Jr., Henby, E. B., Smithson, G . R., Jr., Tappi (1967) 50(10), 64A. Kleinegger, J. D., Tappi (1969) 52, 1291. Markant, H . P., McIlroy, R. ., Matty, R. E., Tappi (1962) 45, 849. Walther, J. E., Amberg, H . R., Hamby, ., III, Chem. Eng. Progr. (1973) 69(6), 100. Collins, T . T . , Jr., Schick, P. E., Pap. Trade J. (1970) 154(24), 39. Cederquist, K. N . , Ahlborg, N . K. G . , Lunden, B., Wentworth, T . O., Tappi (1960) 43(8), 702. Kennedy, . H . , Tappi (1960) 43, 683. Tanner, T., Clement, J. L . , Tappi (1973) 56, (9), 63. Sconce, J. S., in "Kirk-Othmer Encyclopedia of Chemical Technology," 2nd E d . , 18, pp. 510-515, 1969. Mitachi, K., Chem. Eng. (1973) 80(24), 78.
RECEIVED April 4, 1974
2
The Allied Chemical Sulfur Dioxide Reduction Process for Metallurgical Emissions
W. D. HUNTER, JR., J. C. FEDORUK, A. W. MICHENER, and J. E. HARRIS
Allied Chemical Corp., Industrial Chemicals Div., P.O. Box 1139-R, Morristown, N. J. 07960
Allied Chemical
technology for reducing sulfur dioxide to in 1970 as the emission facility sulof sulfur as 12% Allied's sulfur
elemental sulfur was commercialized which received up to 500 tons/day fur dioxide. than 90% reduction reduction dioxide of the entering sulfur.
control system for a Canadian sulfide ore roasting
In the next 2 yrs, this plant recovered more dioxide to gas streams
technology can now be applied
containing 4-100% sulfur dioxide, dry basis. Sulfur dioxide may be used directly to control emissions from smelting processes. Where sulfur is below about 4%, process. and/or gas concentration roasters and continuous
composition fluctuates widely, the reduction process is combined with a preliminary concentrating
Targe-scale commercialization of technology for sulfur dioxide reduction to sulfur was accomplished by Allied Chemical Corp. in 1970 with the start-up of a prototype facility for a large new metallurgical operation at Falconbridge, Ontario. The technology, used initially for the emission control system at this plant, was developed through a major R & D program in the 1960's. Specifically over 90% ing pyrrhotite ore at rates earlier papers ( J , 2). up to of the sulfur dioxide was removed one-half million tons/year. The from a gas stream resulting from fluidized bed roasting of nickel-containprocess installed in the Canadian plant has been discussed in detail in The single-train plant design, which is capable of receiving sulfur dioxide equivalent to as much as 500 long tons/day of sulfur, and other operating experience in this unique emission control project have been described in previous publications (3, 23 In Sulfur Removal and Recovery; Pfeiffer, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1975. 4).
24
S U L F U R
R E M O V A L
T h e reliability of A l l i e d Chemical's sulfur dioxide reduction techn o l o g y w a s p r o v e d d u r i n g 2 yrs of successful o p e r a t i o n i n w h i c h the c a p a b i l i t y o f a c h i e v i n g a 9 0 % o n - s t r e a m factor w a s e s t a b l i s h e d . A l l of t h e o r i g i n a l process d e s i g n a n d p e r f o r m a n c e c r i t e r i a w e r e c o n f i r m e d . Turnd o w n characteristics of t h e s y s t e m w e r e d e m o n s t r a t e d d u r i n g e x t e n d e d o p e r a t i o n at as l o w as o n e - t h i r d of d e s i g n c a p a c i t y w i t h n e a r l y constant o p e r a t i n g efficiencies ( i n terms of o v e r a l l s u l f u r d i o x i d e r e m o v a l a n d r e d u c i n g agent u t i l i z a t i o n ) b e i n g a c h i e v e d at a l l rates. E l e m e n t a l s u l f u r p r o d u c e d i n t h e process w a s u s e d i n t e r c h a n g e a b l y w i t h F r a s c h s u l f u r at v a r i o u s A l l i e d locations to p r o d u c e h i g h q u a l i t y s u l f u r i c a c i d f o r t h e U . S . merchant market. Commercial Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch002 Plant Description
A flow d i a g r a m of the s u l f u r d i o x i d e r e d u c t i o n process as i t is a p p l i e d to a sulfide o r e r o a s t i n g o p e r a t i o n l i k e that at F a l c o n b r i d g e is s h o w n i n F i g u r e 1. T h e h o t s u l f u r d i o x i d e gas f r o m t h e roasters is passed t h r o u g h h o t gas heat exchangers ( 1 ) a n d ( 2 ) w h e r e p a r t of the heat content of the gases is u s e d to reheat other process gas streams. These w i l l be d e s c r i b e d i n m o r e d e t a i l later. A t this p o i n t the roaster gas s t i l l contains fine d u s t p a r t i c l e s as w e l l as gaseous c o n t a m i n a n t s w h i c h m u s t b e r e m o v e d before t h e gas reaches t h e r e d u c t i o n reactor. T h i s gas p u r i f i c a t i o n is a c c o m p l i s h e d i n a two-stage aqueous s c r u b b i n g system c o n s i s t i n g of a t w o - l e g gas c o o l i n g t o w e r ( 3 ) a n d a p a c k e d c o n d e n s i n g t o w e r ( 4 ) . T h e b u l k o f the dust a n d other c o n t a m i n a n t s a r e c o l l e c t e d i n t h e gas c o o l i n g
SO, GAS
, v
4
CONDENSING TOWER
COLD GAS BY-PASS ^^] STEAM '
mm
HEATl REGENERATOR: . g|
,
10
1 &!
~ u | COALESCER
HEAT REGENERATOR
1 SULFUR t
SULFUR \ SULFUR 1 SULFUR T O STORAGE SULFUR HOLDING PIT
Figure
1.
Allied Chemical
sulfur dioxide reduction gas application
technology typical
roaster
2.
H U N T E R
E T
A L .
Allied
Chemical
Reduction
Process
25
t o w e r w h i l e the gas is c o o l e d a n d s a t u r a t e d b y a r e c i r c u l a t e d w e a k s u l f u r i c a c i d s o l u t i o n . T h e d e m i s t e r p a d at t h e t o w e r outlet is c o n t i n u o u s l y sprayed w i t h weak a c i d from the condensing tower. T h e underflow from the gas c o o l i n g t o w e r is t r e a t e d w i t h l i m e to p r e c i p i t a t e d i s s o l v e d m e t a l l i c impurities removed f r o m the gas a n d to n e u t r a l i z e t h e a c i d i t y b e f o r e by b e i n g d e l i v e r e d to a waste p o n d w h e r e the solids are a l l o w e d to settle. T h e process gas is f u r t h e r c o o l e d i n the c o n d e n s i n g t o w e r ( 4 ) heat exchangers ( 5 ) . c i r c u l a t i n g w e a k a c i d w h i c h is c o o l e d e x t e r n a l l y i n i m p e r v i o u s g r a p h i t e E n t r a i n e d droplets of a c i d m i s t are r e m o v e d f r o m D r i p s f r o m the p r e c i p i t a t o r s the gas i n electrostatic p r e c i p i t a t o r s ( 6 ) . are r e t u r n e d to the gas c o o l i n g tower. T h e t e m p e r a t u r e of the c l e a n gas is t h e n r a i s e d a b o v e the d e w p o i n t of s u l f u r i c a c i d b y a d m i x i n g w i t h a r e h e a t e d s t r e a m of t h e same gas i n Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch002 the mist tower (7). T h i s r e c y c l e gas stream is h e a t e d b y c i r c u l a t i o n (2). T h e process gas is d r a w n t h r o u g h the h o t gas heat exchanger blower (8)
t h r o u g h the w e t p u r i f i c a t i o n system a n d t h e n f o r c e d b y a c e n t r i f u g a l t h r o u g h the b a l a n c e of the p l a n t . N a t u r a l gas, w h i c h serves heat as t h e r e d u c i n g agent, is i n t r o d u c e d i n t o t h e process gas s t r e a m at the b l o w e r d i s c h a r g e , a n d the m i x t u r e is passed t h r o u g h the h o t gas exchanger (1) before e n t e r i n g the r e d u c t i o n reactor system. T h e p r i n c i p a l f u n c t i o n of the c a t a l y t i c r e d u c t i o n system is to m a x i m i z e use of the r e d u c t a n t w h i l e p r o d u c i n g b o t h s u l f u r a n d hydrogen sulfide, so the h y d r o g e n s u l f i d e / s u l f u r d i o x i d e r a t i o i n t h e gas s t r e a m l e a v i n g the system is essentially that r e q u i r e d for the subsequent C l a u s reaction. A l t h o u g h the c h e m i s t r y of the p r i m a r y r e a c t i o n system is e x t r e m e l y c o m p l e x a n d i n c l u d e s reactions i n v o l v i n g 11 different elements a n d c o m p o u n d s , i t m a y be s u m m a r i z e d i n the f o l l o w i n g e q u a t i o n s : to raise its t e m p e r a t u r e a b o v e the d e w p o i n t of s u l f u r
CH
+
4
S0
C0
H 0 + S
2 2
4 C H + 6 S0
4 C0 + 4 H 0 + 4 H S + S
2 2
T h e p r e h e a t e d process a n d n a t u r a l gas m i x t u r e enters the c a t a l y t i c r e d u c t i o n system t h r o u g h a f o u r - w a y flow reversing valve (9) (11). a n d is f u r t h e r p r e h e a t e d as it flows u p w a r d t h r o u g h a p a c k e d - b e d heat r e g e n erator ( 1 0 ) b e f o r e e n t e r i n g the r e d u c t i o n reactor T h e r m a l l y stable catalysts d e v e l o p e d b y A l l i e d C h e m i c a l f o r this
f a c i l i t y cause r a p i d a n d efficient r e a c t i o n of the n a t u r a l gas w i t h the s u l f u r d i o x i d e to f o r m h y d r o g e n sulfide a n d e l e m e n t a l s u l f u r v a p o r w h i l e s u b s t a n t i a l l y e l i m i n a t i n g the f o r m a t i o n of u n d e s i r a b l e side r e a c t i o n p r o d ucts ( 5 , 6). T h e t e m p e r a t u r e of the gases e n t e r i n g the reactor is h e l d T h e heat that is g e n e r a t e d i n constant b y c o n t i n u o u s l y b y p a s s i n g a v a r y i n g q u a n t i t y of c o l d process gas a r o u n d the u p f l o w heat regenerator.
26
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reactor ( 11 ) b y the e x o t h e r m i c reactions sustains t h e o v e r a l l heat i n t h e system. A f t e r l e a v i n g the reactor, the m a i n gas flow passes d o w n t h r o u g h a s e c o n d heat regenerator ( 1 2 ) , g i v i n g u p its heat to t h e p a c k i n g i n t h a t vessel before l e a v i n g the c a t a l y t i c r e d u c t i o n system t h r o u g h flow reversi n g v a l v e ( 9 ). A t h e r m a l b a l a n c e is m a i n t a i n e d i n the system b y p a s s i n g a m i n o r flow of the hot gases f r o m the reactor ( 1 1 ) , a r o u n d the d o w n f l o w regenerator a n d the flow r e v e r s i n g v a l v e ( 9 ) , a n d r e m i x i n g i t w i t h t h e m a i n stream b e f o r e e n t e r i n g s u l f u r condenser ( 17 ). T h e p r i m a r y f u n c t i o n of the heat regenerators ( 1 0 ) and (12), then, and The is to r e m o v e heat f r o m the gases l e a v i n g the c a t a l y t i c reactor ( 1 1 ) p o i n t w h e r e the s u l f u r d i o x i d e - n a t u r a l gas r e a c t i o n w i l l b e g i n . Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch002
to use this heat to raise the t e m p e r a t u r e of the i n c o m i n g gases to the d i r e c t i o n of flow t h r o u g h the t w o regenerators is p e r i o d i c a l l y r e v e r s e d to i n t e r c h a n g e t h e i r functions of h e a t i n g a n d c o o l i n g the gases b y u s i n g the flow r e v e r s i n g v a l v e ( 9 ) a n d f o u r w a t e r - c o o l e d b u t t e r f l y valves (14), (15), and (16). T h e v a l v e a r r a n g e m e n t s h o w n i n the flow (13), dia-
g r a m is s p e c i a l l y d e s i g n e d to m a i n t a i n the gas flow t h r o u g h t h e c a t a l y t i c reactor (11) i n one d i r e c t i o n o n l y . A l l five valves are o p e r a t e d f r o m a c e n t r a l c o n t r o l system w h i c h s y n c h r o n i z e s t h e i r m o v e m e n t so t h a t e a c h flow r e v e r s a l is c o m p l e t e d i n less t h a n 1 sec. T h e e l e m e n t a l s u l f u r t h a t is f o r m e d i n the p r i m a r y reactor system is c o n d e n s e d i n a horizontal shell-and-tube steaming condenser (17). T h i s represents over 4 0 % of t h e t o t a l r e c o v e r e d s u l f u r . T h e process gas s t r e a m t h e n enters the first stage ( 18 ) of a two-stage C l a u s reactor system w h e r e the f o l l o w i n g e x o t h e r m i c r e a c t i o n o c c u r s : 2 H S +
2
S0
> 3/2 S
2 H 0
2
A f t e r the first stage of C l a u s c o n v e r s i o n , the gas is c o o l e d i n a v e r t i c a l s t e a m i n g condenser v e r s i o n of h y d r o g e n i n the second (19) to condense a d d i t i o n a l sulfur. (20). Further conplace in pad sulfide a n d s u l f u r d i o x i d e to s u l f u r takes A coalescer (22) containing a mesh
stage C l a u s reactor
T h i s s u l f u r is c o n d e n s e d
a third steaming unit (21).
t h e n removes e n t r a i n e d l i q u i d f r o m the gas stream. M o l t e n s u l f u r f r o m t h e three condensers a n d the coalescer is c o l l e c t e d i n a s u l f u r h o l d i n g p i t (23) f r o m w h i c h i t is p u m p e d to storage. R e s i d u a l h y d r o g e n sulfide i n of the gas f r o m the process is o x i d i z e d to s u l f u r d i o x i d e i n the presence t h r o u g h a stack fits. (25).
excess a i r i n a n i n c i n e r a t o r ( 24 ) b e f o r e b e i n g e x h a u s t e d to t h e a t m o s p h e r e T h i s r e a c t o r - h e a t r e g e n e r a t o r system offers s e v e r a l i m p o r t a n t b e n e T e m p e r a t u r e profiles i n h e r e n t l y f a v o r a p p r o a c h to c h e m i c a l e q u i l i b r i u m a n d m a x i m u m use of t h e gaseous r e d u c i n g agent over a w i d e r a n g e of o p e r a t i n g rates. Y e t , w i t h t h e c o n s i d e r a b l e heat c a p a c i t y of t h e
2.
H U N T E R
E T
A L .
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p a c k e d beds, the system is n o t seriously upset b y flow rate changes a n d m i n o r v a r i a t i o n s i n f e e d gas c o m p o s i t i o n . A t the same t i m e , the r e a c t o r heat regenerator d e s i g n solves the e n g i n e e r i n g m a t e r i a l s p r o b l e m s c a u s e d b y the h i g h l y corrosive n a t u r e of the s t r o n g l y r e d u c i n g sulfurous gases. I n fact, at the e l e v a t e d temperatures i n v o l v e d , the use of m e t a l l i c c o n s t r u c t i o n materials is i m p r a c t i c a l . C o m b i n i n g the regenerator f u n c t i o n of r e a c t i o n heat storage a n d use w i t h the fixed b e d singlestage reactor, t h e n , results i n a r u g g e d a n d efficient d e s i g n ( 7 ) . e n c e d i n the F a l c o n b r i d g e f a c i l i t y . Continuing Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch002 Technology Development T h i s system is p a r t i c u l a r l y advantageous for l a r g e process gas v o l u m e s s u c h as those e x p e r i -
I n v i e w of the c o n s i d e r a b l e interest i n s u l f u r d i o x i d e r e d u c t i o n to s u l f u r b o t h i n this c o u n t r y a n d a b r o a d , A l l i e d C h e m i c a l e x t e n d e d t h e use of this t e c h n o l o g y to c o n t r o l s u l f u r d i o x i d e emissions f r o m other m e t a l l u r g i c a l operations as w e l l as f r o m fossil f u e l c o m b u s t i o n . T h e experience g a i n e d i n d e s i g n , c o n s t r u c t i o n , a n d o p e r a t i o n of facility p r o v i d e d the perspective parallel engineering development. A t the outset, t w o major goals w e r e e s t a b l i s h e d to a c h i e v e a p p l i c a b i l i t y for s u l f u r d i o x i d e r e d u c t i o n i n emission c o n t r o l . broad first to The the large C a n a d i a n for c o n t i n u i n g process research a n d
g o a l was to d e v e l o p process c a p a b i l i t y e n c o m p a s s i n g the w i d e s t p r a c t i c a l r a n g e of i n l e t s u l f u r d i o x i d e concentrations w h i l e the s e c o n d w a s carbons c o u l d be u s e d as r e d u c i n g agents. T h e first g o a l has b e e n a c h i e v e d , a n d the s p e c t r u m of f e e d sources gas to w h i c h t h e A l l i e d C h e m i c a l s u l f u r d i o x i d e r e d u c t i o n t e c h d e v e l o p process modifications so that v a r i o u s gaseous a n d l i q u i d h y d r o -
n o l o g y m a y n o w b e a p p l i e d is the p r i n c i p a l subject of d i s c u s s i o n i n this p a p e r . T h e effort to use r e d u c i n g agents other t h a n n a t u r a l gas i n these systems has also a d v a n c e d t h r o u g h f e a s i b i l i t y studies i n t o t h e m e n t stage, i n v o l v i n g alternatives r a n g i n g f r o m p r o p a n e and developbutane
t h r o u g h m i d d l e distillates s u c h as N o . 2 f u e l o i l . A l l i e d C h e m i c a l n o w expects to offer a f a m i l y of processes p e r m i t t i n g s u l f u r d i o x i d e r e d u c t i o n operations to b e t a i l o r e d to t h e specific r e q u i r e m e n t s of i n d i v i d u a l l o c a tions a n d projects. W h i l e the C a n a d i a n p l a n t o p e r a t i o n w a s d o c u m e n t i n g process p e r f o r m a n c e w i t h a 1 2 - 1 3 % s u l f u r d i o x i d e source, w o r k w a s b e i n g d o n e to establish the basis for designs of systems to process m o r e concentrated Lower for f e e d streams, c o n t a i n i n g u p to 1 0 0 % s u l f u r d i o x i d e ( d r y b a s i s ) . were
s u l f u r d i o x i d e concentrations a n d the i n f l u e n c e of o x y g e n i n f e e d gases also b e i n g s t u d i e d so the l o w e r l i m i t b o u n d a r y c o n d i t i o n s identified. process a p p l i c a b i l i t y c o u l d b e This was realized through
28
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AND
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d e t a i l e d i n v e s t i g a t i o n of the k i n e t i c s of the c o m p l e x r e a c t i o n c h e m i s t r y i n this system. A c o m p r e h e n s i v e m a t h e m a t i c a l m o d e l of the system w a s subsequently developed w h i c h incorporated the unsteady state heat transfer f u n c t i o n s i n a d d i t i o n to c h e m i c a l k i n e t i c s a n d t h e r m o d y n a m i c s . B e c a u s e of these efforts i t is n o w p o s s i b l e to evaluate p r e c i s e l y a b r o a d r a n g e of process alternatives a n d m o d i f i c a t i o n s , as w e l l as to c o n d u c t d y n a m i c s i m u l a t i o n s o n m o d e l s of p a r t i c u l a r interest. P r e s e n t e n g i n e e r i n g d e s i g n c a p a b i l i t y a l l o w s efficient process profiles to b e establ i s h e d over a w i d e s p e c t r u m of f e e d gas c o m p o s i t i o n s w h i l e o p t i m i z i n g m a j o r p a r a m e t e r s , i n c l u d i n g r e d u c i n g agent use, o v e r a l l s u l f u r r e c o v e r y , a n d m a j o r e q u i p m e n t duties. O p e r a t i n g considerations s u c h as t u r n d o w n a n d the influence of p o t e n t i a l system upsets m a y also b e e v a l u a t e d . Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch002 Feed Gas Considerations
M o s t s u l f u r d i o x i d e f e e d streams, a n d e s p e c i a l l y m e t a l l u r g i c a l sources, c o n t a i n dust p a r t i c l e s a n d other i m p u r i t i e s s u c h as arsenic a n d s e l e n i u m oxides. I n o r d e r to p r o d u c e h i g h q u a l i t y s u l f u r , t h e gases m u s t b e c l e a n e d as t h o r o u g h l y as i f s u l f u r i c a c i d w e r e to b e p r o d u c e d . T h i s c a n b e r e l i a b l y a c c o m p l i s h e d i n a w e t p u r i f i c a t i o n system s i m i l a r to t h a t u s e d i n t h e F a l c o n b r i d g e p l a n t . N o t o n l y c a n the gases be f r e e d of most c o n t a m i nants, b u t the s c r u b b i n g t r e a t m e n t recovers a n y v a l u a b l e m i n e r a l content w h i c h m a y h a v e b e e n c a r r i e d b y the e n t e r i n g gas. O n c e the f e e d stream has b e e n p u r i f i e d , the s u l f u r d i o x i d e a n d o x y g e n d i m e n s i o n s m u s t b e defined. D e p e n d i n g u p o n its source, the s u l f u r d i (dry basis), in comThe to o x i d e m a y v a r y f r o m a f e w tenths of 1 % to 1 0 0 %
b i n a t i o n s w i t h o x y g e n f r o m 0 % u p to the l i n e s h o w n o n F i g u r e 2. d i o x i d e ( d r y b a s i s ) is d i l u t e d w i t h a i r . T h e o n l y gas c o m p o s i t i o n s
d o t t e d l i n e represents the gas c o m p o s i t i o n that results w h e n 1 0 0 % s u l f u r w h i c h A l l i e d C h e m i c a l s u l f u r d i o x i d e r e d u c t i o n t e c h n o l o g y is not d i r e c t l y a p p l i c a b l e are those i n t h e s h a d e d area at the l o w e r left of this d i a g r a m . T h i s l o w e r b o u n d a r y represents a p r a c t i c a l l i m i t w h i c h has b e e n establ i s h e d b y heat b a l a n c e a n d t h e r m o d y n a m i c considerations r a t h e r t h a n b y e c o n o m i c factors. I n the A l l i e d process, b o t h o x y g e n a n d s u l f u r d i o x i d e i n the f e e d gas react c h e m i c a l l y w i t h t h e r e d u c i n g agent i n i d e n t i c a l v o l u m e t r i c p r o p o r t i o n s . H o w e v e r , the heat released i n the r e d u c t i o n o f s u l f u r d i o x i d e is o n l y a f r a c t i o n of that l i b e r a t e d b y the r e a c t i o n of the r e d u c t a n t w i t h oxygen. C o n s e q u e n t l y , the process d e s i g n m u s t not o n l y o b t a i n the o p t i E v a l u a t i o n of t h e effects of v a r y i n g b o t h the conm u m r e a c t i o n p r o d u c t c o m p o s i t i o n b u t also m u s t c o n t r o l t h e temperatures t h r o u g h o u t the system. tant. o x y g e n a n d s u l f u r d i o x i d e contents d u r i n g o p e r a t i o n is therefore i m p o r E x c e p t f o r cases i n v o l v i n g v e r y w e a k s u l f u r dioxideoxygen centrations, the q u a n t i t y of gas b e i n g t r e a t e d is not a m a j o r factor because
2.
H U N T E R
E T A L .
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loo r v
100% S 0 Diluted With Air
2
60 h
%so
Operating Range Direct S O 2 Reduction
40 h
20 h
Falconbridge
<>'
0 2
4 %o
6
2
10
Figure 2.
Allied Chemical sulfur dioxide reduction, positions in volume % (dry basis)
gas com-
the d e s i g n a n d o p e r a t i o n c a n b e adjusted to a c h i e v e a w o r k a b l e heat b a l a n c e for duties as s m a l l as 5 - 1 0 t o n s / d a y o f s u l f u r i n the feed. T h e gas c o m p o s i t i o n f r o m the fluidized b e d roasters at F a l c o n b r i d g e w a s a s o m e w h a t s p e c i a l c i r c u m s t a n c e i n that the o x y g e n content proached position. Combination with Sulfur Dioxide Concentration was q u i t e l o w , a p p r o x i m a t e l y 1 % , a n d the s u l f u r d i o x i d e c o n c e n t r a t i o n a p t h e t h e o r e t i c a l m a x i m u m f o r p y r r h o t i t e o r e roasting. T h e A l l i e d r e a c t o r - r e g e n e r a t o r system was i d e a l l y s u i t e d t o this gas c o m -
S i n c e the p r o p o r t i o n o f r e d u c i n g agent i n t r o d u c e d s h o u l d b e r e g u l a t e d p r e c i s e l y to a c h i e v e t h e d e s i r e d p r o d u c t gas c o m p o s i t i o n , t h e s u l f u r d i o x i d e a n d o x y g e n concentrations i n the f e e d gas t o the r e d u c t i o n u n i t s h o u l d b e f a i r l y stable. A c c o r d i n g l y , the direct application of sulfur d i o x i d e r e d u c t i o n to gases f r o m the c y c l i c o p e r a t i o n o f the converters u s e d i n c o n v e n t i o n a l c o p p e r s m e l t i n g is not c o n s i d e r e d p r a c t i c a l . I n these cases, s u l f u r d i o x i d e s h o u l d b e r e m o v e d b y a regenerable r e c o v e r y system a n d s u b s e q u e n t l y released i n c o n c e n t r a t e d , l o w o x y g e n f o r m at a c o n t r o l l e d rate. Some s u l f u r d i o x i d e c o n c e n t r a t i n g systems c a n b e d e s i g n e d t o a c c e p t gases w i t h fluctuating volumes a n d sulfur loadings. T h e sulfur dioxide is either p h y s i c a l l y o r c h e m i c a l l y b o u n d i n a s o l i d o r l i q u i d m e d i u m i n
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A N D
R E C O V E R Y
these systems a n d is r e t a i n e d i n i n v e n t o r y . T h e m a t e r i a l is t h e n t h e r m a l l y r e g e n e r a t e d or steam s t r i p p e d , a n d the s u l f u r d i o x i d e is d e l i v e r e d to the final p r o c e s s i n g step at a constant rate. O n l y m i n o r modifications of the F a l c o n b r i d g e process are t h e n necessary to r e d u c e s u c h r e g e n e r a t e d gas streams c o n t a i n i n g u p to 1 0 0 % s u l f u r d i o x i d e ( d r y b a s i s ) to elemental sulfur. T h e a d a p t a b i l i t y of this s u l f u r d i o x i d e r e d u c t i o n t e c h n o l o g y to a f e e d gas c o n t a i n i n g 1 0 0 % s u l f u r d i o x i d e ( d r y basis) w i l l be d e m o n s t r a t e d at t h e D . H . M i t c h e l l S t a t i o n of the N o r t h e r n I n d i a n a P u b l i c S e r v i c e C o . ( N I P S C O ) at G a r y , I n d i a n a ( 8 ) . provide Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch002 a complete flue gas I n this a p p l i c a t i o n the process w i l l be process a to for 115-MW c o m b i n e d w i t h t h e W e l l m a n L o r d s u l f u r d i o x i d e recovery d e s u l f u r i z a t i o n system
coal-fired b o i l e r i n a project j o i n t l y f u n d e d b y N I P S C O a n d the E n v i r o n mental Protection Agency. As is the case i n c y c l i c c o p p e r converter operations, s u b s t a n t i a l changes i n s u l f u r l o a d i n g are e n c o u n t e r e d i n emissions f r o m fossil f u e l fired boilers. V a r i a t i o n s i n gas v o l u m e , a n d hence i n the s u l f u r l o a d i n g , w i l l be accommodated at N I P S C O b y p r o v i d i n g l a r g e storage c a p a c i t y for the sodium sulfite-bisulfite scrubbing solution. T h e sulfur dioxide w i l l b e d e s o r b e d f r o m the s o l u t i o n b y h e a t i n g , a n d a steady flow of s u l f u r d i o x i d e gas w i l l be d e l i v e r e d to the r e d u c t i o n u n i t . E n g i n e e r i n g , p r o c u r e m e n t , a n d c o n s t r u c t i o n of the entire f a c i l i t y at N I P S C O is t h e r e s p o n s i b i l i t y of D a v y P o w e r g a s , I n c . A l l i e d C h e m i c a l is p r o v i d i n g the s u l f u r d i o x i d e r e d u c t i o n process technology as w e l l as
Figure 3.
Typical compositions of gases from metallurgical
operations
2.
HUNTER E T A L .
Allied
Chemical
Reduction
Process
31
Total Reductant Requirement M SCF CH4/LT. Sulfur 48 r GAS COMPOSITION IN VOLUME % (DRY BASIS)
12
0% 02 S O 2 Requirement Only
8 4 0 5 % SO 10 15
Figure 4.
Gases from roasters and continuous smelting processes
t e c h n i c a l a n d start-up services u n d e r contract w i t h D a v y P o w e r g a s . T h e n , u n d e r a separate agreement w i t h N I P S C O , A l l i e d w i l l operate t h e entire flue gas d e s u l f u r i z a t i o n system a n d w i l l m a r k e t salable b y - p r o d u c t s o n a c o n t i n u i n g basis. Metallurgical Applications
T h e selection of processes f o r c o n t r o l l i n g s u l f u r d i o x i d e emissions f r o m m e t a l l u r g i c a l sources is l a r g e l y g o v e r n e d b y t h e c o m p o s i t i o n o f t h e gases b e i n g treated. T y p i c a l gas compositions f r o m non-ferrous m e t a l l u r g i c a l operations w h i c h h a v e r e l a t i v e l y constant s u l f u r d i o x i d e a n d o x y g e n contents a r e s h o w n i n F i g u r e 3. A l l i e d C h e m i c a l s u l f u r d i o x i d e r e d u c t i o n t e c h n o l o g y c a n b e a p p l i e d d i r e c t l y to m e t a l l u r g i c a l gases across the e n t i r e range of compositions represented b y t h e w i d e b a n d . T h e A l l i e d t e c h n o l o g y is n o t d i r e c t l y a p p l i c a b l e to gases f r o m r e v e r b e r a t o r y furnace operations i n w h i c h b o t h t h e s u l f u r d i o x i d e a n d oxygen contents are g e n e r a l l y less t h a n 3 % . B e c a u s e of the l o w s u l f u r d i o x i d e c o n c e n t r a t i o n a n d large v o l u m e of gases f r o m these sources, a c o n c e n t r a t i n g system w o u l d b e used to recover the s u l f u r d i o x i d e f o r subsequent r e d u c t i o n . A i r d i l u t i o n of t h e gas at t h e source s h o u l d b e r e s t r i c t e d w h e r e v e r possible, as this m i n i m i z e s t h e v o l u m e o f gas to b e h a n d l e d i n the system
32
S U L F U R
R E M O V A L
A N D
R E C O V E R Y
Figure 5.
Composition of gases from sulfur dioxide trating systems (dry basis)
concen-
Figure 6.
Gas compositions in emission control systems (dry basis)
2.
H U N T E R
E T
A L .
Allied
Chemical
Reduction
Process
33
a n d the q u a n t i t y of r e d u c t a n t r e q u i r e d as s h o w n i n F i g u r e 4 . T h e s h a d e d a r e a represents the r a n g e of c o m p o s i t i o n s n o r m a l l y f o u n d i n gases f r o m roasters a n d c o n t i n u o u s s m e l t i n g processes. T h e r e is o b v i o u s l y a cost p e n a l t y i n terms of a d d i t i o n a l r e d u c i n g agent c o n s u m p t i o n associated w i t h the d i r e c t r e d u c t i o n of gases h a v i n g h i g h e r o x y g e n contents. A l t h o u g h there p r o b a b l y w i l l b e situations i n conw h i c h i t w i l l b e advantageous to a c c e p t a h i g h e r r e d u c i n g agent
s u m p t i o n , the p e n a l t y m u s t be w e i g h e d against t h e t o t a l costs w h i c h w o u l d b e i n c u r r e d i f a s u l f u r d i o x i d e p r e c o n c e n t r a t i o n f a c i l i t y w e r e to be used. T h e c o m p o s i t i o n of gases o b t a i n e d f r o m s e v e r a l types of s u l f u r d i o x i d e r e c o v e r y a n d c o n c e n t r a t i n g systems is s h o w n i n F i g u r e 5. O n e of the features of the A l l i e d C h e m i c a l s u l f u r d i o x i d e r e d u c t i o n system is Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch002 that i t is c a p a b l e of p r o c e s s i n g t h e gases f r o m these s u l f u r d i o x i d e c o n c e n t r a t i n g systems d i r e c t l y w i t h o n l y the r e d u c t a n t a d d e d . A s a result, e q u i p m e n t size is m i n i m i z e d . B y contrast, i n m a n u f a c t u r i n g s u l f u r i c a c i d , the gases f r o m these c o n c e n t r a t i n g systems t y p i c a l l y w o u l d be d i l u t e d w i t h a i r to g i v e a n o x y g e n / s u l f u r d i o x i d e r a t i o of 1.3:1 to o b t a i n satisf a c t o r y c o n v e r s i o n of s u l f u r d i o x i d e to s u l f u r t r i o x i d e . system to b e d e m o n s t r a t e d at N I P S C O ) plant. Table I. Relative Process Gas Volumes" Total Gas VolumeM From Recovery Unit
0
The resulting
gas v o l u m e s are c o m p a r e d i n T a b l e I. I n the soda s c r u b b i n g case ( t h e the gas v o l u m e to the s u l f u r d i o x i d e r e d u c t i o n u n i t is less t h a n one q u a r t e r the v o l u m e to the a c i d
SCFM To Acid Plant
Sulfur
Dioxide
Recovery
System
To Reduction Unit
d
M a g n e s i u m oxide s c r u b b i n g 12% S 0 , 1% 0 C a r b o n sorption 40%SO ,0%O S o d a s c r u b b i n g or organic solvent 100^ % SO S0

2 2 2 2 f2 t
a b c d e
12.1 3.6 1.5
13.0 4.4 2.3
21.2 12.7 10.6
Basis 100 long tons/day sulfur equivalent in process gas. D r v basis at 60F. and 14.7 psig. S 0 volume 1.46 M S C F M (standard cubic ft/min). Includes reductant as 100% C H . Includes dilution air to give 1.3:1 0 / S 0 ratio.
2 4 2 2
I n s u m m a r y , A l l i e d C h e m i c a l t e c h n o l o g y for r e d u c i n g s u l f u r d i o x i d e to e l e m e n t a l s u l f u r c a n be a p p l i e d d i r e c t l y to a b r o a d range of s u l f u r d i o x i d e concentrations. A s i l l u s t r a t e d i n F i g u r e 6, the p r a c t i c a l range f o r a p p l i c a t i o n of this t e c h n o l o g y extends f r o m a b o u t 4 % u p to 1 0 0 % (dry
34
S U L F U R
R E M O V A L
b a s i s ) w i t h o x y g e n contents u p to t h e a f o r e m e n t i o n e d e c o n o m i c b r e a k p o i n t . I n some instances, process considerations m a y j u s t i f y d i r e c t s u l f u r dioxide reduction with higher oxygen contents i n the feed gas a n d attendant higher reductant consumption. H o w e v e r , w i t h sulfur dioxide
contents of less t h a n a b o u t 4 % , use of a s u l f u r d i o x i d e p r e c o n c e n t r a t i n g system w i t h t h e s u l f u r d i o x i d e r e d u c t i o n process a p p l i e d d i r e c t l y t o t h e p r o d u c t gas is r e c o m m e n d e d . Literature Cited

2
1. Wright, J. P., "Reduction of Stack Gas S O to Elemental Sulphur," Sulphur (May/June, 1972) No. 100, 72. 2. Hunter, W . D., Jr., "Application of S O Reduction in Stack Gas Desulfurization Systems," E P A Flue Gas Desulfurization Symposium, New Orleans, May 1973. 3. Hunter, W . D . , Jr., Michener, A. W . , "New Elemental Sulphur Recovery System Establishes Ability to Handle Roaster Gases," E/MJ (June 1973) 174 (6), 117. 4. Hunter, W . D . , Jr., "Reducing S O in Stack Gas to Elemental Sulfur," Power (September, 1973) 117 (9), 63. 5. U.S. Patent 3,653,833 (April 4, 1972). 6. U.S. Patent 3,755,551 (August 28, 1973). 7. Bierbower, R. G . , VanSciver, J. H . , "Design of Allied Chemical S O Reduction System Circumvents Major Corrosion Problems," Chem. Eng. Prog. (Aug. 1974) 70 (8), 60. 8. Mann, E . L . , " S O Abatement System Builds on Success," Elec. World (November 1, 1972) 70.
2 2 2 2
R E C E I V E D A p r i l 4, 1974
3
Reduction of Sulfur Dioxide to Sulfur: The Elemental Sulfur Pilot Plant of A S A R C O and Phelps Dodge Corp.
JAMES M . H E N D E R S O N and J O H N B. P F E I F F E R Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch003 Central Research Laboratories, American Smelting and Refining Co., South Plainfield, N . J. 07080
The thermodynamic
equilibria involved in reducing
sulfur primary
dioxide with fossil fuels were used to specify the reactor operating conditions of 350C plant was built at ASARCO's initial phase of operation, covered: physical overheating degradation
and 1 atm with a ratio the
of reformed gas to sulfur-bearing gas of 4.14:1. A pilot scale El Paso smelter. During two process problems were disof the catalyst pellets and A boiling sulfur has
of the reactor, resulting in a major failure.
new primary reactor was designed and built using of operation with the new primary reactor on 12% dioxide feed, neither of these operating occurred.
media cooling with a new, stronger catalyst. After 90 days problems
' T h e elemental sulfur pilot plant financed by American Smelting and

i
Refining Co.
(ASARCO)
and Phelps Dodge
Corp. is located at
A S A R C O ' s E l Paso, Tex., copper-lead smelter. Technology pioneered by both companies is used in this plant. The sulfur dioxide reduction process was developed by A S A R C O while a process for reforming natural gas developed by Phelps Dodge provides the reducing gases. A n y large scale process for reducing sulfur dioxide to elemental sulfur will likely depend on a fossil fuel. Whether the fuel is used to reduce sulfur to such compounds as hydrogen sulfide or carbonyl sulfide which are then used as the reductant for sulfur dioxide or whether the fuel itself is the sulfur dioxide reductant, the overall thermochemistry is similar. 35
36 Thermochemistry of Sulfur Dioxide
S U L F U R
R E M O V A L
A N D
R E C O V E R Y
Reduction
T h e H - C - O - S System. F o l l o w i n g the u s u a l c o n v e n t i o n , the h y d r o g e n c a r b o n - o x y g e n - s u l f u r system is r e p r e s e n t e d as a t e t r a h e d r o n w i t h the f o u r p u r e elements at the apexes as d e p i c t e d b y F i g u r e 1. I n t h e r e d u c t i o n of s u l f u r d i o x i d e b y fossil fuels, i f w e assume the f u e l to b e the sole
H
Hydrogen-carbon-oxygensulfur system source of c a r b o n a n d h y d r o g e n , selection of a p a r t i c u l a r fossil f u e l fixes t h e a t o m i c r a t i o of h y d r o g e n to c a r b o n , thus l i m i t i n g t h e r e g i o n of i n terest i n the H - C - O - S system to a p l a n e . defines the r e g i o n of t h e H - C - O - S If m e t h a n e , w i t h a n a t o m i c r a t i o of h y d r o g e n to c a r b o n of 4.0, is the fossil f u e l , t h e n p l a n e A S O system w i t h i n w h i c h a l l p o s s i b l e c o m p o s i t i o n s m u s t l i e . W h e n a p p r o p r i a t e e q u i l i b r i a c o m b i n a t i o n s consistent w i t h significant constituents h a v e b e e n selected, e.g. S 0 , H S , C O S ,
2 2
C S , S 0 , H , H 0 , C O , C 0 , S - S and, where applicable, C ( s ) and S ( l ) ,

2 3 2 2 2 2 8
a n d t e m p e r a t u r e a n d pressure h a v e b e e n specified, t h e n c a r b o n a n d s u l f u r s a t u r a t i o n lines m a y b e l o c a t e d . onto the carbon-oxygen-sulfur projection. C a r b o n a n d s u l f u r s a t u r a t i o n lines are ternary. T h i s is not a s i m p l e v e r t i c a l s y m b o l i c a l l y i l l u s t r a t e d i n F i g u r e 1 o n p l a n e A S O as are t h e i r projections R a t h e r , t h e p r o j e c t i o n of a n y p o i n t o n this p l a n e lies at the
i n t e r s e c t i o n w i t h the c a r b o n - o x y g e n - s u l f u r t e r n a r y of a straight l i n e c o n n e c t i n g the h y d r o g e n apex a n d the p o i n t b e i n g p r o j e c t e d , i.e., i n F i g u r e 1, p o i n t D ' lies o n the extension of a straight l i n e c o n n e c t i n g the h y d r o g e n apex a n d p o i n t D . U s i n g this t e c h n i q u e , a t o m i c s t o i c h i o m e t r i c r e l a t i o n ships i n v o l v i n g c a r b o n , o x y g e n , a n d s u l f u r a p p e a r i n g i n t h e p r o j e c t i o n are i d e n t i c a l to those i n the p l a n e p r o j e c t e d . t h r o u g h o u t this discussion. I n F i g u r e 2, regions of c a r b o n , l i q u i d s u l f u r , a n d h o m o g e n e o u s gas s t a b i l i t y are p l o t t e d f o r the specified a t o m i c r a t i o of h y d r o g e n to c a r b o n , 3 2 3 C ( 6 0 0 K ) , a n d 1 a t m absolute pressure. I n a n y p r a c t i c a l process T o s i m p l i f y the g r a p h i c a l i l l u s t r a t i o n s , the p l a n e of interest w i l l be p r o j e c t e d onto the C - O - S t e r n a r y
3.
H E N D E R S O N
A N D
PFEiFFER
Elemental
Sulfur Pilot
Plant
37
I C(solid)\Gas
0
1
Carbon Saturation Maturation HornbeneousGas
l^^^fSulfur 'S(liquid)+ Gas)
A
%*0.5
Figure 2. Regions of carbon, liquid sulfur, and homogeneous gas stability. H/C = 4.0, S/O = 0.5, = 323C (600), = 1.0 atm. carbon
for r e d u c i n g s u l f u r d i o x i d e to e l e m e n t a l s u l f u r , t h e r e g i o n of s a t u r a t i o n is a v o i d e d . bed.
I n this r e g i o n not o n l y w o u l d t h e y i e l d of s u l f u r
v a p o r be v i r t u a l l y zero, b u t c a r b o n p r e c i p i t a t i o n w o u l d f o u l the catalyst T h e r e are s i m i l a r reasons for a v o i d i n g the s u l f u r - s a t u r a t e d r e g i o n of the system, a l t h o u g h there are e q u a l l y v a l i d reasons f o r i n t e n t i o n a l s u l f u r c o n d e n s a t i o n o n a catalyst, f o l l o w e d b y a catalyst r e g e n e r a t i o n step, e.g., to a t t a i n i n a single c a t a l y t i c stage s u l f u r y i e l d s otherwise o n l y a t t a i n a b l e i n t w o or t h r e e stages. A S A R C O chose to a v o i d s u l f u r c o n d e n s a t i o n o n the catalyst. T h e r e is, h o w e v e r , a n a d d i t i o n a l constraint o n the r e g i o n of p r a c t i c a l interest. S i n c e w e are c o n c e r n e d w i t h s u l f u r d i o x i d e r e d u c t i o n , w e n e e d o n l y to e x a m i n e the system c h e m i s t r y o f the h o m o g e n e o u s gas r e g i o n l y i n g a l o n g or to the r i g h t of L i n e A C of F i g u r e 2, w h i c h denotes a n a t o m i c r a t i o of s u l f u r to o x y g e n of 0.5, i.e., at a n a t o m i c r a t i o of s u l f u r to o x y g e n e q u a l to or less t h a n that for s u l f u r d i o x i d e . Proportioning of Reformed Gas and Sulfur Dioxide. W e w i s h to L e t us d e t e r m i n e the p r o p e r p r o p o r t i o n of s u l f u r d i o x i d e to r e d u c e r .
e x a m i n e the v a r i a t i o n i n e q u i l i b r i u m c o m p o s i t i o n a n d s u l f u r v a p o r y i e l d a l o n g L i n e A C of F i g u r e 2. T h e s e d a t a are g r a p h i c a l l y s h o w n i n F i g u r e 3,
I
sion
H
too
21 S0A V V
^^^^^
COS
1
1
0.4
i
40 20
O.I
0.2
0.3 C/o
0.5
Figure 3. Gas phase composition. H/C = 4.0, S/O = 0 . 5 , = 323C (600), = 1.0 atm.
38
S U L F U R
R E M O V A L
A N D
R E C O V E R Y
w h e r e gas phase c o m p o s i t i o n is expressed i n terms of l o g p a r t i a l pressures. W i t h fixed a t o m i c ratios of h y d r o g e n to c a r b o n a n d s u l f u r to oxygen, F i g u r e 3 illustrates the c h a n g e i n e q u i l i b r i u m gas phase c o m p o s i t i o n w i t h v a r y i n g c a r b o n - t o - o x y g e n r a t i o , e.g., as t h e p r o p o r t i o n i n g of m e t h a n e a n d p u r e s u l f u r d i o x i d e is v a r i e d f r o m f u e l - l e a n to f u e l - r i c h . T h e c u r v e of F i g u r e 3 r e p r e s e n t i n g e q u i l i b r i u m p e r c e n t a g e c o n v e r s i o n of s u l f u r d i o x i d e to s u l f u r v a p o r illustrates the i m p o r t a n c e of p r o p o r t i o n i n g s u l f u r d i o x i d e a n d r e d u c i n g gas. W i t h m e t h a n e as the r e d u c t a n t , m a x i m u m s u l f u r v a p o r y i e l d occurs at a system a t o m i c r a t i o of c a r b o n to o x y g e n of 0.25, consistent w i t h the f o l l o w i n g s i m p l i f i e d o v e r a l l reaction: 2 S0 Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch003 (g) + CH (g) -> S (g) + C0 (g) + 2 H 0 (g)
2
(1)
I n the A S A R C O s u l f u r d i o x i d e process, h o w e v e r , r e f o r m e d n a t u r a l gas is the r e d u c e r . If w e assume n a t u r a l gas to be c o m p r i s e d solely of m e t h a n e , reformed n a t u r a l gas f o r m a t i o n i n the process d e v e l o p e d by Phelps D o d g e C o r p . m a y be expressed i n terms of R e a c t i o n 2: CH (g) + 0.5 0 (g) -> C O (g) + 2 H (g) (2) expressed: (3)
S u l f u r d i o x i d e r e d u c t i o n to e l e m e n t a l s u l f u r v a p o r m a y be 1.5 S 0 (g) + CO + 2 H 0.75 S (g) + C 0
(g) + 2 H 0
2
I n R e a c t i o n 3 as i n R e a c t i o n 1 the a t o m i c r a t i o of c a r b o n to o x y g e n is also 0.25. I n theory, the m a x i m u m y i e l d of s u l f u r v a p o r w o u l d d e p e n d o n a t e m p e r a t u r e - d e p e n d e n t a t o m i c r a t i o of c a r b o n to oxygen. I n other w o r d s , m a x i m u m y i e l d of s u l f u r v a p o r d e p e n d s o n a c a r b o n m o n o x i d e - t o c a r b o n d i o x i d e r a t i o ( o r a h y d r o g e n - t o - w a t e r r a t i o ) w h i c h is i n t u r n temperature dependent. W h i l e the absolute v a l u e of the c a r b o n m o n o x i d e - t o - c a r b o n d i o x i d e r a t i o c o r r e s p o n d i n g to m a x i m u m c o n v e r s i o n of s u l f u r d i o x i d e to s u l f u r v a p o r changes w i t h t e m p e r a t u r e , e q u i l i b r i u m p a r t i a l pressures of c a r b o n m o n o x i d e or h y d r o g e n are essentially zero over a b r o a d t e m p e r a t u r e range. T h u s , i n a p r a c t i c a l sense, w h e n m e t h a n e or r e f o r m e d m e t h a n e is the r e d u c t a n t for s u l f u r d i o x i d e , m a x i m u m e q u i l i b r i u m c o n v e r s i o n of s u l f u r d i o x i d e to s u l f u r v a p o r w i l l o c c u r at a n a t o m i c r a t i o of c a r b o n to o x y g e n of 0.25 regardless of t e m p e r a t u r e i n a c c o r d a n c e w i t h the s i m p l e s t o i c h i o m e t r y of R e a c t i o n s 1 a n d 3. N a t u r a l gas of the s o u t h w e s t e r n U n i t e d States contains, i n a d d i t i o n to m e t h a n e , s e v e r a l p e r cent ethane a n d lesser percentages of h i g h e r m o l e c u l a r w e i g h t h y d r o c a r b o n s , u p to a n d i n c l u d i n g pentane. T h e a t o m i c r a t i o of h y d r o g e n to c a r b o n i n this f u e l is a b o u t 3.80. R e f o r m i n g this
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n a t u r a l gas b y t h e P h e l p s D o d g e process t y p i c a l l y p r o d u c e s a gas stream of the c o m p o s i t i o n g i v e n i n T a b l e I. T h e E l Paso e l e m e n t a l s u l f u r p i l o t p l a n t is d e s i g n e d to p e r m i t r e d u c t i o n of 1 2 - 1 0 0 % s u l f u r d i o x i d e i n gas streams. I n the r e d u c t i o n of p u r e s u l f u r d i o x i d e , s t o i c h i o m e t r i c p r o p o r t i o n i n g of r e f o r m e d gas to s u l f u r d i o x i d e m a y be defined b y : S0
2
(0.170 C O +
2
0.313 H
2
0.017 C 0
2
0.042 H 0 +
2 2
0.458 N )
2
-> 0.5 S
+ (0.187 C 0
0.355 H 0 +
0.458 N )
(4)
where =
moles of r e f o r m e d g a s / m o l e of s u l f u r d i o x i d e . S o l v i n g for x,
the s t o i c h i o m e t r i c p r o p o r t i o n i n g of r e d u c t a n t to s u l f u r d i o x i d e r e q u i r e d Table I. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch003 Constituent CO H C0 H 0 N

2 2 2 2
T y p i c a l Reformed Gas Composition Volume 17.0 31.3 1.7 4.2 45.8 %
4.141 moles of r e f o r m e d g a s / m o l e of s u l f u r d i o x i d e . P i l o t p l a n t process d e s i g n for r e d u c i n g p u r e s u l f u r d i o x i d e therefore p r o v i d e s for b l e n d i n g of r e f o r m e d gas a n d s u l f u r d i o x i d e i n the s t o i c h i o m e t r i c v o l u m e r a t i o of 4.141 to 1 a n d i n t r o d u c t i o n of this m i x e d gas stream i n t o t h e p r i m a r y or first-stage c a t a l y t i c reactor. T h i s leads to a system c o m p o s i t i o n defined b y the f o l l o w i n g a t o m i c r a t i o s : H / C = 3.797, S / O 0.331, C / O = 0.257. Temperature and Pressure Specification. S i n c e e q u i l i b r i u m c o n v e r s i o n of s u l f u r d i o x i d e to s u l f u r v a p o r increases w i t h d e c r e a s i n g t e m p e r a ture, the r e d u c t i o n process was d e s i g n e d so t h a t the p r i m a r y r e d u c t i o n stage operates at the m i n i m u m t e m p e r a t u r e consistent w i t h reaction kinetics w h i c h a v o i d s s u l f u r c o n d e n s a t i o n o n the catalyst. T a k i n g these factors i n t o account, the p r i m a r y c a t a l y t i c reactor is o p e r a t e d at 3 5 0 C (623K). It was e s t i m a t e d t h a t a c t u a l o p e r a t i n g pressure at the p r i m a r y reactor outlet w o u l d b e 2.7 l b / s q i n . gage, e q u i v a l e n t at the E l Paso e l e v a t i o n to 1.04 a t m absolute. S i n c e s u l f u r d i o x i d e r e d u c t i o n w i l l e n t a i l a v o l u m e s h r i n k a g e c a u s e d p r i m a r i l y b y f o r m a t i o n of p o l y a t o m i c s u l f u r v a p o r species, i t is e s t i m a t e d , w i t h the a i d of R e a c t i o n 4, t h a t t h e gas stream l e a v i n g the p r i m a r y reactor w i l l h a v e a n i t r o g e n content of 4 3 . 5 % , e q u i v a l e n t to a n i t r o g e n p a r t i a l pressure of 0.45 a t m . A t the temperatures a n d pressures of interest, n i t r o g e n m a y b e c o n s i d e r e d a n i n e r t gas. In terms of gaseous species i n v o l v e d i n e q u i l i b r i a w i t h i n the H - C - O - S syst e m , the s u m of t h e i r p a r t i a l pressures m u s t b e e q u a l to t h e t o t a l pressure at the p o i n t i n the reactor w h e r e e q u i l i b r i u m is a p p r o a c h e d less the p a r -
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t i a l pressure of n i t r o g e n a n e s t i m a t e d H - C - O - S system pressure i n this case of 1.04 m i n u s 0.45, or 0.59 a t m . Equilibrium Gas Phase Composition. H a v i n g d e f i n e d o p t i m u m p r o p o r t i o n i n g of reformed c gas and sulfur dioxide and having specified
t e m p e r a t u r e a n d pressure at 3 5 0 C ( 6 2 3 K ) a n d 0.59 a t m , r e s p e c t i v e l y , the e q u i l i b r i u m gas p h a s e c o m p o s i t i o n m a y b e c a l c u l a t e d . T h e system c o m p o s i t i o n , d e n o t e d as p o i n t A , together w i t h c a r b o n a n d s u l f u r s a t u r a t i o n lines is d e p i c t e d i n F i g u r e 4. A t the specified p r i m a r y reactor o p e r a t i n g c o n d i t i o n s the system c o m p o s i t i o n is w e l l i n s i d e the h o m o g e n e o u s gas r e g i o n . Table II. F r o m the gas p h a s e c o m p o s i t i o n i n T a b l e I I , it m a y be c a l c u l a t e d that 7 9 . 4 % s u l f u r d i o x i d e is c o n v e r t e d to s u l f u r v a p o r . C o o l i n g this gas i n the absence of a catalyst leads to no e q u i l i b r i u m shift other t h a n that associated w i t h s u l f u r v a p o r c o n d e n s a t i o n ; this has b e e n b o r n e out i n the C l a u s process. B y c o o l i n g a gas stream of the c o m p o s i t i o n c i t e d i n T a b l e I I to 1 4 0 C (413 K ) , e q u i l i b r i u m s u l f u r c o n d e n s a t i o n sponds to 7 8 . 4 % Table II. Constituent C0 H 0 H S S0
2 2 2 2 a
E q u i l i b r i u m gas phase c o m p o s i t i o n at p o i n t A is g i v e n i n
corre-
first-stage
r e c o v e r y of l i q u i d sulfur.
Equilibrium Composition of Gases Leaving First-Stage Reactor Vol. % Constituent Vol. 0.09 0.01 0.05 0.30 1.08 0.67 0.68 %
N
a
17.62 31.07 3.20 1.59 43.64
s
S
2
3
S S
2
s s s
4 s 6
7 8
C O , H , COS, C S , and SO 3 are present in negligibly small concentrations.

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A f t e r the c o n d e n s a t i o n of s u l f u r v a p o r , most of t h e s u l f u r r e m a i n i n g i n t h e gas phase is present as h y d r o g e n sulfide a n d s u l f u r d i o x i d e i n t h e v o l u m e r a t i o of 2 to 1. W i t h s u l f u r c o n d e n s a t i o n , the a t o m i c r a t i o of s u l f u r to o x y g e n i n the gas phase is r e d u c e d w h i l e the other a t o m i c ratios r e main unchanged. G r a p h i c a l l y , this e q u i l i b r i u m c o n d e n s a t i o n of s u l f u r v a p o r , d e c r e a s i n g the gas phase r a t i o of s u l f u r to o x y g e n to 0.071, is r e p r e s e n t e d i n F i g u r e 4 b y the shift f r o m p o i n t A to p o i n t a l o n g t h e l i n e h a v i n g a constant a t o m i c r a t i o of c a r b o n to o x y g e n of 0.257. W i t h the gaseous s u l f u r - b e a r i n g species b e i n g p r e d o m i n a n t l y h y d r o g e n sulfide a n d s u l f u r d i o x i d e , f u r t h e r r e c o v e r y of e l e m e n t a l s u l f u r d e pends o n the C l a u s r e a c t i o n : 2 H S (g) + S 0
2
(g) -
1.5 S
(g) +
2 H 0 (g)
2
(5)
T o a v o i d c o n d e n s i n g s u l f u r v a p o r o n the catalyst u s e d i n the secondary, or C l a u s - t y p e reactor, gases l e a v i n g the p r i m a r y s u l f u r condenser be reheated. must F o r the p l a n t o p e r a t i n g c o n d i t i o n s u n d e r d i s c u s s i o n , t h e
gas stream is r e h e a t e d to 2 0 5 C (478 K ) . A s the C l a u s r e a c t i o n is s l i g h t l y e x o t h e r m i c , i t is e s t i m a t e d that the t e m p e r a t u r e of the gas stream w i l l rise, a l l o w i n g for t h e r m a l losses, b y a b o u t 3 5 C to 2 4 0 C (513 K ) e q u i l i b r i u m is a p p r o a c h e d . as A l l o w i n g for the e x p e c t e d pressure d r o p as
the process gas s t r e a m passes t h r o u g h the process t r a i n a n d for the c h a n g e i n r e l a t i v e v o l u m e of inert n i t r o g e n as c o m p a r e d w i t h the t o t a l v o l u m e of " a c t i v e " gaseous species, w e c a n estimate that H - C - O - S system p r e s sure w i l l b e 0.50 a t m . S u l f u r a n d c a r b o n s a t u r a t i o n lines c o n f o r m i n g to this pressure a n d the expected t e m p e r a t u r e of 2 4 0 C (513 K ) are also s h o w n i n F i g u r e 4. conditions, avoided. Table III. P o i n t B , c o r r e s p o n d i n g to system c o m p o s i t i o n , lies Therefore, under e q u i l i b r i u m secondary reactor catalyst is on the to the r i g h t of the s u l f u r s a t u r a t i o n line. sulfur condensation
T h e t h e o r e t i c a l e q u i l i b r i u m gas phase c o m p o s i t i o n is l i s t e d i n
Table III. Constituent" C0 H 0 H S

2 2 2
Equilibrium Composition of Gases Leaving Second-Stage Reactor Vol. % Constituent Vol. 0.01 0.18 0.11 0.25 %
so
N
a
18.53 34.41 0.75 0.37 45.39

2 2
s s
6 7
Se
C O , H 2, COS, C S , S , S3, and S 4 are present in negligibly small concentrations.
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F r o m t h e d a t a of T a b l e s I I a n d I I I , i t m a y be c a l c u l a t e d that e q u i l i b r i u m c o n v e r s i o n of h y d r o g e n sulfide a n d s u l f u r d i o x i d e to s u l f u r v a p o r i n the s e c o n d a r y reactor is 7 8 . 0 % . reactor o u t p u t . C o o l i n g this gas stream to 140C (413 K ) w i l l l e a d to a l i q u i d s u l f u r r e c o v e r y of 7 6 . 1 % of the s e c o n d a r y O v e r a l l r e c o v e r y i n the t w o stages, t h e n , m a y b e c a l c u l a t e d to be 9 4 . 9 % . O v e r a l l recovery c o u l d be increased slightly b y a d d i n g a t h i r d catal y t i c stage. H o w e v e r , it w a s not d e e m e d necessary to use a t h i r d stage techi n the A S A R C O - P h e l p s D o d g e p i l o t p l a n t because i t represents n o l o g y w e l l e s t a b l i s h e d i n the C l a u s process. Laboratory Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch003 Development Program
T h e i n i t i a l l a b o r a t o r y i n v e s t i g a t i o n of t h e process n o w b e i n g p i l o t e d at the A S A R C O E l Paso p l a n t i n v o l v e d b e n c h scale evaluations of different p r i m a r y s u l f u r d i o x i d e r e d u c t i o n catalysts. A l s o , fluid-bed catalysis w e r e c o m p a r e d , fixed-bed 19 and
a n d various construction materials
w e r e e v a l u a t e d i n the corrosive h y d r o g e n sulfide a n d s u l f u r v a p o r atmosp h e r e g e n e r a t e d i n gas phase r e d u c t i o n of s u l f u r d i o x i d e . F o l l o w i n g c o m p l e t i o n of the b e n c h scale test p r o g r a m , a n e n g i n e e r i n g c o n t r a c t o r c o n d u c t e d a s t u d y a n d p r e p a r e d the p r e l i m i n a r y d e s i g n for a p i l o t p l a n t h a v i n g a n o m i n a l p r o d u c t i o n c a p a c i t y of 20 short tons s u l f u r / d a y w h e n treating pure sulfur dioxide. fixed-bed catalysis w a s more practical. fixed-bed The d e s i g n , therefore, p r o v i d e d for a This study found preliminary pilot of that plant
p r i m a r y reactor of t h e s h e l l -
a n d - t u b e t y p e i n w h i c h the catalyst w o u l d b e i n the tubes. B a s e d o n this e n g i n e e r i n g s t u d y w e c o n c l u d e d t h a t f u r t h e r l a b o r a t o r y studies s h o u l d b e m a d e m o r e f u l l y to define the p r i m a r y reactor catalyst l o a d i n g s r e q u i r e d to a p p r o a c h e q u i l i b r i u m c o n v e r s i o n of s u l f u r d i o x i d e to s u l f u r v a p o r o v e r t h e r a n g e of p i l o t p l a n t o p e r a t i n g c o n d i t i o n s . T h e reactor u s e d i n this a d d i t i o n a l s t u d y d u p l i c a t e d as n e a r l y as possible the g e o m e t r y of t h e p r o p o s e d p i l o t p l a n t reactor. T h e l a b o r a t o r y reactor w a s f a b r i c a t e d of t y p e 304 stainless steel p i p e . A n electrically heated m o l t e n l e a d b a t h m a i n t a i n e d the d e s i r e d o p e r a t i n g t e m p e r a t u r e . G a s streams f o r the e x p e r i m e n t a l r e a c t o r c o n t a i n e d n i t r o g e n , h y d r o gen, c a r b o n m o n o x i d e , s u l f u r d i o x i d e , a n d i n some cases o x y g e n , u r a l gas a n d a s u l f u r d i o x i d e - b e a r i n g gas stream of the d e s i r e d position. T h e composition of this h e a d gas stream w a s m o n i t o r e d b y a n o n - l i n e process c h r o m a t o g r a p h . from comc y l i n d e r s , w h i c h w e r e b l e n d e d to synthesize a m i x t u r e of r e f o r m e d n a t continuously
T h e m i x e d gas stream
w a s s a t u r a t e d w i t h w a t e r v a p o r at a c o n t r o l l e d t e m p e r a t u r e a n d pressure to p r o v i d e a w a t e r v a p o r content consistent w i t h t h a t i n a c t u a l p l a n t operation.
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G a s samples f r o m the reactor w e r e a n a l y z e d b y mass
a n d gas c h r o m a t o g r a p h y a n d conversions of s u l f u r d i o x i d e to s u l f u r v a p o r w e r e c o m p u t e d f r o m the c o m b i n e d a n a l y t i c a l d a t a . I n this large-scale test p r o g r a m , effects o n catalyst l o a d i n g of a n u m b e r of v a r i a b l e s w e r e e x a m i n e d i n d e t a i l . W h i l e the l a b o r a t o r y e x p e r i m e n t a t i o n h a d b e e n q u i t e extensive, o p e r a t i o n of a p i l o t p l a n t was c o n s i d e r e d necessary to p e r m i t scale-up of the process to the 2 0 0 - 3 0 0 t o n / d a y plants c o n c e i v a b l y r e q u i r e d i n the f u t u r e . The Elemental Sulfur Pilot Plant B e c a u s e of f u e l costs a
Operating Conditions of the Pilot Plant.
sulfur d i o x i d e - b e a r i n g gas s t r e a m of r e l a t i v e l y l o w o x y g e n content is n e c essary to p e r m i t p r a c t i c a l a p p l i c a t i o n of the A S A R C O s u l f u r d i o x i d e r e d u c Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch003 t i o n process. decreases. A d d i t i o n a l l y , for a n y g i v e n s u l f u r p r o d u c t i o n rate, e q u i p m e n t size increases as s u l f u r d i o x i d e c o n c e n t r a t i o n i n the gas stream T h e r e is, therefore, some l o w e r s u l f u r d i o x i d e c o n c e n t r a t i o n to concentrate the s u l f u r d i o x i d e w h e r e i t becomes m o r e e c o n o m i c a l
before r e d u c t i o n . P r e l i m i n a r y c a p i t a l a n d o p e r a t i n g cost estimates i n d i c a t e d that this b r e a k i n g p o i n t w a s i n the range of 1 2 - 1 5 % s u l f u r d i o x i d e . F o r these reasons, the p i l o t p l a n t w a s d e s i g n e d to treat gas streams c o n taining 12-100% sulfur dioxide. W e a n t i c i p a t e d that t h e major opera t i o n a l effort w o u l d be d i r e c t e d first to t r e a t i n g a gas stream c o n t a i n i n g 1 2 % sulfur dioxide. S u c h a gas stream is t y p i c a l of that generated i n T h e second p r i n c i p a l m o d e of flash s m e l t i n g of c o p p e r concentrates or i n the n e w e r c o p p e r s m e l t i n g processes p r e s e n t l y u n d e r d e v e l o p m e n t . o p e r a t i o n w i l l r e d u c e p u r e s u l f u r d i o x i d e , i n response to the r e q u i r e m e n t for c o n c e n t r a t i n g the s u l f u r d i o x i d e i n m o r e d i l u t e gas streams b e f o r e r e d u c t i o n . S u l f u r p r o d u c t i o n c a p a b i l i t y i n the. latter case amounts to 20 short-tons/day. H o w e v e r , since p l a n t d e s i g n p r o v i d e s for h a n d l i n g esto a p p r o x i s e n t i a l l y the same t o t a l process gas v o l u m e regardless of s u l f u r d i o x i d e c o n c e n t r a t i o n i n the h e a d gas, s u l f u r p r o d u c t i o n decreases m a t e l y 8.5 s h o r t - t o n s / d a y w h e n t r e a t i n g a 1 2 % gas stream. A s u s u a l i n the c o n v e n t i o n a l c o p p e r as 1 2 % . or l e a d smelter, n o n e of the E l Paso smelter gas streams has a s u l f u r d i o x i d e c o n c e n t r a t i o n as h i g h I n the p i l o t p l a n t , t h e n , the 1 2 % s u l f u r d i o x i d e gas stream is generated b y b u r n i n g m o l t e n s u l f u r i n a s p r a y - t y p e s u l f u r b u r n e r to p r o d u c e a gas stream c o n t a i n i n g 1 8 % s u l f u r d i o x i d e . T h i s hot gas stream, at 1 3 5 0 C (1623 K ) , is c o o l e d to a b o u t 3 6 0 C (633 ) i n a waste heat boiler. W h e n t h e p i l o t p l a n t is o p e r a t i n g w i t h this 1 8 % gas, process t a i l gases are r e c y c l e d to d i l u t e the 1 8 % h e a d gas s t r e a m to 1 2 % . I n a n alternate m o d e of o p e r a t i o n , l i q u i d s u l f u r d i o x i d e is v a p o r i z e d to generate t h e p u r e gas. sulfur dioxide-bearing
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T h e P h e l p s D o d g e r e f o r m i n g process ( 1 ) uses c a t a l y t i c p a r t i a l c o m b u s t i o n of n a t u r a l gas w i t h p r e h e a t e d a i r to p r o d u c e by volume. a reformed gas s t r e a m h a v i n g a t o t a l h y d r o g e n p l u s c a r b o n m o n o x i d e content of 4 8 - 5 0 % T h e r e f o r m e r is a r e f r a c t o r y l i n e d , v e r t i c a l , c y l i n d r i c a l steel A i r , p r e h e a t e d to 430vessel p a c k e d w i t h n i c k e l i z e d a l u m i n a pellets.
4 8 0 C ( 7 0 3 - 7 5 3 K ) , together w i t h n a t u r a l gas at a v o l u m e r a t i o of 2.8-3.0 to 1, r e s p e c t i v e l y , is i n t r o d u c e d t h r o u g h a m i x e r i n t h e t o p of t h e r e f o r m e r . I n p a s s i n g t h r o u g h the catalyst b e d , the gas stream approaches the e q u i l i b r i u m c o m p o s i t i o n c o r r e s p o n d i n g to the outlet t e m p e r a t u r e a n d pressure of 1 0 0 0 C (1273 K ) a n d 1.15 a t m absolute. T h e r e f o r m e d gas w h i c h is g e n e r a t e d is free of c a r b o n p a r t i c l e s a n d contains o n l y traces of u n reacted hydrocarbons. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch003 A c o n t r o l l e d p o r t i o n of the h o t r e f o r m e d gas is d i v e r t e d t h r o u g h a w a t e r - c o o l e d s h e l l - a n d - t u b e heat exchanger to m a i n t a i n a r e f o r m e d gas t e m p e r a t u r e of 4 2 0 - 4 6 0 C ( 6 9 3 - 7 3 3 K ) . R e f o r m e d n a t u r a l gas a n d gases f r o m either the s u l f u r b u r n e r or the s u l f u r d i o x i d e v a p o r i z e r are c o m b i n e d s t o i c h i o m e t r i c a l l y a n d i n t r o d u c e d i n t o the p r i m a r y c a t a l y t i c reactor at 3 5 0 C temperature. (623 K). The reformed a n d s u l f u r b u r n e r gases are c o o l e d to m a i n t a i n the m i x e d stream at this T h e p r i m a r y reactor is a v e r t i c a l s h e l l - a n d - t u b e heat exc h a n g e r w i t h the t u b e filled w i t h catalyst. S i n c e s u l f u r d i o x i d e r e d u c t i o n is h i g h l y e x o t h e r m i c , a n o r g a n i c heat transfer fluid is c i r c u l a t e d t h r o u g h t h e s h e l l side to c o n t r o l reactor t e m p e r a t u r e . C o o l a n t l e a v i n g the p r i m a r y r e a c t o r is s p l i t i n t o t w o streams. O n e stream is c i r c u l a t e d t h r o u g h a k e t t l e - t y p e heat exchanger w h e r e steam at 35 l b / s q i n . gage is generated. T h e o t h e r stream passes t h r o u g h a s h e l l - a n d - t u b e heat exchanger w h i c h reheats the process gas s t r e a m before i t is i n t r o d u c e d into the c a t a l y t i c reactor. T h e gas stream leaves the p r i m a r y reactor at a p p r o x i m a t e l y t h e i n l e t t e m p e r a t u r e a n d is essentially at e q u i l i b r i u m , w h i c h amounts to c o n v e r sions of s u l f u r d i o x i d e to s u l f u r v a p o r of a p p r o x i m a t e l y 6 9 % w h e n t r e a t i n g a 12% dioxide. F o l l o w i n g the p r i m a r y reactor, the A S A R C O - P h e l p s D o d g e pilot p l a n t d u p l i c a t e s t y p i c a l C l a u s process p r a c t i c e . T a i l gases f r o m the p r i m a r y r e a c t o r are c o o l e d i n a h o r i z o n t a l s h e l l - a n d - t u b e condenser to c o n dense s u l f u r a n d are t h e n r e h e a t e d to a p p r o x i m a t e l y 205 C (478 K ) a n d p a s s e d t h r o u g h a second c a t a l y t i c stage. T h i s is a fixed-bed reactor w i t h n o i n t e r n a l c o o l i n g . T h e o n l y r e a c t i o n i n v o l v e d i n t h e second stage is a shift i n the e q u i l i b r i u m b e t w e e n h y d r o g e n sulfide a n d s u l f u r d i o x i d e to y i e l d a d d i t i o n a l s u l f u r v a p o r . T h e process gas stream f r o m the s e c o n d a r y reactor passes t h r o u g h a s e c o n d a r y condenser to recover a d d i t i o n a l s u l f u r a n d , thence, to a n i n c i n e r a t o r w h e r e r e s i d u a l h y d r o g e n sulfide a n d traces of s u l f u r v a p o r are b u r n e d a n d exhausted to the atmosphere. s u l f u r d i o x i d e gas a n d a b o u t 8 0 % w h e n reducing pure sulfur second
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Operational Problems of the Pilot Plant. P i l o t p l a n t o p e r a t i o n b e g a n i n late A u g u s t 1971 a n d i n i t i a l l y i n v e s t i g a t e d t r e a t m e n t of a 1 2 % s u l f u r d i o x i d e gas stream. A n u m b e r of m i n o r s t a r t - u p p r o b l e m s w e r e r e s o l v e d , and a r e l a t i v e l y stable, a r o u n d - t h e - c l o c k operation was achieved by mid-September. w e r e logged. O p e r a t i o n i n this m o d e c o n t i n u e d , w i t h some i n t e r r u p -
tions, u n t i l late F e b r u a r y 1972. D u r i n g this p e r i o d 91 days of o p e r a t i o n T y p i c a l l y , s u l f u r recoveries a v e r a g e d 8 8 - 9 2 % as c o m p a r e d Other w i t h a t h e o r e t i c a l r e c o v e r y of a p p r o x i m a t e l y 9 3 % . E l e v e n days of d o w n t i m e w e r e a t t r i b u t e d to c u r t a i l e d i n d u s t r i a l use of n a t u r a l gas. t h a n this, most of the d o w n t i m e w a s caused b y t w o p r o b l e m s . T h e first p r o b l e m i n v o l v e d g e n e r a t i o n of the 1 2 % b e a r i n g gas stream. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch003 sulfur dioxideC o n d e n s a t i o n of trace amounts of s u l f u r t r i o x i d e ,
g e n e r a t e d i n b u r n i n g s u l f u r , caused severe c o r r o s i o n of tubes a n d t u b e sheets i n t h e w a s t e heat b o i l e r . W h i l e not t y p i c a l of p o t e n t i a l p r o b l e m s w h i c h m i g h t be encountered i n c o m m e r c i a l a d a p t a t i o n of t h e s u l f u r process, this c o r r o s i o n p r o b l e m d i d cause t h e p l a n t to be shut d o w n for almost a m o n t h w h i l e the b o i l e r w a s r e p a i r e d . O p e r a t i n g the b o i l e r at a h i g h e r pressure, l e a d i n g to a h i g h e r t u b e w a l l t e m p e r a t u r e , has l a r g e l y eliminated sulfur trioxide corrosion. T h e second major p r o b l e m i n v o l v e d the catalyst u s e d for the p r i m a r y reactor. S p e c i f i c a l l y , d e c r e p i t a t i o n of catalyst pellets i n the first few inches of the b e d i n c r e a s e d t h e pressure d r o p t h r o u g h the p r i m a r y reactor. N o loss of catalyst a c t i v i t y has b e e n detected. a l t e r n a t i v e solutions. T h e p i l o t p l a n t b e g a n o p e r a t i n g w i t h a m i x t u r e of r e f o r m e d n a t u r a l gas a n d v a p o r i z e d s u l f u r d i o x i d e i n late M a r c h 1972. A f t e r o p e r a t i o n i n this m o d e for a p p r o x i m a t e l y 10 days, a second l i q u i d flowing out of the p r i m a r y s u l f u r condenser was n o t e d , a n d the p l a n t was i m m e d i a t e l y shut d o w n . A t that t i m e the p l a n t w a s p r o d u c i n g s u l f u r at the m a x i m u m d e s i g n t h r o u g h p u t o f 20 t o n s / d a y w i t h 9 0 - 9 2 % r e c o v e r y as c o m p a r e d w i t h a t h e o r e t i c a l r e c o v e r y of s l i g h t l y over 9 4 % . T h e second l i q u i d p r o v e d to be the o r g a n i c heat transfer fluid. L e a k s w e r e f o u n d i n the p r i m a r y reactor a n d the s e c o n d a r y reactor preheater. failure. R e m o v a l o f the p r i m a r y reactor heads r e v e a l e d w a r p a g e over a p p r o x i m a t e l y o n e - h a l f of the u p p e r t u b e sheet a n d s h o w e d e v i d e n c e leakage at a n u m b e r of points o n the b o t t o m t u b e sheet. of M a n y tubes i n from T h e leaks i n the preheater w e r e r e l a t i v e l y m i n o r , b u t the p r o b l e m i n the p r i m a r y reactor i n v o l v e d a m a j o r A n extensive l a b o r a t o r y i n v e s t i g a t i o n i s o l a t e d the cause of p h y s i c a l f a i l u r e a n d e v a l u a t e d possible
the area of the u p p e r t u b e sheet w a r p a g e w e r e b u r n e d t h r o u g h w h i l e the space b e t w e e n these tubes w a s s o l i d l y b l o c k e d w i t h c a r b o n t h e r m a l d e c o m p o s i t i o n of t h e o r g a n i c coolant. R e v i e w of t h e reactor
d e s i g n i n d i c a t e d that c o o l i n g of the reactor s h o u l d h a v e b e e n m o r e t h a n
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a d e q u a t e i f the coolant flowed u n i f o r m l y to a l l parts of the reactor.
The
f a i l u r e was a t t r i b u t e d to a c o m b i n a t i o n of the c o n d i t i o n s discussed b e l o w . B y p a s s i n g of t h e c o o l a n t t h r o u g h the a n n u l a r space b e t w e e n tubes a n d baffles w a s c a u s e d b y t i g h t t u b e p i t c h , close baffle s p a c i n g , a n d s m a l l w i n d o w area, a n d this r o b b e d the far side of the reactor of coolant. Byp a s s i n g i n this m a n n e r w a s the o n l y w a y i n w h i c h flow c o u l d h a v e b e e n m a i n t a i n e d f o l l o w i n g h e a v y c a r b o n d e p o s i t i o n . It is l i k e l y that b y p a s s i n g r e s u l t e d i n o v e r h e a t i n g m o r e t h a n h a l f of the reactor, c a u s i n g c a r b o n i z a t i o n of the coolant a n d subsequent t u b e f a i l u r e . A v a p o r l o c k i n the reactor c o u l d h a v e p r e v e n t e d l i q u i d phase c o o l i n g near the t o p of the reactor. O r g a n i c heat transfer fluids u n d e r g o some d e g r a d a t i o n w i t h use, l e a d i n g to the f o r m a t i o n of m o r e v o l a t i l e Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch003 compounds or to p o l y m e r i z a t i o n , f o r m i n g h i g h e r b o i l i n g compounds. T h r o u g h o u t the p i l o t p l a n t o p e r a t i o n there was n o t i c e a b l e f o r m a t i o n of " l o w b o i l e r s / ' W h i l e these w e r e a u t o m a t i c a l l y v e n t e d f r o m t h e system, there is some e v i d e n c e that v e n t i n g w a s not adequate. A f t e r a t h o r o u g h r e v i e w of possible alternatives, w e d e c i d e d that b o i l i n g m e d i a heat r e m o v a l w a s c o n c e p t u a l l y a better c h o i c e for r e a c t i o n system. T h e b o i l i n g heat transfer coefficient as m u c h of our is several times An
greater t h a n the l i q u i d film coefficient, so i t is advantageous to use t h e b o i l i n g m e d i a over the reactor l e n g t h as possible. extensive l a b o r a t o r y scale test p r o g r a m g e n e r a t e d heat transfer d a t a to c o n f i r m that e x p e c t e d heat fluxes are l o w e n o u g h t o p r e v e n t t r a n s i t i o n f r o m n u c l e a t e to film b o i l i n g . T h i s t r a n s i t i o n c o u l d cause v a p o r b l a n k e t i n g of the tubes a n d possible t u b e f a i l u r e . B a s e d o n the results of this p r o g r a m , a n e w p r i m a r y reactor has b e e n d e s i g n e d a n d i n s t a l l e d at E l Paso. 1 2 % s u l f u r d i o x i d e f e e d gas. O p e r a t i o n was r e s u m e d at E l Paso o n O c t o b e r 28, 1973, u s i n g a 1 2 % s u l f u r d i o x i d e f e e d gas. O n l y m i n o r o p e r a t i o n a l difficulties h a v e been e n c o u n t e r e d to d a t e w i t h this feed. H o w e v e r , c u r t a i l e d n a t u r a l gas use T h i s reactor p r o d u c e s 10 tons of on s u l f u r / d a y w h e n u s i n g p u r e s u l f u r d i o x i d e feed a n d 7.8 t o n s / d a y
f o r c e d s h u t d o w n of the p l a n t o n several occasions. T h e f u t u r e a v a i l a b i l i t y of n a t u r a l gas for i n d u s t r i a l use c o u l d l i m i t a p p l i c a t i o n of the A S A R C O s u l f u r d i o x i d e r e d u c t i o n process. has yet to b e p r o v e d . B a s e d o n the l a b o r a t o r y w o r k discussed a b o v e , a s o m e w h a t different catalyst w a s specified for this p i l o t r u n . T h e r e is e v i d e n c e that the r a t e o f catalyst d e c r e p i t a t i o n has b e e n decreased. the plant. T h e catalyst d e c r e p i t a t i o n p r o b l e m w i l l b e c o n c l u s i v e l y r e s o l v e d t h r o u g h l o n g e r t e r m o p e r a t i o n of It is p r o b a b l e that a s u i t a b l e r e d u c i n g gas c a n be generated u s i n g other fossil fuels, a l t h o u g h this a l t e r n a t i v e
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T h e c a p i t a l cost of t h e A S A R C O - P h e l p s D o d g e p i l o t p l a n t w a s $1,610,000. A n o t h e r $1,300,000 has b e e n b u d g e t e d f o r o p e r a t i o n . Many questions w i l l b e a n s w e r e d b y t h e o p e r a t i o n o f this p l a n t , i n c l u d i n g s u c h cost-related questions as catalyst l i f e f o r t h e d i f f e r i n g m o d e s of o p e r a t i o n . I n terms of c a p i t a l cost, i t is e s t i m a t e d that a p l a n t c a p a b l e of r e d u c i n g p u r e s u l f u r d i o x i d e gas to p r o d u c e 200 tons of e l e m e n t a l s u l f u r / d a y c a n be c o n s t r u c t e d f o r a p p r o x i m a t e l y $10,000,000. A l l o w i n g f o r t h e cost of equipment, c o n n e c t i n g flues, t h e r e q u i r e d h i g h l y efficient gas c l e a n i n g
a n d a p l a n t f o r a b s o r b i n g a n d c o n c e n t r a t i n g t h e s u l f u r d i o x i d e , s u c h as a p l a n t u s i n g t h e A S A R C O d i m e t h y l a n i l i n e process, i t also has b e e n estim a t e d that the o v e r a l l c a p i t a l r e q u i r e m e n t f o r facilities c a p a b l e of recoverPublication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch003 i n g 2 0 0 s h o r t - t o n s / d a y of e l e m e n t a l s u l f u r f r o m c o p p e r converter gases w o u l d b e about $30,000,000. D i r e c t o p e r a t i n g cost o f s u c h a p l a n t is These e s t i m a t e d at $ 3 0 - 3 5 / s h o r t - t o n o f sulfur, d e p e n d i n g o n f u e l costs.
estimates a r e b a s e d o n 1972 c o n s t r u c t i o n a n d o p e r a t i n g l a b o r costs a n d m u s t b e v i e w e d as b u d g e t a r y estimates o n l y , b a s e d o n i n c o m p l e t e p i l o t p l a n t e v a l u a t i o n of t h e process. Literature Cited
1. Kuzell, C. R., Fowler, M . G . , Klein, L . , Davis, J. H . , Jr., U.S. Patent #3,071,454 (Jan. 1, 1963).
R E C E I V E D A p r i l 4, 1974. Certain process details and specific laboratory and pilot data have been omitted from this discussion of the A S A R C O sulfur dioxide reduction process because of their proprietary nature.
American Chemical Society Library

1155 16th St. N. W. Washington, D. C. 20036
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Sulfuric Acid Plants for Copper Converter Gas
J. B. RINCKHOFF Davy Powergas Inc., Lakeland, Fla. 33803
Conventional sulfuric acid plants have traditionally been used to recover sulfur dioxide from smelter gases, but these are inadequate to meet the proposed sulfur dioxide emission standards. Double absorption, which removes sulfur trioxide from the partially converted sulfur dioxide gas stream, reduces the sulfur dioxide emission to less than 500 ppm in the undiluted stack gas. Two double absorption plants using Lurgi technology have been operating with copper converter gas since early 1973. In spite of the wide and frequent variations in gas volume and sulfur dioxide concentration, these plants have consistently maintained sulfur dioxide emission levels well below 500 ppm. This paper presents data on the design and operating conditions for these plants.
^ smelting of nonferrous metals, primarily copper, zinc, and lead, generally causes sulfur dioxide emissions varying from as much as 15% to less than 1% sulfur dioxide depending on the type of operation. Some sulfur dioxide is recovered as sulfuric acid. T h e nonferrous smelter industryeither in operation or under construction in 1974has a total sulfuric acid production capacity of about 15,000 tons/day. About one third of this output comes from lead and zinc smelters which produce a reasonably steady gas stream containing 5-14% sulfur dioxide, depending on the type of roaster or sinter machine used. W i t h a steady gas flow and sulfur dioxide concentration, designing a sulfuric acid plant to use this off-gas presents few problems except for cleaning the gas in the purification section of the plant.
A
However, this paper is primarily concerned with sulfuric acid production from copper smelters where most of the sulfur dioxide is in a gas stream which varies widely and frequently, both in gas volume and in sulfur dioxide concentration. This gas stream presents a real challenge 48
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to t h e s u l f u r i c a c i d p l a n t designer, e s p e c i a l l y i n v i e w of the
Environmental Protection Agency ( E P A ) regulation w h i c h w o u l d limit s u l f u r d i o x i d e emissions f r o m the a c i d p l a n t to a n average of 650 p p m o v e r a 6-hr p e r i o d . I n the c o n v e n t i o n a l process w h i c h has b e e n u s e d for m a n y years, the m a x i m u m c o n v e r s i o n of s u l f u r d i o x i d e to s u l f u r t r i o x i d e is 9 8 % . T h i s process w i l l r e d u c e the s u l f u r d i o x i d e i n a gas c o n t a i n i n g W i t h a gas c o n t a i n i n g 4 % sulfur dioxide, 9 8 % conversion w i l l 8.0% reduce s u l f u r d i o x i d e to a b o u t 1800 p p m i n the stack gas l e a v i n g the absorber. the stack gas to 850 p p m . B o t h of these concentrations are greater t h a n the p r o p o s e d E P A l i m i t a t i o n of 650 p p m , a n d a different a p p r o a c h is required. T h i s has b e e n a c c o m p l i s h e d i n the d o u b l e - c a t a l y s i s process d e v e l oped by Bayer and Lurgi. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch004 D a v y P o w e r g a s , w h o is a L u r g i licensee for this process, b u i l t the o n l y t w o p l a n t s of this t y p e i n the U n i t e d States w h i c h use c o p p e r converter gas. T h e y h a v e k e p t s u l f u r d i o x i d e emissions w e l l b e l o w the g u a r a n t e e d 500 p p m l e v e l . I n the c o n v e n t i o n a l p l a n t s u l f u r d i o x i d e is c o n v e r t e d to s u l f u r t r i o x i d e i n a series of three or f o u r catalyst b e d s w i t h c o o l i n g b e t w e e n t h e beds to r e m o v e the heat of r e a c t i o n . T h e o v e r a l l c o n v e r s i o n is l i m i t e d b y t h e e q u i l i b r i u m for the r e l a t i v e p a r t i a l pressures of s u l f u r d i o x i d e , s u l f u r t r i o x i d e , a n d o x y g e n a n d the t e m p e r a t u r e of t h e converter exit gas. T h i s e q u i l i b r i u m is e q u i v a l e n t to a b o u t 9 8 . 5 % conversion. I n the d o u b l e - c a t a l y s i s p l a n t a major p o r t i o n of the s u l f u r t r i o x i d e is r e m o v e d f r o m the gas i n a n i n t e r m e d i a t e a b s o r p t i o n t o w e r after t h e second stage of c o n v e r s i o n . T h e b a l a n c e of the gas, w h i c h is r e t u r n e d to the c o n v e r t e r for the final t w o stages of c o n v e r s i o n , is a v e r y w e a k s u l f u r d i o x i d e gas w i t h a h i g h oxygen-to-sulfur d i o x i d e ratio. T h e e q u i l i b r i u m c o n d i t i o n s for this gas l e a v i n g the c o n v e r t e r are v e r y close to 1 0 0 % c o n v e r s i o n of the t o t a l s u l f u r d i o x i d e e n t e r i n g the converter. In steady state o p e r a t i o n , w h i c h is not p o s s i b l e w i t h c o p p e r converter gas, over 9 9 . 8 % c o n v e r s i o n of s u l f u r d i o x i d e to s u l f u r t r i o x i d e is e x p e c t e d i n double-catalysis plants. Capper Smelter Operation
A b r i e f d e s c r i p t i o n of a t y p i c a l c o p p e r smelter o p e r a t i o n w i l l h e l p i n u n d e r s t a n d i n g the e x t r e m e l y v a r i a b l e n a t u r e of the s u l f u r d i o x i d e gas s t r e a m to b e processed. T h e c o p p e r concentrates d e l i v e r e d to the smelter are a m i x t u r e of c o p p e r a n d i r o n sulfides. I n c u r r e n t p r a c t i c e these are processed i n t w o or three steps to p r o d u c e 9 9 % b l i s t e r c o p p e r . I n some smelters the concentrates are first p a r t i a l l y roasted, r e m o v i n g of the s u l f u r . T h i s produces a r e l a t i v e l y strong, steady gas containing 4 - 1 4 % 20-50% stream
s u l f u r d i o x i d e , d e p e n d i n g o n t h e t y p e of roaster u s e d .
50
S U L F U R
R E M O V A L
A N D
R E C O V E R Y
T h e p a r t i a l l y r o a s t e d m a t e r i a l , or g r e e n concentrates if n o r o a s t i n g step is i n c l u d e d , is t h e n c h a r g e d to t h e r e v e r b e r a t o r y f u r n a c e . H e r e the c h a r g e is m e l t e d , a n d a m a t t e c o n t a i n i n g 2 5 - 5 0 % copper and 4 0 - 2 0 % S o m e of i r o n settles to the b o t t o m w h i l e a n i r o n slag floats to the t o p . q u i r e d to p r o v i d e t h e necessary heat. an additional 1 0 - 3 0 %
the s u l f u r i n the c h a r g e is b u r n e d b u t a d d i t i o n a l fossil f u e l firing is r e I f the c h a r g e has b e e n roasted, W i t h green conof the s u l f u r w i l l be b u r n e d .
centrate f e e d a b o u t 2 0 - 4 0 % of the s u l f u r w i l l be b u r n e d . T h e off-gas f r o m the r e v e r b e r a t o r y f u r n a c e is a steady flow b u t it contains o n l y V i 2 V i % sulfur dioxide. The verters. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch004 final step, a b a t c h o p e r a t i o n , takes p l a c e i n the c o p p e r fluxing material. conM a t t e , w i t h d r a w n f r o m the r e v e r b e r a t o r y f u r n a c e , is c h a r g e d A i r is b l o w n with
to the c o n v e r t e r a l o n g w i t h a siliceous f o r m i r o n o x i d e a n d s u l f u r d i o x i d e gas.
t h r o u g h the m o l t e n charge, a n d the i r o n sulfide is selectively o x i d i z e d to T h e iron oxide combines the flux to f o r m a slag. W h e n s l a g g i n g is essentially c o m p l e t e the a i r b l o w i n g is s t o p p e d a n d the slag is s k i m m e d off. c o n v e r t e r charge is c o m p l e t e d . A d d i t i o n a l matte and flux is c h a r g e d to the converter, a n d the o p e r a t i o n is r e p e a t e d u n t i l a f u l l T h i s m a y r e q u i r e f o u r to eight separate The individual charges, d e p e n d i n g o n the c o m p o s i t i o n of the matte.
slag b l o w s m a y e a c h last as l o n g as 1. h r . N o a i r is b l o w n for a b o u t 15 m i n b e t w e e n charges w h i l e the slag is b e i n g s k i m m e d a n d a n a d d i t i o n a l c h a r g e is a d d e d . W h e n the c h a r g e is c o m p l e t e a n d essentially a l l of the i r o n has b e e n slagged, the final c o p p e r b l o w is started to b u r n t h e r e m a i n i n g c o p p e r sulfide. T h i s c o p p e r b l o w m a y last for s e v e r a l h o u r s before a l l the s u l f u r is r e m o v e d a n d a 9 9 % b l i s t e r c o p p e r is o b t a i n e d . T h e c o n verter is t h e n u n l o a d e d a n d m a d e r e a d y for the next charge. gas d u r i n g slag a n d c o p p e r b l o w s operating. M o s t smelters h a v e at least three converters, a n d one or m o r e c o n verters s h o u l d b e o n the o p e r a t i n g c y c l e at a l l times to p r o v i d e a r e a s o n a b l y constant gas flow. T h e o p e r a t i n g t i m e for one c y c l e m a y b e f r o m 6 to 12 h r , d e p e n d i n g o n the o p e r a t i o n of the p a r t i c u l a r smelter a n d the t y p e of concentrates b e i n g treated. T h e gas flow d u r i n g the f u l l converter c y c l e is i n t e r m i t t e n t because it is necessary to shut off the air b l o w d u r i n g slag s k i m m i n g a n d c h a r g i n g . T h e s u l f u r d i o x i d e c o n c e n t r a t i o n i n t h e gas d i r e c t l y a b o v e the c o n verter c h a r g e is close to t h e o r e t i c a l a b o u t 1 6 % d u r i n g slag b l o w s a n d 2 1 % d u r i n g copper blows. T h e converter hoods, h o w e v e r , are not t i g h t because the converter m u s t b e r o t a t e d for c h a r g i n g a n d s k i m m i n g . F r o m 100 to 3 0 0 % a i r w i l l leak i n to p r e v e n t a p p r e c i a b l e s u l f u r d i o x i d e leakage i n t o the w o r k i n g area a r o u n d the converters. I n a t y p i c a l o p e r a t i o n the for a plant w i t h two Figure 1 converters shows t y p i c a l v a r i a t i o n s i n s u l f u r d i o x i d e concentrations i n the c o n v e r t e r
4.
RiNCKHOFF
Sulfuric Acid
Pfonts
51
ELAPSED
TIME - HOURS
Figure 1.
Variation of sulfur dioxide concentration converter gas
in a typical
copper
off-gas f r o m t h e c o n v e r t e r m a y average a b o u t 4 % s u l f u r d i o x i d e d u r i n g the slag b l o w s a n d 8 % d u r i n g t h e c o p p e r b l o w . 60-80% c h a r g e d d i r e c t l y to t h e r e v e r b e r a t o r y f u r n a c e . b e i n t h e c o n v e r t e r off-gas. Plant Design Considerations T h i s gas w i l l c o n t a i n i f t h e y are of t h e t o t a l s u l f u r c o n t a i n e d i n t h e concentrates
I f t h e concentrates are of the s u l f u r w i l l
p a r t i a l l y roasted before s m e l t i n g o n l y a b o u t 3 0 - 5 0 %
F r o m t h e p o i n t of v i e w of the s u l f u r i c a c i d p l a n t designer i t w o u l d be advantageous i f the smelter h a d a roaster g e n e r a t i n g a h i g h s t r e n g t h s u l f u r d i o x i d e gas f o r t h e base l o a d . T h i s w o u l d r e d u c e t h e effect of t h e w i d e swings i n t h e s u l f u r d i o x i d e c o n c e n t r a t i o n of the c o n v e r t e r gas. U n f o r t u n a t e l y , most o f t h e e x i s t i n g roasters p r o d u c e the c o n v e r t e r gas. F o r this e x a m p l e of a c i d p l a n t d e s i g n considerations, assume t h a t a smelter has three c o p p e r converters a n d t h a t the a c i d p l a n t m u s t b e a b l e to t a k e a l l of t h e c o n v e r t e r gas a n d m a i n t a i n a s u l f u r d i o x i d e l e v e l of less t h a n 500 p p m i n t h e a c i d p l a n t stack gas. T h e m a x i m u m gas flow f r o m a very weak sulfur d i o x i d e gas, a n d t h e s u l f u r i c a c i d p l a n t m u s t b e d e s i g n e d to use o n l y
52
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A N D RECOVERY
e a c h converter is 30,000 s t a n d a r d e u f t / m i n ( S C F M ) , a n d no m o r e t h a n t w o converters w i l l be o n the l i n e at a n y t i m e . T h e m a x i m u m sulfur The plant sulfur dioxide. d i o x i d e c o n c e n t r a t i o n w i t h the m a x i m u m gas flow w i l l b e 8 % . is to be a u t o t h e r m a l w h e n o p e r a t i n g w i t h as l o w as 4 % b a l a n c e i f the gas has at least 4 % less t h a n 4 % sulfur dioxide.
T h i s means that no f u e l f i r i n g w i l l be r e q u i r e d to k e e p the p l a n t i n t h e r m a l F o r gas c o n t a i n i n g s u l f u r d i o x i d e , a f u e l - f i r e d i n d i r e c t heater w i l l b e r e q u i r e d . sulfur
T o m e e t these c o n d i t i o n s t h e a c i d p l a n t m u s t b e d e s i g n e d to h a n d l e 60,000 S C F M of gas. W h e n this gas contains t h e m a x i m u m of 8 % d i o x i d e the a c i d p r o d u c t i o n rate is e q u i v a l e n t to 960 t o n s / d a y . coolers m u s t b e d e s i g n e d for this a c i d p r o d u c t i o n rate. D e f i n i n g the m i n i m u m s u l f u r d i o x i d e c o n c e n t r a t i o n for the p l a n t Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch004 establishes c e r t a i n other d e s i g n c r i t e r i a . If o n l y one converter is o n the fine w i t h a slag b l o w p r o d u c i n g 4 % s u l f u r d i o x i d e gas, the e q u i v a l e n t T h i s is s t i l l not the m i n i m u m S o m e of the gas-cooling a c i d p r o d u c t i o n rate is o n l y 240 t o n s / d a y . S i n c e this
c o n d i t i o n m a y persist for at least 1 h r , the catalyst l o a d i n g a n d the a c i d
o p e r a t i n g rate since t h e r e w i l l b e p e r i o d s , p r e s u m a b l y short, w h e n t h e s u l f u r d i o x i d e c o n c e n t r a t i o n decreases to 1 % or e v e n zero. r e q u i r e m e n t w i t h 60,000 S C F M of 4 % sulfur dioxide. The gas-to-gas heat exchangers m u s t be s i z e d to m a i n t a i n the a u t o t h e r m a l f a c i l i t i e s i n t h e p u r i f i c a t i o n section of the p l a n t m u s t b e able to r e d u c e t h e w a t e r content of t h e gas sufficiently to p e r m i t the p r o d u c t i o n of 9 3 % sulfuric acid w i t h 4 % gas to a b o u t 85 F . s u l f u r d i o x i d e gas. T h i s necessitates c o o l i n g the for concentrations. F i g u r e 2 shows the r e q u i r e d gas t e m p e r a t u r e
v a r i o u s p l a n t elevations a n d s u l f u r d i o x i d e
A n o t h e r m a j o r c o n s i d e r a t i o n i n the d e s i g n of the p l a n t is the n a t u r e a n d q u a n t i t y of i m p u r i t i e s i n the gas stream d e l i v e r e d to the a c i d p l a n t . N o a c i d p l a n t c a n operate s a t i s f a c t o r i l y w i t h a n i n a d e q u a t e gas p u r i f i c a t i o n section. T h e gas w i l l n o r m a l l y b e d e l i v e r e d to the a c i d p l a n t at about 600 F after most of the dust has b e e n r e m o v e d i n electrostatic p r e c i p i tators. H o w e v e r , t h e gas m a y s t i l l c o n t a i n dust, as w e l l as s u l f u r t r i o x i d e , halogens, arsenic, a n d other m e t a l l i c vapors. Gas Purification I n the p u r i f i c a t i o n section of the a c i d p l a n t the gas first enters a w e a k a c i d s c r u b b e r w h e r e its t e m p e r a t u r e is r e d u c e d to a b o u t 130 F b y w a t e r e v a p o r a t i o n . It is t h e n c o o l e d to a b o u t 85 F to r e d u c e its w a t e r content to t h e r e q u i r e d l e v e l . F i n a l l y , it is c l e a n e d i n electrostatic m i s t p r e from T h e t y p e of e q u i p m e n t u s e d cipitators w h e r e the last traces of dust a n d the a c i d m i s t f o r m e d t h e s u l f u r t r i o x i d e i n the gas are r e m o v e d . d i t i o n s a n d operator preferences.
i n t h e p u r i f i c a t i o n section w i l l v a r y s o m e w h a t w i t h i n d i v i d u a l p l a n t c o n -
4.
RiNCKHOFF
Sulfuric
Acid
Fiants
53
Figure 2.
Gas cooling required to produce 93%
or 98%
sulfuric
acid
G A S S C R U B B I N G A N D C O O L I N G . If the gas contains fluorine, t w o s c r u b b i n g towers i n series m a y b e r e q u i r e d to r e m o v e the section of the a c i d p l a n t . Excess fluorine completely. contact second the T h i s step is necessary p r i m a r i l y to protect the catalyst i n the scrubbing liquor from
s c r u b b e r is t r a n s f e r r e d to the first s c r u b b e r , a n d the w e a k a c i d p u r g e f r o m the system is t a k e n f r o m the first s c r u b b e r . Since fluorine w i l l attack the u s u a l a c i d - p r o o f refractory m a t e r i a l s , the first s c r u b b e r , w h i c h is subject to the h i g h e s t fluorine content, is l i n e d w i t h c a r b o n b r i c k . T h e s c r u b b e r m a y be either a v e n t u r i - t y p e or a n o p e n s p r a y - t y p e t o w e r i n w h i c h the gas is q u e n c h e d to its s a t u r a t i o n t e m p e r a ture. W e a k a c i d is r e c i r c u l a t e d over this t o w e r to r e m o v e as m u c h of the dust a n d fluorine as possible, as w e l l as to q u e n c h the gas. I n the second t o w e r t h e gas m u s t be c o o l e d to meet the r e q u i r e d w a t e r b a l a n c e for a c i d p r o d u c t i o n . T h i s is u s u a l l y a p a c k e d - or t r a y - t y p e t o w e r w i t h l i q u o r coolers i n the r e c i r c u l a t e d w e a k a c i d stream. T h e t e m p e r a t u r e to w h i c h the gas m u s t be c o o l e d is d e t e r m i n e d b y its s u l f u r d i o x i d e content, the p r o d u c t a c i d strength d e s i r e d , a n d the e l e v a t i o n of the p l a n t a b o v e sea l e v e l . A s s h o w n i n the chart, e a c h of these factors has a n i m p o r t a n t effect o n the r e q u i r e d t e m p e r a t u r e . A n a l l o w a n c e has
54
SULFUR
REMOVAL
AND RECOVERY
b e e n m a d e i n the c a l c u l a t i o n to p e r m i t the a d d i t i o n of some w a t e r to the s t r o n g a c i d system to p r o v i d e m o r e If the fluorine flexible c o n t r o l of a c i d strength. or dust content of the gas is n o t excessive, a single D i r e c t c o o l i n g of the gas w i t h two
p a c k e d - o r t r a y - t y p e t o w e r w i t h c o o l i n g of the r e c i r c u l a t e d l i q u o r c a n be u s e d f o r b o t h gas s c r u b b i n g a n d c o o l i n g . once-through reasons. c o o l i n g w a t e r is no longer c o n s i d e r e d p r a c t i c a l for
F i r s t , the w a t e r w i l l b e c o n t a m i n a t e d w i t h d u s t a n d the a c i d
f o r m e d f r o m t h e s u l f u r t r i o x i d e i n the gas, m a k i n g d i s p o s a l a p r o b l e m . S e c o n d , some of the s u l f u r d i o x i d e w i l l be a b s o r b e d i n the w a t e r , a n d the a m o u n t of s t r i p p i n g a i r r e q u i r e d to recover this a n d a v o i d a n u i s a n c e w i l l d i l u t e the m a i n gas stream excessively. M a t e r i a l s of c o n s t r u c t i o n are a n i m p o r t a n t c o n s i d e r a t i o n i n the gas s c r u b b i n g system because Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch004 and fluorine a n d c h l o r i n e m a y b e present. sulfuric acid below The s c r u b b i n g l i q u o r is u s u a l l y less t h a n 1 0 % 135 F , pumps,
a stainless steel ( s u c h as 20 a l l o y ) w o u l d be suitable for
v a l v e s , a n d l i q u o r coolers i f halogens are not present.
T h e alternatives
are glass- or p l a s t i c - l i n e d , g r a p h i t e or h i g h e r alloys. T h e towers are u s u a l l y a c a r b o n steel s h e l l w i t h a n i m p e r v i o u s m e m b r a n e a n d a n a c i d b r i c k l i n i n g , a l t h o u g h p l a s t i c c a n b e u s e d i n some areas.

ELECTROSTATIC MIST PRECIPITATORS. The gas l e a v i n g the scrubbers
is essentially free of halogens a n d dust b u t i t still contains a c i d m i s t . T h e a m o u n t of a c i d m i s t d e p e n d s p r i m a r i l y o n c o n d i t i o n s i n t h e smelter. In gas f r o m c o p p e r converters, the s u l f u r t r i o x i d e content m a y v a r y f r o m 2 to 1 0 % of the t o t a l s u l f u r oxides. T h e a m o u n t of s u l f u r t r i o x i d e f o r m e d d e p e n d s l a r g e l y o n the t e m p e r a t u r e a n d t i m e the gas contacts t h e i r o n o x i d e i n the dust a n d the scale o n the c a r b o n steel flues. T h e sulfur t r i o x i d e c o m b i n e s w i t h the m o i s t u r e i n t h e gas to f o r m s u l f u r i c a c i d v a p o r . W h e n the gas is c o o l e d i n the scrubbers, most of this v a p o r condenses as a finely d i v i d e d a c i d m i s t , a l t h o u g h some of i t is a b s o r b e d scrubber liquor. be particles less t h a n 5 , is v e r y difficult to remove from i n the to gas a S u l f u r i c a c i d m i s t , w h i c h is g e n e r a l l y c o n s i d e r e d
stream, so o n l y a p o r t i o n of the m i s t w i l l b e r e m o v e d i n t h e s c r u b b e r . If the r e m a i n i n g m i s t w e r e a l l o w e d to enter the contact section of the a c i d p l a n t it w o u l d corrode the c a r b o n steel ducts a n d heat a n d the m a i n b l o w e r . possible i n the p u r i f i c a t i o n section of the p l a n t . i n the electrostatic m i s t p r e c i p i t a t o r s . T h e s e p r e c i p i t a t o r s are u s u a l l y m a d e of sheet l e a d . T h e y p e n d e d i n the center of e a c h of the 10-in. d i a m e t e r tubes. flowing resemble susgas, The a v e r t i c a l t u b u l a r exchanger w i t h h i g h voltage d i s c h a r g e electrodes exchangers It m u s t , therefore, be r e m o v e d as c o m p l e t e l y as T h i s is a c c o m p l i s h e d
u p w a r d t h r o u g h the tubes, is exposed to a c o r o n a d i s c h a r g e f r o m
the electrodes w h i c h d r i v e s t h e mist p a r t i c l e s to the g r o u n d e d t u b e w a l l s . T h e c o l l e c t e d a c i d runs d o w n the tubes a n d is c o l l e c t e d i n the l o w e r
4.
RiNCKHOFF
Sulfuric Acid
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55
h e a d e r as 5 - 1 0 %
s u l f u r i c a c i d . T h e a c i d , w h i c h is s a t u r a t e d w i t h s u l f u r
d i o x i d e a n d w h i c h contains the last traces of d u s t f r o m the gas, is u s u a l l y r e t u r n e d to the s c r u b b e r c i r c u l a t i n g system. T h e gas l e a v i n g the scrubbers m a y c o n t a i n as m u c h as 100 m g / S C F of s u l f u r i c a c i d as a c i d m i s t , a n d t w o m i s t p r e c i p i t a t o r s are u s u a l l y i n stalled i n series to o b t a i n 9 9 % r e m o v a l efficiency. T h i s efficiency c o u l d power b e o b t a i n e d i n a single l a r g e r u n i t g i v i n g the same t o t a l r e s i d e n c e t i m e b u t this w o u l d be less r e l i a b l e . T h e efficiency is a f u n c t i o n of w h i c h a r c i n g occurs i n the tubes. i n p u t to the d i s c h a r g e electrodes, a n d this is l i m i t e d b y the voltage at E n t r a i n e d a c i d d r o p l e t s i n the gas stream w i l l aggravate the a r c i n g a n d r e q u i r e r e d u c e d i n p u t voltage w h i c h lowers the u n i t efficiency. W i t h t w o units i n series the v o l t a g e is r e d u c e d o n l y o n the first u n i t so that the o v e r a l l efficiency is affected o n l y s l i g h t l y . Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch004 T h e i m p u r i t i e s r e m o v e d f r o m the gas i n the p u r i f i c a t i o n system m u s t be p u r g e d f r o m t h e system, a n d the p u r g e is n o r m a l l y t a k e n f r o m t h e s c r u b b i n g tower. M a k e u p w a t e r is u s u a l l y r e q u i r e d to p r o v i d e this p u r g e because the gas e n t e r i n g the s c r u b b e r n o r m a l l y contains less w a t e r t h a n the c o o l e d s a t u r a t e d gas l e a v i n g the m i s t p r e c i p i t a t o r s . T h e q u a n t i t y of m a k e u p w a t e r r e q u i r e d is the t o t a l of the a m o u n t a d d e d to t h e gas stream a n d the a m o u n t r e q u i r e d to m a i n t a i n the a c i d a n d / o r the dust c o n c e n t r a t i o n i n the s c r u b b e r l i q u o r b e l o w a selected l i m i t i n g figure. T h e p u r g e stream is saturated w i t h s u l f u r d i o x i d e a n d is d i s c h a r g e d f r o m the system
Figure 3.
Flow diagram of a double-catalysis
sulfuric acid plant
56
SULFUR
REMOVAL
A N D RECOVERY
t h r o u g h a s t r i p p e r w h e r e most of the s u l f u r d i o x i d e is r e c o v e r e d i n a s m a l l stream of s t r i p p i n g a i r w h i c h is a d d e d to t h e m a i n gas stream. T h e gas l e a v i n g the m i s t p r e c i p i t a t o r s s h o u l d c o n t a i n o n l y sulfur d i o x i d e , o x y g e n , n i t r o g e n , a n d w a t e r v a p o r , b u t there w i l l be some traces of i m p u r i t i e s w h i c h are not h a r m f u l to the contact section of the a c i d p l a n t . If the gas has not b e e n a d e q u a t e l y c l e a n e d , the contact section the p l a n t w i l l h a v e c o n t i n u i n g o p e r a t i n g p r o b l e m s . tion. Improper of operation
of the m i s t p r e c i p i t a t o r s w i l l p e r m i t a c i d m i s t to enter the c o n t a c t secT h i s w i l l result i n c o r r o s i o n a n d sulfate a c c u m u l a t i o n i n the gas T h e c o r r o s i o n is p a r t i c u l a r l y ducts, the b l o w e r , a n d the heat exchangers.
severe i n the heat exchangers b e c a u s e the tube w a l l t e m p e r a t u r e , w i t h h o t s u l f u r t r i o x i d e gas i n the tubes, exceeds 3 0 0 F . T h e sulfate a c c u m u l a t i o n on the d u c t w a l l s is n o r m a l l y not a serious corrosion p r o b l e m Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch004 converter. T h i s sulfate, a n d also a n y dust that m a y pass t h r o u g h efficiency a n d increases the pressure d r o p t h r o u g h but the the it e v e n t u a l l y breaks loose a n d is c a r r i e d onto the catalyst beds i n the p u r i f i c a t i o n section, w i l l g r a d u a l l y b l i n d the catalyst beds. T h i s reduces the c o n v e r s i o n plant.
Contact
Section
I n t h e contact section of the p l a n t , the saturated gas is first d r i e d b y contact w i t h 9 3 % a c i d a n d t h e n the s u l f u r d i o x i d e i n the gas is o x i d i z e d to s u l f u r t r i o x i d e . sulfuric acid. verters. T o o b t a i n essentially c o m p l e t e o x i d a t i o n of s u l f u r d i o x i d e to s u l f u r t r i o x i d e excess o x y g e n i n the gas a b o v e the s t o i c h i o m e t r i c r e q u i r e m e n t is necessary. ratio. T h e r e are times d u r i n g the o p e r a t i n g c y c l e of t h e c o p p e r w h e n the oxygen-to-sulfur converter Durd i o x i d e r a t i o is l o w e r t h a n is desirable. T h e v o l u m e of o x y g e n i n the gas s h o u l d at least be e q u i v a l e n t to that of the s u l f u r d i o x i d e , a n d it is p r e f e r a b l e to h a v e a s l i g h t l y h i g h e r T h e s u l f u r t r i o x i d e is a b s o r b e d i n 9 8 % acid w h e r e it c o m b i n e s w i t h the free w a t e r present to p r o d u c e a d d i t i o n a l double-catalysis con-
F i g u r e 3 is a t y p i c a l flow d i a g r a m of a
s u l f u r i c a c i d p l a n t o p e r a t i n g w i t h s u l f u r d i o x i d e gas f r o m c o p p e r
i n g these p e r i o d s d i l u t i o n a i r m u s t be m i x e d w i t h t h e gas e n t e r i n g the d r y i n g t o w e r of the c o n t a c t section of the p l a n t to increase its o x y g e n content. T h e gas is d r i e d b y c o n t a c t w i t h r e c i r c u l a t e d 9 3 % passes u p t h r o u g h the p a c k i n g i n t h e d r y i n g tower. a c i d as the gas and T h e a c i d absorbs
t h e m o i s t u r e f r o m the gas a n d is h e a t e d b y m o i s t u r e c o n d e n s a t i o n t h r o u g h coolers before i t is r e t u r n e d to the t o p of the tower.
b y the resultant a c i d d i l u t i o n . T h i s heat is r e m o v e d b y p u m p i n g the a c i d
4.
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Phnts
57
S i n c e d r i e d gas is not corrosive, c a r b o n steel ducts are u s e d for t h e r e m a i n d e r of the p l a n t . T h e gas leaves the d r y i n g t o w e r at a b o u t 1 1 0 F , a n d after p a s s i n g t h r o u g h a n e n t r a i n m e n t separator i t goes to the m a i n blower. T h e b l o w e r p r o v i d e s sufficient s u c t i o n to d r a w the gas t h r o u g h T h e t o t a l pressure drop the p u r i f i c a t i o n section a n d the d r y i n g t o w e r a n d sufficient pressure to d e l i v e r i t t h r o u g h the b a l a n c e of the p l a n t . t h r o u g h a c l e a n d o u b l e - c a t a l y s i s p l a n t , i n c l u d i n g the p u r i f i c a t i o n system, is u s u a l l y a b o u t 200 i n . W G (7.25 p s i ) , a n d a n a d d i t i o n a l 2 5 - 3 0 i n . W G is u s u a l l y a d d e d for the d e s i g n of the b l o w e r to a l l o w for pressure b u i l d u p i n the system. Conversion. T h e gas leaves the b l o w e r at a b o u t 175 F a n d is h e a t e d i n the s h e l l side of a series of gas-to-gas s h e l l a n d t u b e heat exchangers to the r e q u i r e d c o n v e r t e r i n l e t t e m p e r a t u r e of 8 2 0 F . Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch004 I n the converter, f o u r catalyst beds are a r r a n g e d one a b o v e the other w i t h d i v i s i o n plates b e t w e e n the beds. T h e gas l e a v i n g e a c h catalyst b e d is c o o l e d i n the t u b e side of the s h e l l a n d t u b e heat exchangers to the d e s i r e d t e m p e r a t u r e before e n t e r i n g the next b e d . T h e t e m p e r a t u r e rise i n the catalyst beds w i l l v a r y c o n s i d e r a b l y w i t h the w i d e v a r i a t i o n i n t h e sulfur d i o x i d e content of the feed gas. T h e q u a n t i t y of catalyst i n s t a l l e d i n each b e d w i l l be d e t e r m i n e d b y the m a x i m u m s u l f u r d i o x i d e flow, w h i c h is u s u a l l y a n 8 % gas. T h e r e f o r e the catalyst l o a d i n g is greater t h a n r e q u i r e d for a w e a k e r s u l f u r d i o x i d e gas, a n d a h i g h e r c o n v e r s i o n w i l l b e o b t a i n e d o n the first b e d . T h i s is e n h a n c e d b y the l o w e r t e m p e r a t u r e rise o b t a i n e d w i t h a w e a k s u l f u r d i o x i d e gas for a g i v e n percentage c o n v e r s i o n of s u l f u r d i o x i d e to s u l f u r t r i o x i d e . F o r e x a m p l e , a p p r o x i m a t e l y 6 5 % of a n w i t h a t e m p e r a t u r e rise of 2 8 5 F . With a 4% 8% s u l f u r d i o x i d e gas w i l l be c o n v e r t e d to s u l f u r t r i o x i d e i n the first b e d s u l f u r d i o x i d e gas a b o u t The difThe 8 5 % w i l l b e c o n v e r t e d w i t h a t e m p e r a t u r e rise of o n l y 190 F .
ferences a n d t e m p e r a t u r e rises w i l l be less o n subsequent beds.
extent of c o n v e r s i o n approaches e q u i l i b r i u m o n each b e d , a n d the gas m u s t be c o o l e d after e a c h b e d so that f u r t h e r c o n v e r s i o n c a n b e a c h i e v e d i n the next b e d . Absorption. I n a t y p i c a l d o u b l e - c a t a l y s i s p l a n t , the gas l e a v i n g the second stage of c o n v e r s i o n passes to the interstage a b s o r p t i o n tower sulfur w h e r e the s u l f u r t r i o x i d e is a b s o r b e d f r o m the gas. W i t h a n 8 % s u l f u r t r i o x i d e at this p o i n t , a n d w i t h a 4 %
d i o x i d e gas m o r e t h a n 8 5 % of the s u l f u r d i o x i d e has b e e n c o n v e r t e d to gas over 9 5 % has b e e n c o n T h e heat a v a i l a b l e v e r t e d . T h e gas l e a v i n g the converter m u s t be c o o l e d at least to 450 F b u t not b e l o w 300 F before e n t e r i n g the absorber. to t h e t h i r d stage of c o n v e r s i o n . O n e of the m a j o r p r o b l e m s i n d e s i g n i n g a d o u b l e - c a t a l y s i s p l a n t is to m a k e i t a u t o t h e r m a l w h e n o p e r a t i n g w i t h a w e a k s u l f u r d i o x i d e gas. The f r o m this c o o l i n g is u s e d to reheat the gas r e t u r n i n g f r o m t h e absorber
58
SULFUR REMOVAL
A N D RECOVERY
o n l y heat a v a i l a b l e to the c o n v e r t e r - h e a t exchanger system is the exot h e r m i c heat of r e a c t i o n of o x i d i z i n g s u l f u r d i o x i d e to s u l f u r t r i o x i d e a n d the heat of c o m p r e s s i o n i n t h e m a i n gas b l o w e r . Some of the heat c a n cooled b e r e c o v e r e d f r o m the gas g o i n g f r o m the converter to the absorbers b u t this gas stream, w i t h its s u l f u r t r i o x i d e content, s h o u l d not b e b e l o w 300 F to a v o i d possible a c i d c o n d e n s a t i o n i n the heat exchanger. I n a c o n v e n t i o n a l t y p e p l a n t w i t h a single absorber it is p r a c t i c a l to d e s i g n the p l a n t to b e a u t o t h e r m a l w i t h a gas c o n t a i n i n g as little as 3 % s u l f u r d i o x i d e because heat is o n l y lost w h e n the gas goes to the absorber p l u s t h e n o r m a l heat lost to atmosphere. I n the d o u b l e - c a t a l y s i s process, In h e a t is lost f r o m t h e gas s t r e a m g o i n g to e a c h of the t w o absorbers.
the n o r m a l d e s i g n of absorber, i f the t o t a l gas stream leaves the interstage a b s o r b e r at 1 7 0 - 1 8 0 F to be r e h e a t e d to converter t e m p e r a t u r e it w o u l d Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch004 be i m p o s s i b l e for the p l a n t to be a u t o t h e r m a l w i t h 4 % s u l f u r d i o x i d e gas. A s o l u t i o n to this p r o b l e m , d e v e l o p e d a n d p a t e n t e d b y L u r g i , uses a v e n t u r i - t y p e interstage absorber. T h e a c i d a n d gas flows are c o - c u r r e n t d o w n t h r o u g h the v e r t i c a l v e n t u r i so that the gas leaves the absorber at essentially the same t e m p e r a t u r e as the a c i d . W i t h s u i t a b l e adjustment of the a c i d c i r c u l a t i n g rate the gas exit t e m p e r a t u r e c a n be m a i n t a i n e d at 250 F . 4% T h i s a d d i t i o n a l 7 0 - 8 0 F insures a u t o t h e r m a l o p e r a t i o n w i t h s u l f u r d i o x i d e gas i n a d o u b l e - c a t a l y s i s p l a n t . S o m e a d d i t i o n a l heat T h i s , h o w e v e r , increases the q u a n t i t y of
a d v a n t a g e c a n be g a i n e d b y b y p a s s i n g a p o r t i o n of the gas d i r e c t f r o m the second to the t h i r d stage. s u l f u r t r i o x i d e i n t h e gas l e a v i n g the converter, t h e r e b y r e d u c i n g the m a x i m u m c o n v e r s i o n that c a n b e a c h i e v e d . S u l f u r t r i o x i d e a b s o r p t i o n i n the interstage absorber is essentially c o m p l e t e , a n d v e r y little passes to t h e final stages f r o m this source. T h e absorber c i r c u l a t i n g a c i d is m a i n t a i n e d at 9 8 % s u l f u r i c a c i d to o b t a i n g o o d a b s o r p t i o n . T h e heat r e s u l t i n g f r o m a b s o r b i n g s u l f u r t r i o x i d e a n d c o o l i n g the gas is r e m o v e d f r o m the a c i d i n coolers b e f o r e the a c i d is r e t u r n e d to the absorbers. T h e gas e n t e r i n g the t h i r d stage of the converter has a v e r y l o w s u l f u r d i o x i d e content w i t h a h i g h o x y g e n - t o - s u l f u r d i o x i d e r a t i o so t h a t a h i g h c o n v e r s i o n is p o s s i b l e i n the last t w o stages. Adequate facilities for c o o l i n g b e t w e e n these stages are i m p o r t a n t , so that the final converter exit t e m p e r a t u r e c a n b e l o w to p r o v i d e the best e q u i l i b r i u m c o n d i t i o n s for m a x i m u m overall conversion. T h i s c o o l i n g also p r o v i d e s a safety factor against upsets i n o p e r a t i o n of the first t w o beds w h i c h w o u l d r e q u i r e m o r e t h a n n o r m a l c o n v e r s i o n i n the last t w o beds w i t h a h i g h e r t e m p e r a t u r e rise. T h e c o n v e r t e r exit t e m p e r a t u r e is a c o n t r o l l i n g factor i n the degree of c o n v e r s i o n that c a n b e a c h i e v e d , a n d it s h o u l d b e m a i n t a i n e d as l o w as possible, p r e f e r a b l y b e l o w 8 0 0 F . T h e gas l e a v i n g the final stage of t h e converter is c o o l e d i n heat exchangers b e f o r e g o i n g to the final absorber. T h e heat r e c o v e r e d i n
4.
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Phnts
59
these exchangers a n d i n those c o o l i n g the gas after the first a n d t h i r d stages of the c o n v e r t e r is u s e d to p r e h e a t the sulfur d i o x i d e gas l e a v i n g the b l o w e r to the r e q u i r e d c o n v e r t e r inlet t e m p e r a t u r e . I n the final absorber, w h i c h is s i m i l a r to the d r y i n g t o w e r , the s u l f u r t r i o x i d e is a b s o r b e d f r o m the gas. a d e m i s t e r w h i c h removes a c i d m i s t . Automatic Controls. A c e r t a i n a m o u n t of a u t o m a t i c c o n t r o l of process o p e r a t i n g c o n d i t i o n s is necessary to c o p e w i t h f r e q u e n t large changes i n s u l f u r d i o x i d e content of the gas. A s u l f u r d i o x i d e a n a l y z e r , i n d i c a t i n g t h e s u l f u r d i o x i d e content of the gas at the m a i n b l o w e r , controls t h e a d m i s s i o n of d i l u t i o n a i r to the d r y i n g t o w e r w h e n the sulfur d i o x i d e content of the f e e d gas exceeds 8 % . Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch004 A s e c o n d a n a l y z e r records t h e s u l f u r d i o x i d e content of the gas l e a v i n g t h e final absorber. T h e t e m p e r a t u r e of the gas e n t e r i n g e a c h of the first t w o catalyst beds is a u t o m a t i c a l l y c o n t r o l l e d b y a d j u s t i n g the heat exchanger bypasses. T h e a c i d strength a n d levels i n e a c h of the three p u m p tanks s e r v i n g t h e d r y i n g a n d a b s o r p t i o n towers are c o n t r o l l e d a u t o m a t i c a l l y b y r e g u l a t i n g t h e v a r i o u s cross transfers, a d d i n g w a t e r , a n d d e l i v e r i n g the p r o d u c t a c i d to storage. T h e s e controls t a k e care of the adjustments for w i d e changes i n a c i d p r o d u c t i o n , f r e e i n g the operator to m a k e the m i n o r changes w h i c h o p t i m i z e the o p e r a t i o n .
R E C E I V E D April 4, 1 9 7 4
T h e r e m a i n d e r of the gas, w i t h a
s u l f u r d i o x i d e content b e l o w 5 0 0 p p m , is v e n t e d to the atmosphere t h r o u g h
5
Dual-Catalyst Beds to Reduce Sulfur Dioxide to Elemental Sulfur in the Presence of Water Vapor
S. E . KHALAFALLA and L. A. HAAS
Bureau of Mines Twin Cities Metallurgy Research Center, U.S. Department of the Interior, Twin Cities, Minn. 55111
Water vapor decreases the effectiveness of an monoxide.
iron-alumina
bifunctional catalyst in reducing sulfur dioxide with carbon This problem can be averted by enriching the The water-gasmonoxide A post-catairon content in the bifunctional catalyst.
-shift reaction between water vapor and carbon generates an equivalent quantity of hydrogen.
lyst bed of pure alumina must be used because of the hydrogen sulfide which is generated in the reduction step with hydrogen as well as that which is produced from the hydrolytic decomposition the hydrogen of the carbonyl sulfide byproduct. from By deliberately releasing some sulfur dioxide (equal to half of sulfide produced) the first catalyst, both pollutants can be suppressed by a Claus reaction on a post-catalyst.
the search for solutions to the problem of sulfur dioxide pollution, one of the techniques that has been considered by the Bureau of Mines is catalytic reduction with carbon monoxide. S0 + 2 C 0 -> 2 C 0 + - S (1)
varies between 2 and 8 for = 2: AF

700
- 3 1 . 5 kcal; # =
7
- 4 8 . 9 kcal -61.3 kcal
for a: = 8: A F o =
7 0
- 3 4 . 1 kcal; # =
7
This method has several advantages: nitrogen oxides can be simultaneously reduced, carbon monoxide can be made available in the required 60
5.
K H A L A F A L L A A N D HAAS
Dual-Catalyst
Beds
61
concentrations as a flue gas constituent f r o m furnaces o p e r a t i n g near or s l i g h t l y o v e r the s t o i c h i o m e t r i c r a t i o of f u e l to a i r , a n d the m a i n r e a c t i o n p r o d u c t , s u l f u r , c a n be easily stored. S i n g l e - b e d catalysts h a d b e e n u s e d to p r o d u c e s u l f u r f r o m d r y s u l f u r d i o x i d e gases. R y a s o n (1,2) on alumina. u s e d either C u , P d , A g , C o , or N i s u p p o r t e d (3) o p t i m i z e d the c o m p o s i t i o n of Khalafalla and Haas
i r o n - a l u m i n a catalysts to p r o d u c e s u l f u r f r o m d r y gases c o n t a i n i n g s u l f u r dioxide and carbon monoxide. Q u e r i d o a n d S h o r t (4) d e m o n s t r a t e d the power f e a s i b i l i t y of r e d u c i n g s u l f u r d i o x i d e b y c a r b o n m o n o x i d e o n a c o p p e r a l u m i n a catalyst at concentrations a n d temperatures t y p i c a l of p l a n t stack gases. R e c e n t l y O k a y a n d Short ( 5 ) r e p o r t e d that t h e s u l f u r d i o x i d e r e d u c t i o n a c t i v i t y of Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch005 the s i n g l e - b e d c o p p e r - a l u m i n a catalyst was reduced w h e n w a t e r was a d d e d to a n i n l e t gas c o n t a i n i n g 0 . 2 % sulfur dioxide. could
N e i t h e r h y d r o g e n n o r h y d r o g e n sulfide was d e t e c t e d i n t h e i r experiments a l t h o u g h t h e r m o d y n a m i c c a l c u l a t i o n s i n d i c a t e that these gases f o r m at d e t e c t a b l e concentrations. T h e objective of this i n v e s t i g a t i o n was to e x a m i n e the effect of w a t e r v a p o r o n the r e d u c t i o n of s u l f u r d i o x i d e w i t h c a r b o n m o n o x i d e o n a n i r o n - a l u m i n a b i f u n c t i o n a l catalyst a n d to devise d o u b l e - c a t a l y s t beds to c o p e w i t h the deleterious effect of w a t e r . T h e catalyst t e m p e r a t u r e of the first b e d i n this d o u b l e - b e d system was v a r i e d to adjust the r a t i o of reactants e n t e r i n g the s e c o n d b e d i n o r d e r to m a x i m i z e the r e m o v a l of sulfurous gases. Experimental Apparatus and Procedure
T h e major p o r t i o n of t h e e x p e r i m e n t a l a p p a r a t u s is d e s c r i b e d i n p r e v i o u s p u b l i c a t i o n s (3, 6). A w a t e r injector p u m p was i n s e r t e d i n t o the p r e h e a t i n g p o r t i o n of the f u r n a c e . T h e exit gas lines a n d gas c h r o m a t o g r a p h w e r e m a i n t a i n e d a b o v e 100 C b y h e a t i n g tape to p r e v e n t water condensation. A F i s h e r p a r t i t i o n e r gas c h r o m a t o g r a p h was u s e d to a n a l y z e for C O , C0 ,
2
S C O , H S , a n d S 0 . T h e analyzers w e r e c a l i b r a t e d w i t h c o m m e r 2 2
c i a l gas m i x t u r e s . H e l i u m , r a t h e r t h a n n i t r o g e n , was u s e d as a d i l u e n t t h r o u g h o u t this w o r k not o n l y b e c a u s e the h e a t i n g a n d c o o l i n g p e r i o d s are decreased b y its h i g h heat c o n d u c t i v i t y a n d l o w heat c a p a c i t y b u t also because the n i t r o g e n c h r o m a t o g r a p h i c p e a k interferes w i t h t h a t of c a r b o n m o n o x i d e o n c o l u m n s of 13 X on Teflon. In a p r e v i o u s p u b l i c a t i o n ( 7 ) , i t was s h o w n t h a t n a t u r a l l y o c c u r r i n g m i n e r a l s or s o l i d waste b y p r o d u c t s c o n t a i n i n g m a i n l y a l u m i n a a n d i r o n c a t a l y z e d R e a c t i o n 1, sometimes as effectively as s y n t h e t i c i r o n - a l u m i n a m o l e c u l a r sieve a n d 1 5 % Uncon
62
SULFUR
REMOVAL
AND
RECOVERY
Table I. Chemical Catalyst Berbece b a u x i t e R e d bauxite J a m a i c a n red m u d S u r i n a m red m u d

6
a 6
Chemical and Physical (%) CaO 0.5 3.8 6.3 Na 0

2
Analysis Si0
2
AhO
FeO 1.5 9.4 39.1 22.4
80.0 53.1 23.0 20.7
7.5 2.5 3.9 15.0
3.8 10.4
Surface areas of indurated samples were determined by the B E T method. Average analysis.
m i x t u r e s . F o r p r a c t i c a l reasons some of these s o l i d wastes w e r e u s e d as catalysts i n this i n v e s t i g a t i o n . T h e samples w e r e d r i e d , p u l v e r i z e d to 100 m e s h , b r i q u e t t e d i n t o Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch005 m i n u s 16- p l u s 20-mesh pellets, a n d i n d u r a t e d at 6 0 0 C for 6 h r . T h e B e r b e c e b a u x i t e , a p r o d u c t of B r i t i s h G u i a n a , w a s o b t a i n e d from D a v i d N e w - M i n e r a l s , Providence, Utah. The from c h e m i c a l a n d p h y s i c a l p r o p e r t i e s of these catalysts are g i v e n i n T a b l e I. M i l w h i t e C o . , Inc., H o u s t o n , T e x . T h e A r k a n s a s r e d b a u x i t e w a s o b t a i n e d The Jamaican and Surin a m r e d m u d samples w e r e s u p p l i e d b y t h e F e d e r a l B u r e a u of M i n e s A l b a n y Metallurgy Research Center, Albany, Oreg. I n a t y p i c a l e x p e r i m e n t , a n a p p r o p r i a t e q u a n t i t y of the d r i e d catalyst was p l a c e d i n a V y c o r t u b e (1.2 c m d i a m e t e r ) o n a p e r f o r a t e d p o r c e l a i n d i s k , h e a t e d i n n i t r o g e n to 6 0 0 C for 2 h r , r e d u c e d i n h y d r o g e n for 1 h r , a n d t h e n c o o l e d to o p e r a t i n g t e m p e r a t u r e i n h e l i u m . T h e gas m i x t u r e (1.1 a t m , a b s o l u t e ) flow was m e t e r e d t h r o u g h the catalyst b e d at a n o m i n a l of 0.5 1. ( S T P ) / m i n . T h e flow of t h e reactants t h r o u g h the catalyst
was m a i n t a i n e d for several hours u n t i l a steady-state gas analysis r e p r e sentative of c a t a l y t i c r e a c t i o n was o b t a i n e d . T h i s p r e c o n d i t i o n i n g of t h e catalyst is necessary c h e m i c a l reactions f r o m the c a t a l y t i c ones ( 7 ) . to separate the I n the first f e w m i n u t e s , shown gaseous
the i r o n surface transforms to c a t a l y t i c a l l y a c t i v e p y r r h o t i t e , as sponding increase i n carbon dioxide production. The initial
( 7 ) b y the g r a d u a l increase i n c a r b o n m o n o x i d e c o n s u m p t i o n a n d c o r r e sulfide b y - p r o d u c t s react w i t h t h e i r o n i n the catalyst to f o r m i r o n sulfides. I n a p r e v i o u s p u b l i c a t i o n ( 8 ) , i t was s h o w n that l a t t i c e s u l f u r is a m o r e versatile a n d useful carbon monoxide-sufurizing agent than molecular sulfur. T h e hypothesis tested w a s that m e t a l sulfides w i t h r e l a t i v e l y w e a k m e t a l - t o - s u l f u r b o n d s are m o r e effective i n f o r m i n g the active i n t e r m e d i ate (9) c a r b o n y l sulfide.
2 2 x
S 0 + 2 S C O -> 2 C 0 + 3/x S varies between 2 a n d 8 for = 2 : A F o = - 1 4 . 2 k c a l ; # = - 4 . 9 kcal for a: = 8: ^ = - 2 1 . 7 k c a l ; # = - 4 2 . 1 k c a l

70 7 0 0 70 7 0
(2)
5.
Dudl-C'otalySt
Beds
63
Properties of the
Catalysts Analysis MgO 0.03 0.21 0.05 (%) LOI 2.5 26.4 16.2 11.3 P2O5 Surface Area (m /g)
a 2
Chemical K0
2
Ti0
0.03
2.5 6.4 10.3
0.4
230 100 12 8
E x p e r i m e n t s w e r e c o n d u c t e d at different c a r b o n m o n o x i d e ratios, r, defined as Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch005

Pco y[Po ]
v
4 P N Q J
2Pso2 w h e r e is the p a r t i a l pressure of the s u b s c r i p t gaseous species, y c a n be 2 or 3 for oxygen, a n d c a n b e 1 or 2 for n i t r i c oxide. I n the present w o r k , Po
v
and P ()
N
i n the f e e d gas w e r e a l w a y s zero. Discussion
Results and
T h e effect of w a t e r v a p o r o n t h e r e m o v a l of s u l f u r d i o x i d e w i t h v a r i ous i r o n - c o n t a i n i n g a l u m i n a catalysts w a s e x a m i n e d first. A gas consisti n g of 3 % sulfur dioxide, 6 % carbon monoxide, 0 - 2 5 % w a t e r , a n d the b a l a n c e h e l i u m was passed at a f l o w rate of 0.5 1. ( S T P ) / m i n t h r o u g h a 2-g b e d of B e r b e c e b a u x i t e at 4 7 5 C , a n d the exit gases w e r e a n a l y z e d for s u l f u r d i o x i d e . T h e decrease i n s u l f u r d i o x i d e r e m o v a l w h e n w a t e r T h e seMorenot was a d d e d is i l l u s t r a t e d b y c u r v e a of F i g u r e 1. R e m o v i n g t h e w a t e r d i d not b r i n g the catalyst b a c k to its o r i g i n a l a c t i v i t y ( c u r v e a'). q u e n c e of tests, s h o w n b y t h e a r r o w s , i n d i c a t e s that as t h e w a t e r content w a s i n c r e a s e d f r o m 0 to 2 . 5 % , the catalyst a c t i v i t y d e t e r i o r a t e d . over, w h e n the w a t e r flow w a s s t o p p e d , the o r i g i n a l a c t i v i t y w a s
restored. T h i s indicates that w a t e r is h e l d r a t h e r s t r o n g l y o n this catalyst a n d t h a t its d e s o r p t i o n is v e r y slow. T h e same t r e n d w a s o b s e r v e d w i t h a 2-g catalyst of A r k a n s a s r e d b a u x i t e . H o w e v e r , the h i g h e r i r o n content i n c r e a s e d the s u l f u r d i o x i d e r e m o v a l as s h o w n i n curves h, b , a n d b"
f
of
F i g u r e 1. W h e n a n i r o n - r i c h catalyst s u c h as J a m a i c a n r e d m u d (20 g at 3 8 0 C ) was u s e d i n this test, i t not o n l y e x h i b i t e d m u c h h i g h e r levels of c a t a l y t i c a c t i v i t y , b u t it was also o n l y s l i g h t l y affected b y the presence of u p to 2 5 % w a t e r v a p o r i n the i n l e t gas. T h i s is d e m o n s t r a t e d b y c u r v e c of F i g u r e 1. T h u s , i n o r d e r to suppress the adverse effect of water v a p o r o n the c a t a l y t i c r e d u c t i o n of s u l f u r d i o x i d e w i t h c a r b o n m o n o x i d e ,
64
SULFUR
REMOVAL
AND
RECOVERY
a n i r o n - r i c h a l u m i n a catalyst is n e e d e d because t h e i r o n c o m p o n e n t c a n also c a t a l y z e t h e w a t e r - g a s - s h i f t r e a c t i o n :
H 0
2
+
m
CO =
C0
(3)
AF7oo =
- 3 . 1 k c a l ; AH
- 9 . 0 kcal ~1/ 1 1 1 r
10
15
20
25
30
WATER VAPOR, percent Figure 1. Effect of water vapor on sulfur dioxide conversion using iron-containing alumina catalysts various
Because hydrogen
is also a r e d u c t a n t of s u l f u r d i o x i d e , the d e c a y i n w i l l decrease b y i n c r e a s i n g t h e i r o n
s u l f u r d i o x i d e r e m o v a l efficiency
content u p to 2 7 . 4 % of t h e catalyst. H o w e v e r , the b e n e f i c i a l effect of i r o n is d i s t u r b e d b y the h y d r o g e n sulfide w h i c h is p r o d u c e d a c c o r d i n g to R e a c t i o n s 4, 5, a n d 6:
S0 AF
m
+
70
3 H -> H S +
2 2
2H 0
2
(4)
- 3 8 . 7 k c a l ; SCO +
7 0
= H 0
2
- 5 2 . 0 kcal H S +
2
C0
(5)
AJF7OO =
- 7 . 7 kcal; # = SCO - 4 . 6 k c a l ; AH + = H
- 8 . 3 kcal
7 =
5 H S + +0.8 kcal
2 2
CO
(6)
T h i s gas is r e c o g n i z e d b y its offensive s m e l l i n t h e p r e s e n c e of l a r g e a m o u n t s of w a t e r v a p o r . F o r t u n a t e l y , h y d r o g e n sulfide w i l l r e a c t w i t h s u l f u r d i o x i d e a c c o r d i n g to t h e C l a u s r e c a t i o n :
5.
K H A L A F A L L A AND HAAS
Dual-Catalyst
Beds
65
S0
2H S " 2 H 0 + - S X
2 2
(7)
v a r i e s between 2 a n d 8 for = 2 : AF
m
- 4 . 4 kcal; #
7 0
=
7 0
+12.6
kcal
for = 8: A F o =
7 0
- 1 1 . 8 kcal; #
- 2 4 . 5 kcal A n i d e a l r e m o v a l system
to p r o d u c e e l e m e n t a l s u l f u r a n d w a t e r v a p o r .
s h o u l d c o n v e r t 6 7 % of the s u l f u r d i o x i d e to h y d r o g e n sulfide i n a p r i m a r y i r o n - a l u m i n a c a t a l y s t before t h e r e m a i n i n g s u l f u r d i o x i d e w i l l r e a c t w i t h the n e w l y f o r m e d h y d r o g e n sulfide o n a s e c o n d a r y C l a u s catalyst. Single-Bed Isothermal b a u x i t e at 4 7 5 C . Catalysts. D e t a i l e d analyses of exit gases 5.9% f r o m s i n g l e - b e d i s o t h e r m a l catalysts w e r e d e t e r m i n e d w i t h 2 g of r e d T h e i n l e t gas c o n t a i n e d 3 . 4 % sulfur dioxide,
carbon monoxide, and 90.7% helium.
F i g u r e 2 ( S e c t i o n A ) shows t h a t I n other words,
the s u l f u r d i o x i d e analysis d e c r e a s e d f r o m 3.4 to 0.8. m o n o x i d e r a t i o , r, of 0.87. However, when 3 %
a b o u t 7 6 % of the s u l f u r d i o x i d e was r e m o v e d i n the d r y state at a c a r b o n water vapor was a d d e d 1.9%, was flow ( S e c t i o n B ) , the s u l f u r d i o x i d e i n t h e exhaust gas i n c r e a s e d to i l l u s t r a t i n g the p o i s o n i n g effect of w a t e r . W h e n water vapor s t o p p e d , the s u l f u r d i o x i d e exhaust analyses d e c r e a s e d s l o w l y
(Section
66
SULFUR
REMOVAL
AND RECOVERY
C ) b u t d i d not r e t u r n to t h e i n i t i a l v a l u e ( S e c t i o n A ) w i t h i n 40 m i n . T h e a d d i t i o n of 1 5 % w a t e r v a p o r ( S e c t i o n D ) f u r t h e r decreased the s u l f u r d i o x i d e r e m o v a l efficiency. C u r v e b i n F i g u r e 2 d e p i c t s the analyses of c a r b o n d i o x i d e w h e n the b a u x i t e catalyst w a s s u b j e c t e d to the w a t e r treatment. T h e m i r r o r i m a g e r e s e m b l a n c e of curves b a n d a i n F i g u r e 2 suggests that the r e a c t i o n s t o i c h i o m e t r y is closely r e p r e s e n t e d b y E q u a t i o n 1 a n d that the p o i s o n i n g effect of w a t e r is essentially c a u s e d b y its c o m p e t i t i o n for c h e m i s o r p t i o n o n the a l u m i n a L e w i s a c i d sites w i t h the s u l f u r p r e c u r s o r of t h e i n t e r m e d i a t e ( 9 ) r e d u c t a n t c a r b o n y l sulfide. T h e p r e c e d i n g test was r e p e a t e d w i t h 20 g of J a m a i c a n r e d m u d catalyst r e p l a c i n g the r e d b a u x i t e at 420 C . T h e results i n F i g u r e 3 i n d i cate t h a t u p to 2 0 % Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch005 w a t e r v a p o r s l i g h t l y i n h i b i t e d the s u l f u r d i o x i d e I n absence of w a t e r , c a r b o n y l c) c o n v e r s i o n o n this i r o n - r i c h catalyst. was formed instead. T h e r m o d y n a m i c e q u i l i b r i u m compositions were calculated b y O k a y a n d Short (5) for the s u l f u r d i o x i d e r e d u c t i o n reactions i n t h e r e a c t o r f e e d gases w i t h a n d w i t h o u t w a t e r . E q u i l i b r i u m w a s c a l c u l a t e d b y t h e t e c h n i q u e of m i n i m i z i n g the free e n e r g y w h i c h uses a m o d i f i e d steepest
sulfide was f o r m e d ( c u r v e a), b u t w i t h w a t e r , h y d r o g e n sulfide ( c u r v e
40
80
120
160
200
TIME, minute
Figure 3. Effect of water vapor on the catalytic activity of Jamaican red mud: a = carbonyl sulfide, b = sulfur dioxide, c = hydrogen sulfide, d = carbon dioxide
5.
Dual-Catalyst
Beds
67
descent
search.
They concluded
that at a g i v e n t e m p e r a t u r e , h i g h e r T h e y d i d not, however, of
c a r b o n m o n o x i d e ratios are r e q u i r e d i n the presence of w a t e r to convert a c e r t a i n percentage of the s u l f u r d i o x i d e feed. detect h y d r o g e n sulfide i n t h e i r experiments. T h e thermodynamics
the system f a v o r h y d r o g e n sulfide p r o d u c t i o n i n the presence of w a t e r , whereas i n the d r y system c a r b o n y l sulfide p r o d u c t i o n is the o n l y adverse r e a c t i o n . A l s o , the water-gas-shift r e a c t i o n is t h e o r e t i c a l l y f a v o r e d i n the t e m p e r a t u r e range of 3 0 0 - 5 0 0 C , p r o d u c i n g h y d r o g e n sulfide. A Fortran I V computer program developed by Redifer and W i l s o n (10) was u s e d to p r e d i c t t h e r m o d y n a m i c e q u i l i b r i u m c o m p o s i t i o n s for 4 0 0 - 7 0 0 a n d 1 a t m t o t a l pressure. T h e c a l c u l a t i o n s are b a s e d o n a i n w h i c h the series-consecutive
p r o c e d u r e p r e s e n t e d b y M e i s s n e r , K u s i k , a n d D a l z e l l (11) set of simultaneous reactions is s i m p l i f i e d to a set of Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch005 reactions.
E a c h r e a c t i o n is c a r r i e d out i n t u r n o n t h e reactant m i x t u r e
as t h o u g h a set of i d e a l b a t c h e q u i l i b r i u m reactors w e r e a l i g n e d i n series i n w h i c h the p r o d u c t s f r o m one e q u i l i b r i u m stage b e c o m e reactants for the next reactor. A f t e r a l l the reactions h a v e b e e n c o m p l e t e d , p r o d u c t s E q u i l i b r i u m of a l l components is c o m p l e t e w h e n f r o m the last reactor are r e c y c l e d to the first reactor, a n d the r e a c t i o n sequence is r e p e a t e d . cal. the p r o d u c t c o m p o s i t i o n s at the e n d of t w o consecutive cycles are i d e n t i T h e m e t h o d compares f a v o r a b l y w i t h the free energy m i n i m i z a t i o n T h e r m o c h e m i c a l d a t a n e e d e d to c a l c u l a t e the e q u i l i b r i u m gas c o m positions w e r e t a k e n f r o m the J a n a f tables (12).
2 3 4 5
t e c h n i q u e a n d is u s e f u l for c h a n g i n g c o n d i t i o n s or i n p u t parameters. T h e free energy e q u a 6 7 8
tions for the s u l f u r v a p o r p o l y m e r s S , S , S , S , S , S , a n d S w e r e d e r i v e d b y K e l l o g g ( 1 3 ) , b a s e d o n s e c o n d l a w correlations of t h e i r mass spectrometric data. F i g u r e 4 shows the v a r i a t i o n w i t h t e m p e r a t u r e of the e q u i l i b r i u m m o l e fractions for a f e w feed gas compositions. and 3.4% h y d r o g e n sulfide a n d 5 . 9 % T h e curves i n Sections A represent the e q u i l i b r i u m state for m i x t u r e s i n i t i a l l y c o m p o s e d of c a r b o n m o n o x i d e i n the absence a n d
presence of 1 5 % w a t e r v a p o r , respectively. H e l i u m m a d e u p the b a l a n c e i n e a c h gas m i x t u r e . Species present at less t h a n the m i c r o m o l a r f r a c t i o n l e v e l w e r e i g n o r e d . T o c o n d u c t the same c o m p u t e r p r o g r a m o n e a c h gas m i x t u r e , a n e x t r e m e l y l o w c o n c e n t r a t i o n of w a t e r v a p o r (4.5 X was a s s u m e d i n cases A a n d C of F i g u r e 4. monoxide 10" % )
5
Sections C a n d D i n this A s expected, both
figure illustrate t h e effect of 7 % w a t e r v a p o r f o r a s u l f u r d i o x i d e - c a r b o n m i x t u r e at the l o w c o n c e n t r a t i o n l e v e l . h y d r o g e n sulfide a n d h y d r o g e n w e r e present w i t h the w a t e r v a p o r , a n d the concentrations of h y d r o g e n sulfide a n d c a r b o n y l sulfide i n c r e a s e d w i t h t e m p e r a t u r e u p to 7 0 0 C . T h e d i s p a r i t y b e t w e e n these results a n d those r e p o r t e d b y Okay a n d S h o r t ( 5 ) o n a c o p p e r - a l u m i n a catalyst c a n best b e e x p l a i n e d i n the
68
SULFUR
REMOVAL
AND
RECOVERY
A: S 0 - 3 . 4 , and C O - 5 . 9
2
B: S 0
"3.4, CO "5.9, and 0 - 15.0
Figure 4. Effect of temperature on the equilibrium composition of sulfurons gas mixtures in the absence and presence of water vapor. The balance in each mixture was helium. Species present at less than 10~ mole % were ignored.
4
l i g h t of the k n o w n (14)
facts r e g a r d i n g the catalysis of the w a t e r - g a s -
shift r e a c t i o n ( R e a c t i o n 3 ) o n i r o n a n d c o p p e r . I n gases c o n t a i n i n g r e l a t i v e l y large q u a n t i t i e s of s u l f u r , i r o n sulfide is the best a v a i l a b l e catalyst for the water-gas-shift r e a c t i o n (14). I n general, i r o n oxide is a g o o d c o m m e r c i a l , h i g h t e m p e r a t u r e shift catalyst. It is inexpensive, stable, a n d c a n w i t h s t a n d c o n s i d e r a b l e q u a n t i t i e s of i m p u r i t i e s w i t h o u t b e i n g p o i s oned. H o w e v e r , r e l a t i v e l y h i g h temperatures, t y p i c a l l y over 3 5 0 C , are commercial is m u c h m o r e active t h a n i r o n o x i d e a n d r e q u i r e d b e f o r e t h e catalyst is sufficiently active for most a p p l i c a t i o n s . C o p p e r m e t a l (14)
therefore has p r a c t i c a l a p p l i c a t i o n s e v e n b e l o w 2 0 0 C . Its h i g h cost a n d
5.
Dual-Catalyst
Beds
69 outThe facts 450
s u s c e p t i b i l i t y to poisons
are m i n o r disadvantages, b u t they are
w e i g h e d b y the h i g h conversions that are o b t a i n e d b e l o w 2 5 0 C . t e m p e r a t u r e r a n g e , a b o v e w h i c h a c t i v i t y is r a p i d l y lost. These
c o p p e r l o w t e m p e r a t u r e - s h i f t catalyst c a n b e u s e d o n l y w i t h i n a l i m i t e d e x p l a i n w h y O k a y a n d Short ( 5 ) d i d not o b t a i n h y d r o g e n sulfide i n the presence of w a t e r v a p o r o n t h e i r c o p p e r - a l u m i n a catalyst b e t w e e n and 500 C . T h e y also i n d i c a t e that h y d r o l y t i c d e c o m p o s i t i o n of c a r b o n y l sulfide a c c o r d i n g to R e a c t i o n 5 cannot p l a y a n i m p o r t a n t role. T h i s agrees w i t h a recent o b s e r v a t i o n b y P e a r s o n ( 15 ) that the h y d r o l y s i s of c a r b o n y l sulfide is i n h i b i t e d b y s u l f u r d i o x i d e s o r p t i o n o n the catalyst surface. Single-Bed, Nonisothermal Catalysts. I n a n a t t e m p t to c i r c u m v e n t of the u n d e s i r a b l e f o r m a t i o n of h y d r o g e n sulfide i n the presence of w a t e r v a p o r , a n o n i s o t h e r m a l reactor was c o n s t r u c t e d b y p l a c i n g 536 g Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch005 J a m a i c a n r e d m u d catalyst i n a 2-cm d i a m e t e r 9 6 % - s i l i c a tube. T h e c a t a lyst-filled t u b e w a s inserted i n t o the b o t t o m h a l f of the f u r n a c e . T h i s r e s u l t e d i n a 15-cm u n i f o r m t e m p e r a t u r e hot zone a n d a 2 5 - c m zone w i t h temperatures g r a d u a l l y d e c r e a s i n g to a b o u t 1 0 0 C at the l o w e r reactor exit. T h e i n l e t gas consisted of 1 7 % w a t e r v a p o r , 5 . 8 % c a r b o n m o n o x i d e , and 3 . 0 % s u l f u r d i o x i d e , a n d 7 4 . 2 % h e l i u m . F i g u r e 5 shows the d e p e n d ence of the exhaust gas analysis o n the hot-zone t e m p e r a t u r e of the J a m a i can r e d m u d catalyst. N o s u l f u r d i o x i d e w a s r e m o v e d at hot-zone t e m p e r atures l o w e r t h a n 2 4 0 C . A t 2 5 0 C , some s u l f u r d i o x i d e w a s r e m o v e d , a n d s m a l l q u a n t i t i e s of h y d r o g e n sulfide w e r e f o r m e d . Above 300C, more t h a n 8 0 % of the s u l f u r d i o x i d e a n d v i r t u a l l y a l l of the c a r b o n m o n o x i d e
1 r
150
200 250 300 HOT ZONE TEMPERATURE, *C
350
400
Figure 5. Effect of temperature of Jamaican red mud catalyst on exhaust gas analysis. Inlet gas: 3% sulfur dioxide, 5.8% carbon monoxide, and 17% water vapor in helium.
70
SULFUR
REMOVAL
AND RECOVERY
w e r e r e m o v e d , a n d no h y d r o g e n sulfide or c a r b o n y l sulfide was detected. T h e exhaust gas w a s m a i n l y c o m p o s e d of c a r b o n d i o x i d e , w a t e r v a p o r , sulfur, a n d the u n r e a c t e d s u l f u r d i o x i d e w h i c h was the result of the s l i g h t insufficiency of c a r b o n m o n o x i d e i n the i n l e t gas. R e a c t i o n s 1-6 p r o b a b l y o c c u r r e d i n the hot z o n e a b o v e 275 C , whereas R e a c t i o n 7 p r o b a b l y occ u r r e d d o w n - s t r e a m f r o m the h o t zone. T h e h y d r o g e n sulfide a n d s u l f u r d i o x i d e concentrations ( curves b a n d e, F i g u r e 5 ) w e r e c o n s i d e r a b l y l o w e r t h a n those o b s e r v e d w i t h a n i s o t h e r m a l reactor at 4 2 0 C ( F i g u r e 3 ) . D o u b l e - B e d C a t a l y s t s . B e c a u s e the t e m p e r a t u r e of the c o l d e r sect i o n i n the n o n i s o t h e r m a l catalyst b e d c o u l d not b e r e a d i l y c o n t r o l l e d , a n a p p a r a t u s w a s c o n s t r u c t e d t h a t c o n t a i n e d t w o separate furnaces, e a c h c o n t a i n i n g 20 g of S u r i n a m r e d m u d . T h e t e m p e r a t u r e of the first b e d w a s v a r i e d to d e t e r m i n e the o p t i m u m o p e r a t i n g c o n d i t i o n s w i t h a n i n l e t Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch005 gas of 0 . 5 7 % s u l f u r d i o x i d e , 0 . 8 9 % c a r b o n m o n o x i d e , a n d 3 % w a t e r v a p o r i n h e l i u m . T h e exhaust gas analyses f r o m the first f u r n a c e are s h o w n i n F i g u r e 6. T h e s e results i n d i c a t e that the h y d r o g e n sulfide a n d s u l f u r d i o x i d e r e m o v a l efficiency increases w i t h t e m p e r a t u r e u p to a b o u t 400 C . B e y o n d this t e m p e r a t u r e there is little i m p r o v e m e n t . T h e o p t i m u m t e m p e r a t u r e of the second than 3 % water vapor. catalyst b e d w a s determ i n e d w i t h the first catalyst b e d o p e r a t i n g at 430 C b u t w i t h 7 % r a t h e r T h e effect of t h e second r e a c t o r t e m p e r a t u r e o n the sulfurous content of the final exhaust gases is s h o w n i n F i g u r e 7, curves a a n d b. T h e results i n d i c a t e t h a t this second catalyst is m o r e
300
350
400
450
500
550
FIRST FURNACE TEMPERATURE,
Figure 6. Effect of first furnace temperature on the exit gas composition. Inlet gas: 0.57% sulfur dioxide, 0.89%? carbon monoxide, and 3% water vapor in helium.
5.
Dual-Catalyst
Beds
71
50 Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch005
100 150 200 250 SECOND FURNACE TEMPERATURE, C

e
300
Figure 7. Effect of second catalyst temperature on the exit gas composition. a,b Surinan red mud catalyst. Inlet gas to first catalyst: 0.57% sulfur dioxide, 0.89% carbon monoxide, and 7% water vapor in helium. a',b' = Berbece bauxite in second catalyst. Inlet gas to first catalyst: 0.44% sulfur dioxide, 0.80% carbon monoxide, and 20% water vapor in helium. efficient b e t w e e n 150 a n d 2 5 0 C . E x c e p t for e l e m e n t a l sufur, c a r b o n sulfur dioxide and 0.04% hydrogen =
d i o x i d e , a n d w a t e r v a p o r , the final exhaust gas i n this t e m p e r a t u r e range s h o w e d a flat m i n i m u m at 0 . 1 3 % sulfide. T h i s corresponds to 7 0 % c o n v e r s i o n of s u l f u r d i o x i d e ( a t r
0.86) to e l e m e n t a l sulfur. W i t h a s i n g l e - b e d catalyst at 430 C , F i g u r e 6 p r e d i c t s a n exit gas c o n t a i n i n g 0 . 1 3 % h y d r o g e n sulfide a n d 0 . 0 8 % s u l f u r d i o x i d e i n the presence of 3 % water vapor. T h i s corresponds to t h e r e m o v a l of 6 3 % of the sulfurous gases, i.e., a decrease of 7 p e r c e n t a g e points ( o r 1 0 % o n a r e l a t i v e b a s i s ) f r o m the r e m o v a l efficiency w i t h a double-bed catalyst. T h e decrease i n efficiency w o u l d p r o b a b l y have conb e e n greater i f the s i n g l e - c a t a l y s t b e d tests ( F i g u r e 6 ) h a d b e e n d u c t e d i n the presence of 7 % w a t e r v a p o r . E x p e r i e n c e i n catalysis (16) t r a n s i t i o n metals. of t h e C l a u s R e a c t i o n 7 i n d i c a t e s t h a t of content the a c t i v i t y of p u r e a l u m i n a is s o m e w h a t d e c r e a s e d b y the presence H e n c e , a n a l u m i n a catalyst w i t h l o w e r i r o n s h o u l d b e m o r e efficient t h a n one w i t h a h i g h i r o n content.
W h e n the
s e c o n d catalyst ( S u r i n a m r e d m u d c o n t a i n i n g 1 5 . 7 % i r o n ) i n the p r e c e d i n g e x p e r i m e n t was r e p l a c e d w i t h B e r b e c e b a u x i t e ( 1 . 1 % i r o n ) w i t h the other e x p e r i m e n t a l c o n d i t i o n s r e m a i n i n g constant, t h e s u l f u r d i o x i d e a n d h y d r o g e n sulfide exhaust analyses i n the range of 1 4 0 - 5 7 C w e r e c o n siderably lowered. dioxide, 0.80% T h i s is i l l u s t r a t e d b y curves a' a n d b
f
of F i g u r e 7. sulfur
T h e i n l e t gas to the first catalyst i n this test consisted of 0.44%
carbon monoxide, and 2 0 % water vapor i n helium. In
this l o w t e m p e r a t u r e range, S u r i n a m r e d m u d was not a c t i v e e n o u g h to
72
SULFUR
REMOVAL
AND RECOVERY
d r i v e t h e C l a u s r e a c t i o n . A b o v e 140 C , the difference b e t w e e n the r e d m u d a n d b a u x i t e catalyst activities decreases. T h e effect of the second-catalyst t e m p e r a t u r e o n the conversion efficiency of s u l f u r d i o x i d e to e l e m e n t a l s u l f u r is s h o w n i n F i g u r e 8.
50
100 SECOND
150 FURNACE
200
250
300
TEMPERATURE,C
Figure 8. Effect of second catalyst temperature on the removal efficiency of sulfurons gases, a = Surinan red mud on second catalyst. Inlet gas to first catalyst: 0.57% sulfur dioxide, 0.89% carbon monoxide, and 7% water vapor in helium, d Berbece bauxite in second catalyst. Inlet gas to first catalyst: 0.44%o sulfur dioxide, 0.80% carbon monoxide, and 20%) water vapor in helium. C u r v e a represents t h e d a t a w i t h S u r i n a m r e d m u d i n the second c a t a l y s t a n d illustrates a d e c l i n e i n s u l f u r p r o d u c t i o n efficiency w i t h t h e s e c o n d catalyst t e m p e r a t u r e e i t h e r a b o v e 250 or b e l o w = 150C. (at r on a of the no U s i n g B e r b e c e b a u x i t e at 5 8 C i n the second b e d , u p to 7 9 % is a n i m p r o v e m e n t of m o r e t h a n 16 percentage points ( o r 2 5 % b e d at 4 3 0 C ( F i g u r e 6 ) . U n f o r t u n a t e l y , the h i g h efficiencies
0.91 ) of the sulfurous gases w e r e r e m o v e d ( c u r v e a', F i g u r e 8 ). T h i s
r e l a t i v e basis ) over the r e m o v a l efficiency w i t h a s i n g l e S u r i n a m r e d m u d b a u x i t e second b e d b e l o w 1 2 0 C ( m e l t i n g p o i n t of s u l f u r ) are of peratures would plug the reactor a n d necessitate frequent
p r a c t i c a l v a l u e because the a c c u m u l a t i o n of s o l i d s u l f u r at these t e m catalyst regenerations. A d d i t i o n a l tests w i t h 20 g of S u r i n a m r e d m u d i n the catalyst w e r e conducted with s u l f u r d i o x i d e - r i c h gases, double-bed simulating a
s m e l t e r gas. T h e t e m p e r a t u r e of the first reactor w a s 475 C a n d that of the s e c o n d was 230 C . T h e i n l e t gas i n t o t h e first catalyst b e d c o n t a i n e d 3.15% sulfur dioxide, 5.97% helium. carbon monoxide, and 3 % water vapor in secA f t e r several h o u r s , the exhaust gas analyses f r o m the
5.
Dual-Catalyst
Beds
73 and 0.26% hydrogen
ond
reactor
indicated
0 . 1 3 % sulfur
dioxide
sulfide. second
W i t h this d u a l - c a t a l y s t b e d a r r a n g e m e n t , 8 8 % o f t h e s u l f u r l o w - t e m p e r a t u r e catalyst offset t h e deleterious effect o f w a t e r
d i o x i d e w a s c o n v e r t e d to e l e m e n t a l sulfur. T h e results i n d i c a t e t h a t t h e v a p o r o n t h e c a t a l y t i c r e d u c t i o n of s u l f u r d i o x i d e . Summary and Recommendations
W a t e r v a p o r decreases t h e efficiency of c a t a l y t i c r e d u c t i o n of s u l f u r dioxide w i t h carbon monoxide. A two-stage c a t a l y t i c r e d u c t i o n m e t h o d was d e s i g n e d to solve this p r o b l e m . T h e o p t i m u m t e m p e r a t u r e of t h e first reactor w a s a b o u t 4 3 0 C , w h e r e a s the s e c o n d reactor ( C l a u s ) w a s most efficient b e l o w 2 5 0 C . Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch005 H o w e v e r , t h e i m p r o v e d t h e r m o d y n a m i c efficiency at l o w e r t e m p e r a t u r e s is h a m p e r e d b y other m e c h a n i c a l considerations. I n p r a c t i c e , t h e C l a u s reactor s h o u l d b e o p e r a t e d a b o v e 120 C to avoid mechanical problems resulting from solid sulfur plugging the Therefore, catalyst. A l s o , t h e v i s c o s i t y of l i q u i d s u l f u r exhibits a s h a r p p e a k at
1 9 0 C a n d exceeds 300 c e n t i p o i s e b e t w e e n 170 a n d 2 3 0 C .
unless t h e t e m p e r a t u r e of the s e c o n d catalyst is c a r e f u l l y c o n t r o l l e d b e t w e e n 120 a n d 1 7 0 C , i t s h o u l d b e o p e r a t e d a b o v e 2 3 0 C , a n d p r e f e r a b l y 250 C , to a v o i d c a t a s t r o p h i c p l u g g i n g of t h e catalyst. I t m a y also b e d e s i r a b l e to condense stages stages. Acknowledgment T h e authors are i n d e b t e d to J o h n S. W i l s o n o f t h e M o r g a n t o w n E n e r g y R e s e a r c h C e n t e r , F e d e r a l B u r e a u of M i n e s , M o r g a n t o w n , W . V a . for h i s assistance i n t h e t h e r m o c h e m i c a l c a l c u l a t i o n . Literature Cited with the sulfur produced f r o m t h e first b e d b e f o r e devices between successive entrance i n t o t h e s e c o n d b e d a n d to cascade t h e second b e d i n t o different intermittent sulfur collection
1. Ryason, P. R., Harkins, J., Air Pollut. Contr. Ass. (1967) 17, 796. 2. Ryason, P. R., U.S. Patent 3,454,355 (July 8, 1969). 3. Khalafalla, S. E . , Foerster, E . F., Haas, L . ., Ind. Eng. Chem. Prod. Res. Develop. (1971) 10, 133. 4. Querido, R., Short, W . L . , Ind. Eng. Chem. Prod. Res. Develop. (1973) 12, 10. 5. Okay, V. C., Short, W . L . , Ind. Eng. Chem. Prod. Res. Develop. (1973) 12, 291. 6. Khalafalla, S. E . , Haas, L . ., J. Catal. (1972) 24, 115. 7. Ibid., 121. 8. Haas, L . ., McCormick, T. H., Khalafalla, S. E., Bur. Mines Rep. Invent. (1972) 7647, 14 pp. 9. Haas, L . ., Khalafalla, S. E . , J. Catal. (1973) 29, 264.
74
SULFUR R E M O V A L A N D RECOVERY
10. Redifer, M . W., Wilson, J. S., Bur. Mines Inform. Circ. (1973) 8606, 42 pp. 11. Meissner, J. P., Kusik, C. L . , Dalzell, W . H . , Ind. Eng. Chem., Fundam. (1969) 8, 659. 12. JANAF Thermochemical Tables, Clearing House for Federal Scientific and Technical Information, Washington, D . C . (1966). 13. Kellogg, H . H . , Met. Trans. (1971) 2, 2161. 14. Campbell, J. S., Craven, P., Young, P. W., in "Imperial Chemical Industries Catalyst Handbook," p. 98, Springer-Verlag, New York, 1970. 15. Pearson, M . J., Gas Process. (Canada) (May-June 1973) 22. 16. Doumani, T. F . , Deery, R. F . , Bradley, W . E . , Ind. Eng. Chem. (1944) 36, 332. R E C E I V E D April 4, 1974. Reference to specific brands is made for identification only and does not imply endorsement by the Bureau of Mines.
6
Effect of Basicity of the Catalyst on Claus Reaction
. M. GEORGE Research Council of Alberta, Edmonton, Alberta, Canada T6G 2C2
The catalytic activities of acids and bases for Claus reaction were investigated by supporting these on Chromosorb-A (a relatively inactive gas chromatographic solid support) and other materials and obtaining the relative activities of these compounds for Claus reaction based on initial rates at flow reactor using low partial pressures of reactants. (1-8 wt %) induced 240C. Acidity The experiments were carried out in a fixed-bed integral did not enhance catalytic activity but the deposition of bases a dramatic increase in the catalytic activity for Claus reaction. Attempts were made to measure the basicities of these catalysts and relate these to the observed catalytic activity for Claus reaction.
1972 Alberta produced 8 amount of hydrogen sulfide. using alumina-based catalysts. H S +

2
10 long-tons of elemental sulfur by

6
sweetening sour gas ( 1 ), i.e., a natural gas containing an appreciable Hydrogen sulfide and other sulfur comT h e basic chemical reactions are: H 0 +
2 2
pounds are converted to sulfur by the well known modified Claus process
3/2 0 S0
2
->
S0
2 H S +
2
;= 2 H 0 +
3/x 8
(Claus reaction)
Bauxite catalysts (or alumina) are generally used in the Claus catalytic converters because of their high activity, durability, and low cost. Maximum equilibrium conversions are obtained at the lowest operating temperatures in the Claus catalytic converters. Theoretically, at this reactor temperature (~230C), 99% equilibrium conversion is possible. However, because the Claus reaction is a complex equilibrium reaction, the temperature cannot be lowered too much as sulfur will condense on the 75 In Sulfur Removal and Recovery; Pfeiffer, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1975.
76
SULFUR
REMOVAL
AND RECOVERY
catalyst, a n d r e g e n e r a t i o n of the a l u m i n a - b a s e d catalyst poses serious p r o b l e m s b e c a u s e of s u l f a t i o n f o r m a t i o n of a l u m i n u m sulfate, w h i c h is not a catalyst for C l a u s r e a c t i o n . F u r t h e r , at the l o w e r t e m p e r a t u r e the c o n v e r s i o n rates are l o w . O n the other h a n d , c a r b o n y l sulfide a n d c a r b o n disulfide, w h i c h are p r o d u c e d d u r i n g the h i g h t e m p e r a t u r e o x i d a t i o n of sour gas i n the C l a u s f u r n a c e , o n l y react w i t h s u l f u r d i o x i d e i n the C l a u s reactor at f a i r l y h i g h temperatures. Consequently a compromise must b e m a d e o n the o p e r a t i n g t e m p e r a t u r e , a n d as a result, most of the C l a u s s u l f u r p l a n t s i n A l b e r t a operate at 9 5 - 9 7 % efficiency, u s i n g three-stage c a t a l y t i c converters w i t h i n t e r v e n i n g s u l f u r r e m o v a l . T h e u n r e a c t e d s u l f u r c o m p o u n d s i n the t a i l g a s c a r b o n d i s u l f i d e , h y d r o g e n sulfide, s u l f u r d i oxide, a n d c a r b o n y l s u l f i d e a r e c o n v e r t e d to s u l f u r d i o x i d e b y i n c i n e r a t i o n a n d v e n t e d f r o m stacks. B e c a u s e of the stringent a n t i p o l l u t i o n regulations Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch006 w h i c h r e q u i r e r e d u c e d s u l f u r d i o x i d e emissions a n d because of the h i g h cost of e q u i p m e n t for t a i l gas c l e a n u p , i t is i n c r e a s i n g l y i m p o r t a n t to a c h i e v e m a x i m u m conversions i n the C l a u s c a t a l y t i c reactors. D u r i n g o u r i n v e s t i g a t i o n i n t o the k i n e t i c s of C l a u s a n d r e l a t e d r e actions ( 2 ) , w e b e c a m e interested i n d e t e r m i n i n g those properties n e c essary for a g o o d C l a u s catalyst. I n e x p l o r a t o r y studies of the effectiveness of acids, bases, sulfides, oxides, a n d salts as catalysts for the C l a u s r e a c t i o n the basic oxides e n h a n c e d C l a u s a c t i v i t y the most. s u m m a r i z e d i n this report. We c o n t i n u e d to s t u d y the effect of catalyst b a s i c i t y o n C l a u s r e a c t i o n , a n d the results are
Experimental
Procedures and Results
T h e reactants, h y d r o g e n sulfide a n d s u l f u r d i o x i d e , w e r e d i l u t e d w i t h h e l i u m , a n d t h e n w e r e passed over the catalyst w h i c h w a s c o n t a i n e d i n a % i n . - i . d . 316 stainless steel t u b e b y a 100-mesh stainless steel screen. A s s h o w n i n F i g u r e 1, p r o v i s i o n was m a d e for analysis of reactant a n d p r o d u c t streams, for p r e h e a t i n g the reactants before c o n t a c t i n g the c a t a lyst, a n d for c o n d e n s i n g the p r o d u c t s u l f u r . S i n c e the details of these operations are g i v e n i n a p r e v i o u s p u b l i c a t i o n ( 2 ) , o n l y b r i e f d e s c r i p t i o n s w i l l b e p r o v i d e d here. T h e p r e h e a t e r w a s 5 X sec. % in. i.d. packed with stainless steel shavings a n d gave a d e q u a t e p r e h e a t i n g u p to 60 m l h e l i u m / T h e p r e h e a t e r a n d the reactor w e r e h e a t e d b y the same f u r n a c e w h i c h c o u l d easily b e r e p l a c e d b y a D e w a r c y l i n d e r of l i q u i d n i t r o g e n to p e r m i t m e a s u r e m e n t of n i t r o g e n a d s o r p t i o n b y the u s u a l d y n a m i c m e t h o d ( 3 ) , u s i n g a r e l a t i v e pressure p/p T h e s u l f u r condenser w a s a 16 X
Q
0.06. With
1 i n . i.d.-stainless steel t u b e a n d
h a d baffles e v e r y i n c h to f a c i l i t a t e the c r i t i c a l s u l f u r c o n d e n s a t i o n .
a n u n h e a t e d condenser, s u l f u r c o n d e n s e d at the condenser exit a n d i n t o
6.
S R M V SL PH C D
GEORGE
Catalyst
Basicity
77
- Saturator - Reactants - Mixing Chamber - Valve - Sampling Loop - Preheater - Catalyst - Thermocouple - Detector T . C .
REC SCR FM SC G
Recorder Scrubber Flow Meter Sulfur Condensor Thermostated Box
Figure 1.
Diagram of flow reactor N o attempt w a s
the s a m p l i n g section r e s u l t i n g i n u n r e l i a b l e conversions.
m a d e to k e e p t h e s u l f u r a b o v e t h e m e l t i n g p o i n t i n t h e condenser as this has b e e n r e p o r t e d (4) to c a t a l y z e the C l a u s r e a c t i o n . A f t e r e x t e n d e d exp e r i m e n t a t i o n w e f o u n d that i f t h e c o n n e c t i n g t u b e f r o m t h e reactor outlet a n d p a r t of the condenser exit section w e r e k e p t a b o u t 1 5 0 C ( t h e t e m p e r a t u r e i n t h e u n h e a t e d section of the condenser w a s a r o u n d 6 0 C ) , sulfur condensed satisfactorily. P e r i o d i c a l l y t h e condenser a n d other parts o f t h e system h a d to b e h e a t e d to r e m o v e the sulfur. N i t r o g e n w a s i n t r o d u c e d w i t h the reactants as a m a r k e r . T h e a n a l y ses of the feed a n d p r o d u c t streams, c a r r i e d o u t w h e n t h e catalyst w a s b y p a s s e d , s h o w e d that no other p a r t of t h e system w a s c a t a l y z i n g t h e r e a c t i o n , even w h e n there w a s a p p r e c i a b l e c o n d e n s e d s u l f u r i n the c o n denser. T h e t o t a l pressure of t h e system w a s m e a s u r e d b y a pressure t r a n s d u c e r ( W h i t t a k e r , m o d e l D M 1 ) l o c a t e d a h e a d of t h e reactor. A s s h o w n i n F i g u r e 1, there are t w o t h e r m a l c o n d u c t i v i t y detectors w i t h Teflon-coated filaments a n d t h e r m o s t a t e d at 125 C . O n e is l o c a t e d i m m e d i a t e l y after t h e catalyst a n d measures r e t e n t i o n v o l u m e a n d s u r face area. T h e second detector is l o c a t e d after t h e a n a l y t i c a l c o l u m n a n d analyzes f e e d a n d p r o d u c t samples. T h i s detector o u t p u t at m a x i m u m
78 sensitivity was fed
SULFUR
REMOVAL
AND RECOVERY
to a H e w l e t t - P a c k a r d electronic
integrator The
(No. pure
3 3 7 0 A ) as w e l l as to a c o n v e n t i o n a l s t r i p - c h a r t recorder.
detector-
i n t e g r a t o r system w a s c a l i b r a t e d b y i n j e c t i n g 2.0 m l samples of of the a n a l y t i c a l c o l u m n .
reactants at different pressures ( m e a s u r e d b y a d i g i t a l m a n o m e t e r ) a h e a d T h e a p p a r a t u s was p r o v i d e d w i t h 5.0 m l - s a m p l i n g loops that b o t h f e e d a n d p r o d u c t streams c o u l d b e m o n i t o r e d . B y o p e r a t i n g a seven-port s a m p l i n g v a l v e , the separate gas c h r o m a t o g r a p h i c h e l i u m stream w o u l d s w e e p the contents of t h e s a m p l i n g l o o p onto the a n a l y t i c a l c o l u m n of 8 ft X % i n . P o r o p a k Q f o l l o w e d b y 2 ft P o r o p a k T , m a i n t a i n e d at 125 C . It p r o v i d e d g o o d separations of n i t r o g e n , h y d r o g e n sulfide, w a t e r , a n d sulfur dioxide i n about 5 m i n ( F i g u r e 2 ) . Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch006 very unlikely. A f t e r p r o l o n g e d use the a n a l y t i c a l c o l u m n t u r n e d y e l l o w a l t h o u g h at 1 2 5 C , s u l f u r c o n d e n s a t i o n is H o w e v e r , separate experiments s h o w e d t h a t this d i d not A d s o r p t i o n measurements u s i n g interfere w i t h the analysis efficiency. previously (2).
f r o n t a l c h r o m a t o g r a p h y w e r e s t u d i e d i n another a p p a r a t u s , as d e s c r i b e d Materials. T h e c h r o m a t o g r a p h i c firebrick ( C h r o m o s o r b - A ) was m a n u f a c t u r e d b y J o h n s - M a n v i l l e . T h e m a t e r i a l as r e c e i v e d w a s s l i g h t l y a l k a l i n e a n d h a d a m e a s u r e d surface area of 2.0 m / g . It was w a s h e d , d r i e d , a n d s i e v e d to 2 0 / 3 0 m e s h before use. T h e c o b a l t - m o l y b d a t e o n g a m m a - a l u m i n a catalyst ( G i r d l e r G - 3 5 ) was m a n u f a c t u r e d a n d k i n d l y s u p p l i e d b y C h e m e t r o n C o r p . , L o u i s v i l l e , K y . It was r e p o r t e d to h a v e 3 . 5 % C o O a n d 1 0 . 0 % M o O . T h e catalyst, i n Ys X Ys i n . tablets, w a s c r u s h e d a n d sieved to 2 0 / 3 0 m e s h granules for
2 a
Figure 2. Chromatographic separation of 2, H S, H 0, and S0 . Analytical column: 8 ft X Vs in. Poropak Q (5080 mesh) followed by 2 ft X Vs in. Poropk (50-80 mesh) operated at 125C. Thermal conductivity detector: Teflon coated, 250 ma, thermostated at 125C. He flow rate: 1.34 ml/sec.
2 2 2
6.
GEORGE
Catalyst
Basicity
2
79
k i n e t i c studies. It h a d a m e a s u r e d surface area of 180 m / g , u s i n g the o n e - p o i n t i s o t h e r m , c o m p a r e d w i t h 192 m / g b y the B E T m e t h o d . T h e porous a l u m i n a catalyst was s u p p l i e d b y . I. Parsons, D e p a r t m e n t of E n e r g y , M i n e s a n d Resources, O t t a w a , C a n a d a . It h a d a measu r e d surface area of 220 m / g ( o n e - p o i n t i s o t h e r m ) , a n d a s l u r r y of the m a t e r i a l i n d i s t i l l e d w a t e r h a d a p H of 10.0. T h e p o r e size v a r i e d b e t w e e n 1000 a n d 4 0 0 A , a n d the p o r e v o l u m e w a s 1.9 m l / g ( 5 ) . T h e a c t i v e a l u m i n a w a s m a n u f a c t u r e d b y t h e A l u m i n u m C o . of A m e r i c a , P o r t l a n d , Ore. P o r a s i l ( s p h e r i c a l porous s i l i c a b e a d s ) is a s o l i d s u p p o r t m a n u f a c t u r e d for W a t e r s Associates, M a s s . , b y P e c h i n e y - S t . G o b a i n , F r a n c e . T h e P o r a s i l - F u s e d i n this s t u d y h a d a r e p o r t e d surface area of 4 m / g a n d a n average p o r e d i a m e t e r greater t h a n 1500A. T h i s m a t e r i a l was s l i g h t l y basic. B a u x i t e ( P o r a c e l ) is a c o m m e r c i a l s u l f u r r e c o v e r y catalyst m a n u f a c t u r e d a n d s u p p l i e d b y P h i l i p C o r p . , M e n l o P a r k , N . J . It w a s 9 0 % A 1 0 w i t h a b o u t 5 % F e 0 a n d s m a l l e r amounts of T i Q a n d S i 0 a n d h a d a r e p o r t e d surface area of 215 m / g . H o w e v e r , a m e a s u r e d surface area of 142 m / g w a s d e t e r m i n e d u s i n g the o n e - p o i n t i s o t h e r m . T h e catalyst samples u s e d i n this s t u d y w e r e g e n e r a l l y 2 0 / 3 0 m e s h granules a n d w e r e a c t i v a t e d i n flowing h e l i u m at t h e r e a c t i o n t e m p e r a t u r e for 3 h r . Reactants. H S a n d S 0 w e r e s u p p l i e d b y M a t h e s o n a n d h a d a p u r i t y of m o r e t h a n 99 m o l e % . T r a c e s of C 0 w e r e present i n b o t h gases. Pretreatment o f Catalysts. A C I D I T Y . D i l u t e a c i d s h y d r o c h l o r i c ,
2 2 2 2 3 2 3 2 2 2 2 2 2 2
sulfuric, a n d phosphoric acidswere deposited b y soaking C h r o m o s o r b - A i n the d i l u t e a c i d s o l u t i o n a n d d e c a n t i n g a n d d r y i n g the granules at 1 0 0 C . F o r the a c i d - l o a d e d C h r o m o s o r b - A , no a c t i v i t y increase for C l a u s r e a c t i o n was detected. p H a b o u t 5. BASICITY. Basessodium, potassium, and lithium hydroxideswere T h e exact l o a d i n g w a s d e t e r m i n e d d e p o s i t e d b y s o a k i n g the catalyst i n the a p p r o p r i a t e aqueous s o l u t i o n a n d d r y i n g the catalyst granules at 1 0 0 C . b y l e a c h i n g the adsorbate w i t h hot d i s t i l l e d w a t e r for 72 h r at 70 C a n d t i t r a t i n g w i t h 0.02IV h y d r o c h l o r i c a c i d to p H 7. A t base l o a d i n g s u p to 7%, the base c o u l d b e l e a c h e d f r o m the catalyst, a n d the a p p r o x i m a t e o r i g i n a l a c t i v i t y was restored. W i t h h i g h e r base l o a d i n g s ( 1520% ) the base r e a c t e d w i t h t h e C h r o m o s o r b - A ( n e w s o l i d p h a s e s ) a n d also d e creased the surface area of a l u m i n a catalysts. H o w e v e r , these m a t e r i a l s w e r e not u s e d i n this study. T h e effect of b a s i c i t y o n the f o l l o w i n g catalysts for C l a u s r e a c t i o n w a s investigated: Chromosorb-A; cobalt-molybdate; activated alumina; bauxite; a n d P o r a s i l . T h e base l o a d i n g s w e r e 1-6 w t % . Rate Studies. R e a c t i o n rates, b a s e d o n t h e d i s a p p e a r a n c e of h y d r o g e n sulfide, w e r e d e t e r m i n e d o n l y after steady-state c o n d i t i o n s w e r e establ i s h e d . T h i s was i n d i c a t e d w h e n successive analyses w e r e w i t h i n 0 . 5 % , u s u a l l y a b o u t 10 m i n f r o m start-up. S e v e r a l flow rates w e r e u s e d , w i t h T h e a c i d - l o a d e d C h r o m o s o r b - A (>2% ) at the e n d of the r e a c t i o n w a s s t i l l a c i d i c ; a s l u r r y of the catalyst i n d i s t i l l e d w a t e r h a d a
80 conversions of 5 - 3 0 %
SULFUR
REMOVAL
AND
RECOVERY
w i t h a n u n c e r t a i n t y of 2 % .
T h e i n i t i a l rate w a s
o b t a i n e d b y fitting the e x p e r i m e n t a l d a t a to t h e expression = C tanh[D(F7F)] i n g, s e c / is:
w h e r e is the f r a c t i o n a l c o n v e r s i o n of h y d r o g e n sulfide, W/F m m o l e h y d r o g e n sulfide, a n d C a n d D are constants. T h e d e r i v a t i v e of t h e a b o v e f u n c t i o n w i t h respect to W/F

d x
d(W/F)
(C)D)(Sech*[D(W/F)])
A t W/F = 0, w h i c h is e q u a l to the i n i t i a l rate ( r ) , t h e a b o v e d e r i v a t i v e reduces to C D . T h e best values of C a n d D w e r e o b t a i n e d b y a g r a d i e n t search u s i n g a d i g i t a l P D P - 9 c o m p u t e r . M e z a k i a n d K i t t r e l l (6) have d e m o n s t r a t e d that this expression is a c o n v e n i e n t a n d r e l a t i v e l y n o n d i s c r i m i n a t i n g w a y to extrapolate to zero conversion. T h e r a n g e of p a r t i a l pressures ( torr ) of reactants u s e d w e r e h y d r o g e n sulfide, 4 - 2 2 , a n d sulfur dioxide, 2-22.
0
. ... ^ / m m o l e of H S reacted\ ,, , , T h e i n i t i a l rate 1 was fitted to the expression \ sec-g /

2 n
kp R S
a 2
pS0 .
2
F o r C h r o m o s o r b - A , k i n e t i c measurements w e r e m a d e at three t e m p e r a t u r e s 4 3 4 , 400, a n d 3 5 8 C a n d for v a r y i n g p a r t i a l pressures of h y d r o g e n sulfide a n d s u l f u r d i o x i d e . A n e x a m p l e of t h e d a t a at a g i v e n t e m p e r a t u r e is g i v e n i n T a b l e I. T w o levels of s o d i u m h y d r o x i d e l o a d Table I. H2S (torr) 4.00 4.00 4.00 4.00 22.03 22.31 22.52 4.02 4.04 4.05
a 2
Kinetic Data for Claus Reaction over Chromosorb-A at434 2 C

a
S02 (torr) 2.00 2.00 2.00 2.00 2.02 2.03 2.04 20.52 20.51 20.53
2
Fr. Conv. HS
2
W/F (g, sec/mmole 46.0 71.2 85.0 155.0 8.0 12.5 24.0 55.0 97.5 180.0
H S)
2
r (computed)
0 6
0.105 0.167 0.184 0.285 0.066 0.096 0.138 0.161 0.257 0.390
0.0024
0.0088
0.0029
H S order one and S 0 order zero. At 390C, the kinetic orders in H S and S 0 (over Chromosorb-A) were one and zero, respectively. The accuracy of the kinetic orders is =b 10%. mmoles H S reacted/sec,g.
2 6 2
6.
GEORGE
Catalyst
Basicity
81
Table II. Kinetic Data for Claus Reaction over Chromosorb-A Loaded with 5 % Sodium Hydroxide at 242 =t 2 C
a
H2S
S02
0.166 0.110 0.240 0.071 0.168 0.105 0.185 0.294 0.410
W/F 47.8 31.6 11.0 8.6 32.4 15.0 33.9 64.3 106.3
(computed) 0.0039
4.00 4.00 4.00 12.23 12.21 12.23 4.04 3.95 4.01

2 2
2.00 2.00 2.00 2.01 2.03 2.01 10.15 10.12 10.22
0.0082
0.0054
H S order, 0.7; S 0 , 0.2. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch006 ings3.9 a n d 5.0% o n Chromosorb-Awere studied. Measurements were m a d e at five temperatures b e t w e e n 209 a n d 3 4 4 C f o r t h e 3 . 9 % s o d i u m h y d r o x i d e l o a d i n g a n d a t three t e m p e r a t u r e s b e t w e e n 2 0 0 a n d 2 9 0 C f o r the 5 . 0 % l o a d i n g . T a b l e I I gives t h e measurements a t 242 C . T h e rate g, t o r r ) d e t e r m i n e d constants k ( m m o l e s h y d r o g e n sulfide r e a c t e d / s e c , plot. Reaction Orders and Activation Energies. F r o m the variation i n i n i t i a l rate w i t h the p a r t i a l pressure o f reactants i t w a s o b s e r v e d t h a t t h e k i n e t i c o r d e r w i t h respect t o s u l f u r d i o x i d e w a s zero a n d t h a t w i t h respect
10"
2
f o r e a c h set o f measurements are s u m m a r i z e d i n F i g u r e 3 as a n A r r h e n i u s
k "
4
10"
1.40
1.60
1.80 1000/
2.00
2.20
Figure 3. Arrhenius plot for Chromosorb-A with and without NaOH. 4.0 torr H S, 2.0 torr S0 . k, mmoles H S reacted/sec, g torr.
2 2 2
82
SULFUR
REMOVAL
A N D RECOVERY
to h y d r o g e n sulfide it w a s one for C l a u s r e a c t i o n over the C h r o m o s o r b - A (Table I). H o w e v e r , o n the 5 . 0 % sodium hydroxide-loaded Chromos o r b - A the k i n e t i c orders w i t h respect to h y d r o g e n sulfide a n d s u l f u r d i o x i d e w e r e 0.7 a n d 0.2, r e s p e c t i v e l y ( T a b l e I I ) . F r o m t h e t e m p e r a t u r e coefficient of t h e r a t e constant, t h e a c t i v a t i o n e n e r g y for the C l a u s r e a c t i o n over the C h r o m o s o r b - A w a s d e t e r m i n e d to b e 25.0 k c a l / m o l e a n d for the s o d i u m h y d r o x i d e - l o a d e d C h r o m o s o r b - A it was about 15 k c a l / m o l e . T h e a p p a r e n t c h a n g e i n t h e slope of the A r r h e n i u s p l o t m i g h t i n d i c a t e some t r a n s i t i o n i n the c o n t r o l l i n g m e c h a n i s m . O v e r the c o b a l t - m o l y b d e n a catalyst, the C l a u s r e a c t i o n a p p e a r e d to b e d i f f u s i o n - c o n t r o l l e d w i t h a n a c t i v a t i o n energy of 5.5 k c a l / m o l e (2). Reversibility of Sodium Hydroxide Loading. T h e a n a l y t i c a l m e t h o d for d e t e r m i n i n g t h e degree of base l o a d i n g assumes t h a t t h e base is t o t a l l y Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch006 extractable w h e n the i m p r e g n a t e d a n d a c t i v a t e d catalyst is l e a c h e d w i t h hot water. A n e x p e r i m e n t w a s p e r f o r m e d o n the e x t r a c t e d catalyst to of 260, t h e f r a c t i o n a l c o n v e r s i o n c h e c k its a c t i v i t y . A t 3 0 0 C , a n d a W/F
of h y d r o g e n sulfide was 0.208 as c o m p a r e d w i t h the e x p e c t e d 0.200, d e m o n s t r a t i n g a l m o s t c o m p l e t e r e v e r s i b i l i t y of s o d i u m h y d r o x i d e l o a d i n g . H o w e v e r , after the catalyst h a d b e e n u s e d for 6 h r , the a m o u n t of ext r a c t a b l e base d e c r e a s e d b y a b o u t 4 0 % . Degree of Sodium Hydroxide Loading vs. Claus Reactivity. S a m p l e s of C h r o m o s o r b - A w i t h l o a d i n g s of 0.5, 1.0, 3.9, 7.2, a n d 10.5 w t % s o d i u m h y d r o x i d e w e r e p r e p a r e d . T h e C l a u s r e a c t i o n w a s c a r r i e d o u t at 309 W/F 2 C , u s i n g 4.0 t o r r h y d r o g e n sulfide a n d 2.0 torr s u l f u r d i o x i d e a n d a of 2 9 - 3 1 . A n y v a r i a t i o n i n the p a r t i a l pressure of reactants o n the o b s e r v e d c o n v e r s i o n was a d j u s t e d o n t h e basis t h a t t h e k i n e t i c orders w i t h respect to h y d r o g e n sulfide a n d s u l f u r d i o x i d e w e r e one a n d zero, respect i v e l y . T h e results are r e p o r t e d as rates against s o d i u m h y d r o x i d e l o a d i n g i n F i g u r e 4. A s the s o d i u m h y d r o x i d e l o a d i n g w a s i n c r e a s e d , the rate w e n t t h r o u g h a m a x i m u m . T h e r a t e d e c l i n e at h i g h e r s o d i u m h y d r o x i d e l o a d i n g s c o u l d b e c a u s e d b y the d e c r e a s e d surface area. T h e o n e - p o i n t i s o t h e r m m e t h o d u s e d to measure the surface area w a s n o t sensitive
1 2
" 4 NaOH
1 6
I 8
I 10
I 12
Loading, Wt %
Figure 4. Effect of NaOH loading on Chromosorb-A vs. Claus reaction rate. 309 C, W / F 2 9 - 3 1 . 4.0 torr H S, 2.0 torr S0 . Rate, mmoles H S reacted/ sec, g.
2 2 2
6.
GEORGE
Catalyst
Basicity
83
Figure 5. Polarizing power of Na , L i , and K on Claus reaction. 4.0 torr H S, 2.0 torr S0 , 309C. Constant He flow rate of 1.44 mmole/sec.
+ + + 2 2
e n o u g h to detect s u c h a surface area loss of C h r o m o s o r b - A ( 2 m / g ) .

2
On
cobaltmolybdate, as t h e s o d i u m h y d r o x i d e l o a d i n g w a s i n c r e a s e d , losses i n c a t a l y t i c a c t i v i t y a n d surface area w e r e n o t e d . Effect of the Cation (of Group 1 A ) . w e r e p r e p a r e d c o n t a i n i n g 1.8, 3.3, a n d 1.2% ium h y d r o x i d e s , respectively. S a m p l e s of Chromosorb-A sodium, potassium, and lithThe
T h e catalysts w e r e a c t i v a t e d a n d e x p e r i -
ments c a r r i e d out at a constant h e l i u m flow rate of 1.44 m m o l e / s e c .
results are s u m m a r i z e d i n F i g u r e 5 w h e r e the r a t e / m m o l e base is p l o t t e d against e/r, w h i c h is the p o l a r i z i n g p o w e r of the c a t i o n . T h e results i n d i cate a strong c o r r e l a t i o n b e t w e e n p o w e r of the c a t i o n . Comparison of the Effect of Sodium Hydroxide on Different C a t a lysts for Claus Reaction. T a b l e I I I c o m p a r e s a n u m b e r of i n d u s t r i a l l y T h e effect of s o d i u m h y It is e v i i m p o r t a n t C l a u s catalysts a n d C h r o m o s o r b - A . catalyst a c t i v i t y a n d the p o l a r i z i n g
d r o x i d e l o a d i n g ( 3 . 9 % ) o n C h r o m o s o r b - A is also i n d i c a t e d . I n T a b l e I V the effect of s o d i u m h y d r o x i d e o n these catalysts is presented. d e n t that the s o d i u m h y d r o x i d e - l o a d e d C h r o m o s o r b - A is 1530 times m o r e active p e r u n i t surface area t h a n c o m m e r c i a l catalysts a n d that t h e effect of s o d i u m h y d r o x i d e o n the a l u m i n a - b a s e d catalysts is n o t v e r y significant, compared with Chromosorb-A. CHROMOSORB-A.
3
F i g u r e 3 shows t h a t at a b o u t 240 C t h e rate c o n ( 3 . 9 % ) is a b o u t cobalt-molybdate 2 C , the i n i -
stant for the s o d i u m h y d r o x i d e - l o a d e d C h r o m o s o r b - A 1 0 times h i g h e r t h a n the o r i g i n a l sample. C O B A L T - M O L Y B D A T E O N -ALUMiNA. A s a m p l e of
w a s p r e p a r e d c o n t a i n i n g 3 . 9 % s o d i u m h y d r o x i d e . A t 309
84 Table III.
SULFUR REMOVAL
AND RECOVERY
Comparison of Different Catalysts for Claus Reaction at 240 2 C Surface Area (m /g)
2 6
Catalyst Activated alumina Bauxite Porous alumina C o b a l t - m o l y b d a t e on 7-alumina Porasil Chromosorb-A

6
Relative Relative Initial Rate Initial Rate Initial Rate X 10 (m ) (g) (g)
3 2
140 140 180 220 4 2
5.2 5.6 40.0 14.4 1.5 0.0024 (extrapolated) 4.0
2,100 2,300 16,000 6,000 600 1
30 30 150 60 300 1
Chromosorb-A with 3.9% N a O H

a
2
S0 .
2
1,000
1,000
4.0 torr H S and 2.0 torr

2
Initial rate adjusted to 240C using an activation energy of 7.5 kcal/mole
{21).
t i a l rate for (Figure 6). BAUXITE.
this catalyst w a s 3 0 %
h i g h e r t h a n the o r i g i n a l s a m p l e sodium 20%.
A t 2 9 2 C t h e i n i t i a l rate w a s 0.0166. W i t h 2 . 2 %
h y d r o x i d e l o a d i n g t h e i n i t i a l rate w a s 0.020, a n increase of a b o u t
M o r e t h a n 9 0 % of the base c o u l d b e l e a c h e d out, a n d the surface area w a s u n c h a n g e d . A t 5 % s o d i u m h y d r o x i d e l o a d i n g , there w a s c o n s i d e r a b l e a c t i v i t y loss f o r the C l a u s r e a c t i o n a n d a decrease i n surface area to 70 m /g.
2
ACTIVATED A L U M I N A . 1.72 10" .

2 2
A t 295 C , t h e i n i t i a l rate for this s a m p l e was increase. sodium deter-
A t 2.8%
s o d i u m h y d r o x i d e l o a d i n g , the i n i t i a l rate w a s
2.32
10" , a b o u t 3 0 %
PORASIL.
A t 2 4 0 C , for t h e P o r a s i l s a m p l e c o n t a i n i n g 2 . 1 % Catalyst basicity was
h y d r o x i d e , t h e i n i t i a l rate h a d i n c r e a s e d b y a factor of t w o ( T a b l e I V ) . Determination of Catalyst Basicity. m i n e d b y m a k i n g a suspension of a b o u t 0.50 g of the catalyst i n 25.0 m l Table IV. Surface Area Catalyst Chromosorb-A C o b a l t - m o l y b d a t e on 7-alumina Bauxite P o r a s i l (silica beads) Activated alumina (mVg) 2 220 140 4 140 Effect of Base (Sodium Hydroxide) Reaction Temp. (C) 240 309 292 242 295 Initial Rate, mmoles H S Reacted /sec, g
2
2.40 X " (extrapolated) 1.91 "

6 2
1.66 X 1.52 1.72 X
10" 10-
2 3
6.
GEORGE
Catalyst
Basicity
85
10.0
0 1.60 1.80 1000/ 2.00 2.20
Figure 6. Effect of 3.9% NaOH on cobaltmolybdate on Claus reaction. Initial rate, 4.0 torr >S, 2.0 torr S0 . cobalt-molybdate catalyst; A = cobalt-molybdate catalyst with 3.9% NaOH.
2
b e n z e n e a n d a d d i n g 1.0 m l i n d i c a t o r s o l u t i o n , 0.128 g b r o m o t h y m o l b l u e i n 100.0 m l benzene. of t h e conjugate base. benzoic peared. I f t h e catalyst possessed b a s i c sites, t h e y e l l o w color T h e suspension w a s t h e n t i t r a t e d against 0 . 0 1 N u n t i l t h e green color of t h e granules d i s a p d y e r e a c t e d w i t h t h e base b y electron transfer t o y i e l d t h e green a c i d i n benzene
T h e details of t h e m e t h o d a r e g i v e n i n t h e p a p e r b y T a n a b e
a n d Y a m a g u c h i ( 7 ) . C a t a l y s t basicities are g i v e n i n T a b l e V as m m o l e / g . F o r the 250C-activated catalysts t h e green color d e v e l o p e d q u i c k l y w i t h porous a l u m i n a a n d C h r o m o s o r b - A c o n t a i n i n g base. W i t h bauxite, the color d e v e l o p m e n t w a s v e r y slow. Sometimes t h e color w a s b l u i s h - g r e e n . Samples of porous a l u m i n a , a c t i v a t e d a l u m i n a , b a u x i t e , a n d C h r o m o sorb-A w i t h 3 . 9 % sodium hydroxide were a l l heated i n d r y h e l i u m to 5 0 0 C f o r 3 h r , a n d t h e b a s i c sites w e r e d e t e r m i n e d o n a l i q u o t s . (0.27 m m o l e / g ) . Only Chromosorb-A w i t h 3 . 9 % sodium hydroxide o n it showed any basicity A l l of t h e samples w e r e t h e n exposed t o w a t e r v a p o r Probat r o o m t e m p e r a t u r e ( 2 4 t o r r ) f o r 1 h r , a n d t h e t i t r a t i o n w a s r e p e a t e d . I n t e r e s t i n g l y , a l l samples except C h r o m o s o r b - A s h o w e d b a s i c i t y . on Catalysts for Claus Reaction NaOH Loading (wt %) 3.9 3.9 2.2 2.1 2.8 Initial Rate for Base-loaded Catalyst 2.39 " 2.53 X 1 0 2.05 X 1 0 4.51 " 2.32 "
3
Relative Increase in Initial Rate 1000 0.31 0.24 2.0 0.35
2 3 2
86
SULFUR
REMOVAL
AND RECOVERY
a b l y for the a l u m i n a - b a s e d samples, b a s i c sites are p r o d u c e d w h e n w a t e r is a d d e d . It is not clear w h y t h e C h r o m o s o r b - A w i t h s o d i u m h y d r o x i d e did o n i t f a i l e d to r e s p o n d to t h e b a s i c i t y test u n t i l i t w a s a c t i v a t e d . B a s i c i t i e s d e t e r m i n e d b y the b e n z o i c a c i d t i t r a t i o n ( T a b l e V ) not a p p e a r to b e q u a n t i t a t i v e as the green color r e a p p e a r e d p e r i o d i c a l l y Table V . Determination of Basicity (mmole/g) by Benzoic A c i d Titration Basicity Following Activation by:
Catalyst Activated alumina Porous alumina Bauxite Chromosorb with 3.9% N a O H

a 6
250C in Flowing He for 8 hrs a 0.14 0.02 0.06
500C in Flowing He for 8 hrs
500C in Flowing He Followed by Exposure to Water Vapor (24 torr) at Room Temp, for 1 hr 0.57 0.64 0.12
6
0.27
D i d not turn green. The green color reappeared after 15 min.
o n s t a n d i n g , a n d w i t h C h r o m o s o r b - A c o n t a i n i n g s o d i u m h y d r o x i d e , the e n d p o i n t w a s not a l w a y s sharp. T h i s m e t h o d c o u l d not be u s e d w i t h c o b a l t - m o l y b d a t e b e c a u s e of the intense b l u e color of the granules. C h r o m o s o r b - A c o n t a i n i n g 1.0 m m o l e s o d i u m h y d r o x i d e / g a p p e a r e d to h a v e o n l y 0.27 m m o l e / g b a s i c sites as d e t e r m i n e d b y b e n z o i c a c i d t i t r a t i o n . H o w e v e r , f o r p o r o u s a l u m i n a c o n t a i n i n g 0.7 m m o l e s o d i u m h y d r o x i d e / g, a v a l u e of 0.64 m m o l e / g w a s d e t e r m i n e d b y b e n z o i c a c i d m e t h o d . The l o w v a l u e r e p o r t e d for C h r o m o s o r b - A m a y be associated w i t h the diffic u l t y of d e t e r m i n i n g the e n d p o i n t . T h e v a r i a t i o n i n i n i t i a l rates o n p o r o u s a l u m i n a , b a u x i t e , a n d C h r o m o s o r b - A w i t h 3 . 9 % s o d i u m h y d r o x i d e is c o m p a r e d to the b a s i c i t y change of the catalyst i n T a b l e V I . Adsorption of Sulfur Dioxide and Hydrogen Sulfide on Chromosorb-A. T h e f r o n t a l c h r o m a t o g r a p h y a p p a r a t u s w a s s i m i l a r to that u s e d previously (2). O n the C h r o m o s o r b - A , 4 t o r r h y d r o g e n sulfide a d s o r p t i o n T h e gas c h r o m a t o g r a p h i c b r e a k t h r o u g h w a s not sharp. socoverage). at 2 5 0 C a m o u n t e d to 0.020 m m o l e / g , c o r r e s p o n d i n g to a surface c o v e r age of a b o u t 6 % . T h e h y d r o g e n sulfide a d s o r p t i o n o n C h r o m o s o r b - A c o n t a i n i n g 3 . 9 % d i u m h y d r o x i d e w a s 0.093 m m o l e / g , a f o u r - f o l d increase ( 2 8 % 2 0 % of the totals g i v e n above. T h e s u l f u r d i o x i d e a d s o r p t i o n o n the other h a n d s h o w e d sharp b r e a k t h r o u g h for b o t h catalysts. F o r the 3 . 9 % s o d i u m h y d r o x i d e o n C h r o m o -
O n b o t h catalysts the i r r e v e r s i b l e a d s o r p t i o n of h y d r o g e n sulfide w a s a b o u t
6.
GEORGE
Catalyst
Basicity
87
s o r b - A , 2 t o r r s u l f u r d i o x i d e a d s o r p t i o n at 2 5 0 C w a s e q u i v a l e n t to 0.020 m m o l e / g , c o r r e s p o n d i n g to a b o u t 6 % c o v e r a g e b a s e d o n t o t a l surface. T h i s w a s almost t w i c e (0.012 m m o l e / g ) t h e v a l u e f o r C h r o m o s o r b - A . T h e i r r e v e r s i b l e a d s o r p t i o n of s u l f u r d i o x i d e w a s a b o u t 2 0 % i n b o t h Discussion T h e significant observations f r o m this s t u d y a r e : 1. A c i d i t y o f t h e catalyst d i d n o t affect t h e rate of C l a u s r e a c t i o n over C h r o m o s o r b - A . 2. A d d i t i o n of s m a l l amounts of base to a v e r y i n a c t i v e catalyst ( C h r o m o s o r b - A ) i n c r e a s e d its a c t i v i t y to the same o r d e r of m a g n i t u d e as c o m m e r c i a l catalysts w h i l e base a d d i t i o n to t h e latter catalysts h a d little effect. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch006 3. T h e a c t i v a t i o n energy f o r C l a u s r e a c t i o n over t h e 3.9, o r 5 . 0 % s o d i u m h y d r o x i d e - l o a d e d C h r o m o s o r b - A w a s a b o u t 15 k c a l / m o l e . 4. T h e a c t i v i t y of t h e b a s e - l o a d e d C h r o m o s o r b - A f o r C l a u s r e a c t i o n was K < N a < L i .
+ + +
cases.
A f a c i l e e x p l a n a t i o n of t h e f a i l u r e of a c i d i t y to enhance a c t i v i t y of a n y of t h e catalysts w h i l e base enhances t h e a c t i v i t y of a p o o r catalyst w i t h o u t affecting the active ones is t h a t t h e C l a u s active catalysts o w e t h e i r a c t i v i t y to b a s i c sites. I n general, a l u m i n a shows strong surface a c i d i t y w h e n a c t i v a t e d at 450 C i n v a c u u m , a n d intensive i n v e s t i g a t i o n has s h o w n this to h a p p e n i n L e w i s a c i d sites (8). T h e r e is also e v i d e n c e that b a s i c sites o c c u r o n a l u m i n a . S c h w a b a n d K r a i ( 9 ) o b t a i n e d e v i d e n c e for basic sites b y b o r o n t r i f l u o r i d e a d s o r p t i o n o n a l u m i n a , a n d Y a m a d a y a et al. (10) r e p o r t e d u p to 0.4 m m o l e / g of b a s i c sites o n a l u m i n a f r o m obtained indirect evib e n z o i c a c i d titrations. P i n e s a n d M a n a s s e n (11)
d e n c e of s u c h sites f r o m studies of t h e d e h y d r a t i o n of p r i m a r y alcohols. Table V I . Comparison of Catalyst Basicity and Catalytic A c t i v i t y for Claus Reaction Basicity (mmole/m )
a 2
Catalyst Porous alumina Bauxite Chromosorb-A 3.9% N a O H

a
Relative Basicity 7 1 300
240C
( X 10*) 0.22 0.04 2.0
r /m ,
0 2
Relative Initial Rate 5 1 50
0.0007 0.0001 0.030
250C activation.
T h e r e v i e w of a c t i v e a l u m i n a b y L i p p e n s a n d Steggerda
(12)
a n d the
m o n o g r a p h b y T a n a b e (13) m a y b e c o n s u l t e d f o r f u r t h e r details. It a p pears reasonable therefore to c o n c l u d e t h a t C l a u s r e a c t i o n is c a t a l y z e d b y b a s i c sites o n the catalysts.
88
SULFUR
REMOVAL
AND
RECOVERY
T h e n a t u r e of a c i d i c a n d b a s i c sites o n a l u m i n a c a n b e r e p r e s e n t e d as f o l l o w s (14): H OH H
OH Heat
oH 0
2
0+
o-
-0-1-0-1
' \ \- 0
2
A1+0 A l / I \ (Lewis) acid

A
Al 0 A l / \ / I \ / I \ / \ Bronsted (Basic) acid protons

/ \
1
/ ! \
(Basic) site
T h e L e w i s a c i d is a p o s i t i v e l y c h a r g e d a l u m i n u m i o n , a n d t h e b a s i c site is a n e g a t i v e l y c h a r g e d o x y g e n i o n , O " .
2
P e r i (15,
16)
has p r o p o s e d a structure f o r t h e surface of a l u m i n a
h e a t e d to 8 0 0 C i n w h i c h five different types of O H " w e r e i d e n t i f i e d b y I R spectra, a n d e a c h site has a different l o c a l c h a r g e density. T y p e A w i t h f o u r O " ions as neighbors was the most basic, a n d the O H " i s o l a t e d
2
f r o m O " n e i g h b o r s was the most a c i d i c .

2
P e r i (17) i n his r e p o r t o n the a m m o n i a a d s o r p t i o n o n a l u m i n a suggested that the r e a c t i o n NH

2 3
O-
> N H
- +
OH-
o c c u r r e d o n the O " basic site. It is e v i d e n t therefore that o n a l u m i n a different k i n d s of c a t a l y t i c a l l y a c t i v e sites are present d e p e n d i n g u p o n the p r e p a r a t i o n a n d p r e t r e a t m e n t . O n a p a r t i a l l y d e h y d r a t e d a l u m i n a , the surface contains O " ions, a n d
2
AL
( L e w i s a c i d ) ions are present i n t h e p l a n e i m m e d i a t e l y b e l o w the

2
100 p l a n e . It is suggested that these O " ( b a s i c sites) are c a t a l y t i c a l l y a c t i v e for C l a u s r e a c t i o n . Adsorption of Hydrogen Sulfide. I R studies of h y d r o g e n sulfide a d s o r p t i o n o n a l u m i n a suggest t h a t (18, the f o l l o w i n g s t r u c t u r e : 19) hydrogen bonding produces
6.
GEORGE
Catalyst
Basicity
89
or
-S
I
Al
I
Al (+) It
I r r e v e r s i b l e a d s o r p t i o n of h y d r o g e n sulfide has b e e n r e p o r t e d (2, 20). O " sites:

2
is p r o p o s e d t h a t h y d r o g e n sulfide a d s o r p t i o n c o u l d also take p l a c e v i a
II S '
2
HS-
or
.0 [Chemisorbed
(19)]
Sulfur Dioxide Adsorption. T h i s m a y take p l a c e o n b a s i c sites, a n d c o n s i d e r a b l e i r r e v e r s i b l e a d s o r p t i o n has b e e n r e p o r t e d (2, 18). 0 0 Further,
/
Al
\
Al
\
Al
the a d s o r p t i o n of h y d r o g e n sulfide a n d s u l f u r d i o x i d e m a y take p l a c e o n adjacent sites, a n d the m e c h a n i s m for C l a u s r e a c t i o n c a t a l y z e d b y a base may be: S H+[B(s)] 0 SH0 SH+ BH+ (1)
II
S +
II II s -o-
II s SH O
(2)
II
S - O H + OH-
II
S
(3)
90
SULFUR
REMOVAL
AND RECOVERY
I
S + OH
oI
SH^
II s I
I I s
S
S -
SH
OH I S
!! s
S-
(4)
I I
^ S + I! S OH-
S SI! S
(5)
[B(s)*]-basic site on surface of the catalyst.
T h e i n c r e a s e d rate of C l a u s r e a c t i o n o v e r the b a s i c catalyst c o u l d b e a result of m o r e effective use of t h e a v a i l a b l e surface for r e a c t i o n . T h e z e r o - o r d e r d e p e n d e n c e i n s u l f u r d i o x i d e for C l a u s r e a c t i o n o n
Chromosorb-A
indicates that under
the r e a c t i o n c o n d i t i o n s
the
catafirstFor
l y t i c a l l y a c t i v e sites are s a t u r a t e d w i t h a d s o r b e d s u l f u r d i o x i d e . T h e d r o g e n sulfide w i t h the a d s o r b e d s u l f u r d i o x i d e is rate c o n t r o l l i n g . the Chromosorb-A containing 5.0% w e r e 0.7 a n d 0.2 i n h y d r o g e n Chromosorb-A sponsible. sulfide a n d s u l f u r d i o x i d e ,
o r d e r d e p e n d e n c e i n h y d r o g e n sulfide suggests that the r e a c t i o n of h y s o d i u m h y d r o x i d e , t h e k i n e t i c orders respectively.
T h e r e is no s i m p l e e x p l a n a t i o n for t h e f r a c t i o n a l orders o n the b a s e - l o a d e d a l t h o u g h different m e c h a n i s m s could be potentially reK i n e t i c orders of 0.8 a n d 0.5 i n h y d r o g e n sulfide a n d s u l f u r
d i o x i d e w e r e r e p o r t e d b y D a l l a L a n a et al. ( 21 ) for C l a u s r e a c t i o n over a b a u x i t e catalyst. E v e n t h o u g h the r e l a t i v e basicities of the catalysts d e t e r m i n e d at least for the three catalysts e x a m i n e d , there is a c o r r e l a t i o n by b e n z o i c a c i d w e r e n o t q u a n t i t a t i v e , e x a m i n a t i o n of T a b l e V I reveals t h a t , between c a t a l y s t b a s i c i t y a n d a c t i v i t y . T h e f a i l u r e of active a l u m i n a - b a s e d c a t a lysts to r e s p o n d s i g n i f i c a n t l y to the base a d d i t i o n s i n d i c a t e s t h a t these u n t r e a t e d catalysts a p p r o a c h e d t h e i r m a x i m u m b a s i c i t y u n d e r t h e r e a c t i o n conditions. T h i s e x p l a n a t i o n agrees w i t h t h e observations of L i u (22). S u l f u r d i o x i d e a d s o r p t i o n at 2 5 0 C ( 2 t o r r s u l f u r d i o x i d e ) m o s o r b - A c o n t a i n i n g 3 . 9 % s o d i u m h y d r o x i d e a m o u n t e d to 0.02 suggests that s u l f u r d i o x i d e is a d s o r b e d dioxide adsorption corresponded the catalyst. T h e effect of the p o l a r i z i n g p o w e r of t h e c a t i o n o n t h e C l a u s a c t i v i t y ( F i g u r e 5 ) c o u l d result f r o m the fact t h a t t h e b a s i c sites ( O " ) associated
2
on C h r o mmole/g This
c o m p a r e d w i t h 0.06 m m o l e / g b a s i c sites b y b e n z o i c a c i d t i t r a t i o n . o n the b a s i c sites. to 6 %
T h e sulfur
c o v e r a g e of t h e t o t a l surface of
w i t h L i are m o r e effective i n d i s s o c i a t i v e a d s o r p t i o n of h y d r o g e n sulfide

+
t h a n those associated w i t h N a or K .
+ +
T h e p o r o u s a l u m i n a u s e d i n this s t u d y is v e r y a c t i v e for C l a u s r e a c t i o n . O n the basis of i n i t i a l r a t e / g i t was a b o u t three times m o r e a c t i v e
6.
GEORGE
Catalyst
Basicity
91
t h a n c o b a l t - m o l y b d a t e a n d a b o u t seven times m o r e a c t i v e t h a n b a u x i t e or a c t i v a t e d a l u m i n a . T h e large p o r e o p e n i n g s , <1000A a l l o w reactants a n d p r o d u c t s to diffuse i n a n d out of the pores w i t h ease, a n d t h e i n creased area, 220 m / g ( c o m p a r e d w i t h 1 4 0 - 1 9 0 m / g for other a l u m i n a
2 2
catalysts) enables i t to b e m o r e active. of this catalyst ( 2 . 8 %
F u r t h e r , the i n c r e a s e d b a s i c i t y
sodium hydroxide by hydrochloric acid titration i n
aqueous s l u r r y a n d 0.64 m m o l e / g b a s i c sites b y b e n z o i c a c i d , T a b l e V ) w o u l d enhance its C l a u s r e a c t i v i t y . L e a c h i n g of the base f r o m this catalyst was a s l o w process. E x p e r i m e n t s w i t h the l e a c h e d porous a l u m i n a s h o w e d fairly h i g h activity. I n the c o m m e r c i a l C l a u s reactors the a l u m i n a - b a s e d catalysts m a y h a v e i n t r i n s i c basic sites to i n i t i a t e C l a u s r e a c t i o n . A s w a t e r is p r o d u c e d d u r i n g the r e a c t i o n or i n t r o d u c e d b y the f e e d , m o r e b a s i c sites c o u l d b e Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch006 generated as o b s e r v e d i n t h e b a s i c i t y d e t e r m i n a t i o n s i n this study. Acknowledgments T h e porous a l u m i n a catalyst w a s k i n d l y s u p p l i e d b y . I. Parsons of the M i n e s B r a n c h , D e p a r t m e n t of E n e r g y , M i n e s a n d Resources, O t t a w a . M a n y v a l u a b l e discussions w i t h H. W . H a b g o o d d u r i n g the course of this w o r k are d e e p l y a p p r e c i a t e d . E x c e l l e n t t e c h n i c a l assistance w a s p r o v i d e d by J . J . Mendiuk. Literature Cited
1. M o h t a d i , M. F . , Rowe, R. D . , Joint Chem. Eng. Conf., 4th, Vancouver, Sept. 1973. 2. George, . M., J. Catal. (1974) 32, 261. 3. Nelsen, F . M., Eggersten, F . T., Anal. Chem. (1958) 30, ( 8 ) , 1387. 4. Karren, B . , M.Sc. Thesis, University of Alberta, 1972. 5. Shaw, G . T . , Parsons, . I., Research Rept. 199, Department of Energy, Mines and Resources, Mines Branch, Ottawa, Canada, 1968. 6. M e z a k i , R., Kittrell, J . R., Can. J. Chem. Eng. (1966) 44, (10), 285. 7. Tanabe, K . , Yamaguchi, T., J. Res. Inst. Catal. Hokkaido Univ. (1964) 11, 179. 8. Pines, H., H o a g , W . O., J. Amer. Chem. Soc. (1960) 82, 2471. 9. Schwab, G . M., K r a l , H., Proc. Intern. Congr. Catal., 3rd, Amsterdam (1964) N o . 20 (64). 10. Yamadaya, M., Shimomura, K . , Konoshita, T., U c h i d a , H., Shokubai (Tokyo) (1965) 7, ( 3 ) , 313. 11. Pines, H., Manassen, J., Advan. Catal. (1966) 16, 49. 12. Lippens, B. C . , Steggerda, J . J . , i n "Physical and Chemical Aspects of A d sorbents and Catalysts," B . G . Linsen, E d . , Academic, 1970. 13. Tanabe, K . , "Solid Acids and Bases," Academic, 1970. 14. H i n d i n , S. G . , Weller, S. W . , J. Phys. Chem. (1956) 60, 1501. 15. Peri, J . B . , J. Phys. Chem. (1965) 69, 220. 16. Ibid. 211. 17. Ibid. 231. 18. Deo, ., D a l l a L a n a , I. G . , Habgood, H. W . , J. Catal. (1971) 21, 270.
92
19. Slager, T . L . , Amberg, C. H . , Can. J. Chem. (1972) 50, 3416. 20. Glass, R. W . , Ross, A. R., J. Phys. Chem. (1973) 77, 2576. 21. Dalla Lana, E . G . , McGregor, D. E., Liu, C. L . , Cormode, . ., V . Eur. and 2nd Int. Symp. Chem. Reaction Eng., Amsterdam, May 1972, Paper 2-2. 22. L i u , C. L . , M.Sc. Thesis, University of Alberta, 1971. R E C E I V E D April 4, 1974. This paper is Contribution No. 656 from the Research Council of Alberta.
7
Beavon Sulfur Removal Process for Claus Plant Tail Gas
DAVID K. BEAVON The Ralph M. Parsons Co., Pasadena, Calif. 91124 RAY N. FLECK
Union Oil Co. of California, Brea, Calif. 92621
The Beavon sulfur removal process for the cleanup of Claus plant tail gas is a two-step process in which the sulfur contaminants are first catalytically hydrolyzed and/or hydrogenated to hydrogen sulfide and the hydrogen sulfide is then converted to elemental sulfur and recovered in a Stretford process unit. Commercial 1-3 plants reduce the concentration of sulfur compounds as hydrogen sulfide in the tail gas from vol % to less than 100 ppm. The treated gas contains The chemistry, design less than 1 ppm hydrogen sulfide. are discussed.
criteria, operating experience, and economics of the process
/ ^ l a u s plants are used in petroleum refineries and elsewhere to partially ^ oxidize hydrogen sulfide to elemental sulfur using air as the oxidant. amounts 3-10% The efficiency of such plants is limited, and a nitrogen-rich tail gas is produced which contains water, carbon dioxide, and smaller of other substances including sulfur compounds. Typically, about
of the entering sulfur is produced with the tail gas as carbonyl sulfide, methyl mercaptan, carbon disulfide, hydrogen sulfide, sulfur dioxide, and elemental sulfur as vapor or entrained droplets. contains about 10,000-20,000 ppm sulfur dioxide. A number of commercial plants are now using the Beavon sulfur removal process to convert the sulfur content of Claus tail gas first to hydrogen sulfide and finally to elemental sulfur. These plants reduce the sulfur content of the tail gas from about 1-3% to less than 100 ppm of which less than 1 ppm is present as hydrogen sulfide. The foregoing con93 Disposal of the incinerated tail gas has in the past been an air pollution problem because it
94
SULFUR
REMOVAL
AND RECOVERY
centrations are c a l c u l a t e d as the s u l f u r d i o x i d e e q u i v a l e n t o n a v o l u m e basis. T h e p r o c e s s e d t a i l gas c a n b e d i r e c t l y d i s c h a r g e d t o t h e atmosphere without environmental problems. Chemistry of the Claris Process I n a C l a u s p l a n t a b o u t o n e - t h i r d of the h y d r o g e n sulfide is c o m b u s t e d to s u l f u r d i o x i d e , a n d the b a l a n c e reacts a c c o r d i n g to R e a c t i o n 1; t h e r m a l l y at h i g h temperatures a n d c a t a l y t i c a l l y at l o w e r temperatures (i, 2): 2 H S + S0
2 2
? 3 S + 2 H 0
2
(1)
T h e c a t a l y t i c r e a c t i o n p r o c e e d s stagewise w i t h interstage r e m o v a l of the s u l f u r to shift t h e e q u i l i b r i u m . (3) w i t h solid sulfur. D u r i n g the c o m b u s t i o n of the h y d r o g e n sulfide some of t h e s u l f u r reacts w i t h h y d r o c a r b o n s n o r m a l l y present to f o r m c a r b o n d i s u l f i d e a n d m e t h y l m e r c a p t a n . C a r b o n y l sulfide is also f o r m e d e i t h e r b y the p a r t i a l h y d r o l y s i s of c a r b o n d i s u l f i d e a n d / o r b y the r e a c t i o n of c a r b o n d i o x i d e a n d h y d r o g e n sulfide. Some hydrogen and carbon monoxide are also f o r m e d i n the C l a u s c o m b u s t i o n step. Chemistry of the Catalytic Reactor Interstage r e m o v a l of w a t e r to shift t h e e q u i l i b r i u m e v e n f u r t h e r is i m p r a c t i c a l because of p l u g g i n g p r o b l e m s
T h e heart of t h e B e a v o n process is a c a t a l y t i c reactor w h i c h converts essentially a l l of t h e s u l f u r i n t h e t a i l gas to h y d r o g e n sulfide either b y hydrognation or h y d r o l y s i s . H y d r o l y s i s reactions are t y p i f i e d b y R e a c tions 2 a n d 3: CS + 2 H 0 ^ 2 H S + C0
2 2 2
(2) (3)
COS +
H 0 H S + C 0
2
R e s i d u a l c a r b o n y l sulfide a n d c a r b o n d i s u l f i d e t y p i c a l l y t o t a l a b o u t 25 p p m c a l c u l a t e d as s u l f u r d i o x i d e . Hydrognation reactions are t y p i f i e d b y R e a c t i o n s 4, 5, a n d 6: S + H S0

2
>H S
2 2 2
(4) (5)
4
+ 3 H
3
-> H S + 2 H 0
2
CH SH +
-> H S + C H
2
(6)
7.
BEAVON AND FLECK
Beavon Sulfur Removal
Process
95 to by
W h i l e c a r b o n d i s u l f i d e a n d c a r b o n y l sulfide c a n also b e c o n v e r t e d h y d r o g e n sulfide b y hydrognation, b o t h are p r e d o m i n a n t l y c o n v e r t e d hydrolysis. The s u p p l y of h y d r o g e n is s u p p l e m e n t e d b y the
carbon
m o n o x i d e content of the reactor f e e d gas w h i c h undergoes R e a c t i o n 7, the w a t e r - g a s shift r e a c t i o n : CO + H 0 < = > H

2
C0
(7)
Chemistry of the Stretford Process T h e h y d r o g e n s u l f i d e - c o n t a i n i n g stream f r o m the c a t a l y t i c step c a n be p r o c e s s e d several w a y s to r e c o v e r the s u l f u r content. mercial development Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch007 uses the S t r e t f o r d process (4-10) T h e initial comto convert the
h y d r o g e n sulfide to e l e m e n t a l s u l f u r b y a w e t c h e m i s t r y process d e v e l o p e d b y T . N i c k l i n a n d others at N o r t h W e s t G a s of S t r e t f o r d , E n g l a n d . T h e S t r e t f o r d process has b e e n a c c e p t e d w i d e l y for t r e a t i n g coke o v e n gas a n d r e c e i v e d the Queen's A w a r d for i n d u s t r i a l developments. I n this process the gas is first c o n t a c t e d i n a n absorber w h e r e h y d r o g e n sulfide is a b s o r b e d i n t o a n a l k a l i n e s o l u t i o n a n d e v e n t u a l l y c o n v e r t e d to s u l f u r b y R e a c t i o n 8 w h e r e V 2 V+ The reduced V
+ 4 5 + 5
is present as s o d i u m m e t a v a n a d a t e .
4
H S - 2 V+
2
2H+ + S
(8)
is l a t e r o x i d i z e d b y a i r b l o w i n g i n t h e presence of the
d i s o d i u m salt of a n t h r a q u i n o n e , 2,7-disulfonic a c i d ( A D A ) . T h e o v e r a l l o x i d a t i o n is r e p r e s e n t e d b y R e a c t i o n 9: 2V Sulfur formed

+ 4
+ 2H++
1/2 0
-> 2 V +
H 0
2
(9)
i n R e a c t i o n 8 is r e c o v e r e d
b y flotation d u r i n g the a i r
b l o w i n g i n R e a c t i o n 9. S o m e of the h y d r o g e n sulfide f e e d u n d e r g o e s side reactions a n d is c o n v e r t e d to s o d i u m t h i o s u l f a t e a n d s o d i u m sulfate. m o r e of the i n c o m i n g h y d r o g e n e l e m e n t a l sulfur. Plant Design T h e B e a v o n s u l f u r r e m o v a l process was s t u d i e d i n a G e n e r a l process o p e r a b i l i t y w a s e s t a b l i s h e d at this T h e d e s i g n for a c o m m e r c i a l p l a n t is s h o w n However, 9 8 % or to sulfide f e e d is n o r m a l l y c o n v e r t e d
Pilot Plant. c o m m e r c i a l units. stage.
p i l o t p l a n t w h e r e the scale-up f a c t o r w a s 100 a n d 200 for t h e first t w o
Commercial Design.
s c h e m a t i c a l l y i n F i g u r e 1. R e d u c i n g gas is generated b y p a r t i a l o x i d a t i o n
96
CLAUS TAIL GAS
SULFUR
REMOVAL
AND RECOVERY CLEAN OFF G A S
FUEL GAS
cru
ABSORBER OXIDIZER
SULFUR
REDUCING GAS GENERATOR
CATALYST BED
WASTE HEAT BOILER
FROTH FILTER & WASH
SULFUR MELTER
Figure 1. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch007
Flow diagram of the Beavon sulfur removal process T h e hot r e d u c i n g gas also preheats the t a i l gas.
of a f u e l gas a n d t h e n m i x e d w i t h the f e e d t a i l gas as a source of h y d r o g e n and carbon monoxide. T h e m i x e d gases flow to the c a t a l y t i c step after w h i c h the b u l k of the w a t e r m a y b e r e m o v e d , a n d t h e gas stream is passed to the S t r e t f o r d absorber. I n the S t r e t f o r d process, e l e m e n t a l s u l f u r r e c o v e r e d as a f r o t h i n the o x i d i z e r is filtered, w a s h e d , a n d passed to a m e l t e r to separate m o l t e n s u l f u r a n d the e n t r a i n e d w a t e r . Special Design Considerations. T h e i n i t i a l plants consisted of two C l a u s / B e a v o n strings so that w h e n one s t r i n g w a s shut d o w n the other c o u l d process the h y d r o g e n sulfide l o a d f r o m the e n t i r e refinery w i t h o u t p o l l u t i o n . S o m e p l a n t s n o w u n d e r c o n s i d e r a t i o n w i l l h a v e o n l y a single s t r i n g w i t h s p a r i n g of some items of e q u i p m e n t , e.g., p u m p s , to p r o v i d e sufficient r e l i a b i l i t y . H y d r o l y s i s , hydrognation, a n d the shift r e a c t i o n take p l a c e c o n c u r r e n t l y at m o d e r a t e temperatures a n d a t m o s p h e r i c pressure over a n ext r u d e d c o b a l t m o l y b d a t e catalyst w h i c h is sulfided. Space velocities are a b o u t 2000 c u ft of t a i l gas p l u s r e d u c i n g g a s / h r / c u ft of catalyst. B e cause of the excessive heat released w h e n sufficient a i r contacts especially d u r i n g start-up a n d shutdown. F o r m a x i m u m c o n v e r s i o n of s u l f u r c o m p o u n d s i t is d e s i r a b l e to o p erate as close to c h e m i c a l e q u i l i b r i u m as possible. w i t h respect to the c o n v e r s i o n of s u l f u r c o m p o u n d s . reactions t h r o u g h o u t the reactor together with e q u i l i b r i u m c o m p l i c a t e s process analysis. S e v e r a l things w e r e d o n e at the p i l o t p l a n t stage to m i n i m i z e reactor scale-up problems. T h e catalyst p a r t i c l e size i n the p i l o t p l a n t w a s the same as that n o w u s e d i n c o m m e r c i a l p l a n t s . C a t a l y s t b e d d e p t h s i n the p i l o t a n d c o m m e r c i a l u n i t s w e r e s i m i l a r i n order to h a v e s i m i l a r mass B o t h the p i l o t p l a n t The many competing a close a p p r o a c h to a n d c o m m e r c i a l plants a t t a i n e d a f a i r l y close a p p r o a c h to e q u i l i b r i u m these catalysts, extraneous a i r m u s t b e e x c l u d e d f r o m the catalyst at a l l times,
7.
BEAVON AND FLECK
Beavon
Sulfur Removal
Process
97
velocities t h r o u g h b o t h beds.
B e c a u s e of the large gas v o l u m e s a n d l o w This prevent
pressure d r o p r e q u i r e m e n t s , the catalyst b e d is r e l a t i v e l y s h a l l o w . d e s i g n r e q u i r e s p r o p e r gas d i s t r i b u t i o n at the reactor i n l e t to
channeling. T h e pilot plant operated exclusively on a commercial Claus p l a n t t a i l gas i n o r d e r to i n c l u d e the effects of a n y a n d a l l u n k n o w n t a i l gas constituents i n the process e v a l u a t i o n . F i n a l l y , the p i l o t p l a n t w a s o p e r a t e d for over 3 months to m a k e c e r t a i n that the catalyst d i d not deter i o r a t e r a p i d l y w i t h use. A s of m i d - J a n u a r y 1974, U n i o n ' s t w o c o m m e r c i a l units h a d each o p e r a t e d for 6 m o n t h s w i t h o u t o b s e r v a b l e catalyst d e a c t i v a t i o n . T h e u l t i m a t e catalyst l i f e is e x p e c t e d to b e m o r e t h a n a year. U n f o r t u n a t e l y , upsets i n a n o i l refinery C l a u s u n i t are r o u t i n e because of f r e q u e n t s u d d e n changes i n f e e d c o m p o s i t i o n a n d Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch007 s u l f u r d i o x i d e surges. flow. The Beavon hydrogenate u n i t p r o v i d e s excess h y d r o g e n i n the c a t a l y t i c section to
T h e r e s u l t i n g h y d r o g e n sulfide surges as w e l l as Because the exThe
those f r o m the C l a u s u n i t are h a n d l e d i n the S t r e t f o r d u n i t b y p r o v i d i n g a s u i t a b l e excess of c h e m i c a l s i n the S t r e t f o r d s o l u t i o n . hydrognation reactions are e x o t h e r m i c , s u l f u r d i o x i d e surges, for a m p l e , w i l l increase the t e m p e r a t u r e rise across the catalyst b e d . d e s i g n tolerates surges w i t h o u t d a m a g i n g the catalyst. A waste-heat b o i l e r m a y be i n s t a l l e d o n the reactor outlet gas l i n e i f the i n s t a l l a t i o n is large e n o u g h to generate steam e c o n o m i c a l l y . S t e a m m a y b e g e n e r a t e d at a n y pressure u p to a b o u t 200 p s i g . W a t e r b u i l d u p m u s t be p r e v e n t e d i n the S t r e t f o r d l i q u o r . i n the S t r e t f o r d process. Water enters the S t r e t f o r d u n i t w i t h the feed gas a n d is also a r e a c t i o n p r o d u c t A d d i t i o n a l w a t e r enters w i t h the filter w a s h . A n B e c a u s e the b a c k prese v a p o r a t i v e cooler evaporates excess w a t e r a n d controls t e m p e r a t u r e . T h e absorber is a s i m p l e splash-deck tower. sure of h y d r o g e n sulfide over S t r e t f o r d s o l u t i o n is n e g l i g i b l e , the a b s o r b e r c a n b e s i z e d to r e d u c e the i n l e t h y d r o g e n sulfide c o n c e n t r a t i o n b y a f a c t o r of 100,000. C o m m e r c i a l absorbers have met this d e s i g n c r i t e r i o n . can when I n p r a c t i c e the o x i d a t i o n of S t r e t f o r d s o l u t i o n b y R e a c t i o n 9 is k i n e t i c a l l y l i m i t e d so that a s u b s t a n t i a l i m p r o v e m e n t i n p e r f o r m a n c e be o b t a i n e d b y s t a g i n g the process. d e n c e t i m e i n the o x i d i z e r c a n be decreased b y as m u c h as 5 0 % three o x i d i z e r stages are u s e d i n p l a c e of a single stage. a three-stage o x i d i z e r is u s e d in which power-driven air i n t o s m a l l b u b b l e s . size is s u i t a b l y s m a l l . Operating Experience fifteen more It is e s t i m a t e d that the o v e r a l l r e s i Commercially, stirrers c h u r n performance
A n analysis of c o m m e r c i a l o x i d i z e r
i n d i c a t e s that mass transfer is not a significant factor.
H e n c e the b u b b l e
A t the present t i m e seven units are o p e r a t i n g a n d a b o u t
are i n v a r i o u s stages of e n g i n e e r i n g a n d c o n s t r u c t i o n . B y the t i m e of this
98
SULFUR
REMOVAL
AND RECOVERY
p u b l i c a t i o n , t h e t o t a l o p e r a t i n g t i m e l o g g e d w i l l b e a b o u t 36 u n i t - m o n t h s . T o d a t e t h e h y d r o g e n sulfide content of t h e treated t a i l gas has e x c e e d e d 1 p p m o n l y d u r i n g severe upsets. T h e aggregate t i m e of these upsets is p r o b a b l y less t h a n h a l f a d a y . T h e treated t a i l gas p u r i t y has at a l l times e x c e e d e d t h e most r i g i d regulations b y a w i d e m a r g i n . Operating Problems. D u r i n g t h e startups of t h e first t w o p l a n t s there w a s some difficulty, w i t h s o l u t i o n o v e r l o a d i n g , m a i n l y because of upsets i n t h e C l a u s u n i t s a n d i n spite of the fact t h a t these plants are d e s i g n e d w i t h generous C l a u s units. over-capacity. T h e frequency deficiency of these upsets q u i c k l y i n t h e a m o u n t of a i r i n d e c r e a s e d as p e r s o n n e l l e a r n e d to m a i n t a i n p r o p e r o p e r a t i n g ratios i n t h e F o r example, a 5 % the C l a u s unit c a n double the load o n the B e a v o n plant. T h e f r o t h filter w a s t h e most t r o u b l e s o m e single p i e c e of m e c h a n i c a l Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch007 e q u i p m e n t . T r o u b l e s d i m i n i s h e d g r e a t l y as t h e operators b e c a m e f a m i l i a r w i t h this n e w t y p e of e q u i p m e n t . M e t h o d s to e l i m i n a t e t h e filter h a v e n o w b e e n d e v e l o p e d a n d w i l l b e tested o n a c o m m e r c i a l scale. Construction Materials. C a r b o n steel is u s e d for most of t h e p l a n t s ; i n s o m e areas i t is p r o t e c t e d against r u s t i n g b y a c o a l t a r e p o x y c o a t i n g . T h e w a t e r o u t l e t l i n e of t h e s u l f u r m e l t e r is stainless steel. N o n o t a b l e c o r r o s i o n has o c c u r r e d . Table I. Commodity Power F u e l gas Soft w a t e r Catalyst replacement Chemicals T o t a l costs L e s s c r e d i t for 50 p s i g s t e a m L e s s c r e d i t for incinerator fuel N e t cost
a 6
Beavon Sulfur Removal Process Operating Costs" Unit Cost 0.725*f/kw-hr S1.00/MM Btu 20/ g a l Consumption Rate 300 k w 125 M M B t u 12 M g a l / d a y Daily Cost ($) 52 125 2 8 140 327 S 1 . 0 0 / M lb $1.00/MM Btu 2,500 l b / h r 250 M M B t u 60 250 17
Basis: 100 long-ton/day Claus Unit. Assumed catalyst life is 3 yrs. Economics. T h e c a p i t a l i n v e s t m e n t f o r a B e a v o n p l a n t to process t a i l
gas f r o m a 1 0 0 - l o n g - t o n / d a y C l a u s u n i t is a b o u t $1,250,000. r e q u i r e d b y t h e process
Operating
costs f o r a u n i t of this size a r e g i v e n i n T a b l e I. T h e f u e l a n d steam is less t h a n o n e - f o u r t h of that r e q u i r e d f o r s i m p l e i n c i n e r a t i o n . S h o u l d f u e l gas cost increase to $ 2 / M M B t u as has b e e n forecast, t h e energy savings w o u l d m a k e t h e o p e r a t i o n profitable.
7.
BEAVON AND F L E C K
Beavon Sulfur Removal Process
99
Conclusions The Beavon sulfur removal process is now a reliable, established method for cleaning up Claus plant tail gas well beyond any proposed regulations. As with any new process, work is currently directed toward reducing capital and operating costs. T h e capital investment has already been reduced by about 2 0 % over the original design. sibilities of this process. Literature Cited A further cost reduction now seems possible, thereby increasing the application pos-
1. Gamson, B. W., Elkins, R. H . , Chem. Eng. Progr. (1953) 49, 203. 2. Palm, J. W., Hydrocarbon Process. (1972) 51 (3), 105. 3. Bailleul, M . R., Berthier, P., Guyot, G., Proc. Ann. Conv., Nat. Gas Process. Ass., 49th (March 17-19, 1970) 89. 4. Nicklin, T., Brunner, E . , "Hydrogen Sulfide Removal by the Stretford Liquid Purification Process," Inst. Gas Eng. Meetg. (May 16-19, 1961), Publication No. 593. 5. Nicklin, T., Brunner, E . , Hydrocarbon Process. Petrol. Refiner (1961) 40(12), 141. 6. Ellwood, P., Chem. Eng. (1964) 71(15), 128. 7. Oil Gas J. (1971) 69(41), 68. 8. Nicklin, T., et al., U.S. Patent #2,997,439 (Aug. 22, 1961). 9. Ibid., #3,035,889 (May 22, 1962). 10. Ibid., #3,097,926 (July 16, 1963). RECEIVED April 4, 1974. The process is patented in the U.S. (#3,752,877, D. K. Beavon, Aug. 14, 1973) and Canada (#916,898, D. K. Beavon, Dec. 19, 1972), and patents are being sought in other countries. The process is licensed by the Union Oil Co. of California and is designed by the Ralph M . Parsons Co.
8
Sulfur Recovery in O i l Refineries Using IFP Processes
YVES BARTHEL, ANDRE DESCHAMPS, SIGISMUND FRANKOWIAK, and PHILLIPE RENAULT Institut Franais du Ptrole, Rueil-Malmaison, France PIERRE BONNIFAY and JOHN W. ANDREWS
Institut Franiais du Ptrole, New York, N. Y. 10022

The IFP-1500 process converts mixed hydrogen Claus reaction using a proprietary catalyst. sulfide/sul-
fur dioxide streams to sulfur and water by a liquid-phase The exit gas dioxide from the reactor contains 1000-2000 ppm sulfur
after incineration. Plant investment and operating costs are both relatively low, and there is no problem with corrosion. The IFP-150 process takes sulfur dioxide streams down to 150-250 ppm sulfur dioxide by ammonia scrubbing and reaction with hydrogen sulfide-containing gas in a scheme similar to the IFP-1500. Nineteen IFP-1500 plants and four IFP-150 are now operating or under construction. A scheme is shown for converting all solid, liquid, and gaseous sulfur wastes in a refinery to water and sulfur, reducing dioxide concentration to 150250 ppm. sulfur
V I T T h e n control of sulfur emission became an urgent concern of refineries and other plants operating on hydrocarbon feeds, a host of processes were developed on paper ( I ) . The past 2 yrs have seen a shakedown and thinning of these processes. O f the more than 60 originally proposed, only about half a dozen have been developed commercially. This paper concerns itself with two of those commercially proved processes developed by the French Petroleum Institute (2, 3); one for taking emissions down to about 1500 ppm sulfur dioxide after incineration and the other for reducing sulfur dioxide to one tenth that level. At this time 19 IFP-1500 plants are licensed as are four of the IFP-150 plants. 100
8.
BARTHEL E T AL. Process
Sulfur Recovery
in Oil
Refineries
101
The IFP-1500
Process D e s c r i p t i o n . T h e I F P - 1 5 0 0 process is best u s e d to c l e a n u p C l a u s u n i t t a i l gas. T h e t e c h n o l o g y i n v o l v e d is essentially a n extension of t h e C l a u s r e a c t i o n itself b u t c a r r i e d out i n the l i q u i d p h a s e as s h o w n i n F i g u r e 1. T h e t a i l gas at C l a u s u n i t exit pressure is i n j e c t e d i n t o
TREATED GAS TAIL GAS FROM CLAUS PLANT TO INCINERATOR STEAM CONDENSATE
SOLVENT MAKE-UP
STEAM FOR START UP
LIQUID S U L F U R PRODUCT
Figure 1.
IFP Claus tail gas clean-up
process
the b o t t o m of a p a c k e d t o w e r w h i c h p r o v i d e s h i g h contact area b e t w e e n gaseous a n d l i q u i d phases. T h e t o w e r is s i z e d to m a i n t a i n pressure A low to and d r o p w i t h i n a c c e p t a b l e l i m i t s , a v o i d i n g the n e e d for a b l o w e r .
v a p o r pressure p o l y e t h y l e n e g l y c o l solvent w h i c h contains a p r o p r i e t a r y c a r b o x y l i c a c i d salt catalyst i n s o l u t i o n circulates c o u n t e r c u r r e n t the gas. The catalyst forms a complex with hydrogen sulfide
s u l f u r d i o x i d e w h i c h i n t u r n reacts w i t h m o r e of t h e gases to regenerate t h e catalyst a n d f o r m e l e m e n t a l sulfur. T h e r e a c t i o n is e x o t h e r m i c , a n d the heat is r e m o v e d by i n j e c t i n g a n d v a p o r i z i n g steam condensate. the T e m p e r a t u r e is m a i n t a i n e d a b o u t 2 5 0 - 2 7 0 F , sufficient t o k e e p
s u l f u r m o l t e n b u t not h i g h e n o u g h to cause m u c h loss of s u l f u r or g l y c o l o v e r h e a d . T h e s u l f u r a c c u m u l a t e s i n the b o o t of t h e t o w e r a n d is d r a w n off c o n t i n u o u s l y t h r o u g h a seal l e g . P u r i t y of t h e p r o d u c t s u l f u r is v e r y g o o d as s h o w n i n T a b l e I. O v e r h e a d s f r o m the t o w e r are sent to the
102 Table I.
SULFUR
REMOVAL
AND RECOVERY
T y p i c a l Analysis of Sulfur from IFP-1500 Claus T a i l Gas Clean-up Plants Design Actual" 99.96 100 130 bright yellow
P u r i t y (% S) H y d r o c a r b o n (ppm) A s h (ppm) Color
99.7 100 200 yellow
From I F P unit serving a 270 long tons/day ( L T / D ) Claus plant. s a m e i n c i n e r a t o r u s e d to i n c i n e r a t e C l a u s t a i l gases w e r e the I F P u n i t absent. S i n c e there is n o w a t e r b u i l d u p i n t h e I F P process, c o r r o s i o n is T h e w h o l e u n i t is f a b r i c a t e d f r o m c a r b o n steel. no p r o b l e m . Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch008
Sulfur Dioxide and Hydrogen Sulfide Concentration and Ratio. D e s i g n c o n v e r s i o n of I F P - 1 5 0 0 units d e p e n d s o n c o n c e n t r a t i o n of h y d r o g e n sulfide a n d s u l f u r d i o x i d e i n the C l a u s p l a n t t a i l gas a n d o n the a m o u n t of p a c k i n g i n the I F P t o w e r . F i g u r e 2 s h o w s curves for plants F o r a given IFP-1500 plant, w i t h t w o different amounts of p a c k i n g .
c o n v e r s i o n varies w i t h the c o n c e n t r a t i o n of h y d r o g e n sulfide i n the f e e d . T h i s is r e s p o n s i b l e for t h e b a l a n c i n g effect w h i c h I F P - 1 5 0 0 u n i t s exert to a c e r t a i n extent o n C l a u s p l a n t o p e r a t i o n : as the C l a u s catalyst b e -
8.
BARTHEL E T AL.
Sulfur Recovery
in Oil Refineries
103
cornes spent, t h e t a i l gas contains i n c r e a s i n g l y h i g h e r concentrations of h y d r o g e n sulfide w h i c h i n t u r n increases conversions i n t h e I F P - 1 5 0 0 u n i t . F i g u r e 3 shows a c t u a l p e n traces f r o m t h e stack s u l f u r d i o x i d e m o n i tor of a r e c e n t l y c o m m i s s i o n e d I F P - 1 5 0 0 u n i t . 2000 PPM 1000 PPM 2000 PPM 1000 PPM Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch008 2000 PPM 1000 PPM 28 2000 PPM 1000 PPM 2000 PPM 1000 PPM 56 Figure 3.
63
42
S u l f u r d i o x i d e at t h e
Stack sulfur dioxide
concentration
stack m o u t h r e a c h e d as l o w as 1000 p p m u s i n g o n l y a c o n v e n t i o n a l n o n b a u x i t e catalyst i n t h e t w o stage C l a u s u n i t . F i g u r e 4 is a c o m p o s i t e of readings m a d e d u r i n g t h e start-up of t h e same p l a n t , s h o w i n g that s u l f u r d i o x i d e emissions w e r e b r o u g h t as l o w as 800 p p m . E x t r a p o l a t i n g these results to 1 0 0 % c o n v e r s i o n shows t h a t a b o u t 4 0 0 p p m s u l f u r d i o x i d e a r e left. T h i s corresponds to e q u i l i b r i u m s u l f u r a n d to c a r b o n y l sulfide a n d c a r b o n d i s u l f i d e generated i n t h e C l a u s u n i t . react i n t h e I F P - 1 5 0 0 process. These compounds do not T o keep t h e m at a m i n i m u m o n e c a n r u n
the first reactor of t h e C l a u s p l a n t s o m e w h a t hotter t h a n u s u a l a n d use a n u m b e r of c o m m e r c i a l l y a v a i l a b l e catalysts ( 4 , 5 ) . T h e r a t i o of h y d r o g e n sulfide to s u l f u r d i o x i d e is e s p e c i a l l y i m p o r t a n t at h i g h conversions. F i g u r e 5 shows a c t u a l traces f o r s u l f u r d i o x i d e , h y d r o g e n sulfide, a n d t h e h y d r o g e n s u l f i d e / s u l f u r d i o x i d e r a t i o f o r t h e f e e d to a n I F P - 1 5 0 0 p l a n t w i t h a d e s i g n c o n v e r s i o n of 9 0 % . F i g u r e 6 shows t h e effect of v a r y i n g t h e r a t i o o n c o n v e r s i o n f o r a p l a n t of 9 3 % d e s i g n c o n v e r s i o n . T h e d e s i g n r a t i o here is a b o u t 2.2. A r a t i o that is t o o h i g h or too l o w cuts conversions s h a r p l y . O n e that is too l o w also reduces
104 1900
SULFUR
REMOVAL
AND RECOVERY
60
65
70
75
80
85
90
95
100
CONVERSION ( % ) Figure 4. Conversion vs. stack sulfur dioxide concentration for an IFP unit with 93% design conversion C a r e f u l c o n t r o l of the C l a u s u n i t to
the q u a l i t y of t h e p r o d u c t sulfur.
m a i n t a i n p r o p e r r a t i o not o n l y o p t i m i z e s c o n v e r s i o n i n the I F P - 1 5 0 0 u n i t , b u t also i n the C l a u s p l a n t itself. Operating Factors. A n a d v a n t a g e of the I F P - 1 5 0 0 process is its of i n s e n s i t i v i t y to changes i n gas flow rates. W h e n the first i n d u s t r i a l scale u n i t w a s s t a r t e d u p i n J a p a n , it o p e r a t e d o n flows as l o w as 3 0 % d e s i g n w i t h o u t adverse effect. A n o t h e r a d v a n t a g e of the I F P - 1 5 0 0 p r o c -
ess is t h a t s t r e a m factor is l o n g , g e n e r a l l y i n t h e r a n g e of 2 yrs. A f t e r
8.
BARTHEL E T AL.
Sulfur Recovery
in Oil Refineries
105
1.8
2.0
2.2
24
2
2.6
2
2.8
3.0
3.2
34
3.6
3.8
4.0
H S / S 0 RATIO IN FEED GAS Figure 6. Conversion vs. H S/S0 ratio in feed gas for IFF unit with 93% design conversion
2 2
106
SULFUR
REMOVAL
AND
RECOVERY
a b o u t 24 months a s h u t d o w n is n e e d e d to w a s h a w a y catalyst w h i c h has b e e n c o n v e r t e d to sulfates a n d d e p o s i t e d o n the p a c k i n g i n the t o w e r . A s i m p l e w a s h w i t h w a t e r is u s e d . ator h i m s e l f runs the I F P - 1 5 0 0 u n i t . Table II. Feed Specifications for a Two-stage 100 L T / D Claus Plant at 9 5 % Conversion Lb-mol/hr H S SOo Sx COS + C S Balance
2
T h e r e is n o e x t r a o r d i n a r y m a i n t e -
n a n c e r e q u i r e d , a n d there is n o l a b o r n e e d e d since the C l a u s p l a n t oper-
8.5 4.2 1.9 0.3 879.4 894.0
Total Economics. Claus +
T a b l e I I gives specifications for f e e d f r o m a two-stage
100 L T / D C l a u s p l a n t w i t h 9 5 % c o n v e r s i o n . T a b l e I I I shows the o v e r a l l I F P - 1 5 0 0 conversions possible for plants t r e a t i n g t a i l gas f r o m 90%, T a b l e I V gives i n v e s t m e n t a n d o p e r a t i n g costs t h a t C l a u s u n i t , w i t h I F P - 1 5 0 0 plants of v a r y i n g d e s i g n c o n v e r s i o n : 8 0 % , 7 0 % , and 6 0 % . for these I F P u n i t s . It is i n t e r e s t i n g to e x a m i n e the e c o n o m i c s of the I F P - 1 5 0 0 process f r o m another p o i n t of v i e w . Starting w i t h a fixed a m o u n t of money a v a i l a b l e for I F P p l a n t i n v e s t m e n t , one c a n d e t e r m i n e h o w m a n y c a t a l y t i c stages s h o u l d b e i n s t a l l e d i n a C l a u s p l a n t to r e a c h v a r i o u s s u l f u r d i o x i d e e m i s s i o n levels. T a b l e V shows t y p i c a l analyses for t a i l gas f r o m the first, second, and third converters of a 100 L T / D Claus plant. T a b l e V I shows conversions p o s s i b l e i n a n I F P - 1 5 0 0 u n i t after t r e a t i n g Table III. Overall Recovery as a Function of IFP U n i t Design Conversion
a
Feed T o t a l free a n d c o m bined S (lb-mol/hr) Overall Claus + I F P r e c o v e r y (%)
% IFP 90
Design Conversion, 80 2.9 99.0 70 4.2 98.6
HS
2
+ 60
S0
14.9
1.7 99.4
5.5 98.1
Total feed = 894.0 lb-mol/hr e a c h of these three effluent gas streams, expressed as p e r c e n t I F P c o n v e r s i o n a n d p p m s u l f u r d i o x i d e g o i n g to t h e i n c i n e r a t o r . T h e s e figures are b a s e d o n s p e n d i n g h a l f a m i l l i o n dollars o n the I F P - 1 5 0 0 u n i t i n e a c h case. W h e r e r e g u l a t i o n s s p e c i f y 1500-2000 p p m ( ) , a C l a u s p l a n t m a y
8.
BARTHEL
ET AL.
Sulfur Recovery in Oil
Refineries
107
Table IV.
Investment and Operating Costs % IFP 90 Design Recovery (H S

2
S0 )
2
80 99.0 330 1.65 320 17
70 98.6 280 1.57 280 16
60 98.1 240 1.54 250 15
Overall recovery Claus + I F P (%) Battery limits investment ($000) Solvent and catalyst consumption ($/hr) Utilities Condensate (lb/hr) Power ( K W H r / h r )
a
99.4 510 1.67 370 21
Erected project cost including engineering, royalties, process data book, and solvent inventory (January 1973)
Table V . Analysis H S S0 S H 0 COS CS Balance

2 2 2 2
Analyses of T a i l Gas 100 L T / D Claus Plant Converter No. 1 1.48 0.74 1.26 28.58 .02 .01 67.91 1025.27 Converter No. 2 0.59 0.29 0.14 29.96 .02 .01 68.99 1009.13 Converter No. 3 0.34 0.17 0.13 30.25 .02 .01 69.08 1007.77
(mol %)
F l o w rate ( l b - m o l / h r )
Table V I .
Conversions Possible with Fixed $500,000 Investment in IFP Unit for a 100 L T / D Claus P l a n t
0
Treating Converter No. 1 90 3000 1.67 400 25
Tail Gas After Converter No. 2 86 2000 1.66 180 25 Converter No. 3 85 1700 1.65 100 25
I F P unit conversion, H S + S0 (%) S u l f u r c o m p o u n d s to the i n c i n e r a t o r (as p p m S 0 ) Solvent and catalyst consumption ($/hr) Utilities Condensate (lb/hr) Power ( K W H r / h r )
2 2 2
Battery limits investment including solvent inventory, 1973 basis
108 o n l y n e e d t w o stages.
SULFUR
REMOVAL
AND RECOVERY
T h i s w a s a c t u a l l y the case w h e r e a n I F P - 1 5 0 0
u n i t w a s i n s t a l l e d to c l e a n u p t a i l gas f r o m a l a r g e two-stage C l a u s p l a n t . The IFP-150 Process T h e I F P - 1 5 0 process is b a s i c a l l y a v a r i a t i o n of t h e I F P - 1 5 0 0 process for h a n d l i n g s u l f u r d i o x i d e streams. I n i t , t h e I F P - 1 5 0 0 process is c o u p l e d
TO STACK INCINERATOR
NH MAKE-UP,
3
AMMONIA
SCRUBBER H S-CONTAINING GAS

2
INCINERATOR
TAIL GAS
SULFITE EVAPORATOR AND SO2 REGENERATOR SULFATE REDUCER
Figure 7.
Flow diagram of the IFP-150
process
to a n a m m o n i a s c r u b b i n g section.
W h e r e refinery s u l f u r d i o x i d e levels
m u s t b e b e l o w 200 p p m at t h e stack m o u t h , scrubbers c a n b e set u p at m a n y p o i n t s to c l e a n flue gases a n d v a r i o u s a c i d a n d sour streams. T h e effluents f r o m t h e scrubbers are t h e n p i p e d to a c e n t r a l I F P - 1 5 0 r e a c t i o n section w h e r e s u l f u r - c o n t a i n i n g c o m p o u n d s s u l f u r a n d aqueous are c o n v e r t e d to e l e m e n t a l a m m o n i a is r e c y c l e d to the several s c r u b b i n g secof
tions. T h e r e is i n t e r m e d i a t e storage at several points i n the refinery so t h a t v a r i o u s units c a n operate at t h e i r o p t i m u m rates i n d e p e n d e n t the o p e r a t i o n rate of the I F P - 1 5 0 r e a c t i o n section. Process Description. F i g u r e 7 shows t h e flow scheme. T h e t a i l gas concenis s c r u b b e d w i t h aqueous a m m o n i a , r e d u c i n g the s u l f u r d i o x i d e stack.
t r a t i o n to 1 5 0 - 2 5 0 p p m . T h e c l e a n e d gas is h e a t e d a n d v e n t e d to t h e T h e b r i n e , c o n t a i n i n g m o s t l y a m m o n i u m sulfites, is h e a t e d i n a T h e s e are t a k e n off o v e r h e a d w i t h w a t e r at a b o u t f o r c e d - c i r c u l a t i o n e v a p o r a t o r w h e r e sulfites are d e c o m p o s e d to a m m o n i a and sulfur dioxide. 300 F . B o t t o m s f r o m t h e evaporator c o n t a i n t h e r m o s t a b l e sulfates a n d combustion technology to a v o i d c o r r o s i o n a n d solve
thiosulfates w h i c h are r e d u c e d a c c o r d i n g to a p r o p r i e t a r y I F P process using submerged heat transfer p r o b l e m s . T h e r e a c t i o n is e n d o t h e r m i c a n d uses r e d u c i n g
8.
BARTHEL E T AL.
Sulfur Recovery in Oil
Refineries
109
gases p r o d u c e d b y b u r n i n g f u e l gas i n a deficiency of a i r . I n the r e d u c t i o n , sulfates a n d thiosulfates are c o n v e r t e d to a m m o n i a , s u l f u r d i o x i d e , a n d w a t e r w h i c h are m i x e d w i t h t h e o v e r h e a d s t r e a m f r o m t h e evaporator. A c i d gas or other h y d r o g e n s u l f i d e - r i c h gas a n d t h e b l e n d e d s u l f u r d i o x i d e - a m m o n i a streams are f e d to the I F P - 1 5 0 reactor at rates sufficient to m a i n t a i n a 2 : 1 r a t i o of h y d r o g e n sulfide : s u l f u r d i o x i d e . I n the reactor the h y d r o g e n sulfide a n d s u l f u r d i o x i d e dissolve i n a h i g h b o i l i n g p o i n t g l y c o l to f o r m e l e m e n t a l s u l f u r a n d w a t e r . T h e r e a c t i o n l i q u o r is m a i n t a i n e d s l i g h t l y a b o v e the m e l t i n g p o i n t of s u l f u r , as i n t h e I F P - 1 5 0 0 process, w i t h l i q u i d s u l f u r a c c u m u l a t i n g i n the b o o t of t h e t o w e r a n d b e i n g d r a w n off to storage t h r o u g h a seal l e g . T h e reactor t o w e r operates i n a flooded c o n d i t i o n , w i t h gases b u b b l i n g u p t h r o u g h t h e s o l u t i o n . P e r f o r a t e d trays are u s e d to i m p r o v e c o n Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch008 tact. S o l v e n t c i r c u l a t i n g c o u n t e r c u r r e n t to t h e gases is t a k e n f r o m t h e b o t t o m of t h e t o w e r , p u m p e d t h r o u g h a steam generator a n d b a c k to the t o w e r . T h e heat of r e a c t i o n is thus r e m o v e d , w i t h steam l e a v i n g t h e generator at t w i c e a t m o s p h e r i c pressure. O v e r h e a d s f r o m t h e t o w e r are c o o l e d , a n d aqueous a m m o n i a is c o n d e n s e d a n d r e c y c l e d b a c k to the
FURNACE GAS, CLAUS TAIL G AS, BOILER OFF-GAS RESIDUES TARS FUEL GAS
CAUSTIC & SODI CARBONATES Na / ION EXCHANGE

+
ACID SLUDGE & SODIUM SULFATES CAUSTIC & SODIUM CARBONATES
SOUR WATER Na /NH + ON EXCHANGE

4 +
EVAPORATOR AMMONIUM SULFATES
Figure 8.
Total sulfur recovery using IFP-150 process in a refinery
s c r u b b e r . S o m e non-condensables c o n t a i n i n g i n e r t gases, traces of s u l f u r v a p o r , a n d h y d r o g e n sulfide are i n c i n e r a t e d a n d r e c y c l e d to t h e a m m o n i a scrubber. F i g u r e 8 shows h o w t h e I F P - 1 5 0 process c a n b e i n t e g r a t e d i n t o a n o v e r a l l scheme f o r r e c o v e r i n g s u l f u r f r o m a l l gaseous, l i q u i d , a n d s o l i d s u l f u r - b e a r i n g refinery wastes.
110 Table VII.
T y p i c a l Performance and Economics of a 200 L T / D Claus Plant
1787 lb-mol/hr to incinerator 29.25 lb-mol/hr S compounds (as S 0 ) 250 ppm SO in treated gas
2 2
Investment Scrubbing ($) Sulfur conversion ($) Solvent inventory ($) Utilities Power ( K W H r / h r ) Circulating cooling water ( U S G P M ) Process water ( U S G P M ) M P steam (lb/hr) Chemicals L P G (lb/hr) N H (lb/hr) Solvent (S/yr)
3
400,000 600,000 40,000 190 1400 3 5500 220 4 4000 for the IFP-150 process
Economics.
Table VII gives
economics
applied to Claus unit gaseous effluent. Industrial References
Nineteen full scale IFP-1500 units have been licensed to clean up tail gas from Claus plants: five in the U.S., one in Canada, nine in Japan, three in Russia, and one in Belgium. T h e Claus units recover from 45 to 800 L T / D of sulfur. They produce 4.3-68.7 M M S C F D of tail gas with hydrogen sulfide concentrations ranging from 3,0% 0. 9 . (single stage) to (three stages). Thirteen units are already in operation. Four IFP-150 units are under construction or already operating in Japan and France. This paper was originally presented in January, 1974. A t the time of acceptance for publication, September 1974, 24 IFP-1500 plants were in operation or under construction. Literature Cited
1. Hyne, J. B., Oil Gas J. (Aug. 1972) 70, 64-78. 2. Bonnifay, P., Dutriau, R., Frankowiak, S., Deschamps, ., Chem. Eng. Progr. (Aug. 1972) 68, 51-52. 3. Barthel, Y., Renault, P., Bonnifay, P., Dutriau, R., Ind. Pet. Europe (431), 49-53 (1972). 4. Pearson, M . J., Hydrocarbon Process. (Feb. 1973) 52, 81-85. 5. Bryant, H . S., Oil Gas J. (Mar. 1973) 71, 70-76. 6. Engdahl, R. B., J. Air Pollut. Contr. Ass. (1973) 23, 364-375. RECEIVED June 11, 1974. Confidentiality agreements prevent disclosure of any other operating temperatures and pressures used in the IFP-1500 or IFP-150 processes.
9
The Shell Claus Offgas Treating (SCOT) Process
C. DONALD SWAIM, JR. Ford, Bacon, and Davis Texas, Inc., Dallas, Tex. 75238
The Shell Claus Offgas Treating (SCOT) acceptance by the oil refining industry
Process won instant when it was an-
nounced in September 1972, and today it is the preferred method of meeting the most stringent emission regulations. Its functions are familiar to refinery operators, economical carbon steel is used throughout, and there are no waste discharges except the vent gas containing less than 500 and a clean water condensate. first commercial ppm hydrogen sulfide (250 ppm sulfur dioxide after incineration) This paper describes the SCOT Process and discusses the operating experience of the plants placed on stream. Two small skidin -mounted units were designed and placed in operation California within 8 mos of contract award.
Specified recovery efficiency of sulfur recovery units ( S R U ) ^
used to
be based on economic considerations. Any increase in S R U efficiency
which added to its cost had to increase profits based upon the sales value of the additional sulfur recovered. Sulfur recovery units were based on the classic Claus process which was, and still is, the cheapest way to recover over 90% of the sulfur in hydrogen sulfide-bearing streams. Most were very simple one or two catalytic stage plants. As the problem of reducing sulfur emissions has become more urgent, the complexity and cost of SRU's has risen, partially because of such routine sophisticated modifications as closed loop control of acid gas/air ratio, three or more catalytic reactor stages, high pressure steam reheat, ammonia and hydrogen cyanide handling capability, etc. Such plants are approaching the theoretical limits of sulfur recovery for the Claus process. Following the National Environmental Policy Act of 1969, the drive of federal, state, and local regulations toward zero sulfur emissions has 111
112
SULFUR
REMOVAL
AND RECOVERY
c a u s e d m a n u f a c t u r i n g a n d e n g i n e e r i n g - c o n s t r u c t i o n i n d u s t r i e s to d e v e l o p n u m e r o u s processes to c a p t u r e the r e s i d u a l s u l f u r i n C l a u s t a i l gas. As a p p l i e d specifically to S R U offgas, a f e w of these processes h a v e b e e n successfully c o m m e r c i a l i z e d , n a m e l y the W e l l m a n - L o r d , I F P , a n d P a r sonsBeavon processes. Process. T h e most recent to j o i n this p a r a d e of successful c o m m e r c i a l processes is the S h e l l C l a u s T a i l G a s Offgas T r e a t i n g ( S C O T ) I t is l i c e n s e d i n the U . S . b y S h e l l D e v e l o p m e n t C o . , b y S h e l l N i h o n G i j u t s u i n J a p a n a n d the F a r E a s t , a n d i n a l l other countries b y Shell Internationale Research Maatschappij. Process Description and Chemistry
T h e f o l l o w i n g process d e s c r i p t i o n is f r o m or d e r i v e d f r o m a p a p e r Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch009 p r e s e n t e d b y N a b e r , W e s s l i n g h a n d G r o e n e n d a a l of S I R M (1,2,3). The S C O T process m a y b e d i v i d e d i n t o t w o s e c t i o n s r e d u c t i o n - q u e n c h a n d a m i n e . T h e r e d u c t i o n step converts essentially a l l s u l f u r values i n C l a u s offgas to h y d r o g e n sulfide. T h e e l e m e n t a l s u l f u r a n d s u l f u r d i o x i d e are h y d r o g e n a t e d , a n d the c a r b o n y l sulfide a n d c a r b o n d i s u l f i d e are h y d r o l y z e d to h y d r o g e n sulfide a c c o r d i n g to the f o l l o w i n g m a i n reactions : S + S0
2
H 3H H 0
2
= = = =
H S
2
(1) 2H 0
2
H S +
2
(2) (3)
COS + CS
2
H S +
2
C0
2H 0
2
2H S +
2
C0
(4)
N o r m a l l y , C l a u s S R U t a i l gas contains m o r e t h a n e n o u g h h y d r o g e n a n d c a r b o n m o n o x i d e to r e d u c e the s u l f u r a n d s u l f u r d i o x i d e , b u t a n o u t side source of h y d r o g e n or h y d r o g e n - r i c h gas m u s t be p r o v i d e d i n case of a n upset i n the S R U w h i c h w o u l d cause the s u l f u r d i o x i d e content to rise a b o v e n o r m a l . C a r b o n m o n o x i d e is as g o o d as h y d r o g e n for r e d u c t i o n b y the f o l l o w i n g shift r e a c t i o n : CO + H 0
2
C0
(5)
T h e a m i n e section absorbs most of the h y d r o g e n sulfide f r o m the gas w h i l e c o a b s o r b i n g as l i t t l e c a r b o n d i o x i d e as possible. feed. These acid of gases are r e c y c l e d to the i n l e t of the C l a u s u n i t a n d b e c o m e p a r t of its B e c a u s e t h e solvent selects h y d r o g e n sulfide a n d rejects most the c a r b o n d i o x i d e , the size of the C l a u s S R U is i n c r e a s e d b y o n l y because of r e c y c l i n g inert c a r b o n d i o x i d e . A s s h o w n o n t h e process flow sheet, F i g u r e 1, r e d u c i n g gas is a d d e d to t h e S R U offgas, a n d the t e m p e r a t u r e is r a i s e d to the r e q u i r e d r e a c t o r i n l e t t e m p e r a t u r e i n a fired heater. A l t e r n a t i v e l y , i f a source of r e d u c i n g 5-6%
9.
swAiM
SRU Tail Gas
SCOT
Process
Vent Gas To Incinerator
113
Reducing Gas Air Feed Heater
Quench Tower
Absorber
Reactor Lean Cooler/Waste Heat Quench Cooler
Boiler Feed Water
Condensate
Figure 1.
SCOT process flow diagram
gas is n o t a v a i l a b l e , a r i c h gas b u r n e r m a y b e u s e d w h i c h b u r n s n a t u r a l gas w i t h s u b s t o i c h i o m e t r i c a i r t o y i e l d b o t h the n e e d e d h y d r o g e n a n d c a r b o n m o n o x i d e as w e l l as reactor preheat. P r e h e a t e d gas enters the reactor c o n t a i n i n g a b e d o f c o b a l t - m o l y b d e n u m catalyst w h e r e s u l f u r a n d its c o m p o u n d s are c o n v e r t e d t o h y d r o g e n sulfide a t a b o u t 300 C . H e a t is r e c o v e r e d f r o m the h o t reactor effluent S C O T stripper w h i l e b y g e n e r a t i n g steam i n a w a s t e heat b o i l e r w h i c h p r o v i d e s a b o u t o n e t h i r d o f the steam r e q u i r e d f o r t h e s u b s e q u e n t p a r t i a l l y c o o l i n g t h e reactants. T h e gas is c o o l e d to near a m b i e n t t e m p e r a t u r e b y d i r e c t contact w i t h water i n a packed quench tower. T h e circulating quench water may b e c o o l e d b y c o o l i n g w a t e r or b y a n a i r cooler w i t h c o o l i n g w a t e r t r i m . T h e substantial q u a n t i t y o f w a t e r v a p o r c o n t a i n e d i n n o r m a l s u l f u r r e c o v e r y u n i t t a i l gas is l a r g e l y c o n d e n s e d i n the q u e n c h t o w e r , a n d the condensate is c o n t i n u o u s l y w i t h d r a w n t o m a i n t a i n a constant l e v e l i n the q u e n c h tower bottom. T h i s condensate is i n contact w i t h the h y d r o g e n sulfide i n the gas stream a n d c o n s e q u e n t l y m u s t b e s t r i p p e d b e f o r e d i s c a r d i n g to t h e sewer. I f t h e m a i n p l a n t has a sour w a t e r s t r i p p e r , this w a t e r m a y be p i p e d to that t o w e r , o r i f not, a s m a l l sour w a t e r s t r i p p e r m a y b e a d d e d t o this stream as a n i n t e g r a l p a r t o f the S C O T p l a n t itself. H y d r o gen sulfide is r e t u r n e d either t o the S C O T system o r t o the sour w a t e r strippers so that o n l y c l e a n w a t e r is d i s c h a r g e d f r o m the p l a n t . T h e c o o l e d gas f r o m the t o p o f the q u e n c h t o w e r enters the S C O T absorber where the hydrogen sulfide is a b s o r b e d selectively b y a n
114
SULFUR REMOVAL
A N D RECOVERY
a l k a n o l - a m i n e s o l u t i o n . T h e system is d e s i g n e d so t h a t a l l b u t the s m a l l a m o u n t of h y d r o g e n sulfide a l l o w e d b y a n t i p o l l u t i o n regulations is r e m o v e d f r o m the gas s t r e a m w h i l e o n l y a b o u t 2 0 - 3 0 % d i o x i d e is c o - a b s o r b e d of the carbon b y the a m i n e s o l u t i o n . T h e o v e r h e a d gas f r o m
the absorber c o n t a i n i n g t h e d e s i g n e d a m o u n t of h y d r o g e n sulfide, u s u a l l y a b o u t 2 0 0 - 5 0 0 p p m , is sent to a n i n c i n e r a t o r w h e r e r e s i d u a l s u l f u r c o m p o u n d s are o x i d i z e d to s u l f u r d i o x i d e b e f o r e d i s c h a r g e t h r o u g h a stack to the atmosphere. T h e r i c h a m i n e f r o m the b o t t o m of the S C O T a b s o r b e r is p u m p e d t h r o u g h a l e a n - r i c h exchanger to be h e a t e d w h i l e c o o l i n g the l e a n a m i n e s o l u t i o n a n d is f e d to the S C O T s t r i p p e r . H e a t i n p u t to the S C O T s t r i p p e r t h r o u g h its r e b o i l e r generates w a t e r v a p o r to s t r i p out the c a r b o n d i o x i d e a n d h y d r o g e n sulfide w h i c h t h e n go o v e r h e a d w i t h the w a t e r v a p o r , p a s s i n g t h r o u g h a condenser w h e r e the w a t e r is c o n d e n s e d Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch009 for reflux to the s t r i p p e r . T h e u n c o n d e n s e d gases c o n t a i n i n g n e a r l y a l l of the h y d r o g e n sulfide a n d 2 0 - 3 0 % of the c a r b o n d i o x i d e are t h e n The r e t u r n e d to t h e C l a u s u n i t w h e r e t h e y j o i n the m a i n a c i d gas feed.
hot, r e g e n e r a t e d a m i n e s o l u t i o n is p u m p e d f r o m the b o t t o m of t h e s t r i p p e r t h r o u g h the leanrich e x c h a n g e r a n d a w a t e r - c o o l e d l e a n a m i n e cooler to t h e top of the absorber.
Table I.
S C O T Operating Requirements for 100 L T / D S R U 34 6,400 6.4 2.9 1,200 10,000 2,000 $1,400,000
Electric power ( K W ) S t e a m (50 psig) ( l b s / h r ) B o i l e r feed w a t e r ( G P M ) F u e l gas ( m i l l i o n B t u / h r ) Cooling water ( G P M ) C a t a l y s t , based 3-yr life ( $ / y r ) Alkanolamine (J/yr) C a p i t a l costs
T h e a m i n e section appears c o n v e n t i o n a l b u t w h e r e the u s u a l m o n o e t h a n o l a m i n e ( M E A ) a n d d i e t h a n o l a m i n e ( D E A ) s w e e t e n i n g processes a p p r o a c h the e q u i l i b r i u m s o l u b i l i t y of c a r b o n d i o x i d e a n d h y d r o g e n s u l fide, the s e l e c t i v i t y for a b s o r b i n g h y d r o g e n sulfide a n d r e j e c t i n g c a r b o n T h e a i m is to absorb d i o x i d e is a t t a i n e d b y the difference i n r e a c t i o n rates of the gases w i t h the a m i n e ( u s u a l l y d i i s o p r o p a n o l a m i n e , D I P A ) . n e a r l y a l l the h y d r o g e n sulfide before the c a r b o n d i o x i d e has h a d t i m e to react w i t h the a m i n e . T h e a b s o r p t i o n takes p l a c e at near a t m o s p h e r i c pressure. T h i s differs f r o m t h e c o n v e n t i o n a l a m i n e p l a n t w h i c h u s u a l l y operates at a c o n s i d e r a b l y h i g h e r pressure. U n l i k e the s u l f u r oxide p r o c esses, this process is g e n e r a l l y n o n - c o r r o s i v e a n d c a r b o n steel is u s e d t h r o u g h o u t except i n the f e w cases w h e r e a l l o y is r e q u i r e d because of conditions.
9.
swAiM
SCOT
Process
115
T h e S C O T Process is c o m p e t i t i v e w i t h other processes f o r r e d u c i n g sulfur d i o x i d e levels to the 2 0 0 - 5 0 0 p p m r a n g e . T a b l e I shows c a p i t a l ton/day a n d o p e r a t i n g costs for a t y p i c a l u n i t to serve a 100 l o n g ( L T / D ) S R U o p e r a t i n g at 9 4 % r e c o v e r y efficiency p e r pass. SCOT Process Development
T h e S C O T process was first m a d e p u b l i c i n S e p t e m b e r 1972, at a technical meeting i n Japan b y Shell Internationale Research Maatschappij (SIRM). S h e l l h a d p r o v e d t h e effectiveness a n d l i f e of the catalyst i n t h e r e d u c t i o n step i n b e n c h - s c a l e w o r k at t h e i r A m s t e r d a m l a b o r a t o r y a n d a s e m i - c o m m e r c i a l d e m o n s t r a t i o n o n C l a u s S R U t a i l gas at Shell's G o r dorf, G e r m a n y refinery. C o n f i d e n c e i n the effectiveness Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch009 a n d selectivity of t h e a m i n e a b s o r p t i o n step w a s b a s e d o n S h e l l s extensive use of the A D I P process i n w o r l d w i d e a p p l i c a t i o n s b o l s t e r e d b y l a b o r a t o r y b e n c h scale testing. Commercial Plants
O n the s t r e n g t h of the S I R M w o r k , D o u g l a s O i l C o . ( a s u b s i d i a r y of C o n t i n e n t a l O i l C o . ) a n d C h a m p l i n P e t r o l e u m C o . b o u g h t the S C O T process for t h e i r refineries i n C a l i f o r n i a to m e e t the v e r y strict L o s A n g e l e s A P C D C o d e (4, 5 ) . B o t h of these p l a n t s w e r e a s s e m b l e d , c o m plete w i t h p i p i n g , instrumentation, insulation, a n d electrical w i r i n g , on skids i n the D a l l a s , Texas shops of F o r d , B a c o n a n d D a v i s a n d s h i p p e d b y t r u c k to t h e p l a n t sites. T o w e r s s h i p p e d d i r e c t l y to the jobsite b y t h e i r v e n d o r s w e r e p l a c e d , a l o n g w i t h the skids, o n p r e p a r e d f o u n d a t i o n s i n 1 day. B o t h units w e r e started u p the last w e e k of J u n e 1973, less t h a n Unit. 9 m o n t h s f r o m contract a w a r d . F i g u r e 2 shows t h e C h a m p l i n P e t r o l e u m SCOT T h e s e t w o plants represent n o t o n l y t h e first c o m m e r c i a l a p p l i c a t i o n of the process a n y w h e r e , b u t also the first t i m e the h y d r o g e n a t i o n - q u e n c h section a n d the a m i n e section h a d b e e n o p e r a t e d as a n i n t e r g r a t e d w h o l e . E v e n Shell's p i l o t p l a n t a n d d e m o n s t r a t i o n u n i t h a d not b r o u g h t the separate sections together. W h i l e these C a l i f o r n i a plants w e r e s m a l l u n i t s a d d e d onto e x i s t i n g 9 a n d 15 L T / D S R U ' s r e s p e c t i v e l y , t h e y d i d p r o v i d e the o p p o r t u n i t y to d i s c o v e r a n d r e m e d y the i n e v i t a b l e p r o b l e m s i n a n e w process. M u c h w a s l e a r n e d w h i c h i n c r e a s e d t h e confidence i n the d e s i g n SCOT of m u c h l a r g e r plants w h i c h w e r e f o l l o w i n g o n . A t a n e a r l y date, S h e l l C a n a d a L t d . d e c i d e d to i n s t a l l the process at t h e i r W a t e r t o n , A l b e r t a gas p r o c e s s i n g p l a n t . T h i s p l a n t , d e s i g n e d i n the N e t h e r l a n d s , w i l l treat the t a i l gas f r o m a S R U c a p a c i t y of 2,100 L T / D . B e c a u s e the t o t a l s u l f u r e m i s s i o n a l l o w a b l e f r o m a single
116
SULFUR
REMOVAL
AND
RECOVERY
f a c i l i t y i n A l b e r t a is w e l l a b o v e the c a p a b i l i t y of the S C O T process, this u n i t w i l l treat o n l y a b o u t t w o t h i r d s of the t o t a l S R U c a p a c i t y of Waterton plant. T h e r e m a i n i n g one t h i r d of the S R U t a i l gas m a y i n c i n e r a t e d a l o n g w i t h the S C O T t a i l gas a n d d i s c h a r g e d w i t h o u t e x c e e d i n g the a l l o w a b l e e m i s s i o n rate. the be
to t h e air
Figure
2.
SCOT unit in 15 LT/D SRU of Petroleum Co., Wilmington, Calif.
Champlin
I n q u i c k succession, a n u m b e r of S C O T units w e r e o r d e r e d i n areas w h e r e the a n t i p o l l u t i o n c o d e requires v e r y l o w emission levels. w i t h S C O T plants. These w e r e o n n e w S R U ' s specifically d e s i g n e d to integrate the C l a u s S R U ' s T h e y w e r e B P O i l at M a r c u s H o o k , P a . ; M a r a t h o n SouthO i l at D e t r o i t , M i c h . ; S t a n d a r d O i l C o . ( O h i o ) at L i m a , O h i o ;
w e s t e r n O i l a n d R e f i n i n g C o . at C o r p u s C h r i s t i , T e x . ; a n d T e x a c o Inc. at P o r t A r t h u r , T e x . A t this w r i t i n g , t h i r t e e n S C O T units are u n d e r c o n tract i n the U . S . a n d C a n a d a , as d e t a i l e d i n T a b l e I I . F i g u r e 3 is a m o d e l of a 160 L T / D S C O T u n i t u n d e r construction.
9.
swAiM
SCOT Process Table I I . SCOT U n i t s U . S . and Canada (LT/D) 15 8.8 40 130 160 28 80 325 2100 125 235 40
117
Process
User
Location Wilmington, Calif. Paramount, Calif. Meraux, L a . Clairton, P a . Marcus Hook, P a . Duncan, Okla. Detroit, M i c h . Houston, Tex. Waterton, Alta. Corpus Christi, Tex. Port Arthur, Tex. Norco, L a .
SRU
Startup J u n e 1973 J u n e 1973 m i d 1974 late 1974 late 1974 e a r l y 1975 e a r l y 1975 e a r l y 1975 e a r l y 1975 e a r l y 1975 late 1975 late 1975
Champlin Petroleum Douglas O i l Murphy Oil U . S . Steel Oil Sun O i l Marathon Oil Shell O i l Shell C a n a d a Southwestern O i l & Refining Texaco Inc. Shell O i l
Figure 3.
Model of SCOT unit under construction in 160 LT/D
SRU
I n J a p a n , v i r t u a l l y a l l S R U ' s are i n h i g h p o p u l a t i o n d e n s i t y C o n s e q u e n t l y , the S C O T process has b e e n q u i c k l y a d o p t e d there. teen S C O T units are slated to be b u i l t i n J a p a n at this t i m e .
areas. Seven-
118 Commercial Plants Startup
SULFUR
REMOVAL
AND RECOVERY
and Operation
Problems
W h i l e there w e r e f e w m e c h a n i c a l p r o b l e m s d u r i n g startup of the t w o C a l i f o r n i a plants because of t h e c o n v e n t i o n a l e q u i p m e n t , some process problems delayed full compliance w i t h L o s Angeles A P C D Regulations. Understated Sulfur Load Design. T h i s p r o b l e m is m e n t i o n e d first T h i s u n i t m u s t consistently because it h a d an important bearing on meeting guaranteed performance, even i f there h a d b e e n no other p r o b l e m s . fluctuations r e m o v e t h e last b i t of s u l f u r f r o m a stream that is subject to r a t h e r w i d e c a u s e d b y r o u t i n e changes or upsets i n p r e c e d i n g processes. T h i s is e s p e c i a l l y t r u e i n refineries w h e r e m u l t i p l e a m i n e units a n d v a r i a tions i n refinery feedstocks c a n cause w i d e s w i n g s i n b o t h rate a n d c o m p o s i t i o n of the a c i d gas f e e d i n g the S R U . U p s e t s i n a m i n e units can cause upsets i n the S R U o p e r a t i o n , a n d t h e S R U m a y be subject Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch009 upsets of its o w n i f a d e q u a t e i n s t r u m e n t a t i o n is not p r o v i d e d . B o t h the C a l i f o r n i a plants w e r e a d d e d to e x i s t i n g S R U ' s . T h e s u l f u r content of the off-gases w e r e at times w e l l a b o v e that stated b y the owners for o r i g i n a l d e s i g n of the S C O T units. T h e s o l u t i o n to this p r o b l e m was s i m p l y to a d d i m p r o v e d S R U controls i n o l d e x i s t i n g p l a n t s a n d d e s i g n for o p t i m u m c o n t r o l i n n e w plants a n d / o r p r o v i d e e n o u g h excess c a p a c i t y i n the S C O T u n i t to h a n d l e m a x i m u m a n t i c i p a t e d s u l f u r content of the t a i l gas. Solvent Stripper Design. I n o p e r a t i o n at g r e a t e r - t h a n - d e s i g n s u l f u r loads, i t was f o u n d that the solvent c i r c u l a t i o n rate h a d to be i n c r e a s e d to m e e t the specifications for r e s i d u a l h y d r o g e n sulfide i n the absorber offgas. T o a c c o m p l i s h this, the s t r i p p e r w a s r e p l a c e d w i t h one of l a r g e r d i a m e t e r to a c c o m m o d a t e the i n c r e a s e d l i q u i d a n d v a p o r traffic i n t h e tower. I n c i d e n t a l to the u p g r a d i n g of s t r i p p e r c a p a c i t y w e r e i n c r e a s e d steam to r e b o i l e r , i n c r e a s e d reflux condenser, a n d i n c r e a s e d p u m p c a p a c i t y . T h e s e changes h a v e b e e n a c c o m p l i s h e d at the C h a m p l i n P e t r o leum S C O T u n i t , a n d i t has b e e n operating smoothly w i t h minimal operator a t t e n t i o n a n d b e t t e r i n g its g u a r a n t e e d p e r f o r m a n c e b y a w i d e m a r g i n since O c t o b e r 1973. Sulfur Dioxide Breakthrough. N o r m a l l y , e n o u g h s u l f u r d i o x i d e is c o n v e r t e d to h y d r o g e n sulfide i n the S C O T reactor so t h a t s u l f u r d i o x i d e is not detected i n reactor effluent. I n one of the p l a n t s , t h r o u g h mistakes i n o p e r a t i o n d u r i n g s t a r t u p , the s u l f u r d i o x i d e content was a l l o w e d to rise to the p o i n t w h e r e t h e q u e n c h w a t e r b e c a m e a c i d i c , a n d s u l f u r d i o x i d e was c a r r i e d over i n t o the S C O T absorber w h e r e i t f o r m e d a c o m p o u n d w i t h D I P A that was not r e g e n e r a b l e at s t r i p p e r c o n d i t i o n s . A s a result, the c a r b o n steel q u e n c h w a t e r p u m p a n d the c a r b o n steel quench water pipes where turbulence was h i g h were r a p i d l y corroded a n d the h y d r o g e n sulfide a b s o r b i n g c a p a c i t y of the a m i n e s o l u t i o n w a s lost. to
9.
swAiM
SCOT Process
119
While the consequences of sulfur dioxide breakthrough are serious, it is easy to prevent using the following procedures and precautions: 1. If initial catalyst sulfiding is to be done with sulfur dioxidecontaining S R U tail gas, the reactor effluent must be isolated, bypassing the quench system. 2. There must always be an excess of hydrogen to guard against surges in sulfur dioxide content of S R U tail gas. 3. Protection against contamination of the amine by small amounts of sulfur dioxide is provided by the reaction of sulfur dioxide with hydrogen sulfide to form sulfur in low temperature Claus reaction in the water phase. The quench water itself provides very sensitive early warning of potential trouble from sulfur dioxide breakthrough, and proper instrumentation can sound an alarm and/or divert the S R U tail gas to the incinerator until the breakthrough is corrected. These indicators are color, p H , and turbidity, in order of increasing situation severity. W i t h proper instrumentation the amine should never be contaminated.
#
The possibility of sulfur dioxide contamination of the D I P A has been considered so remote and the rate of D I P A degradation is so low that none of the plants now being designed and constructed have D I P A reclaiming facilities, as is common practice in M E A and D E A amine units. Since November 1973, none of the startup problems have recurred in the Champlin Unit, and the plant has operated well below the sulfur emission levels guaranteed by Shell and required by A P C D regulations. Performance Testing and Compliance
The performance of the Champlin S C O T unit has been tested by the Los Angeles A P C D emission source test team. sulfur dioxide. They found that the emission level was considerably below the statutory limits of 500 p p m The plant has also been subject to a lengthy test by findings. Performance the mobile laboratory of the E P A with similar
tests made by Shell Development Co. proved that the Champlin Plant met and exceeded its guarantee level of 500 ppm hydrogen sulfide in absorber offgas and that the selectivity of the solvent for hydrogen sulfide exceeded Literature expectations. Cited
1. Naber, J. E . , Wesselingh, . ., Groenendaal, W., Chem. Eng. Progr. (Dec. 1973) 6 9 , 29. 2. N G / L N G / S N G Handbook, Hydrocarbon Process. (April 1973) 52, 114. 3. Naber, J. E., Wesselingh, . ., Groenendaal, W., Energy Process. Canada (Sept.-Oct. 1973) 32. 4. The British Sulphur Corp., Ltd., Sulphur (Nov.-Dec. 1972) 103, 53. 5. Ibid., (May-June 1973) 106, 61.
R E C E I V E D June 6, 1974
10
Commercialization of Lime-Limestone Flue Gas Scrubbing Technology
RICHARD S. ATKINS Research-Cottrell, Inc., Bound Brook, N. J. 08805
Research-Cottrell installation. has demonstrated the commercial availaMW
bility of limestone flue gas desulfurization Certain chemistry and process were taken into account in designing occurrence of potential problems.
on a 115
considerations the
and operating these
systems. Methods have been developed to minimize
Q i n c e the first large sulfur dioxide control system was installed at the ^ Battersea plant in London, it has taken almost 50 yrs for calciumto become commercially acceptable. In based scrubbing technology
1926, the 125 M W coal-fired Battersea power plant was equipped with a spray packed tower and final alkaline wash section which removed more than 90% of the sulfur dioxide and particulate ( I ) . Thames River was water provided most of the alkali for absorption, and about 20% made up from lime addition. manner, returning spent reagent to the Thames. Subsequent programs to prevent water and air pollution supported by Imperial Chemicals Industries L t d . , British Power Authority consultants, and Howden Construction Co. led to the development closed-loop, lime-based, sulfur dioxide removal system. of a These types of
The process operated in an open-loop
systems were installed in 1935 at the Swainsea and in 1937 at the Fulham power plants. They operated successfully until World War II when they were shutdown because the vapor plumes provided aerial guidance to the Luftwaffe. For the next 20 yrs no full-scale development work was performed in this area. In fact, during the mid-sixties, there were several steps backward when initial U.S. sulfur dioxide control systems started up and failed. For example, in the boiler injection of limestone followed by wet scrubbing, problems resulted from boiler and preheater rather than flue gas scrubbing. 120 In Sulfur Removal and Recovery; Pfeiffer, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1975. pluggage
10.
ATKINS
Lime-Limestone Status
Flue Gas
Scrubbing
121
Current
Industry
D u r i n g the last 3 yrs m o r e progress has b e e n m a d e i n c a l c i u m s c r u b b i n g t e c h n o l o g y t h a n d u r i n g the p r e c e d i n g q u a r t e r of a c e n t u r y . 7600 M W u n d e r c o n s t r u c t i o n ( 2 ) . Prese n t l y 2500 M W of c a l c i u m - b a s e d scrubbers are o p e r a t i n g w i t h a n o t h e r M a n y of the i n i t i a l l y i n s t a l l e d u n i t s e x p e r i e n c e d difficulties, b u t the n e w e r installations h a v e p e r f o r m e d better as the p o l l u t i o n c o n t r o l i n d u s t r y has g a i n e d confidence a n d experience. E P A and pollution industry-supported development programs have c o n f i r m e d m a n y of the process constraints e s t a b l i s h e d d u r i n g the o r i g i n a l H o w d e n - I C I projects ( 3 ) . T h i s is not to say that w e h a v e m a d e a f u l l Howc i r c l e a n d h a v e l e a r n e d no m o r e t h a n w a s a v a i l a b l e 25 yrs ago. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch010 search results, w e w o u l d p r o b a b l y b e f u r t h e r a h e a d t o d a y .
ever, i f our i n i t i a l d e v e l o p m e n t p r o g r a m s h a d b e e n b a s e d o n p r i o r r e T h e major i m p r o v e m e n t s i n c u r r e n t processes result f r o m the a p p l i c a t i o n of m o d e r n t e c h n o l o g y a n d o p e r a t i n g t e c h n i q u e s to e x t e n d system r e l i a b i l i t y . ResearchCottrelP s Status I n t h e mid-1960's R e s e a r c h - C o t t r e l l entered the s u l f u r d i o x i d e c o n t r o l field as a n expert i n p a r t i c u l a t e c o l l e c t i o n b u t as a n o v i c e i n gaseous removal. I n i t i a l investigations u s e d a flooded disc s c r u b b e r (FDS), w h i c h is essentially a h i g h e n e r g y v e n t u r i r e q u i r i n g 8 - 1 0 i n . w.c. pressure d r o p for 4 0 - 6 0 % s u l f u r d i o x i d e r e m o v a l . I n s t a l l i n g a series of F D S ' s to i m p r o v e a b s o r p t i o n efficiency r e q u i r e d excessive pressure losses. w i t h a p a c k e d t o w e r to increase s u l f u r d i o x i d e r e m o v a l at pressure drops. T h e p i l o t p l a n t studies started i n 1966 a n d h a v e c o n t i n u e d ever since. P i l o t units h a v e b e e n i n s t a l l e d at the T i d d S t a t i o n of A m e r i c a n E l e c t r i c P o w e r , the C h o l l a S t a t i o n of A r i z o n a P u b l i c Service, the B i g B r o w n S t a t i o n of Texas U t i l i t i e s , a n d Res ear c h - C o t t r ell's F i n d e r n e R e s e a r c h facility. D e v e l o p m e n t studies h a v e b e e n s u p p o r t e d b y E P A , b y joint 5,6). efforts w i t h utilities, a n d b y this c o m p a n y (4, Therefore, R e s e a r c h - C o t t r e l l b e g a n investigations of the F D S i n c o m b i n a t i o n moderate
A s a d i r e c t result of this p i l o t effort, a w e t t e d film p a c k i n g was f o u n d w h i c h exhibits excellent s u l f u r d i o x i d e a b s o r p t i o n w i t h a n e x c e p t i o n a l l y l o w pressure d r o p . T h i s p a c k i n g has o u t s t a n d i n g mass transfer c h a r a c surface area. T h e packing developed by teristics a n d h i g h specific r e m o v a l system. L a s t O c t o b e r R e s e a r c h - C o t t r e l l started u p its first gas c l e a n i n g syst e m , a 115 M W limestone wet s c r u b b i n g system at A r i z o n a P u b l i c Service's C h o l l a p l a n t . I n this u n i t p a r t i c u l a t e a n d s u l f u r d i o x i d e are
M u n t e r s C o r p . is a k e y element i n the limestone-based s u l f u r d i o x i d e
122
SULFUR
REMOVAL
AND RECOVERY
r e m o v e d b y a F D S - p a c k e d t o w e r arrangement.
B e c a u s e of the results
o b t a i n e d at this c o m m e r c i a l f a c i l i t y a n d f r o m the p i l o t units, the A r i z o n a P u b l i c S e r v i c e a w a r d e d a n a d d i t i o n a l contract for gas c l e a n i n g e q u i p m e n t o n a n e w 250 M W b o i l e r . I n a d d i t i o n , the c o m p a n y is e n g i n e e r i n g 1900 M W of s u l f u r d i o x i d e r e m o v a l e q u i p m e n t for several m a j o r s o u t h w e s t e r n utilities. R e s e a r c h - C o t t r e l l r e a l i z e d that t h e i n d u s t r i a l a n d u t i l i t y m a r k e t s r e q u i r e d different types of s u l f u r d i o x i d e r e m o v a l e q u i p m e n t . d i o x i d e r e m o v a l t e c h n o l o g y i n the U . S . a n d C a n a d a . B a h c o (7, 8,9). Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch010 Therefore, technology it c o n t r a c t e d w i t h A b B a h c o V e n t i l a t i o n of S w e d e n to m a r k e t t h e i r s u l f u r is p a r t i c u l a r l y a p p l i c a b l e to i n d u s t r i a l b o i l e r a n d process a p p l i c a t i o n s T h e first U . S . B a h c o i n s t a l l a t i o n w i l l h a n d l e seven stoker-type b o i l e r s at the R i c k e n b a c k e r A i r F o r c e B a s e i n C o l u m b u s , O h i o . Comparison of LimeLimestone Wet Scrubbing with Other Systems
S i n c e the u t i l i t y i n d u s t r y represents the major m a r k e t for s u l f u r d i o x i d e c o n t r o l systems, it w a s necessary to d e v e l o p a s i m p l e system w h i c h w o u l d not r e q u i r e a lot of a t t e n t i o n , be i n e x p e n s i v e to operate, h a v e m o d e r a t e c a p i t a l r e q u i r e m e n t s , a n d not take effort a w a y f r o m t h e i r p o w e r p r o d u c i n g f u n c t i o n . C a l c i u m - b a s e d s c r u b b i n g processes meet a l l of these requirements. I n a d d i t i o n , the c a l c i u m reagents are i n e x p e n s i v e a n d f o r m r e l a t i v e l y i n s o l u b l e r e a c t i o n p r o d u c t s w h i c h c a n be d i s p o s e d of i n s a n i t a r y landfills a n d s l u r r y p o n d s . T h e d i s a d v a n t a g e of c a l c i u m - b a s e d t e c h n o l o g y is the l o w salt s o l u b i l i t y w h i c h necessitates the use of v e r y large a b s o r b i n g surface areas, high liquid flow rates, a n d g o o d p H c o n t r o l to p r e v e n t s c a l i n g a n d p l u g g i n g . M o s t recent t e c h n o l o g i c a l advances are i n the areas of c a l c i u m salt scale p r e v e n t i o n a n d c o n t r o l l e d c r y s t a l l i z a t i o n . S o l u b l e - b a s e d systems h a v e better a b s o r p t i o n c a p a b i l i t i e s a n d l i m i t e d scaling and p l u g g i n g problems. H o w e v e r they h a v e p r o b l e m s associated T h e waste d i s p o s a l w i t h s o l u b l e salt d i s p o s a l a n d h i g h e r reagent costs. problems have limited their application. B y - p r o d u c t processes h a v e the advantages of s o l u b l e - b a s e d systems b u t h a v e p r o b l e m s associated w i t h m o r e c o m p l e x o p e r a t i o n , i n c r e a s e d c a p i t a l a n d o p e r a t i n g costs, a n d the n e e d to d e v e l o p b y - p r o d u c t m a r k e t s . Therefore, R e s e a r c h - C o t t r e l l i n i t i a l l y chose to d e v e l o p calcium-based s c r u b b i n g t e c h n o l o g y to best m e e t the e x i s t i n g needs of its customers. System Description
F i g u r e 1 illustrates the c o m p o n e n t s of a t y p i c a l c a l c i u m - b a s e d s u l f u r d i o x i d e s c r u b b i n g system. F l u e gases enter a q u e n c h i n g section w h e r e
10.
ATKINS
Lime-Limestone
Flue Gas Scrubbing
123
Treated Gas Stack
Reheater
4
Mist Eliminator i Sulfur Dioxide Absorber Water
Dirty Stack. Gases
Quencher and Particulate Scrubber
Calcium Reagent
Settling Tank
Scrubber Tank
Absorber Tank
Vacuum Filtration
CaSOi
Fly Ash Waste Disposal Figure 1. Typical calcium-based sulfur dioxide scrubbing system CaS0
3
the gas is c o o l e d a n d p a r t i c u l a t e a n d some s u l f u r d i o x i d e r e m o v a l takes place. T h e q u e n c h e d gas t h e n enters t h e a b s o r p t i o n section w h e r e the F i n a l l y a m i s t e l i m i n a t o r removes T h e c l e a n e d gas is r e h e a t e d a n d r e t u r n e d r e m a i n i n g s u l f u r d i o x i d e is r e m o v e d . w a t e r a n d reagent droplets. to the stack.
124
SULFUR
REMOVAL
AND RECOVERY
C a l c i u m reagent is a d d e d to the absorber t a n k a n d p u m p e d to the s u l f u r d i o x i d e absorber. M o s t of the spent reagent is r e t u r n e d to the a b sorber tank, a n d p a r t is p r o v i d e d as reagent m a k e - u p to the q u e n c h e r system. T h e spent q u e n c h e r reagent, c o n t a i n i n g p a r t i c u l a t e a n d r e a c t i o n salts, is r e m o v e d f r o m the process as a s l u d g e b l o w d o w n . a d d e d p r i m a r i l y as m i s t e l i m i n a t o r w a s h . U s i n g this g e n e r a l a p p r o a c h , several sulfur d i o x i d e r e m o v a l systems have been developed. F i g u r e 2 illustrates t h e C h o l l a sulfur d i o x i d e r e The spent m o v a l system w h e r e a m o d e r a t e e n e r g y s c r u b b e r is u s e d for p a r t i c u l a t e r e m o v a l , gas q u e n c h i n g , a n d i n c i d e n t a l sulfur d i o x i d e r e m o v a l . p a c k e d t o w e r is the m a j o r sulfur d i o x i d e a b s o r p t i o n d e v i c e . Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch010 reagent f r o m the p a c k e d - t o w e r system. reagent is s u p p l i e d to the p a c k e d t o w e r , a n d the F D S receives c u r r e n t to gas flow for m a x i m u m u t i l i z a t i o n . Make-up Make-up w a t e r , to c o m p e n s a t e for e v a p o r a t i o n losses a n d s l u d g e b l o w d o w n , is
T h u s reagent flow is c o u n t e r -
INLET GAS *
REHEATER MAKE-UP WATER PACKED TOWER
FDS
SCRUBBER
>
MAKE-UP WATER
TO SLUDGE DISPOSAL
y
FDS SLURRY TANK TOWER TANK
Figure 2.
Process flow diagram
R e s e a r c h - C o t t r e l l is also s u p p l y i n g a gas c l e a n i n g system u s i n g a n electrostatic p r e c i p i t a t o r for d r y p a r t i c u l a t e c o l l e c t i o n f o l l o w e d b y m u l t i - s t a g e gas l i q u i d contactor for sulfur d i o x i d e r e m o v a l . The stage is a c y c l o n i c q u e n c h e r for gas s a t u r a t i o n a n d m o d e r a t e the m a j o r s u l f u r d i o x i d e a b s o r p t i o n takes p l a c e . a p p l i e d c o u n t e r c u r r e n t to t h e gas flow. a first
sulfur
d i o x i d e a b s o r p t i o n f o l l o w e d b y a spray a n d p a c k e d - t o w e r section w h e r e A g a i n the reagent is
10.
ATKINS
Lime-Limestone
Flue Gas
Scrubbing
125
Process
Chemistry
T h e c h e m i s t r y i n v o l v e d i n l i m e - l i m e s t o n e s c r u b b i n g is v e r y c o m p l e x because of the l i m i t e d s o l u b i l i t y of the n u m e r o u s reagents a n d r e a c t i o n products. Reagent: F l y ash: T h e major c o m p o n e n t s a r e : Ca, Mg, C 0 , O H
3 2 3 L 2 2 2
F l u e gas: S 0 , S 0 , CO >, 0 , N O , N 0 , N N a , C l , K , Fe, C a , M g , Si
T h e m a i n reactions i n c a l c i u m b a s e d s c r u b b i n g are: 1. D i f f u s i o n of s u l f u r d i o x i d e f r o m the gas phase into the l i q u i d phase, S0 (g) < = > S0 (aq)
2 2
(1)
2. H y d r o l y s i s to f o r m sulfurous a c i d , bisulfite, sulfite, a n d h y d r o g e n ions, S0 (aq) +

2 3
H 0 * H S 0
2 2
<= H + +
HS0 ~
3
(2) (3)
H S 0 - + H + +
SOr
3. D i s s o l u t i o n a n d h y d r a t i o n of l i m e or limestone i n a n a c i d m e d i u m c o n t a i n i n g c a r b o n d i o x i d e f r o m the flue gas to f o r m c a l c i u m a n d b i c a r b o n a t e ions, C a O (S) + Ca(OH) (aq)

2
H 0 <= C a ( O H ) ( a q )
2 2
(4)
3
C0 (aq) < = > CaC0 (aq)

2 3
+
3 2
H 0
2
(5) (6) (7) (8)
CaC0
2
(S) <= C a C 0 ( a q ) C0
3 2
< = > Ca + +
2 3
C0
Ca + +
" +
2 +
H + <= C a H C 0 + + HCOr
C a H C O , + + C a
4. R e a c t i o n of c a l c i u m ions f r o m c a l c i u m oxide, c a l c i u m h y d r o x i d e , or c a l c i u m c a r b o n a t e w i t h sulfite ions f r o m s u l f u r i c a c i d to f o r m a n d p r e c i p i t a t e c a l c i u m sulfite. Ca

2 +
S O , " < C a S 0
2
(9)
T h e r e is d a t a i n d i c a t i n g that the h y d r a t i o n of s u l f u r d i o x i d e to s u l furic acid, H , and

+
HSO3", the
and S 0
3 2
d i s s o c i a t i o n of H S 0 " to
3
SO3", the
2
2 +
reaction
of l i m e a n d limestone i n a n a c i d i c m e d i u m to f o r m C a final r e a c t i o n of C a reactions (10).

2 +
ions, a n d t h e
" ions to p r e c i p i t a t e c a l c i u m sulfite are r a p i d
T h e rate c o n t r o l l i n g m e c h a n i s m s are, therefore, either
126
SULFUR
REMOVAL
AND
RECOVERY
gas or l i q u i d diffusion, h y d r a t i o n of c a l c i u m oxide, or d i s s o l u t i o n of the c a l c i u m c a r b o n a t e o r c a l c i u m h y d r o x i d e salts. I n most cases, the gas p h a s e mass transfer s u l f u r d i o x i d e a n d the source of c a l c i u m reagent, its i n t r o d u c t i o n i n t o t h e system, a n d its d i s s o l u t i o n are the c o n t r o l l i n g reactions. R e a c t i o n rates are i n c r e a s e d The solid-phase by m i n i m i z i n g the g a s - l i q u i d interface resistance, m a x i m i z i n g contact surface area, a n d i n c r e a s i n g d i s s o l u t i o n rates. source is i m p o r t a n t i n this c o n s i d e r a t i o n . carbonate (limestone) calcium Naturally occurring calcium H o w e v e r , freshly
reacts s l o w l y w i t h w e a k acids.
p r e c i p i t a t e d c a l c i u m c a r b o n a t e f o r m e d b y c a r b o n a t i o n of c a l c i u m h y d r o x i d e w i t h the c a r b o n d i o x i d e f r o m the flue gas has a h i g h e r specific surface area t h a n limestone a n d dissolves faster. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch010 W h e n carbon dioxide is not present, a n even faster r e a c t i o n occurs b e t w e e n c a l c i u m h y d r o x i d e a n d s u l f u r d i o x i d e since c a l c i u m h y d r o x i d e has a h i g h e r s o l u b i l i t y t h a n c a l c i u m carbonate. I n c r e a s i n g gas v e l o c i t y a n d reactant contact area increases the gas phase s u l f u r d i o x i d e mass transfer rate. R e a c t a n t c o n tact area is e n h a n c e d b y s m a l l e r reagent p a r t i c l e size a n d h i g h e r reagent l i q u i d rates, s t o i c h i o m e t r y , c a l c i u m salt concentrations, a n d l i q u i d h o l d - u p . A t l o w s u l f u r d i o x i d e concentrations is the c o n t r o l l i n g r e a c t i o n . ( < 1000 p p m ) gas diffusion T h e r e is n e g l i g i b l e l i q u i d - p h a s e resistance
because sufficient absorbent is b e i n g d i s s o l v e d to react w i t h the s u l f u r d i o x i d e . H o w e v e r , at i n c r e a s e d s u l f u r d i o x i d e concentrations l i q u i d - p h a s e resistance m a y b e c o m e c o n t r o l l i n g . I n this case the rate of absorbent d i s s o l u t i o n m a y not increase fast e n o u g h to react w i t h the s u l f u r d i o x i d e . Commercial System Design
S u l f u r d i o x i d e a n d p a r t i c u l a t e r e m o v a l are m o r e easily c o n t r o l l e d t h a n the s c a l i n g a n d p l u g g i n g w h i c h reduces system a v a i l a b i l i t y . reliability was of p a r a m o u n t i m p o r t a n c e i n the d e s i g n of Information C o ttrell's v a r i o u s s u l f u r d i o x i d e c o n t r o l systems. System Researchdeveloped from by defined.
i n the H o w d e n - I C I p r o g r a m s p r o v i d e d the t e c h n i c a l b a c k g r o u n d w h i c h the areas of c o n c e r n c o u l d be i n v e s t i g a t e d a n d better H o w d e n - I C I a n d i n v e s t i g a t e d b y R e s e a r c h - C o t t r e l l i n its programs (3).
R e c e n t E P A studies h a v e s u p p o r t e d m a n y of the concepts expressed
development
T h e areas w h i c h w e r e f o u n d to be p a r t i c u l a r l y i m p o r t a n t a r e : a b s o r p t i o n surface selection, c o n t r o l of reagent d e s u p e r s a t u r a t i o n , reagent p H profiles, a n d c l o s e d - l o o p w a t e r b a l a n c e . Absorption Surface Selection
I n the selection of the a b s o r p t i o n surface the f o l l o w i n g r e q u i r e m e n t s must be considered:
10.
ATKINS
Lime-Limestone
Flue
Gas
Scrubbing
127
1. P r o v i d e e v e n l i q u i d a n d gas flow d i s t r i b u t i o n 2. B e n o n - c h o k i n g w i t h r e g a r d to solids 3. H a v e g o o d a b s o r p t i o n characteristics 4. H a n d l e a w i d e r a n g e of l i q u i d rates w i t h o u t 5. H a v e a d e q u a t e gas t u r n d o w n characteristics 6. H a v e a l o w pressure d r o p 7. H a v e a h i g h surf a c e / v o l u m e ratio 8. H a v e a resistance to scale f o r m a t i o n 9. H a v e reasonable c a p i t a l a n d o p e r a t i n g film packing. economics. wetted flow
3 2
flooding
R e s e a r c h - C o t t r e l l ' s process uses a M u n t e r s ' p o l y p r o p y l e n e
T h e cross flow flutes a i d i n u n i f o r m l i q u i d a n d gas
d i s t r i b u t i o n . T h e p a c k i n g has a specific surface area of 4 0 - 7 0 f t / f t g o o d a b s o r p t i o n characteristics. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch010 Table I.
and
Calculated Flooding Points for H i g h Capacity Packings Liquid/Gas Ratio (gal/1000 ACF) Intalox Saddles 420 90 22
Gas Velocity (ft/sec) 4 8 12 24
Munters Packing 690 190 85 16
Pall Rings 580 130 47
T a b l e I lists c a l c u l a t e d flooding mass velocities for M u n t e r s a n d other h i g h c a p a c i t y p a c k i n g s . M u n t e r s ' p a c k i n g c a n tolerate a w i d e r r a n g e of conditions without flooding. T a b l e I I lists the mass transfer (6). coefficients o b t a i n e d i n the e x p e r i m e n t a l w o r k w i t h M u n t e r s p a c k i n g Control of Reagent Desupersaturation
T h e reagent stream m u s t b e c o n t r o l l e d to p e r m i t c a l c i u m salt d e s u p e r s a t u r a t i o n e x t e r n a l to the s c r u b b e r a n d absorber w h i l e m a i n t a i n i n g a d e q u a t e c o n c e n t r a t i o n levels for g o o d a b s o r p t i o n efficiency. d o this a reagent stream c o n t a i n i n g 8 - 1 5 % p o r t i o n is c o m p o s e d of some fly ash components I n o r d e r to solids is c i r c u l a t e d . T h e s o l i d but mainly calcium
carbonate, sulfite, a n d sulfate. S u l f u r d i o x i d e r e m o v a l efficiency dictates the carbonate l e v e l . Sulfite crystals enhance a n d c o n t r o l d e s u p e r s a t u r a t i o n of c a l c i u m sulfate w h i l e p r o v i d i n g n u c l e a t i o n sites for c r y s t a l g r o w t h (12). I n the absorber tank, t i m e for e x t e r n a l d e s u p e r s a t u r a t i o n is p r o v i d e d a n d fresh reagent is a d d e d to raise the p H a n d t h e r e b y p r o m o t e s a t u r a t i o n of the spent reagent stream. T h e d e l a y t a n k p r o v i d e s t i m e for c r y s t a l g r o w t h a n d sulfite a n d sulfate salt p r e c i p i t a t i o n . desupercontact
128
SULFUR
REMOVAL
A N D RECOVERY
Table II. Mass Transfer Coefficients with H i g h Sulfur CoalLimestone Scrubbing Sulfur Dioxide Inlet Concentration (ppm) 1000 1000 1000 1600 1600 1600
a
Limestone Stoichiometry
(%)
100 120 140 100 120 140
Mass Transfer Coefficient (lb-moles/hr sqft atm) .385 .510 .843 .252 .308 .385
Packing = 68 sq ft/cu ft, height = 5 ft, G = 70 lb-moles/hr sq ft, = 1.0 atm, Limestone grind = 75%-200 mesh, L / G = 45 gals M C F .
Reagent pH Profiles L i q u i d reagent p H profiles m u s t b e c o n t r o l l e d to p r e v e n t m a j o r p H changes i n t h e s c r u b b e r w h i c h w i l l change salt s a t u r a t i o n levels a n d cause p r e c i p i t a t i o n a n d e v e n t u a l scale f o r m a t i o n . T h e R e s e a r c h - C o t t r e l l limestone process controls t h e q u a n t i t y o f s u l f u r d i o x i d e r e m o v e d i n e a c h a b s o r p t i o n stage a n d t h e contact t i m e f o r e a c h p r o c e s s i n g step, m a k i n g it possible to m a i n t a i n t h e p H a n d s u l f u r d i o x i d e c o n c e n t r a t i o n w i t h i n d e s i r e d levels. B y m e a s u r e m e n t of the mass flow of s u l f u r d i o x i d e i n t o t h e s c r u b b i n g system, reagent a d d i t i o n is c o n t r o l l e d at a b o u t 9 0 % u t i l i z a t i o n . A s a result, t h e s l u r r y e n t e r i n g t h e s c r u b b e r c i r c u i t has a p H of 6.5 a n d exists at a b o u t a p H 5.8. T h e s l u r r y p H is u s e d o n l y to m o n i t o r t h e process a n d n o t to c o n t r o l i t since t h e system is h i g h l y b u f f e r e d b y t h e a c t i o n of c a r b o n a t e - b i c a r b o n a t e system p H profiles a r e m o r e possible. Water Balance Maintenance a n d s u l f i t e - b i s u l f i t e a n d does n o t react However, i n a lime-based scrubbing d i s t i n c t a n d some c o n t r o l schemes are r e a d i l y to reagent feed rate changes.
T h i c k e n i n g , filtration, a n d c e n t r i f u g a t i o n are g e n e r a l l y u s e d to r e d u c e the w a t e r content of c a l c i u m salts p r o d u c e d i n t h e process. Spent w a t e r Only w h i c h is saturated w i t h v a r i o u s salts is r e t u r n e d to t h e system. o p e r a t i o n leave t h e process. u s e d i n t h e system. P u m p seals a n d d e m i s t e r w a s h receive p r i o r i t y o n f r e s h w a t e r a d d i tions. I n t h e R e s e a r c h - C o t t r e l l process, t w o d e m i s t i n g stages insure a d e q u a t e m i s t r e m o v a l . W a t e r sprays are m o u n t e d b e l o w a n d a b o v e t h e
w a t e r c o n t a i n e d i n t h e effluent sludge a n d e v a p o r a t e d i n t h e q u e n c h i n g T h e q u a n t i t y of m a k e - u p w a t e r is v e r y l i m i t e d , a n d c o n s i d e r a b l e t h o u g h t must b e g i v e n to w h e r e a n d h o w i t is
10.
ATKINS
Lime-Limestone Flue Gas Scrubbing
129
first demister to keep it free from salt deposits and to provide a relatively salt-free mist to the second demisting stage. Conclusion T h e pollution control industry has made significant technical contributions to the sulfur dioxide control field. As we gain more experience, process reliability will increase and operating and investment costs will decrease. Customer acceptance will improve when it is realized that pollution control equipment permits greater flexibility in fuel selection and possibly reduced fuel expenses. Prior to the energy crisis, it could be demonstrated that the cost differential between high and low sulfur fuels would balance the increased Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch010 expenses for operating pollution control equipment. W i t h the current erratic fuel pricing situation it is difficult to make such a comparison. However, Research-Cottrell offers processes capable of meeting federal particulate and sulfur dioxide requirements and thereby allows the user more freedom in his fuel selection. Literature Cited
1. Pearson, J. L . , Nonhebel, G . , Ulander, P. H . N . , J. Inst. Elec. Eng. (1935) 77, (463), 1-48. 2. Ponder, W . H . , "Status of Flue Gas Desulfurization Technology for Power Plant Pollution Control," Thermal Power Conference, Washington State University, Oct. 4, 1974. 3. E P A , "Preliminary Report of Test Results From The E P A Alkali Scrubbing Test Facilities at the T V A Shawnee Power Plant and at Research Triangle Park," December 19, 1973. 4. Gleason, R . J., McKenna, J. D . , "Scrubbing of Sulfur Dioxide From a Power Plant Flue Gas," 69th National Meeting, AIChE, May 1971. 5. Gleason, R . J., Heacock, F . , "Limestone Wet Scrubbing of Sulfur Dioxide From Power Generation Flue Gas for High and Low Sulfur Fuels," 164th National Meeting, ACS, September 1972. 6. Gleason, R . J . , "Pilot Scale Investigation of a Venturi-Type Converter for Removal of SO by the Limestone Wet-Scrubbing Process," E P A Contract EHS-D-71-24, October 1971. 7. McKenna, J . D., Atkins, R . S., International Lime/Limestone Symposium, 2nd, New Orleans, La. (November 1971). 8. Atkins, R . S., McKenna, J. D., Power Eng. (May 1972) 50-51. 9. Atkins, R . S., ADVAN. CHEM. SER. (1973) 127, 161-173. 10. Slack, . V., Falkenberry, H . L . , Harrington, R . E . , "Control of Sulfur Oxides in Stack Gases," 17th National Meeting, AIChE, August 1971. 11. Lessing, R . , J. Soc. Chem. Ind. London Trans. Commun. (November 1938), 373-388.
2
R E C E I V E D April 4,
1974
11
L i m e - L i m e s t o n e S c r u b b i n g : Factors A f f e c t i n g the C o n c e n t r a t i o n o f Sulfur D i o x i d e - A b s o r b i n g Species i n S o l u t i o n
J O H N D. H A T F I E L D and A R C H I E V. S L A C K Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch011 National Fertilizer Development Center, Tennessee Valley Authority, Muscle Shoals, Ala. 35660
The basicity of the aqueous phase in lime and limestone slurries for scrubbing a sulfur dioxide stack gas is increased by increasing the magnesium content in solution and by other factors less subject to control. The computer simulation study of the aqueous phase of the system -Na O-SO2-SO -CO2-HCl-N O -H O
2 3 2 5 2
CaO-MgOvariations dioxide and
included
in the contents of magnesium oxide, sodium oxide, and hydrochloric acid at various values of pH and carbon salts CaSO 0.5H O
2
partial pressures and for several degrees of saturation of the

3
and
CaSO
2H O.
2
Sodium
chloride largely offset each other. Complex
interrelations
3 2
between the pH, the degree of saturation of CaSO 0.5H O, and the carbon dioxide partial pressures occur at constant composition solutions. of other components, giving essentially isobasic
* *1 removal of sulfur dioxide from stack gas by scrubbing with a

A
suspension of lime or limestone involves dissolution, precipitation,

2 2
and oxidation in a nine-component system: C a O - M g O - N a 0 - S 0 - S O a CO2-HCI-N2O5-H2O. Other components also are present, but their concentrates are not significant. A l l alkali componentssodium, potassium, and ammonium oxidesare considered as sodium oxide. Lowell ( 1 ) has summarized the present knowledge of the chemical data for the aqueous system including parameters for activity coefficients, solubility products, Henry's L a w constants, and ionization constants for aqueous species. This paper is concerned with the basicity of the aqueous phase of the system, because the mass transfer of sulfur dioxide from the stack 130 In Sulfur Removal and Recovery; Pfeiffer, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1975.
11.
HATFIELD
AND SLACK
Lime-Limestone
Stubbing
131
gas to the l i q u i d is d e p e n d e n t l a r g e l y o n t h e a v a i l a b i l i t y of b a s i c species to a b s o r b the a c i d i c gas. A c o m p u t e r s i m u l a t i o n s t u d y w a s m a d e of f a c tors t h a t affect t h e t o t a l b a s i c i t y of t h e aqueous phase. Species i n s o l u t i o n are c o n s i d e r e d b a s i c to s u l f u r d i o x i d e i f t h e y w i l l react w i t h s u l f u r d i o x i d e to f o r m a bisulfite ( H S 0 ~ )
3
species.
I n the
n i n e - c o m p o n e n t system u n d e r c o n s i d e r a t i o n t h e f o l l o w i n g reactions m a y occur:
CaOH+ CaS0 + S0 CaC0 + 2S0 CaHC0 + MgOH+ MgS0 + S0 MgC0 + 2S0 MgHC0 NaOH NaC0 ~ + 2S0 NaHC0
3 2 3 2 3 3 2 3 2 3 + 3 2 3
OH- + S0 SO3- + S 0 + H 0 HCO3- + S 0 CO3-2 + 2 S 0 + H 0

2 2 2
2
-> -> -> ->

-> -> -> - -> - -> -> -> -* ->
HSO32HSO3HSO3- + C 0 2HS0 - + C 0
3
2
2
(la) (lb) (lc)

(Id) (le) (If) (lg) (lh) (li) (lj) (lk) (11) (lm) (In) (lo)
+ + + + + + + + + + +
S0 H 0 H 0 S0 S0 H 0 H 0 S0 S0 H 0 S0
2 2 2 2 2
2 2
HSO3- + 2HSO3- + 2HS0 - + HSO3- + HS0 - + 2HSO3- + 2HSO3- + HSO3- + HSO3- + 2HS0 ~ + HS0 - +
3 3 3 3
Ca+ Ca+ Ca+ + C 0 Ca+ + C 0 Mg+ Mg+ Mg+ + C 0 Mg+ + C 0 Na+ Na+ + C 0 Na+ + C 0
2 2 2 2 2 2 2 2 2 2 2
T h u s , i f t h e t o t a l n u m b e r of e q u i v a l e n t s of b a s i c species i n a g i v e n v o l u m e of l i q u i d is e q u a l to t h e n u m b e r of moles of s u l f u r d i o x i d e i n t h e v o l u m e of gas c o n t a c t e d b y t h e l i q u i d , the s t o i c h i o m e t r y is satisfied a n d there s h o u l d b e as c o m p l e t e s u l f u r d i o x i d e a b s o r p t i o n as mass transfer a l l o w s , p r o v i d e d t h e s u l f u r d i o x i d e p a r t i a l pressure of t h e r e s u l t i n g s o l u t i o n is sufficiently l o w . System CaO-S0 ~SO -C0 -H 0
2 s 2 2
T o define a set of v a r i a b l e s r e p r e s e n t i n g t h e n i n e - c o m p o n e n t system, equilibrium was studied i n the C0 -H 0.

2 2
five-component
system, C a O - S 0 - S 0 2 3
I n this system, a k n o w l e d g e of f o u r properties is sufficient to
define the aqueous phase c o m p o s i t i o n a n d t h e c o n c e n t r a t i o n of a l l a q u e ous species. T h e s e properties m a y b e chosen f r o m t h e t o t a l c o n c e n t r a t i o n of c o m p o n e n t s , t h e activities of a n y aqueous species, t h e degrees of s a t u r a t i o n of a n y solids, or t h e p a r t i a l pressures of a n y g a s e s p r o v i d e d n o t w o chosen properties i n v o l v e a single c o m p o n e n t solely. E x p e r i e n c e i n d e t e r m i n i n g l i q u i d phase p r o p e r t i e s f r o m p i l o t p l a n t samples at v a r i o u s points i n the l i m e s t o n e s c r u b b i n g system i n d i c a t e d that the p H v a r i e d f r o m 4.5 to 8; the degree of s u p e r s a t u r a t i o n of C a S 0 v a r i e d f r o m 2 to 12, a n d of C a S 0
4 2 2 3
0 . 5 H O , Si,
2
2 H 0 , S , f r o m 1 to 2; a n d the p a r t i a l
pressure of c a r b o n d i o x i d e v a r i e d f r o m v e r y l o w values over p o n d s a n d h o l d tanks to a b o u t 0.15 a t m i n t h e stack gas. W e chose, therefore, to
132 Table I.
SULFUR
REMOVAL
AND
RECOVERY
Liquid Phase Compositions in the Pco2 (atm)
mmoles/kg H 0
2
0.0003 SO* 19.41 19.83 18.38 19.63 28.69 29.03 27.74 28.87 22.06 23.96 23.95 22.97 16.15 35.06 23.72 pH 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.0 7.0 6.0 6.0 6.0 6.0 6.0
3 2 4 2
No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 a Si = a S = a
2
CaO 21.35 20.61 25.48 22.70 30.40 29.77 34.20 31.80 29.71 25.32 24.46 30.77 18.35 36.92 25.74
C a C a + 2 + 2 S 3 8
S0
Si* 2.0 2.0 8.0 8.0 2.0 2.0 8.0 8.0 4.0 4.0 1.0 16.0 4.0 4.0 4.0
s
2
BASE
3.26 0.907 11.74 3.60 2.79 0.845 10.46 3.36 14.10 1.41 0.705 10.64 3.13 2.49 2.78
2 0 5 H2 2 2 2
1.25 1.25 1.25 1.25 1.953 1.953 1.953 1.953 1.563 1.563 1.563 1.563 1.00 2.441 1.563
0.629 0.644 2.489 2.534 0.621 0.634 2.464 2.496 1.232 1.295 0.317 4.972 1.274 1.235 1.254
a o - a o - /#sp (CaSO 0.5H O) aH o /#sp (CaS0 2H 0)

2
fix the values of the p H of the s o l u t i o n , the values of S i a n d S f o r supers a t u r a t i o n of c a l c i u m sulfite a n d sulfate salts, a n d t h e p a r t i a l pressure of c a r b o n d i o x i d e at v a r i o u s levels. F i f t e e n solutions w e r e s i m u l a t e d at a c a r b o n d i o x i d e p a r t i a l pressure of 0.0003 a t m ( the n o r m a l c a r b o n d i o x i d e content of the earth's a t m o s p h e r e ) i n a B o x - t y p e c e n t r a l composite d e s i g n ( 2 ) i n t h e three v a r i a b l e s : p H , S i , a n d S . T h e s o l u t i o n c o m p o s i t i o n w a s
2
c a l c u l a t e d , a n d the contents of the components
c a l c i u m oxide, s u l f u r 1.0
d i o x i d e , a n d s u l f u r t r i o x i d e w e r e h e l d constant w h i l e the p a r t i a l pressure of c a r b o n d i o x i d e was i n c r e a s e d f r o m 0.0003 to 0.15 a n d a g a i n to (pure carbon dioxide). P o

C a
T h e results ( T a b l e I ) are r e p o r t e d i n terms of ( B A S E ) a n d s h o w the effect of i n c r e a s i n g

2
the s u m of a l l basic species

2
* constant c o m p o s i t i o n u p o n p H , S i , a n d S .
2
T h e fixed levels selected for p H , S i , a n d S
are l i s t e d i n c o l u m n s 5,
6, a n d 7 of T a b l e I for t h e a t m o s p h e r i c c o n d i t i o n s , i.e., w h e r e the p a r t i a l pressure of c a r b o n d i o x i d e , P o , is 0.0003 a t m . T h e c o m p o s i t i o n s of the

C 2
l i q u i d i n terms of concentrations of c a l c i u m oxide, s u l f u r d i o x i d e , a n d s u l f u r t r i o x i d e that satisfy these fixed levels of p H , S i , S , a n d P o

2 C C 2 2
are
g i v e n i n c o l u m n s 2, 3, a n d 4. T h e P o w a s i n c r e a s e d to 0.15 a n d 1.0 a t m , the contents of c a l c i u m o x i d e , s u l f u r d i o x i d e , a n d s u l f u r t r i o x i d e w e r e h e l d constant, a n d n e w values of p H , S i , a n d S first eight compositions

2
were calculated. of
The The the
sums of a l l b a s i c species, B A S E , are g i v e n i n c o l u m n s 8, 12, a n d 16. represent the f a c t o r i a l p o r t i o n ( c u b e )
d e s i g n ; the next six c o m p o s i t i o n s s h o w t h e v a r i a t i o n of e a c h v a r i a b l e to
11.
HATFIELD A N D SLACK
Lime-Limestone
Scrubbing
133
System C a O - S 0 - S O H ^ O : > - H 0 at 122F

2 2
Pco2
(atm)
0.15 pH 5.18 5.41 5.38 5.82 5.16 5.37 5.37 5.78 4.93 5.65 5.12 5.77 5.53 5.48 5.51
6
1.0 S"
2
BASE
pH 4.64 4.70 5.03 5.20 4.62 4.67 5.02 5.17 4.67 4.95 4.46 5.35 4.93 4.88 4.91
Si* 0.33 0.10 3.29 1.29 0.33 0.11 3.21 1.33 1.98 0.31 0.05 5.98 0.57 0.57 0.57
s
2
BASE
1.07 0.46 6.44 3.86 1.05 0.47 6.38 3.90 3.44 1.21 0.21 12.02 1.91 1.88 1.90
1.256 1.260 1.257 1.276 1.959 1.963 1.961 1.979 1.565 1.581 1.567 1.583 1.013 2.454 1.576
0.639 0.653 2.492 2.537 0.634 0.646 2.468 2.499 1.239 1.300 0.335 4.973 1.279 1.244 1.260
1.259 1.261 1.271 1.291 1.961 1.963 1.976 1.993 1.570 1.586 1.566 1.612 1.021 2.461 1.583
0.684 0.694 2.509 2.549 0.684 0.694 2.487 2.516 1.275 1.325 0.407 4.983 1.300 1.274 1.285
B A S E = millimoles/kg H 2 0 of total aqueous species that are basic to (see Equations l a - l o ) .
H S O 3
extreme levels ( o c t a h e d r o n ) ; a n d t h e last c o m p o s i t i o n is t h e center of the design. The at P c o =

2
d a t a i n T a b l e I s h o w a n excellent c o r r e l a t i o n ( F i g u r e 1) o f a l l 0.0003 a n d n o significant effect of p H , S , o r P o

2 C a t
the values of B A S E w i t h t h e degree of s u p e r s a t u r a t i o n of c a l c i u m sulfite

2
constant
c o m p o s i t i o n of c a l c i u m o x i d e , s u l f u r d i o x i d e , a n d sulfur t r i o x i d e u p o n t h e
134 s i m u l a t e d response, BASE.
SULFUR
REMOVAL
AND
RECOVERY
I n c r e a s i n g the p a r t i a l pressure of
carbon both
d i o x i d e at constant c o m p o s i t i o n of the other components decreases the p H a n d Si g r e a t l y , whereas the values of S only slightly. t i v e l y , w i t h increase i n P o
C 2
a n d B A S E are affected
F i g u r e s 2 a n d 3 s h o w t h e changes i n p H a n d Si, respec2
fo
v a r i o u s values of the v a r i a b l e s .
T h e effect of Si o n B A S E i m p l i e s the p r e d o m i n a n t influence at l o w P o

C 2
f the aqueous species c a l c i u m sulfite w h i c h reacts a c c o r d i n g
to
E q u a t i o n If. T h e aqueous e q u i l i b r i a C a + + S 0 - ?=* C a S 0 ^

2 3 2 3
CaS0
0 . 5 H O (s)
2
(2) K$, the

15
a m o n g ions, n e u t r a l species, a n d s o l i d i n v o l v e t w o constants. solubility product.
d i s s o c i a t i o n constant of the aqueous species c a l c i u m sulfite a n d K , Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch011 T a b l e I V - 2 of L o w e l l ( I ) . A t s a t u r a t i o n , Si =
the
T h e constants are n u m b e r e d i n the o r d e r l i s t e d i n 1.0, the a c t i v i t y of the

15 8
b a s i c species, c a l c i u m sulfite, equals t h e r a t i o K /K , of s a t u r a t i o n of C a S 0
w h i c h is i n d e -
p e n d e n t of p H or a n y other s o l u t i o n p r o p e r t y . A n increase i n the degree

3
0 . 5 H O causes a c o r r e s p o n d i n g increase i n t h e
2
a c t i v i t y of the aqueous species c a l c i u m sulfite, t h a t is

^ C a S 0
3
flCaSO.3
= Si
Ku/Kg
(3)
T h u s , the l i n e a r r e l a t i o n of B A S E w i t h Si s h o w n i n F i g u r e 1 is c a u s e d b y the increase i n t h e species c a l c i u m sulfite i n s o l u t i o n w h i c h is the p r e -
4 1
7 1
\ -\
\
02
04 06 Partial pressure of C0 . atm

2
08
10
Figure 2. Effect of C0 pressure on the pH of simuhted solutions in the system CaO-S0 -S0 -C0 -H 0. Numbers on curves indicate degree of supersaturation of CaSO 0.5H O, S when F = 0.0003.
2 2 3 2 2 3 2 C02
11.
HATFIELD
AND SLACK
Lime-Limestone
Scrubbing
135
d o m i n a n t b a s i c specie at l o w c a r b o n d i o x i d e p a r t i a l pressures. A s P c o c a l c i u m sulfite) species, C a C O P o

C a
increases at constant c o m p o s i t i o n , Si ( a n d , therefore, t h e a m o u n t of decreases b y b e i n g r e p l a c e d b y t h e b a s i c and C a H C 0

3 +
carbonate
. s t u d y s h o w that at l o w values of
T h e results of t h e
2
five-component
the factor Si is m o r e i m p o r t a n t t h a n p H i n d e t e r m i n i n g t h e b a s i c ( F i g u r e s 2 a n d 3 ) s h o w that a l l three factors are i m p o r t a n t i n c o r r e 2 H 0 , S , has n o a p p r e c i a b l e effect a n d c a n b e e l i m i n a t e d

2 2
species c o n c e n t r a t i o n . H o w e v e r , t h e interrelations b e t w e e n p H , Si, a n d P o

C 2
lations w i t h the b a s i c i t y of t h e s i m u l a t e d solutions. T h e d e g r e e of s a t u r a t i o n of C a S 0

4
from consideration.
T h e effect of the c a r b o n d i o x i d e p a r t i a l pressure
w o u l d b e e x p e c t e d to d e p e n d o n t h e l e v e l of Si, the p H , a n d t h e c o n c e n t r a t i o n of other cations that f o r m b a s i c c a r b o n a t e species i n s o l u t i o n . System CaO~MgO-Na 0~S0 --S0 -C0 -HCl-N 0 ~H 0
2 2 3 2 2 5 2
C h o i c e o f V a r i a b l e s . D e t e r m i n i n g the properties of t h e aqueous phase i n the f u l l system r e q u i r e s the same p r o c e d u r e , except t h a t e i g h t properties m u s t b e k n o w n . W e h a v e chosen to fix t w o q u a n t i t i e s i n o r d e r to r e d u c e t h e v a r i a b l e s to a m o r e m a n a g e a b l e n u m b e r f o r s t u d y . T h e fixed quantities w e r e s a t u r a t i o n w i t h g y p s u m (S m i n o r influence o n b a s i c i t y a n d N 0
2 5 2
1.0) because of its
10" e q u i v a l e n t s / k g w a t e r b e 6
136
SULFUR
REMOVAL
AND RECOVERY
cause n i t r a t e forms n o s u l f u r d i o x i d e r e a c t i n g species a n d its effect c o u l d b e e x p e c t e d to b e s i m i l a r to t h a t of c h l o r i d e . T h e six v a r i a b l e s chosen for s t u d y are s h o w n i n T a b l e I I . Table I I . Coded Factor xi X2 x x x
3
Six Variables in the F u l l System Coded Levels
Name pH s a t u r a t i o n degree of C a S 0 0.5H O, Si total M g ( m m / k g H 0 ) total N a (mm/kg H 0 ) total CI (mm/kg H 0 )

3 2 2 2 2
-2 5.0 0 0 0 0
-1 5.5 1 50 50 50 0.0003
0 6.0 2 100 100 100 0.075
1 6.5 3 150 150 150 0.15
2 7.0 4 200 200 200
xe
Pco2
(atm)
Experimental Design.
T h e Box-type central composite

5
design
(2) are
was u s e d f o r t h e first five factors, x i - x , w i t h e a c h test m a d e at a l l three levels of c a r b o n d i o x i d e p a r t i a l pressure, x .

6
T h e v a l u e s of B A S E
listed i n T a b l e I I I for the s i m u l a t e d solutions, a n d i n T a b l e I V the f r a c tions of B A S E c a u s e d b y m a g n e s i u m a n d s o d i u m species are g i v e n . I I I a n d I V , the five factors, x i - x , w e r e k e p t constant as P o
5 C
There
is a n i m p o r t a n t difference b e t w e e n these tables a n d T a b l e I. I n T a b l e s

2
was i n -
c r e a s e d f r o m 0.0003 to 0.075 a n d 0.15, a l l o w i n g the c o m p o s i t i o n to change. I n T a b l e I the c o m p o s i t i o n of c a l c i u m o x i d e , s u l f u r d i o x i d e , a n d s u l f u r t r i o x i d e w a s k e p t constant as P o

C 2
w a s i n c r e a s e d , a l l o w i n g the p r o p e r t i e s o n the b a s i c i t y w h e n t h e
of p H , S i , a n d S to change.
2
F i g u r e 4 shows the effects of p H a n d P o

C
degree of s u p e r s a t u r a t i o n of c a l c i u m sulfite is 2.0 a n d the contents of M g , N a , a n d C I e a c h are 100 m m o l e s / k g H 0 . T h e s e fixed c o n d i t i o n s are the
2
v a l u e s at the d e s i g n center a n d are i n the r a n g e t h a t occurs f r e q u e n t l y i n limestone scrubbing. T h e increase i n b a s i c i t y w i t h i n c r e a s e d P o

C 2
is
e x t r e m e l y great at h i g h p H , i n d i c a t i n g t h a t a d d i t i o n a l b a s i c
carbonate
species a d d g r e a t l y to the s u l f u r d i o x i d e a b s o r p t i o n c a p a c i t y at h i g h p H . I n c r e a s i n g t h e p a r t i a l pressure of c a r b o n d i o x i d e at constant p H , S i , a n d m a g n e s i u m content causes a v e r y s l i g h t decrease i n t h e c o n c e n t r a t i o n of t o t a l sulfite at a l l isopleths of p H . H o w e v e r , there is a 0 . 1 % increase i n c a l c i u m content at p H 5.0 a n d a 1 5 % increase at p H 7.0 at a s u p e r s a t u r a t i o n of 2.0 for c a l c i u m sulfite as P o
C 2
changes f r o m 0.0003 to 0.15 a t m .
T h e a d d i t i o n a l c a r b o n a t e t h a t goes i n t o s o l u t i o n also decreases the sulfate content to m a i n t a i n e l e c t r o n e u t r a l i t y a n d to satisfy the g y p s u m s a t u r a t i o n . F i g u r e 5 shows the effects at p H 6.0 o n the b a s i c i t y of e a c h of the v a r i a b l e s , S i , M g , N a , a n d C I , at t h r e e levels of P o .
C 2
I n e a c h case the
o t h e r v a r i a b l e s w e r e h e l d at t h e i r values c o r r e s p o n d i n g to the center of the d e s i g n . T h e effect of t h e s u p e r s a t u r a t i o n of c a l c i u m sulfite is l i n e a r
11.
HATFIELD A N D SLACK
Lime-Limestone
Scrubbing
137
Table III.
The Basicity of the Liquid Phase as Affected by Solution Properties at 1 2 2 F Properties

mmoles/kg H 0
2
BASE" CI 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 100 100 100 100 100 100 100 100 0 200 100
3
(mmoles/kg 0.075 1.006 4.351 2.235 5.608 1.812 5.651 4.468 8.372 1.154 4.571 2.647 6.106 1.978 5.868 4.947 8.907 0.862 4.674 1.739 5.554 1.548 5.639 3.663 7.788 0.991 4.588 2.145 5.762 1.753 5.808 4.266 8.369 1.966 15.360 1.294 5.088 1.792 4.915 2.834 3.547 3.628 2.826 3.221
H 0)
2
When P c o 2 (atm)
is
pH 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.0 7.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0
a b
Mg 1 1 3 3 1 1 3 3 1 1 3 3 1 1 3 3 1 1 3 3 1 1 3 3 1 1 3 3 1 1 3 3 2 2 0 4 2 2 2 2 2 2 2 50 50 50 50 150 150 150 150 50 50 50 50 150 150 150 150 50 50 50 50 150 150 150 150 50 50 50 50 150 150 150 150 100 100 100 100 0 200 100 100 100 100 100
Na 50 50 50 50 50 50 50 50 150 150 150 150 150 150 150 150 50 50 50 50 50 50 50 50 150 150 150 150 150 150 150 150 100 100 100 100 100 100 0 200 100 100 100
0.0003 0.641 0.661 1.870 1.934 1.395 1.425 4.053 4.178 0.780 0.804 2.272 2.353 1.556 1.586 4.525 4.654 0.447 0.465 1.322 1.352 1.104 1.132 3.220 3.311 0.598 0.618 1.752 1.805 1.313 1.342 3.827 3.934 1.837 2.004 0.007 3.811 0.658 3.489 1.531 2.250 2.401 1.448 1.939
0.15 1.373 8.070 2.602 9.312 2.230 9.900 4.887 12.592 1.531 8.359 3.022 9.880 2.403 10.171 5.370 13.181 1.279 8.935 2.155 9.809 1.993 10.176 4.106 12.296 1.387 8,588 2.541 9.750 2.195 10.298 4.708 12.831 2.096 28.878 2.587 6.370 2.934 6.346 4.145 4.850 4.859 4.213 4.508
aqueous species basic to H S 0 ~ Degree of saturation of calcium sulfite
138
SULFUR
REMOVAL
A N D RECOVERY
Table IV. Fraction of Basic Species Caused by Magnesium and Sodium at 1 2 2 F Properties mmoles/kg H 0
2
Fraction CI 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 50 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 150 100 100 100 100 100 100 100 100 0 200 100 0.0003 0.401 0.397 0.394 0.398 0.654 0.649 0.650 0.650 0.396 0.392 0.393 0.393 0.643 0.639 0.641 0.639 0.283 0.281 0.279 0.282 0.632 0.627 0.627 0.628 0.363 0.360 0.358 0.360 0.641 0.636 0.637 0.637 0.546 0.544 0.229 0.549 0.000 0.703 0.525 0.547 0.562 0.499 0.552
as M g and Na Species
C
When P o 2 (atm) is 0.075 0.287 0.138 0.343 0.195 0.542 0.296 0.605 0.411 0.297 0.148 0.350 0.209 0.541 0.301 0.600 0.416 0.193 0.120 0.235 0.145 0.506 0.288 0.574 0.381 0.260 0.143 0.311 0.187 0.527 0.299 0.591 0.402 0.520 0.216 0.145 0.445 0.016 0.560 0.351 0.399 0.413 0.334 0.388 0.15 0.233 0.117 0.307 0.153 0.471 0.245 0.568 0.331 0.247 0.124 0.318 0.165 0.475 0.248 0.566 0.337 0.162 0.111 0.208 0.125 0.436 0.250 0.532 0.314 0.216 0.127 0.278 0.154 0.459 0.255 0.553 0.329 0.496 0.194 0.144 0.383 0.020 0.481 0.286 0.330 0.339 0.277 0.317
pH 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.5 6.5 5.0 7.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0 6.0
St* 1 1 3 3 1 1 3 3 1 1 3 3 1 1 3 3 1 1 3 3 1 1 3 3 1 1 3 3 1 1 3 3 2 2 0 4 2 2 2 2 2 2 2
Mg 50 50 50 50 150 150 150 150 50 50 50 50 150 150 150 150 50 50 50 50 150 150 150 150 50 50 50 50 150 150 150 150 100 100 100 100 0 200 100 100 100 100 100
Na 50 50 50 50 50 50 50 50 150 150 150 150 150 150 150 150 50 50 50 50 50 50 50 50 150 150 150 150 150 150 150 150 100 100 100 100 100 100 0 200 100 100 100
Degree of saturation of calcium sulfite
11.
HATFIELD
AND SLACK
Lime-Limestone
Scrubbing
139
Figure 4. Effects of pH and P of liquid phase on its basicity for S0 absorption

C 0 2 2
at constant values of M g , N a , a n d C I , a n d the isobars of c a r b o n d i o x i d e p a r t i a l pressure are p a r a l l e l . T h e s i m u l a t e d b a s i c i t y response caused b y i n c r e a s i n g the m a g n e s i u m content is s l i g h t l y c o n c a v e u p w a r d , p a r t i c u l a r l y at P o
C 2
0.15 a t m . I n c r e a s i n g the s o d i u m content or d e c r e a s i n g
the
c h l o r i d e content causes the b a s i c i t y to increase a p p r o x i m a t e l y l i n e a r l y . I n e a c h case the isobars of c a r b o n d i o x i d e p a r t i a l pressure s h o w a n i n crease i n b a s i c i t y r e s u l t i n g f r o m the a d d i t i o n a l c a r b o n a t e species. Increasi n g the m a g n e s i u m a n d s o d i u m increases t h e b a s i c i t y b e c a u s e of greater a b u n d a n c e of t h e i r b a s i c species; a d d i n g a m o l e of m a g n e s i u m increases the b a s i c i t y a b o u t seven times that caused b y a d d i n g a m o l e of s o d i u m u n d e r the same c o n d i t i o n s . I n c r e a s i n g the c h l o r i d e content at constant v a l u e of other v a r i a b l e s causes the b a s i c i t y to decrease. T h i s results f r o m the r e q u i r e m e n t s of e l e c t r o n e u t r a l i t y a n d the constant s a t u r a t i o n values assumed. A n increase
140
SULFUR
REMOVAL
AND RECOVERY
Na, mmoles/kg
CI. mmoles/kg
Figure 5. Effects of P in combination and contents of Mg, a, and CI on the at pH 6.0

C 0 2
with S basicity
i n c h l o r i d e results i n a decrease i n other a n i o n i c c o m p o n e n t s s u c h as sulfite a n d sulfate, w h i c h also are c o n t r o l l e d b y a constant degree of s a t u r a t i o n i n this s i m u l a t i o n ; this results i n l o w e r q u a n t i t i e s of sulfite, sulfate, a n d c a r b o n a t e a t t a c h e d to c a t i o n i c species ( C a , M g , a n d N a ) a n d c o n s e q u e n t l y i n l o w e r values of s u l f u r d i o x i d e - a b s o r b i n g species. T h e i o n i c s t r e n g t h also w i l l increase as c h l o r i d e is i n c r e a s e d b u t this w i l l h a v e a m i n o r effect o n the b a s i c i t y because m a n y of the basic species are n e u t r a l ( n o i o n i c c h a r g e ) . Combined Effect of p H , Magnesium Content, Pco >
2 a n c
^ Degree of
Saturation of Calcium Sulfite. T h e a d d i t i o n of large q u a n t i t i e s of m a g n e s i u m at different values of p H a n d degrees of saturation of c a l c i u m sulfite is s h o w n i n T a b l e V for three values of c a r b o n d i o x i d e p a r t i a l pressure w h e n the s o l u t i o n contains 100 m m o l e s N a C l / k g a n d is s a t u r a t e d with gypsum. T h e b a s i c i t y values are g i v e n i n the u p p e r section of T a b l e V w h i l e the l o w e r l i s t i n g gives the values of the l o g a r i t h m of the
11.
HATFIELD
AND SLACK
Lime-Limestone
Scrubbing
141
s p
s o l u b i l i t y p r o d u c t ( 3 ) of d o l o m i t e , C a M g ( C 0 ) . W h e n l o g K
3 2
1,
0, a n d + 1 , solutions are 1/10 s a t u r a t e d , s a t u r a t e d , a n d 1 0 - f o l d s a t u r a t e d , respectively, w i t h dolomite. It is e v i d e n t that at p H 6.5 a n d at c a r b o n d i o x i d e p a r t i a l pressures of 0.075 a n d 0.15 the solutions b e c o m e s u p e r s a t u r a t e d w i t h d o l o m i t e e v e n at m o d e r a t e M g contents. T h e s e s i m u l a t e d compositions t h a t are s u p e r s a t u r a t e d w i t h d o l o m i t e m a y never exist i n a c t u a l s c r u b b i n g solutions because of the p H - P o r e l a t i o n s h i p s h o w n i n
C 2
F i g u r e 2; t h e y are p r e s e n t e d to c o m p l e t e the f a c t o r i a l d e s i g n of T a b l e V and to demonstrate the effects of the v a r i a b l e s o n the b a s i c i t y of the F i g u r e 6 shows the effects of the p a r t i a l pressure of c a r b o n d i o x i d e at p H 5.5 a n d 6.0 for v a r i o u s c o m b i n a t i o n s of m a g n e s i u m contents a n d degrees of s u p e r s a t u r a t i o n of c a l c i u m sulfite. T h e slopes of the l i n e a r Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch011 r e l a t i o n b e t w e e n the b a s i c i t y a n d P o
C 2
aqueous phase.
are essentially constant as Si i n -
creases, t h e y increase s l i g h t l y as the m a g n e s i u m content increases, a n d t h e y increase g r e a t l y as p H increases. P r e c i p i t a t i o n of C a r b o n a t e Salts. I n the A p p e n d i x , equations are
3
g i v e n for the c a l c u l a t e d degrees of s a t u r a t i o n of c a l c i t e , S , a n d of d o l o m i t e , S , b a s e d o n regression of these p r o p e r t i e s at the c o n d i t i o n s s h o w n

4
i n T a b l e I I I . F i g u r e 7 shows the effects of p H a n d P o f o r solutions that

C 2
are saturated w i t h calcite or d o l o m i t e . c h l o r i d e is 200 m m o l e s / k g H 0 .

2
I n e a c h case the solutions are
s a t u r a t e d w i t h c a l c i u m sulfite a n d g y p s u m , a n d the content of s o d i u m In C u r v e 1 of F i g u r e 7 the m a g n e s i u m content is v e r y l o w , 0.001 mmole/kg, and c a l c i t e saturates at a l o w e r carbon dioxide partial pressure for a n y g i v e n p H t h a n d o l o m i t e . W h e n the m a g n e s i u m content is i n c r e a s e d to 100 m m o l e s / k g , C u r v e 2, d o l o m i t e saturates at a l o w e r p a r t i a l pressure of c a r b o n d i o x i d e t h a n c a l c i t e for a n y g i v e n p H . The same is true for C u r v e 3 w h e r e the m a g n e s i u m content is 200 m m o l e s / k g . A n e x t r a p o l a t i o n of the d o l o m i t e s o l u b i l i t y to 600 m m o l e s M g / k g ( 14,600 p p m M g ) , C u r v e 4, shows that v e r y l o w c a r b o n d i o x i d e p a r t i a l pressure is n e e d e d to saturate d o l o m i t e f r o m solutions w i t h these h i g h m a g n e s i u m contents. Application of the Study Results
T h e c o n c e n t r a t i o n of a b s o r b i n g species i n the s c r u b b e r s o l u t i o n is o b v i o u s l y a n i m p o r t a n t c o n s i d e r a t i o n i n s c r u b b i n g stack gas w i t h l i m e l i m e s t o n e s l u r r y . T h u s , the results of this s t u d y are u s e f u l b o t h i n u n d e r standing solution absorptivity and i n p o i n t i n g the w a y to finely possible ground improvement. I n a t y p i c a l limestone s c r u b b i n g system a s l u r r y of l i m e s t o n e p l u s p r o d u c t solids a n d p e r h a p s fly ash is c i r c u l a t e d t h r o u g h
142
SULFUR
REMOVAL
AND
RECOVERY
Table V .
Properties of Solutions BASE*

when P c o 2 (atm)
Containing is
0.0003 pH 5.5 1 2 3 1 2 3 1 2 3 200 Mg 1.75 3.45 5.09 1.76 3.49 5.18 1.78 3.52 5.23 Log S 5.5 1 2 3 1 2 3 1 2 3 -8.825 -8.813 -8.802 -6.833 -6.829 -6.825 -4.835 -4.834 -4.833
4 r f c
600 M g 5.34 10.53 15.59 5.36 10.61 15.74 5.39 10.65 15.81
1000
Mg
6.0
6.5
9.26 18.28 27.07 9.29 18.36 27.25 9.32 18.42 27.34
6.0
6.5
-8.534 -8.526 -8.517 -6.541 -6.539 -6.537 -4.543 -4.543 -4.543
-8.359 -8.351 -8.344 -6.365 -6.364 -6.362 -4.367 -4.367 -4.368
aqueous species basic to HSC>3~ Degree of saturation of calcium sulfite Magnesium content in mmoles/kg H 0
6 c 2
a l o o p c o m p o s e d of the s c r u b b e r a n d a d e l a y , or h o l d , tank. T h e s l u r r y is h e l d i n the t a n k to a l l o w the reactions s t a r t e d i n the s c r u b b e r to go to c o m p l e t i o n a n d also to a l l o w the s u p e r s a t u r a t i o n of C a S 0 CaS0

4 3
0 . 5 H O and
2
2 H 0 to dissipate as m u c h as possible.
2
B o t h salts supersaturate
to a h i g h degree w h i c h m a y cause s c a l i n g i n the s c r u b b e r unless c r y s t a l l i z a t i o n c a n b e i n d u c e d i n the d e l a y tank. T h e f e e d l i m e s t o n e u s u a l l y is f e d i n t o the d e l a y tank. A s i d e s t r e a m of s l u r r y is w i t h d r a w n f r o m t h e t a n k or at a p o i n t just b e f o r e the t a n k , the solids are s e p a r a t e d a n d d i s c a r d e d , a n d the l i q u i d phase is r e t u r n e d to the s c r u b b e r . T h u s , the system is i n a c o n t i n u o u s d y n a m i c state r a t h e r t h a n at e q u i l i b r i u m . I n s u c h a system, the s o l u t i o n is i n c o n t i n u o u s contact w i t h the m a j o r solid p h a s e s C a C 0 , C a S 0
3 3
0 . 5 H O , and C a S 0
2
2 H 0 . The compo2
s i t i o n of the l i q u i d phase is c o n t i n u a l l y c h a n g i n g as solids go i n t o a n d c o m e o u t of s o l u t i o n a n d as s u l f u r d i o x i d e a n d c a r b o n d i o x i d e are a b s o r b e d or d e s o r b e d . M a s s transfer is a n i m p o r t a n t c o n s i d e r a t i o n , both of s u l f u r d i o x i d e i n t o the l i q u i d a n d of the v a r i o u s solids i n t o a n d o u t of
11.
HATFIELD
A N D SLACK
Lime-Limestone
Scrubbing
143
100 mmoles N a C l / k g Water at 1 2 2 F BASE 0.075 200 M g 2.20 3.90 5.54 3.19 4.92 6.60 6.37 8.08 9.77 Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch011 600 M g 5.95 11.14 16.19 7.29 12.53 17.65 11.64 16.85 21.98 1000 Mg 10.00 19.02 27.81 11.66 20.72 29.59 17.05 26.09 34.94 Log -4.028 -4.017 -4.006 -2.035 -2.032 -2.028 -0.034 -0.033 -0.032
d
when P o2
C
(atm) is 0.15
200 M g 2.65 4.35 5.99 4.63 6.35 8.03 10.98 12.67 14.35
600 M g 6.56 11.75 16.80 9.23 14.45 19.57 17.90 23.08 28.16
1000 M g 10.75 19.76 28.55 14.04 23.08 31.94 24.80 33.77 42.57
-3.738 -3.730 -3.721 -1.744 -1.742 -1.740 0.255 0.255 0.255

2 2 sp
-3.563 -3.555 -3.548 -1.569 -1.567 -1.566 0.430 0.429 0.429
-3.426 -3.414 -3.403 -1.432 -1.428 -1.424 0.573 0.574 0.576
-3.136 -3.127 -3.119 -1.142 -1.140 -1.138 0.859 0.859 0.859
-2.961 -2.953 -2.946 -0.966 -0.965 -0.964 1.033 1.032 1.031
S4 = o c a Mg a co /K (dolomite). Negative values are unsaturated solutions, positive values are supersaturated solutions.
the l i q u i d . T h u s , e q u i l i b r i u m d a t a s u c h as o b t a i n e d i n t h e present s t u d y can o n l y b e a n i n d i c a t i o n . T h e a c t u a l s i t u a t i o n w i l l d e p e n d also o n t h e d e s i g n of t h e p a r t i c u l a r s c r u b b e r i n s t a l l a t i o n a n d its o p e r a t i n g c o n d i t i o n s since these affect t h e mass transfer rate i n a d d i t i o n to t h e e q u i l i b r i u m d r i v i n g forces. L i m e s c r u b b i n g is q u i t e s i m i l a r to l i m e s t o n e s c r u b b i n g except that the p H i n t h e d e l a y t a n k is h i g h e r , a b o u t 8 - 1 0 as c o m p a r e d w i t h 5.8-6.0 i n l i m e s t o n e s c r u b b i n g . T h e p H a p p a r e n t l y drops q u i c k l y w h e n t h e s l u r r y returns to t h e s c r u b b e r , c a u s e d b y a b s o r p t i o n of c a r b o n d i o x i d e a n d sulfur d i o x i d e , so that t h e s c r u b b e r exit p H is a b o u t 5.4-5.8 n o m a t t e r w h i c h a b s o r b e n t is u s e d . Calcium Sulfite Supersaturation. O n e o f the m o r e effective w a y s to increase a b s o r b i n g species c o n c e n t r a t i o n , as s h o w n i n F i g u r e s 1, 5, a n d 6, is to increase t h e s u p e r s a t u r a t i o n of C a S 0
3
0 . 5 H O . I n practice such
2
an increase p r o b a b l y c o u l d b e a c c o m p l i s h e d b y d e c r e a s i n g d e l a y t i m e a n d b y s e p a r a t i n g a n d r e c y c l i n g t h e l i q u i d phase f r o m t h e p r o d u c t solids
144
SULFUR
REMOVAL
AND RECOVERY
0 P
C02
0 075 atpH5.5
0 15
0 P
C O 2
0 075 atpH6 0
0 15
Figure 6. Basicity of solution with 100 mmoles NaCl/kg and saturated with gypsum. Numbers on curves denote mmoles Mg/kg H 0.
2
as q u i c k l y as possible. H o w e v e r , since this is l i k e l y to aggravate s c a l i n g it is h a r d l y a p r a c t i c a l course. T h u s , t h e b e n e f i c i a l effect of sulfite s u p e r s a t u r a t i o n comes o n l y f r o m the m i n i m u m v a l u e b e l o w w h i c h i t c a n n o t b e decreased (by extended d e l a y t i m e , c r y s t a l s e e d i n g , a n d h i g h l i q u i d - t o - g a s r a t i o ) i n the effort to a v o i d s c a l i n g . T h e m a x i m u m l e v e l , w h i c h occurs w h e n the p H is highest, appears to be 8 - 1 0 . p H decreases S u p e r s a t u r a t i o n of c a l c i u m sulfite is decreased w h e n ( b y absorbing carbon dioxide and sulfur dioxide), and it
is i n c r e a s e d b y d i s s o l v i n g l i m e or limestone w h i c h adds c a l c i u m a n d increases the p H . Magnesium Content of Limestone. It has b e e n g e n e r a l l y a c c e p t e d ( u n t i l r e c e n t l y ) that the m a g n e s i u m content of the l i m e s t o n e s h o u l d b e m i n i m i z e d to p r e v e n t the p r e s e n c e of p o l l u t i n g s o l u b l e m a g n e s i u m salts i n the p r o d u c t solids. T h e r e is n o w a g e n e r a l t r e n d , h o w e v e r , to s t a b i l i z e
11.
HATFIELD
AND SLACK
Lime-Limestone
Scrubbing
145 I n this
the solids against l e a c h i n g n o m a t t e r w h a t t h e c o m p o s i t i o n . stone i f there w e r e a n y benefit i n the s c r u b b i n g step.
s i t u a t i o n i t w o u l d a p p e a r r e a s o n a b l e to use d o l o m i t e or d o l o m i t i c l i m e If t h e l i m e s t o n e is u s e d as is, h o w e v e r , the d i s s o l u t i o n r a t e of the d o l o m i t e f r a c t i o n is so s l o w that the o v e r a l l effectiveness appears to b e decreased. It m a y b e that w i t h e n o u g h d e l a y t i m e t h e d o l o m i t e w o u l d react a d e q u a t e l y i n the d e l a y t a n k w i t h bisulfite species f o r m e d i n the s c r u b b e r , b u t s u i t a b l e d a t a o n this d o not a p p e a r to b e a v a i l a b l e . W h e n t h e d o l o m i t i c l i m e s t o n e is c a l c i n e d , the r e s u l t i n g m a g n e s i u m oxide h y d r a t e s a n d reacts just as it does i n those processes u s i n g m a g -
62
63
64
65
66
67
PH Figure 7. Effects of pH and P on solutions saturated with dolomite ( ) or calcite ( ) at 50 C. All solutions saturated with CaSO 0.5H O and CaSO,/ 2H 0 and contain 200 mmoles NaCl/kg.
C 0 2 3 2 2
n e s i u m o x i d e as the p r i m a r y absorbent.
I n recent c o m m e r c i a l tests a dolomitic the
m a j o r increase i n a b s o r p t i o n w a s n o t e d w h e n the l i m e w a s 0.2 m o l e Mg

+ 2
r a t h e r t h a n c a l c i t i c . T h e reason for this is s h o w n i n F i g u r e 5, w h e r e o n l y / k g H 0 m o r e t h a n d o u b l e d t h e c o n c e n t r a t i o n of

2
a b s o r b i n g species.
F i g u r e 6 shows i n c r e a s i n g amounts of s u l f u r d i o x i d e -
a b s o r b i n g species as the m a g n e s i u m content is i n c r e a s e d to 1 m o l a l . It s h o u l d b e n o t e d , h o w e v e r , that there is a t h e o r e t i c a l m a x i m u m s o l u b i l i t y for M g

+ 2
species a b o v e w h i c h d o l o m i t e m a y p r e c i p i t a t e ( T a b l e D o l o m i t e has never b e e n p r e c i p i t a t e d , to o u r k n o w l -
IV and Figure 7).
edge, u n d e r c o n d i t i o n s l i k e l y to be e n c o u n t e r e d i n l i m e or l i m e - l i m e s t o n e
146 stack gas s c r u b b i n g . d y n a m i c reasoning.
SULFUR
REMOVAL
AND
RECOVERY
T h e p o s s i b i l i t y , nevertheless, exists f r o m t h e r m o M a g n e s i u m losses t h r o u g h f o r m a t i o n of m a g n e s i a n I n the d e l a y t a n k the l o w
c a l c i t e or aragonite is another p o s s i b i l i t y . F o r t u n a t e l y , the factors affecti n g p r e c i p i t a t i o n t e n d to offset e a c h other. c a r b o n d i o x i d e p a r t i a l pressure offsets t h e p r e c i p i t a t i n g t e n d e n c y of the r e l a t i v e l y h i g h p H , a n d i n the s c r u b b e r the l o w p H offsets t h e effect of the h i g h e r c a r b o n d i o x i d e pressure. T h e c o m b i n a t i o n of h i g h p H i n the s l u r r y r e t u r n i n g to the s c r u b b e r a n d the h i g h c a r b o n d i o x i d e pressure i n the s c r u b b e r m i g h t cause p r e c i p i t a t i o n . H o w e v e r , the p H of t h e r e t u r n s o l u t i o n appears to d r o p r a p i d l y to the g e n e r a l l y l o w p H l e v e l t h r o u g h o u t the s c r u b b e r . T h e steady state c o n c e n t r a t i o n of m a g n e s i u m species i n a s c r u b b e r system u s i n g d o l o m i t i c l i m e w i l l d e p e n d o n s e v e r a l factors, i n c l u d i n g Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch011 m a g n e s i u m content of the limestone, system p u r g e rate, a n d l i m i t i n g m a x i m u m s o l u b i l i t y . W h a t e v e r the c o n c e n t r a t i o n o b t a i n e d , i t seems l i k e l y to h a v e a significant b e n e f i c i a l effect o n a b s o r p t i o n . Addition of Magnesium Salts. scrubbing (4). T h e a d d i t i o n of m a g n e s i u m sulfate slurry i n c r e a s e d the s u l f u r d i o x i d e r e m o v a l i n c l o s e d - l o o p limestone
I n the present s i m u l a t i o n s t u d y of the concentrations of
m a g n e s i u m , s o d i u m a n d c h l o r i n e ( T a b l e I I ) , the extent to w h i c h M g -f0 . 5 N a exceeds 0.5C1 is a p p r o x i m a t e l y e q u i v a l e n t to a d d i n g m a g n e s i u m sulfate because of t h e r e q u i r e m e n t s of e l e c t r o n e u t r a l i t y a n d t h e constant v a l u e of S .

2
A t h i g h m a g n e s i u m concentrations i n limestone slurries t h e b u l k of the a b s o r b i n g species c o n c e n t r a t i o n is i n the f o r m of m a g n e s i u m sulfite, m a k i n g the system s i m i l a r to m a g n e s i u m s c r u b b i n g processes s u c h as C h e m i c o - B a s i c a n d G r i l l o . I n l i m e s l u r r y s c r u b b i n g , the b u l k of a b s o r b i n g species c o n c e n t r a t i o n is i n the f o r m of m a g n e s i u m carbonate M g H C C V at h i g h m a g n e s i u m concentrations. Use of Cooling Tower Blowdown. water. I n some areas the general shortage of w a t e r makes i t d e s i r a b l e to use c o o l i n g t o w e r b l o w d o w n as m a k e u p A s a result, v e r y h i g h concentrations of d i s s o l v e d s a l t s o n the The o r d e r of 1 2 % a r e a t t a i n e d i n the s c r u b b e r l o o p at steady state. and
c o m p o s i t i o n w i l l v a r y d e p e n d i n g o n the n u m b e r of c o o l i n g t o w e r cycles a n d o n the m o d e of o p e r a t i o n of the s c r u b b i n g system. U s u a l l y s o d i u m a n d c h l o r i d e are the m a i n constituents, w i t h lesser a m o u n t of m a g n e s i u m , c a l c i u m , a n d sulfate. T h e results of this s t u d y i n d i c a t e that the s o d i u m a n d trations. T h e m a g n e s i u m , of course, is h e l p f u l . Use of Salt Water. I n some coastal areas the use of sea w a t e r as A g a i n , there s h o u l d b e little effect o n t h e m a k e u p w a t e r is e c o n o m i c a l . chloride l a r g e l y offset e a c h other ( F i g u r e 5 ) w h e n i n c o m p a r a b l e m o l a r c o n c e n -
c o n c e n t r a t i o n of a b s o r b i n g species except that c a u s e d b y i o n i c strength.
11.
HATFIELD
AND SLACK
Lime-Limestone
Scrubbing
147
Stoichiometry and Solids Dissolution. O n e t h o u s a n d c u ft of gas at s t a n d a r d c o n d i t i o n s contains 3.16 g moles of 50 g a l / s t a n d a r d 1000 cu ft, 16.7 of s u l f u r d i o x i d e w h e n of basic species/1, the are the s u l f u r d i o x i d e content of t h e gas is 2500 p p m . mmoles A t a liquid-to-gas ratio V e r y f e w of
r e q u i r e d to react w i t h this a m o u n t of s u l f u r d i o x i d e .
s i m u l a t e d solutions i n T a b l e s I I I a n d I V a t t a i n e d this b a s i c i t y e x c e p t u n d e r e x t r e m e c o n d i t i o n s of the v a r i a b l e s , c o n d i t i o n s u n l i k e l y to be c o n t r o l l e d consistently i n l i m e or l i m e s t o n e s c r u b b i n g . C o n s e q u e n t l y , u n d e r m o s t c o n d i t i o n s , a d d i t i o n a l b a s i c species m u s t enter t h e l i q u i d p h a s e i n the s c r u b b e r to n e u t r a l i z e the d i s s o l v i n g gas. T h e s e species c o m e f r o m the d i s s o l u t i o n of c a l c i u m c a r b o n a t e or c a l c i u m sulfite i n the s c r u b b i n g t o w e r . T h e a m o u n t of solids d i s s o l u t i o n r e q u i r e d to a c h i e v e s t o i c h i o m e t r y is r e d u c e d g r e a t l y b y the presence of l a r g e amounts of m a g n e s i u m i n
solution. Appendix Saturation of the Aqueous Phase W i t h Calcite or Dolomite. Tables

3
s i m i l a r to T a b l e I I I for t h e degree of s a t u r a t i o n of c a l c i t e , C a C 0 , a n d for d o l o m i t e , C a M g ( C 0 ) , w e r e c a l c u l a t e d , a n d the results w e r e q u a n t i 3 2
t a t i v e l y r e p r e s e n t e d b y the e q u a t i o n l o g Sj = b b log
6 0
+ b
3 3
bixi + x
3 2
b x
2
b x
3
5 5
b x
4
+
2
b x
5
+
3 4
P 02
C
+ b
44X4
45
+ b X5 +
2
bi xix + b x x
2
3 4 3 4
+ (1A)
D 5X X5 + b x X 5 + b
3 3 4
3 4 5
x x X5
w h e r e x's are c o d e d values of the i n d e p e n d e n t v a r i a b l e s , n a m e l y ,

X l
x x x x as f o l l o w s 5 5
3
4 5
= = = = =
2(pH-6) Si -2 (Mg-100)/50 (Na-100)/50 (Cl-100)/50

3 4
(2A) (3A) (4A) (5A) (6A)
T h e d e g r e e of s a t u r a t i o n of c a l c i t e , S , a n d of d o l o m i t e , S , are d e f i n e d
= =
a a
C a
+ 2
a 03~ /is (calcite)

2 C P
(7A) (8A)
C a
+ 2
M +2
g
a cz~ /K (dolomite)
2 2 Bp
T h e values of the constants i n E q u a t i o n 1 A are For Constant b bi b

0
Calciie -0.056 0.995 0.006
Dolomite 0.123 1.989 0.006
148
SULFUR
REMOVAL
A N D RECOVERY
For Constant Calcite -0.117 -0.094 0.126 1.003 0.032 0.010 0.007 -0.004 0.038 -0.041 -0.025 0.011 Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch011 Literature Cited Dolomite 0.077 -0.132 0.175 2.006 0.000 0.014 0.006 -0.005 0.051 -0.047 0.009 0.009
1. Lowell, P. S., A Theoretical Description of the Limestone Injection-Wet2. Box, G. E. P., Wilson, . B., J. Roy. Statist. Soc., Ser. B ( 1 9 5 1 ) 13, (1), 1-38. 3. Sillen, L . G., "Stability Constants of Metal-Ion Complexes," Special Publication No. 17, The Chemical Society, Burlington House, London, W . 1, 1964. 4. Potts, J. M . , Slack, . V., Hatfield, J. D., Int. Lime/Limestone Wet-Scrubbing Symp., 2nd, New Orleans, Nov. 8-12, 1971.
R E C E I V E D April 4, 1974 -Scrubbing Process ( 1 9 7 0 ) 1, P B 1 9 3 0 2 9 .
12
Kinetics of the Reaction of Half-Calcined Dolomite with Sulfur Dioxide
R. T. Y A N G , P. T. C U N N I N G H A M , W. I. W I L S O N , and S. A. J O H N S O N
1 2
Chemical Engineering Division, Argonne National Laboratory, 9700 South Cass Ave., Argonne, Ill. 60439 Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch012
Kinetics of the reaction of sulfur dioxide with half-calcined dolomite have been studied using gravimetric water in the reactant gas mixture. techniques. The reaction rate depends significantly on the presence of With water, the reaction concentration. concentration. is first order with respect to the sulfur dioxide is 0.76 order with respect to sulfur dioxide This suggests that the rate-determining apparent activation
Without water, the reaction rate is slower, and the reaction step differs dependwith water
ing on whether or not water is present. The reaction has an energy of 7.3 kcal/mole present in the reactant gas.
' " p h i s paper reports the initial results obtained by a small basic-chemistry
A
support program associated with developing a fluidized-bed combustor
for high-sulfur coal. The combustion of fossil fuels in a fluidized bed containing a material that reacts with and fixes sulfur dioxide in the bed is only one of many processes presently being developed to permit the use of high sulfur fuels in an environmentally acceptable way. fluidized-bed The concept has several variations, but in most cases the sulfur-
fixing material is limestone in a form that reacts with sulfur dioxide to produce calcium sulfate. It is hoped that these initial results will also be useful in developing other processes for sulfur dioxide control such as panel-bed filters. The active material used in this program is half-calcined dolomite, which reacts with sulfur dioxide as indicated in Equation 1: Present address: Physical Chemistry Division, Alcoa Research Laboratories, Alcoa Center, Pa. 15069. To whom correspondence should be addressed.
1 2
149 In Sulfur Removal and Recovery; Pfeiffer, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1975.
150 [CaC0 + MgO] + S0 + 0.5 0
SULFUR
REMOVAL
AND RECOVERY
-> [ C a S 0
+ MgO] + C 0
(1)
F o r e c o n o m i c a n d e n v i r o n m e n t a l reasons, i t is d e s i r a b l e to Equations 2 and 3 [CaS0 [CaS0

4
regenerate
the r e a c t i v e m a t e r i a l f r o m the p r o d u c t b y some s c h e m e s u c h as s h o w n i n
+ MgO] + 4 H
-> [CaS + M g O ] + 4 H 0
2 2
(2a) (2b)
2
+ M g O ] + 4 C O -> [CaS + M g O ] + 4 C 0
2
[CaS + M g O ] + H 0 +
C0
-> [ C a C 0
+ MgO] + H S
(3)
i n w h i c h the h y d r o g e n sulfide r e s u l t i n g f r o m E q u a t i o n 3 is c o n c e n t r a t e d e n o u g h to p e r m i t s u l f u r r e c o v e r y i n a C l a u s p l a n t . A c o n s i d e r a b l e a m o u n t of w o r k , i n c l u d i n g d e t a i l e d k i n e t i c studies Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch012 (1, 2 ) , has b e e n r e p o r t e d o n the r e a c t i o n of c a l c i n e d limestones w i t h sulfur dioxide ( E q u a t i o n 4) CaO + S 0 i n connection w i t h both the + 0.5 0 -* CaS0 (4)
fluidized-bed
combustion and dry-limestone
i n j e c t i o n processes. T h e respective reactions of f u l l y c a l c i n e d a n d h a l f c a l c i n e d limestones w i t h h y d r o g e n sulfide [ C a O + M g O ] + H S -> [CaS + M g O ] +

2
H 0
2 2 2
(5) (6)
[CaC0
+ M g O ] + H S -> [CaS + M g O ] +
2
H 0 + C0
h a v e b e e n s t u d i e d i n some d e t a i l i n c o n n e c t i o n w i t h other d e s u l f u r i z a t i o n schemes (2,3,4,5,6). S o m e results h a v e also b e e n r e p o r t e d o n the r e a c E x p l o r a t o r y experiments a p p l y i n g filtration ( 9 ) h a v e i n d i c a t e d its tions o f w o r k discussed here (7,8,9).
the system c o n s i d e r e d here to p a n e l - b e d
f e a s i b i l i t y . T h e f o l l o w i n g conclusions c a n b e d r a w n f r o m this p r i o r w o r k : 1. D o l o m i t e limestones ( f u l l y c a l c i n e d or h a l f - c a l c i n e d ) are m o r e effective reagents t h a n c a l c i t e a n d s h o w c o n s i d e r a b l e p r o m i s e i n s u l f u r emission control. 2. T h e r e d u c t i o n of the s u l f a t i o n p r o d u c t to the sulfide ( E q u a t i o n 2 ) appears to b e satisfactory. 3. T h e a c t i v e reagent c a n be m o r e r e a d i l y r e g e n e r a t e d ( b y E q u a t i o n 3 ) f r o m sulfide p r o d u c e d b y d i r e c t s u l f i d a t i o n w i t h h y d r o g e n sulfide t h a n f r o m sulfide f o r m e d b y r e d u c t i o n of the s u l f a t e d p r o d u c t r e s u l t i n g from reaction w i t h sulfur dioxide. I n the l i g h t of this p r i o r w o r k , the goals of this p r o g r a m are to d e t e r m i n e the d e t a i l e d k i n e t i c s of E q u a t i o n s 1, 2, a n d 3, to e l u c i d a t e p l a u s i b l e m e c h a n i s m s f o r these reactions, a n d to d e t e r m i n e the c o n d i t i o n s t h a t o p t i m i z e e a c h of these reactions. p r e s e n t e d here. K i n e t i c results for E q u a t i o n 1 are
12.
YANG
ET AL.
Half-Calcined
Dolomite
with Sulfur
Dioxide
151
Experimental Apparatus. T h e e x p e r i m e n t a l a p p a r a t u s is s i m i l a r to t h a t u s e d b y The
other w o r k e r s ( 3 , 5, 8 ) a n d is s c h e m a t i c a l l y d e p i c t e d i n F i g u r e 1.
reactant gas m i x t u r e , w h i c h is p r e p a r e d b y c o n t r o l l i n g the flow of e a c h constituent b y means of a d i a p h r a g m - t y p e r e g u l a t o r a n d c a l i b r a t e d r o tameters, flows u p w a r d t h r o u g h the h e a t e d r e a c t i o n t u b e , past the s a m p l e , a n d exits t h r o u g h a condenser a n d a series of scrubbers.
3
T o t a l flow c a n
b e c o n t r o l l e d f r o m 200 to 400 c m / m i n w i t h a n a c c u r a c y for t h e t o t a l flow a n d for e a c h constituent of a b o u t 2 % . T h e w a t e r content of the reactant gas is c o n t r o l l e d b y a t h e r m o s t a t e d h u m i d i f i e r . S u l f u r d i o x i d e is a d d e d to the stream after h u m i d i f i c a t i o n . T h e s a m p l e is s u s p e n d e d i n a p l a t i n u m basket f r o m one a r m of a r e c o r d i n g b a l a n c e . T h e b a l a n c e , w h i c h Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch012 p r o v i d e s c o n t i n u o u s w e i g h t d a t a f r o m 0.2 to 1.0 g w i t h a n a c c u r a c y of 0 . 1 m g , is p r o t e c t e d f r o m corrosive gases b y a p u r g e flow of n i t r o g e n . T e m p e r a t u r e i n the r e a c t i o n z o n e is c o n t r o l l e d b y a M a r s h a l l s a m p l e w e i g h t o n a recorder. Materials. stainless steel. T h e a p p a r a t u s is f a b r i c a t e d f r o m q u a r t z a n d t y p e C o m m e r c i a l research-grade c y l i n d e r gases are u s e d 304 to furnace w i t h a n a c c u r a c y of 5 C u p to a b o u t 9 5 0 C a n d is r e c o r d e d a l o n g w i t h
m a k e u p the reactant gas stream. T h e stone u s e d i n these
experiments
was B C R - 1 3 3 7 d o l o m i t e o b t a i n e d f r o m C h a r l e s Pfizer a n d C o . , G i b s o n GAS HANDLfNG

RECORDING MICROBALANCE" PURGE GAS INROTOMETERS - BAFFLES
REACTANT GAS OUT=
VENT
REACTANT GAS IN=
REACTOR
SCRUBBERS
Figure 1.
Schematic of the
apparatus
152
SULFUR
REMOVAL
AND RECOVERY
b u r g , O h i o a n d has a n e m p i r i c a l f o r m u l a C a i .
1 4
M g . 8 G ( C 0 ) . Chemical
0 3 2
analysis a n d ptrographie characteristics of this stone h a v e b e e n r e p o r t e d by Harvey (10). P r o c e d u r e . I n a t y p i c a l e x p e r i m e n t , 2 0 0 m g of 1337 d o l o m i t e p a r ticles h a v i n g d i a m e t e r s i n a n a r r o w range a r o u n d 1.1 m m ( 16 to -j-18 U . S . s t a n d a r d s c r e e n ) are p l a c e d i n the a p p a r a t u s u n d e r n i t r o g e n a n d c a r b o n d i o x i d e flow a n d are h e a t e d to 8 0 0 C at a b o u t 2 5 C / m i n to h a l f c a l c i n e the stone. A f t e r c a l c i n a t i o n the w e i g h t c h a n g e of the s a m p l e is o b s e r v e d . W h e n h a l f - c a l c i n a t i o n of the stone is c o m p l e t e ( u s u a l l y after a b o u t 45 m i n ) , the s a m p l e t e m p e r a t u r e is a d j u s t e d to that selected for the e x p e r i m e n t , the s a m p l e is i s o l a t e d u n d e r n i t r o g e n a n d c a r b o n d i o x i d e atmosphere, a n d the reactant gas m i x t u r e is a d j u s t e d to the a p p r o p r i a t e c o m p o s i t i o n a n d flow r a t e for t h e e x p e r i m e n t w h i l e b y p a s s i n g the r e a c t i o n tube. A t t i m e zero, the reactant gas is d i v e r t e d t h r o u g h the r e a c t i o n t u b e a n d the w e i g h t c h a n g e of the s a m p l e is o b s e r v e d as a f u n c t i o n of t i m e . T h e r e a c t i o n is f o l l o w e d u n t i l the rate of w e i g h t c h a n g e is n e g l i g i b l e , t y p i c a l l y a b o u t 2 h r for the experiments r e p o r t e d here. T o s t u d y the r e a c t i o n o f m a g n e s i u m oxide, a s a m p l e of reagent-grade m a g n e s i u m c a r b o n a t e w a s g r o u n d a n d pressed i n t o a dense p e l l e t w h i c h was t h e n b r o k e n u p to o b t a i n a s a m p l e c o n t a i n i n g p a r t i c l e s of the size used i n the other experiments. C a l c i n a t i o n a n d subsequent procedures w e r e i d e n t i c a l to those for other samples. T h e r e a c t i o n rate, r, at a n y t i m e d u r i n g the r e a c t i o n w a s c a l c u l a t e d f r o m the e q u a t i o n 1 r = w dn -: at (7)

w h e r e to is the t o t a l w e i g h t of the s a m p l e b e f o r e c a l c i n i n g , is t h e a m o u n t of sulfate as moles of s u l f u r t r i o x i d e p r o d u c e d , a n d t is t i m e i n sec. Results and Discussion
T y p i c a l e x p e r i m e n t a l results are s h o w n i n F i g u r e 2 w h e r e the f r a c t i o n of the stone r e a c t e d a c c o r d i n g to E q u a t i o n 1 is p l o t t e d against t i m e f o r s e v e r a l different s u l f u r d i o x i d e concentrations. T h e reaction temperaThe t u r e a n d reactant gas c o m p o s i t i o n are g i v e n i n the figure l e g e n d . gas phase d i f f u s i o n affected the r e a c t i o n rate.
flow rate of the reactant gas w a s m a i n t a i n e d w e l l a b o v e the rate at w h i c h It is e v i d e n t that t h e r e a c t i o n rate, a n d h e n c e the extent of the r e a c t i o n at a g i v e n t i m e , is a f u n c t i o n of s u l f u r d i o x i d e c o n c e n t r a t i o n . C u r v e a i n F i g u r e 3 shows these same d a t a , i n a p l o t of the l o g a r i t h m of the i n i t i a l r e a c t i o n rate vs. the l o g a r i t h m of the s u l f u r d i o x i d e c o n c e n t r a t i o n . e v a l u a t e d at t = I n i t i a l rates w e r e a c t u a l l y 0. The in de1 m i n b e c a u s e of scatter i n the d a t a near t =
straight l i n e thus o b t a i n e d has a slope of 1.08 a n d i n d i c a t e s t h a t the r e a c t i o n is first o r d e r w i t h respect to s u l f u r d i o x i d e c o n c e n t r a t i o n Similar first-order the reactant gas u n d e r these r e a c t i o n c o n d i t i o n s .
12.
YANG
ET AL.
Half-Calcined
Dolomite
with Sulfur
Dioxide
153
TIME, minutes
Figure 2. Percent conversion vs. time for various sulfur dioxide concentrations in the reactant gas at 750C. Gas composition in %S0 : a = 3.1; b = 1.1; c = 0.65; d = 0.39; e = 0.20; f = 0.10. C0 : 15.0. 0 : 5.0. H 0: 2.9. N, balance.
2 2 2 2 2
p e n d e n c e for the r e a c t i o n of f u l l y c a l c i n e d 1337 d o l o m i t e w a s r e p o r t e d b y B o r g w a r d t ( J ) , a n d , i n fact, the r e a c t i o n rates r e p o r t e d b y B o r g w a r d t are s i m i l a r to those o b s e r v e d here. W e n o t i c e d i n several e a r l y experiments that the c o n c e n t r a t i o n w a t e r i n the reactant gas a p p e a r e d to i n f l u e n c e the r e a c t i o n rate. series of experiments was p e r f o r m e d i n w h i c h the w a t e r c o n c e n t r a t i o n of other reactants w a s constant. however, i n the reactant gas w a s v a r i e d f r o m about 1.0 to 40 m o l e % of A
concentration w h i l e the to
T h e results i n d i c a t e d ,
that the r e a c t i o n w a s essentially zero o r d e r w i t h respect
w a t e r c o n c e n t r a t i o n . A n o t h e r series of experiments, i n w h i c h the reactant gas w a s d r y a n d the c o n c e n t r a t i o n of s u l f u r d i o x i d e w a s v a r i e d , gave the results s h o w n i n F i g u r e 3, C u r v e b . T h e o b s e r v e d slope of 0.76 indicates that the rate varies w i t h the three-fourths p o w e r of s u l f u r d i o x i d e c o n centration. T h u s , i t appears t h a t the r a t e - d e t e r m i n i n g step is different With concend e p e n d i n g o n w h e t h e r or not w a t e r is present i n the reactant gas. w a t e r present, t h e r e a c t i o n is 0.22 order w i t h respect to o x y g e n t r a t i o n i n the reactant gas stream. T h e t e m p e r a t u r e d e p e n d e n c e of the r e a c t i o n rate w i t h w a t e r present w a s e x a m i n e d f r o m 550 to 8 5 0 C . A t h i g h e r temperatures, the c a r b o n
154
SULFUR
REMOVAL
AND
RECOVERY
S0
CONCENTRATION I0
(mol/cc)
Figure 3. Curve a: initial reaction rate (see text) vs. sulfur dioxide concentration on logarithmic scales. Reaction conditions as noted under Figure 2. Curve b: initial reaction rate vs. sulfur dioxide concentration on logarithmic scales. Reaction conditions as noted under Figure 2 except that water is absent. d i o x i d e c o n c e n t r a t i o n necessary to p r e v e n t c a l c i u m carbonate tion (11) decomposiThe
c o u l d n o t be m a i n t a i n e d w i t h the present a p p a r a t u s .
i n i t i a l r e a c t i o n rate i n c r e a s e d s i g n i f i c a n t l y w i t h t e m p e r a t u r e over this range. A n A r r h e n i u s p l o t of the d a t a ( F i g u r e 4 ) shows a l i n e a r d e p e n d ence of rate o n 1 / T a n d y i e l d s a n a p p a r e n t a c t i v a t i o n energy of 7.3 k c a l / m o l e . A l t h o u g h s u c h a v a l u e does not p o i n t c o n c l u s i v e l y to a m e c h a n i s m i n w h i c h some c h e m i c a l r e a c t i o n is rate c o n t r o l l i n g , the v a l u e is s o m e w h a t greater t h a n one m i g h t expect i f the r e a c t i o n w e r e d i f f u s i o n controlled. I n some e x p e r i m e n t a l r u n s , the c o n v e r s i o n to sulfate b a s e d o n E q u a t i o n 1 w a s greater t h a n t h e o r e t i c a l l y p r e d i c t e d . I t has b e e n r e p o r t e d that m a g n e s i u m o x i d e undergoes s u l f a t i o n (8). A c c o r d i n g l y , to assesss the extent to w h i c h this r e a c t i o n m i g h t interfere w i t h d e t a i l e d analysis of o u r results, the s u l f a t i o n of c a l c i n e d m a g n e s i u m c a r b o n a t e was c a l c i n e d stone. examined. great, T y p i c a l results are s h o w n i n F i g u r e 5 together w i t h results for the h a l f T h e extent of m a g n e s i u m o x i d e s u l f a t i o n is not
12.
YANG
ET AL.
Half-Calcined
Dolomite
with Sulfur
Dioxide
155
V>
D _
5 0.6 h
.7
0.8
0.9
3
1.0 I0 /T (K" )
1
I.I
1.2
1.3
Figure 4. Arrhenius plot for the reaction of sulfur dioxide with half-calcined 1337 dolomite
TIME (minutes)
Figure 5. = {CaO and = %S0 : 0.0.

2
Percent conversion vs. time for: + M g O ] ; = [CaC0 + MgO]; MgO at 750C. Gas composition, in 1.1. COy. = 0.0, = 15.0, = 0 : 5.0. H 0: 2.9. N , balance.
3 2 2 2
156
SULFUR
REMOVAL
AND RECOVERY
a n d t h e r e a c t i o n rate is m u c h s l o w e r t h a n f o r t h e h a l f - c a l c i n e d stone. N e v e r t h e l e s s , t h e effect is too great to b e i g n o r e d i n a n y d e t a i l e d treatm e n t of t h e d a t a f o r h a l f - c a l c i n e d stone. F i g u r e 5 also shows results o b t a i n e d f o r t h e s u l f a t i o n of f u l l y c a l c i n e d stone u n d e r the same c o n d i tions except that c a r b o n d i o x i d e w a s absent i n the reactant gas. T h e s e results a r e v e r y s i m i l a r to those f o r the h a l f - c a l c i n e d stone, as one m i g h t e x p e c t i n v i e w of t h e g e n e r a l l y close c o r r e l a t i o n b e t w e e n this w o r k a n d that of B o r g w a r d t ( 1 ). T o date, there h a v e b e e n several u n s u c c e s s f u l attempts to fit these results to a s i m p l e m o d e l f o r e x a m p l e , one b a s e d o n a s h r i n k i n g u n r e a c t e d core or o n r e a c t i o n of a porous s o l i d . T h e a p p a r e n t role of w a t e r i n t h e m e c h a n i s m suggests that s u l f u r d i o x i d e m a y b e o x i d i z e d to s u l f u r t r i o x i d e o n t h e surface a n d that s u l f u r t r i o x i d e diffuses t h r o u g h a p r o d u c t Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch012 l a y e r to react w i t h c a l c i u m carbonate. T h i s c o n c e p t w o u l d b e consistent w i t h t h e s i m i l a r k i n e t i c s o b s e r v e d f o r h a l f - a n d f u l l y c a l c i n e d stone since t h e r a t e - d e t e r m i n i n g step w o u l d p r e s u m a b l y b e t h e same i n either case. T h i s v i e w is s u p p o r t e d b y t h e o b s e r v a t i o n that r e a c t i v i t y i n a of s u l f u r d i o x i d e o x i d a t i o n b e c o m e less f a v o r a b l e . fluidized b e d decreases s o m e w h a t a b o v e about 850 C because t h e t h e r m o d y n a m i c s O n t h e other h a n d , B o r g w a r d t ' s observations w i t h f u l l y c a l c i n e d stone ( 1 ) suggest that t h e decreased r e a c t i v i t y is c a u s e d b y h a r d - b u r n i n g of t h e stone. F u r t h e r w o r k is n e e d e d to u n d e r s t a n d t h e r o l e of w a t e r i n t h e s u l f a t i o n m e c h a n i s m m o r e f u l l y a n d to extend t h e k i n e t i c studies to t h e r e d u c t i o n a n d r e g e n e r a t i o n reactions o u t l i n e d above. T h e p o t e n t i a l advantages of a process u s i n g d o l o m i t e i n a closed c y c l e f o r s u l f u r d i o x i d e c o n t r o l are sufficiently great to w a r r a n t c o n t i n u e d effort. Literature Cited
1. Borgwardt, R. H . , Environ. Sci. Technol. (1970) 4(1), 59. 2. O'Neill, E . P., Keairns, D . L . , Kettle, W . F . , Intern. Conf. Fluidized-Bed Combust., 3rd, Hueston Woods, Ohio, Oct. 29-Nov. 1, 1972. 3. Pell, M . , Ph.D. Thesis, City University of New York, 1970. 4. Pell, M . , Graff, R. ., Squires, A. M . , in "Sulfur and S O Developments," AIChE (1971). 5. Squires, A. M . , Graff, R. ., Pell, M . , Chem. Eng. Prog. Symp. Ser. (1971) 67, 23. 6. Ruth, L . ., Squires, A. M . , Graff, R. ., Environ. Sci. Technol. (1972) 6(12), 1009. 7. Bertrand, R. R., Frost, A. C., Skopp, ., "Fluid Bed Studies of the Limestone Based Flue Gas Desulfurization Process," Interim Report, Contract No. P H 86-67-103, National Air Pollution Control Administration, Esso Research and Engineering Co., Linden, N . J., Oct. 31, 1968. 8. Narayanan, S. G . , M.S. Thesis, City University of New York, 1971. 9. Squires, A. M . , Graff, R. ., J. Air Pollut. Control Ass. (1971) 21, 272. 10. Harvey, R. D . , "Petrographic and Mineralogical Characteristics of Carbonate Rocks Related to Sulfur Dioxide Sorption in Flue Gases," Final
2
12.
YANG E T A L .
Half-Calcined Dolomite with Sulfur Dioxide
157
Report, Contract No. C P A 22-69-65, Environmental Protection Agency, Illinois State Geological Survey, Urbana, Ill., July 15, 1971. 11. Hill, K. J., Winter, E . R. S., J. Phys. Chem. ( 1 9 5 6 ) 60, 1361. RECEIVED April 4, 1974. Work performed under the auspices of the U . S. Atomic Energy Commission and the Environmental Protection Agency, Office of Research and Monitoring, Control Systems Laboratory, Contract No. EPA-IAG0199.
13
Recent Experience of the Wellman-Lord Sulfur Dioxide Recovery Process
W. JEFF OSBORNE and CHRISTOPHER B. EARL Davy Powergas Inc., Lakeland, Fla. 33803
Plants producing
a stack gas containing sulfur dioxide can WellmanThe process is in-
meet provisions of the Clean Air Act by using the -Lord sulfur dioxide recovery process. stalled commercially
at several locations in the United States applicable
and Japan and has demonstrated long term operation reliability while sulfur dioxide removal has met all environmental regulations. plant including application. This paper describes the process costs for a specific
and reviews the application to tail gases from a Claus sulfur capital and operating
T"\avy
Powergas
Inc., formerly W e l l m a n - L o r d
Inc.,
developed
the It
W e l l m a n - L o r d sulfur dioxide recovery process
in the 1960s to
produce a concentrated sulfur dioxide gas from lean off-gas streams.
can be used in any plant that produces a stack gas containing sulfur dioxide, including power plants, sulfuric acid plants, petroleum refineries, and metallurgical plants. Its best application, however, is treating gases which contain 0.15-3.0% sulfur dioxide by volume. Process Description
This recovery process is based on the simple chemistry of the sodium sulfite/bisulfite system. After appropriate pretreatment, the flue gas containing sulfur dioxide enters the absorber, which reduces of turn-down conditions ( Figure 1 ). The sulfur dioxide-rich gas is contacted countercurrently in the absorber by a sodium sulfite solution. As the sodium sulfite absorbs the sulfur dioxide and forms bisulfite, the solution becomes less saturated. This allows highly reliable fouling- or scaling-free operation of the ab158 In Sulfur Removal and Recovery; Pfeiffer, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1975. the sulfur concentration to the required level and can accommodate a wide range
13.
OSBORNE AND EARL
Wellman-Lord
Sulfur Dioxide
Recovery
159
sorber w h i c h is not possible aborber.
i n systems h a v i n g reverse relationships.
A f t e r b e i n g s t r i p p e d of s u l f u r d i o x i d e , the gas passes out the top of the T h e b i s u l f i t e - r i c h s o l u t i o n is d i s c h a r g e d at the b o t t o m of the t o w e r into a surge tank. F r o m the surge tank, t h e bisulfite s o l u t i o n flows s t e a d i l y i n t o a f o r c e d c i r c u l a t i o n e v a p o r a t o r - c r y s t a l l i z e r , w h i c h is the heart of the r e g e n e r a t i o n system. H e a t c a n b e p r o v i d e d b y the l o w - p r e s s u r e exhaust steam that O p e r a t i n g plants n o r m a l l y w o u l d be d i s c h a r g e d into the atmosphere. l o w e r pressures c a n b e u s e d .
are c u r r e n t l y u s i n g steam at pressures as l o w as 15 l b / s q i n . , b u t e v e n I n l a r g e plants s u c h as p o w e r p l a n t s , the as a double-effect 40-45%. evaporator r e g e n e r a t i o n system s h o u l d b e o p e r a t e d
w h i c h w o u l d r e d u c e steam c o n s u m p t i o n b y Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch013 s o d i u m sulfite a n d s u l f u r d i o x i d e . product quality.
I n the evaporator, the bisulfite s o l u t i o n is t h e r m a l l y d e c o m p o s e d to T h e r e s u l t i n g v a p o r is p a r t i a l l y c o n d e n s e d i n one or m o r e stages to r e m o v e w a t e r a n d to achieve the d e s i r e d
ABSORBER
SOLUTION STORAGE
EVAPORATOR CRYSTALLIZER
DISSOLVING TANK
Figure
1.
Basic flow diagram of the W e l l m a n - L o r d sulfur dioxide system
recovery
T h e s o d i u m sulfite p r e c i p i t a t e s out of the bisulfite s o l u t i o n a n d b u i l d s a dense s l u r r y of crystals i n the evaporator. A p o r t i o n of this s l u r r y is The w i t h d r a w n f r o m the e v a p o r a t o r a n d sent to a d i s s o l v i n g t a n k w h e r e w a t e r f r o m the condenser system is a d d e d to dissolve the sulfite crystals. the absorber to c o m p l e t e the process loop. As the s o l u t i o n contacts the gases i n the absorber, a m o d e r a t e a m o u n t of the c i r c u l a t i n g s o l u t i o n is o x i d i z e d to n o n - r e g e n e r a b l e stream of the s o l u t i o n is p u r g e d f r o m the system. sulfate b y the stream o x y g e n or s u l f u r t r i o x i d e i n the gas. T o c o n t r o l the sulfate l e v e l , a s m a l l This purge r e s u l t i n g s o l u t i o n is sent to another surge t a n k a n d is t h e n f e d b a c k i n t o
160
SULFUR
REMOVAL
AND
RECOVERY
c a n be a c i d i f i e d a n d n e u t r a l i z e d to p r o d u c e a s o d i u m sulfate s t r e a m c o n t a i n i n g essentially n o c h e m i c a l or b i o l o g i c a l o x y g e n d e m a n d s so that i t m a y be d i s c h a r g e d as a n i n n o c u o u s efHuent. A selective c r y s t a l l i z a t i o n system m a y also be u s e d to e n r i c h t h e sulfate i n the stream to m i n i m i z e the s o d i u m loss. T h e s e crystals c a n t h e n b e d r i e d for sale. Current Status
T e n W e l l m a n - L o r d installations p r e s e n t l y o p e r a t i n g i n the U n i t e d States a n d J a p a n h a v e a n aggregate o p e r a t i n g experience of m o r e t h a n 10 y r . T h e t o t a l flue gas v o l u m e h a n d l e d b y these o p e r a t i n g units is Twelve other T h e overall capacity approximately 1 million standard c u f t / m i n ( S C F M ) . plants are i n the d e s i g n a n d c o n s t r u c t i o n stage. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch013
of installations w h i c h are o p e r a t i n g or i n d e s i g n is a b o u t 4 m i l l i o n S C F M . T h e first c o m m e r c i a l a p p l i c a t i o n of the W e l l m a n - L o r d process w a s at the O l i n C o r p . s u l f u r i c a c i d r e g e n e r a t i o n p l a n t i n P a u l s b o r o , N . J . T h i s p l a n t regenerates 700 tons of s u l f u r i c a c i d / d a y a n d h a n d l e s a v a r i e t y of spent acids. T h e s u l f u r d i o x i d e content of the t a i l gas varies as the b l e n d s of these acids change. O l i n s absorber system c a n process 45,000 S C F M of t a i l gas c o n t a i n u p to 6,000 p p m s u l f u r d i o x i d e b y v o l u m e . T h e c l e a n e d gas, c o n t a i n i n g atmosphere. less t h a n 500 p p m of s u l f u r d i o x i d e , is d i s c h a r g e d i n t o the plant to produce sulfuric acid. A t C h i b a , J a p a n , the J a p a n S y n t h e t i c R u b b e r C o . has t w o steam boilers w i t h e v a p o r a t i o n rates of 130 m e t r i c t o n s / h r , e a c h e q u i p p e d w i t h W e l l m a n - L o r d s u l f u r d i o x i d e r e c o v e r y u n i t s . T h e l o a d to e a c h s c r u b b e r is essentially constant, b u t s u l f u r d i o x i d e c o n c e n t r a t i o n varies f r o m 400 to 2,000 p p m because of the v a r y i n g quantities of waste process f r o m the p l a n t . M o r e t h a n 9 0 % of t h e s u l f u r d i o x i d e is r e m o v e d , p r o d u c i n g outlet concentrations t h a t are consistently less t h a n 200 p p m . and production. O n l y one-half m a n / s h i f t is r e q u i r e d to operate the system, i n c l u d i n g waste d i s p o s a l T h i s i n s t a l l a t i o n b e g a n o p e r a t i o n i n J u l y 1971 a n d has o p e r a t e d for 3 y r w i t h essentially 1 0 0 % r e l i a b i l i t y . O n e of the most i m p o r t a n t uses for the W e l l m a n - L o r d process is t r e a t i n g off-gases f r o m C l a u s s u l f u r p l a n t s . S t a n d a r d O i l C o . of C a l i f o r n i a (SOCAL) Angeles is u s i n g this processs at its E l S e g u n d o refinery n e a r Los be (Figure 2). A d d i t i o n a l units are b e i n g d e s i g n e d a n d w i l l gas
T h e r e c o v e r e d s u l f u r d i o x i d e v a p o r is r e t u r n e d to the a c i d - r e g e n e r a t i o n
i n s t a l l e d at the E l S e g u n d o refinery a n d at the R i c h m o n d , C a l i f , refinery. A t E l S e g u n d o , t a i l gases f r o m three 135 l o n g - t o n s / d a y (LTPD) disC l a u s units pass t h r o u g h three g a s - h a n d l i n g trains b e f o r e b e i n g
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c h a r g e d to t h e atmosphere.
E a c h t r a i n i n c l u d e s a n i n c i n e r a t o r , a waste A single evaporator
heat b o i l e r , a q u e n c h c o l u m n , a gas cooler, a n d a n absorber. T h e c h e m i c a l p l a n t consists of a single-effect vacuum
set of surge tanks a n d a s i n g l e c h e m i c a l p l a n t serve a l l three gas trains. system f o r r e g e n e r a t i n g the s o l u t i o n a n d l i b e r a t i n g t h e s u l f u r d i o x i d e . I n d i r e c t heat is s u p p l i e d to t h e f o r c e d - c i r c u l a t i o n e v a p o r a t o r b y u s i n g exhaust steam f r o m t h e refinery. T h e v a c u u m is s u p p l i e d b y a l i q u i d r i n g v a c u u m p u m p w h i c h also p u m p s t h e s u l f u r d i o x i d e b a c k i n t o the front of the C l a u s p l a n t .
Figure 2. The sulfur dioxide recovery process installed on a Claus unit at the Standard Oil Co. of California refinery at El Segundo, Calif. T h e E l S e g u n d o i n s t a l l a t i o n i m m e d i a t e l y l o w e r e d the emissions f r o m the S O C A L refinery C l a u s plants to w i t h i n t h e L o s A n g e l e s area l i m i t s of 500 p p m or less of s u l f u r d i o x i d e . A t R i c h m o n d , regulations are e v e n lower300 levels. p p m or less. T h e W e l l m a n - L o r d recovery units being i n s t a l l e d there are g u a r a n t e e d b y D a v y P o w e r g a s to m e e t those e m i s s i o n
162 Process Advantages
SULFUR
REMOVAL
AND
RECOVERY
A b a s i c a d v a n t a g e of the process is t h a t it a l l o w s c o n s i d e r a b l e
flexi-
b i l i t y i n the c h o i c e of e n d p r o d u c t . T h e c o n c e n t r a t e d s u l f u r d i o x i d e gas c a n b e f e d to c o n v e n t i o n a l s u l f u r i c a c i d p l a n t s , r e d u c e d to e l e m e n t a l s u l f u r , or c o n v e r t e d to l i q u i d s u l f u r d i o x i d e . A n y of these p r o d u c t s c a n b e s o l d to r e c l a i m a p o r t i o n of the r e c o v e r y s y s t e m s o p e r a t i n g costs. T h e a b s o r p t i o n system c a n be p h y s i c a l l y s e p a r a t e d f r o m t h e r e g e n e r a t i o n system i f there are space l i m i t a t i o n s w i t h i n the p l a n t . Gases f r o m m o r e t h a n one u n i t c a n b e t r e a t e d b y i n s t a l l i n g separate absorbers c o m m o n r e g e n e r a t i o n system. F e e d i n g solutions f r o m t h e absorber system a n d the r e g e n e r a t i o n Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch013 system t h r o u g h surge tanks enables the entire r e c o v e r y process to operate s m o o t h l y a n d r e l i a b l y d e s p i t e f r e q u e n t gas flow a n d c o n c e n t r a t i o n fluctuations. I n a d d i t i o n , the surge tanks a l l o w the r e g e n e r a t i o n section to be shut d o w n for u p to 3 days w i t h o u t i n t e r f e r i n g w i t h the s u l f u r d i o x i d e r e m o v a l i n t h e a b s o r p t i o n section. T h i s is possible because t h e absorber is the o n l y p a r t of the system t h a t contacts the flue gas a n d removes the sulfur dioxide. T h e a b i l i t y to shut d o w n the r e g e n e r a t i o n section a l l o w s t i m e for s c h e d u l e d m a i n t e n a n c e o r r e p a i r s a n d increases the system's r e l i a b i l i t y . A l s o , the n e e d for expensive spare e q u i p m e n t is m i n i m i z e d w i t h o u t s a c r i ficing b a s i c p o l l u t i o n c o n t r o l . Typical Cost Analysis for e a c h s u l f u r d i o x i d e source, w i t h a l l the absorbers b e i n g s u p p l i e d b y a
T o i l l u s t r a t e the e c o n o m i c s i n v o l v e d i n a p p l y i n g the W e l l m a n - L o r d process to a C l a u s p l a n t , t h e f o l l o w i n g h y p o t h e t i c a l case w i l l i n d i c a t e the r e l a t i o n s h i p of costs to the p e r f o r m a n c e g i v e n . T h e b a s i c p a r a m e t e r s of this e x a m p l e a r e : 1. T h r e e C l a u s plants at 150 L T P D each. 2. R e c o v e r y efficiency of the C l a u s p l a n t of 9 6 % . 3. I n e a c h gas h a n d l i n g t r a i n o n e waste heat b o i l e r , one q u e n c h c o o l i n g section, a n d one s u l f u r d i o x i d e absorber system for e a c h C l a u s Plant. 4. O n e c o m m o n c h e m i c a l p l a n t for r e g e n e r a t i o n of the s o l u t i o n f r o m a l l three absorbers. 5. S u r g e t a n k a g e for b o t h absorber f e e d a n d a b s o r b e r p r o d u c t s o l u t i o n sufficient for 3 days o u t p u t f r o m the c h e m i c a l p l a n t . T h e gas flow to e a c h absorber is 12,000 S C F M w i t h a s u l f u r d i o x i d e content of a b o u t 1100 l b / h r , so t h e t o t a l s u l f u r d i o x i d e p r o d u c e d i n the e v a p o r a t o r system w i l l b e 2900 l b / h r . T h e c a p i t a l cost of p r o d u c i n g a n exit gas w i t h less t h a n 250 p p m s u l f u r d i o x i d e b y v o l u m e w i l l b e a p p r o x i m a t e l y five m i l l i o n d o l l a r s . T h e
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operating
cost, i n c l u d i n g c a p i t a l charges,
labor, supervision, payroll,
m a i n t e n a n c e , u t i l i t i e s , a n d o v e r h e a d is a b o u t $800,000 a n n u a l l y . T h e J a p a n S y n t h e t i c R u b b e r C o . i n s t a l l a t i o n at C h i b a illustrates costs of a second t y p e of a p p l i c a t i o n . D u r i n g its first 10 m o of o p e r a t i o n , its o p e r a t i n g costs w e r e b r o k e n d o w n as f o l l o w s : 5 0 % f o r interest a n d c a r r y i n g charges, 1 5 % for steam, 1 0 % for electric p o w e r , 1 0 % for c a u s t i c soda c o n s u m p t i o n , a n d 1 5 % for l a b o r a n d m i s c e l l a n e o u s costs. Future Developmental Plants
T h e W e l l m a n - L o r d process c a n b e a significant f a c t o r i n h e l p i n g d o m e s t i c p o w e r plants to m e e t the a i r p o l l u t i o n a b a t e m e n t r e q u i r e m e n t s of the C l e a n A i r A c t of 1970. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch013 T o s h o w its a p p l i c a b i l i t y to the u t i l i t i e s i n d u s t r y , D a v y P o w e r g a s Inc. is b u i l d i n g a d e m o n s t r a t i o n i n s t a l l a t i o n at the D e a n H . M i t c h e l l S t a t i o n of N o r t h e r n I n d i a n a P u b l i c S e r v i c e C o . i n G a r y , I n d . W h e n c o m p l e t e d , it w i l l consist of a W e l l m a n - L o r d s u l f u r d i o x i d e r e c o v e r y u n i t c o n n e c t e d to a n A l l i e d C h e m i c a l C o . s u l f u r d i o x i d e to-sulfur r e d u c t i o n process to p r o d u c e e l e m e n t a l sulfur. D a v y P o w e r g a s guarantees emissions of 200 p p m b y v o l u m e or less of s u l f u r d i o x i d e at this f a c i l i t y . Processes t h a t h a v e b e e n successful i n other i n d u s t r i a l a p p l i c a t i o n s p r e s e n t l y are b e i n g s t u d i e d for i n c l u s i o n i n the W e l l m a n - L o r d process. T h i s w o u l d a l l o w the system to operate as a c l o s e d l o o p w i t h t o t a l s o d i u m and ing s u l f u r d i o x i d e r e c o v e r y a n d w o u l d e l i m i n a t e effluent streams r e q u i r treatment. F u r t h e r test w o r k is necessary, h o w e v e r , b e f o r e i n c l u d i n g process.
another i d e a into the c o m m e r c i a l l y p r o v e d

R E C E I V E D A p r i l 15, 1974
14
Regenerative Aqueous Carbonate Process for Utility and Industrial Sulfur Dioxide Removal
W . V. B O T T S and D. C. G E H R I Atomics International Division, Rockwell International Corp., P.O. Box 309, Canoga Park, Calif. 91304
The aqueous carbonate process (ACP) is a unique regenerative sulfur dioxide removal process which is applicable sodium carbonate solution to utility and industrial installations. This process uses a dilute to remove sulfur dioxide from flue gases. The scrubbant is atomized in a spray dryer. Sodium sulfites and sulfates are formed which are reduced and regenerated to carbonate in an aqueous regenerative subsystem which also produces sulfur. The process eliminates the great quantities of solid waste associated with open loop processes. Reheat is eliminated because the flue gas is not saturated during scrubbing. throughput). Typical economics show a of gas have capital cost of below $70/kw ($32 per 1000/SCF Operating costs from 1 to 3 mills/kw-hr
been estimated. The process, a summary of pilot test results, integration information, and system economics are discussed.
' T ' h e aqueous carbonate process ( A C P ) has been under development at Atomics International for the last 4V2 yr. The program aims to establish a technology which eliminates or minimizes the major problems encountered in operating most other sulfur dioxide removal processes. That technology includes the use of sodium carbonate as the scrubbant in the modified spray dryer and the complete regeneration of the sulfur dioxide removal products to recover elemental sulfur and produce sodium carbonate for reuse in the spray dryer-scrubber. The modified spray dryer provides intimate contact between the sulfur dioxide-containing waste gas and a finely atomized fog of sodium carbonate solution. Only small quantities of the reactive sodium car164
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bonate s o l u t i o n are r e q u i r e d to a c h i e v e excellent s u l f u r d i o x i d e r e m o v a l . T h e r e a c t i o n p r o d u c t is a d r y p o w d e r easily c o l l e c t e d a n d stored, a n d the waste gas does not b e c o m e saturated w i t h w a t e r v a p o r . T h i s k i n d of s c r u b b e r is not subject to s c a l i n g or p l u g g i n g p r o b l e m s , does not r e q u i r e a gas reheater, a n d operates w i t h a l o w l i q u i d - t o - g a s r a t i o . B y p r o v i d i n g surge c a p a c i t y for the s o d i u m carbonate s o l u t i o n a n d storage i n e x p e n s i v e l y d e c o u p l e d f r o m the r e g e n e r a t i o n system. reliability. C o m p l e t e r e g e n e r a t i o n i n the A C P system is a c c o m p l i s h e d b y three basic c h e m i c a l steps. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch014 I n the first step the p r o d u c t s o d i u m sulfite a n d sulfate are r e d u c e d to s o d i u m sulfide. A t o m i c s I n t e r n a t i o n a l has d e v e l o p e d a h i g h t e m p e r a t u r e r e d u c e r w h i c h accepts the p r o d u c t f r o m the s p r a y d r y e r - s c r u b b e r , melts i t , elevates its t e m p e r a t u r e , a n d reduces the s u l f u r - c o n t a i n i n g salts to the d e s i r e d sulfide f o r m w i t h coke or coal. second The r e g e n e r a t i o n step i n v o l v e s d i s s o l v i n g the sulfide i n w a t e r a n d T e c h n o l o g y s i m i l a r to that u s e d capacity for the d r y r e a c t i o n p r o d u c t , the s c r u b b i n g system c a n b e easily a n d T h e net result is a s u l f u r d i o x i d e s c r u b b i n g system w i t h a h i g h degree of o p e r a t i o n a l
c a r b o n a t i n g it to r e f o r m s o d i u m c a r b o n a t e for r e c y c l e to the s c r u b b e r . A h y d r o g e n s u l f i d e - r i c h gas is e v o l v e d . i n c h e m i c a l r e c o v e r y processes i n the p u l p a n d p a p e r i n d u s t r y is used. I n the final step the h y d r o g e n sulfide is c o n v e r t e d to e l e m e n t a l s u l f u r b y a C l a u s process. S i n c e e l e m e n t a l s u l f u r is the o n l y system b y - p r o d u c t , the p r o b l e m s of d i s p o s i n g of s l u d g e or sulfate b l e e d streams are e l i m i n a t e d . T h e A C P system c o m b i n e s a s u l f u r d i o x i d e s c r u b b i n g system b a s e d o n s p r a y d r y e r t e c h n o l o g y w i t h a r e g e n e r a t i o n system b a s e d o n a u n i q u e r e d u c t i o n step c o u p l e d to c h e m i c a l r e c o v e r y a n d C l a u s technologies. sulfur dioxide pollution problems. This c o m b i n a t i o n results i n a n efficient a n d r e l i a b l e process for a p p l i c a t i o n to T h e r e m a i n d e r of this p a p e r discusses the details of t h e process a n d t y p i c a l i n s t a l l a t i o n characteristics a n d also presents process e c o n o m i c s w h i c h i n d i c a t e that the A C P system is econ o m i c a l l y feasible a w e l l as t e c h n i c a l l y s o u n d . Process Description
T h e k e y c o m p o n e n t of t h e A C P s c r u b b i n g system is a m o d i f i e d s p r a y d r y e r w h i c h serves as a r e a c t i o n c h a m b e r for the s u l f u r d i o x i d e r e m o v a l . I n the spray d r y e r , the s o d i u m carbonate s o l u t i o n is a t o m i z e d b y a h i g h speed c e n t r i f u g a l a t o m i z e r a n d m i x e d w i t h the hot gas e n t e r i n g the d r y e r t h r o u g h a v a n e - r i n g . T h e fine m i s t of s o l u t i o n droplets absorbs s u l f u r d i o x i d e w h i l e the t h e r m a l energy of the waste gas v a p o r i z e s the w a t e r w i t h o u t s a t u r a t i n g or excessively c o o l i n g the gas. reaction products f r o m the c o n t a c t o r s o d i u m T h u s , the s p r a y d r y e r carbonate, sulfite, a n d p r o d u c e s a gas l o w i n s u l f u r d i o x i d e b u t c o n t a i n i n g d r y p a r t i c l e s of t h e
166 sulfate.
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REMOVAL
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RECOVERY
T h i s p o w d e r is s u b s e q u e n t l y separated f r o m the gas a n d c o l version. After product collection, the
l e c t e d for d i s p o s a l w i t h the o p e n l o o p system or for processing a n d reg e n e r a t i o n i n the regenerative t r e a t e d waste gas r e m a i n s r e l a t i v e l y h o t a n d is v e n t e d t h r o u g h a stack. F i g u r e 1 is a b l o c k d i a g r a m of the k e y subsystems of a n A C P r e g e n erative system w h i c h are i n t e g r a t e d i n t o a n e x i s t i n g p o w e r p l a n t w h e r e the c l e a n gas is v e n t e d t h r o u g h a n existing stack after i t has b e e n t h r o u g h the s c r u b b e r a n d solids r e m o v a l systems. T y p i c a l l y , a n e w i n d u c e d draft
EXISTING STACK
Na2S0
ELEMENTAL SULFUR
Figure
1.
Regenerative
AC?
block
diagram
f a n is r e q u i r e d to p r o v i d e the pressure to m o v e the gas t h r o u g h the system. D r y p o w d e r f r o m the solids r e m o v a l system is t r a n s f e r r e d to the b l o c k s h o w n as the regenerative system. T h e c h e m i c a l s n e e d e d b y the r e g e n e r a t i o n system i n c l u d e m a k e u p s o d i u m carbonate (soda ash), a c a r b o n source for the r e d u c t i o n step, a n d w a t e r . T h e p r o d u c t s f r o m this system are ash, which is d e r i v e d mainly from the flue gas, and elemental sulfur, w h i c h is a h i g h p u r i t y b y - p r o d u c t . A d d i t i o n a l d e t a i l o n the scrubber
system is s h o w n i n F i g u r e 2 s u c h as the s o l u t i o n f e e d tanks a n d p u m p s , the s p r a y d r y e r , cyclones, a n d , i n this case, for v e r y h i g h p a r t i c u l a t e rem o v a l , a s m a l l electrostatic p r e c i p i t a t o r . I n a d d i t i o n , a solids transfer and system is s h o w n w h i c h conveys the d r y p o w d e r f r o m the cyclones s h o w n i n F i g u r e 2 is s u i t a b l e for retrofit i n t o a n e x i s t i n g p l a n t . A n A C P r e g e n e r a t i o n system flow d i a g r a m is s h o w n i n F i g u r e 3. T h i s d i a g r a m represents t y p i c a l processing steps w i t h o u t p r o p r i e t a r y m o d i f i c a tions or o p e r a t i o n a l details. A s s h o w n , the p r o d u c t salt is c o n v e y e d a l o n g w i t h coke or a n y other c a r b o n source to the m o l t e n salt r e d u c e r . I n the r e d u c e r the salt is h e a t e d , m e l t e d , a n d r e d u c e d i n a single z o n e b y a d d i n g a i r a n d coke. A i r p r o v i d e s some r e o x i d a t i o n of sulfide to generate sensible heat w h i l e the coke acts d i r e c t l y to r e d u c e the sulfite a n d sulfate to sulfide. T h e m o l t e n m i x t u r e is passed i n t o a q u e n c h tank w h e r e it is d i s s o l v e d a n d processed as a l o w t e m p e r a t u r e ( b e l o w the b o i l i n g p o i n t of w a t e r )
p r e c i p i t a t o r to a separate or adjacent r e g e n e r a t i o n system. T h e e q u i p m e n t
14.
Regenerative
Aqueous
Carbonate
Process
167
FROM EXISTING PLANT UTILITIES COOLING WATER PIPING TYPICAL EACH MACHINE
GAS STACK
Figure 2.
Scrubber subsystem loop
aqueous s o l u t i o n . T h e r e d u c e r off-gas is u s e d as the c a r b o n d i o x i d e source for subsequent c a r b o n a t i o n steps a n d as a source of process heat. T h e aqueous s o l u t i o n is c o o l e d a n d filtered to r e m o v e a n y excess coke, c o k e ash, or fly ash. A f t e r filtration, t h e s o l u t i o n is p r e c a r b o n a t e d F i n a l carbonaa n d the w i t h p u r e c a r b o n d i o x i d e r e c o v e r e d f r o m the decomposer. r e d u c e r off-gas.
t i o n occurs i n the b i c a r b o n a t o r - c r y s t a l l i z e r w i t h c a r b o n d i o x i d e f r o m the Gases e v o l v e d f r o m b o t h the p r e c a r b o n a t o r

GAS TO SCRUBBER
W-1 W-2
STEAM CONDENSER STEAM CONDENSER
Figure 3.
Regeneration
subsystem
168
SULFUR
REMOVAL
AND
RECOVERY
b i c a r b o n a t o r - c r y s t a l l i z e r are r i c h i n h y d r o g e n sulfide a n d are c o m b i n e d for subsequent r e c o v e r y of e l e m e n t a l s u l f u r i n the C l a u s p l a n t . T a i l gas f r o m the C l a u s p l a n t is r e t u r n e d to the s c r u b b e r for final c l e a n u p . T h e p r o d u c t f r o m t h e b i c a r b o n a t o r - c r y s t a l l i z e r is a s o d i u m c a r b o n a t e - s o d i u m b i c a r b o n a t e s l u r r y w h i c h is d e c o m p o s e d to p r o d u c e a s o d i u m carbonate s o l u t i o n for r e t u r n to the s c r u b b e r to p r o v i d e p u r e carbon d i o x i d e for the p r e c a r b o n a t o r . T h i s completes t h e r e g e n e r a t i o n c y c l e a n d closes the l o o p for t h e t o t a l A C P system. T h e t e c h n o l o g y i n v o l v e d is a c o m b i n a t i o n of a u n i q u e r e d u c e r a n d aqueous c h e m i c a l processing, most of w h i c h is c o m m e r c i a l l y p r o v e d . So far, d e v e l o p m e n t efforts h a v e c o n c e n t r a t e d o n p i l o t d e m o n s t r a t i o n of the s c r u b b i n g system a n d t h e r e d u c e r . E x t e n s i v e test d a t a h a v e b e e n generated w i t h 5-ft a n d 7-ft d i a m e t e r spray d r y e r - s c r u b b e r s . P r o p r i e t a r y Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch014 test results are a v a i l a b l e f r o m 4-ft a n d 9-ft d i a m e t e r reducers. K e y o p e r a t i n g a n d p e r f o r m a n c e characteristics of the aqueous r e g e n e r a t i o n steps h a v e also b e e n tested. T h e s e p i l o t test results c o m b i n e d w i t h e x i s t i n g d a t a a n d t e c h n o l o g y f r o m the s p r a y d r y i n g a n d p u l p a n d p a p e r i n d u s t r i e s p r o v i d e a firm t e c h n i c a l base for the d e s i g n a n d c o n s t r u c t i o n of large-scale ACP systems. A k e y c o m p o n e n t of the r e g e n e r a t i o n subsystem is the r e d u c e r . T h i s component is a c e r a m i c - l i n e d vessel w h i c h contains the m o l t e n salt at temperatures a p p r o a c h i n g 2000 F . T h e c o m p o n e n t is c o m m o n to several other s u l f u r d i o x i d e a n d c o a l gasification processes a n d has b e e n d e m o n strated at b o t h 4-ft a n d 9-ft d i a m e t e r size scales. I n the r e d u c e r , b o t h the o x i d a t i o n of sulfide to sulfate a n d the r e d u c t i o n of sulfate to sulfide b y the coke p r o c e e d s i m u l t a n e o u s l y . Test Results T h e first p i l o t s c r u b b e r tests w e r e c o n d u c t e d u s i n g s i m u l a t e d flue gas to e s t a b l i s h the f e a s i b i l i t y of s u l f u r dioxide's r e a c t i n g w i t h s o d i u m c a r bonate solutions a n d slurries i n a s p r a y d r y e r . S u b s e q u e n t tests w e r e c o n d u c t e d at t h e M o h a v e g e n e r a t i n g s t a t i o n , w h e r e a 5-ft d i a m e t e r m o d i fied s p r a y d r y e r was u s e d to test s u l f u r d i o x i d e r e m o v a l f r o m a side stream of flue gas f r o m this coal-fired p o w e r p l a n t ( F i g u r e 4 ). T h e s p r a y d r y e r h a d b e e n i n o p e r a t i o n for o v e r 20 y r i n v a r i o u s d r y i n g a p p l i c a t i o n s p r i o r to m o d i f i c a t i o n to a s u l f u r d i o x i d e scrubber. It was u s e d i n over 100 tests at M o h a v e w i t h o u t a single o p e r a t i o n a l p r o b l e m . M o s t of the M o h a v e test d a t a w e r e o b t a i n e d w i t h flue gas c o n t a i n i n g 400 p p m or less s u l f u r d i o x i d e since this is c h a r a c t e r i s t i c for a p o w e r p l a n t b u r n i n g l o w s u l f u r w e s t e r n c o a l . A f e w tests w e r e r u n at v a r i o u s c o n c e n trations u p to 1500 p p m , b u t most of the a v a i l a b l e d a t a at h i g h s u l f u r d i o x i d e concentrations w e r e o b t a i n e d u s i n g s i m u l a t e d flue gas i n a 7-ft
14.
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Aqueous
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169
d i a m e t e r s p r a y d r y e r s c r u b b e r . A f t e r e s t a b l i s h i n g that the d a t a o b t a i n e d at M o h a v e w a s i d e n t i c a l to that o b t a i n e d w h e n u s i n g s i m u l a t e d flue gas, a n extensive r a n g e of tests w a s r u n w i t h the 7-ft u n i t at s u l f u r d i o x i d e concentrations r a n g i n g f r o m 200 to 8000 p p m . T h e s e d a t a c o v e r t h e r a n g e of most u t i l i t y a n d i n d u s t r i a l s c r u b b i n g a p p l i c a t i o n s a n d c a n b e s u p p l e -
Figure 4.
Pilot scrubber
installation
m e n t e d as necessary i n the f u t u r e to c o v e r s p e c i a l or u n u s u a l s u l f u r dioxide removal problems. F i g u r e 5 is a p l o t of some of the d a t a t a k e n d u r i n g t h e M o h a v e test p r o g r a m a n d illustrates a n i m p o r t a n t a n d d e s i r a b l e o p e r a t i o n c h a r a c t e r istic of a s p r a y d r y e r - s c r u b b e r . O n l y a b o u t 0.3 g a l of the 5.5 w t % of s o d i u m carbonate s o l u t i o n was n e e d e d / 1 0 0 0 s t a n d a r d c u ft ( S C F ) dioxide. S u b s e q u e n t tests h a v e c o n f i r m e d that this same
flue gas to o b t a i n greater t h a n 9 0 % r e m o v a l of the 400 p p m i n l e t s u l f u r liquid-to-gas ratio ( L / G ) c a n b e u s e d to r e m o v e greater t h a n 9 0 % of the s u l f u r d i o x i d e f r o m gases c o n t a i n i n g 2 0 0 - 4 0 0 0 p p m s u l f u r d i o x i d e . T h e concentration of s o d i u m c a r b o n a t e i n s o l u t i o n is a d j u s t e d i n p r o p o r t i o n to the s u l f u r d i o x i d e c o n c e n t r a t i o n i n the gas to p r o v i d e sufficient a l k a l i n i t y to n e u t r a l i z e the a b s o r b e d s u l f u r d i o x i d e , b u t the L / G itself r e m a i n s at a b o u t 0.3 g a l / 1 0 0 0 S C F o v e r this r a n g e of concentrations. A b o v e 4000 ppm Hows u l f u r d i o x i d e , i t is necessary to increase the L / G to p r o v i d e e n o u g h d i s s o l v e d s o d i u m c a r b o n a t e to react w i t h the a b s o r b e d s u l f u r d i o x i d e . ever, e v e n at 8000 p p m s u l f u r d i o x i d e , t h e r e q u i r e d L / G is o n l y a b o u t
170
SULFUR
REMOVAL
AND RECOVERY
Figure
5.
Sulfur dioxide removal vs. absorbent flow rate
0.6 g a l / 1 0 0 0 S C F as c o m p a r e d w i t h most other scrubbers w h i c h w o u l d r e q u i r e 1 0 - 1 0 0 g a l / S C F for s u c h a n a p p l i c a t i o n . O n e of the p r i m a r y reasons that the s p r a y d r y e r - s c r u b b e r is able to a c h i e v e excellent sulfur d i o x i d e r e m o v a l w i t h s u c h l o w l i q u i d - t o - g a s ratios is the s m a l l size of the droplets p r o d u c e d b y the h i g h speed c e n t r i f u g a l a t o m i z e r . T h i s t y p e of a t o m i z e r also has a n easily c o n t r o l l e d t u r n d o w n c a p a b i l i t y w h i c h is a d e s i r a b l e feature that has b e e n d e m o n s t r a t e d i n the p i l o t tests. A s gas flow decreases, the a m o u n t of s o d i u m carbonate s o l u t i o n c a n be decreased i n d i r e c t p r o p o r t i o n w i t h o u t i n t e r f e r i n g w i t h s u l f u r d i o x i d e r e m o v a l efficiency. T h e a t o m i z e r a c t u a l l y p r o d u c e s finer droplets at the l o w e r l i q u i d flow rates. T h i s appears to compensate for a n y g a s l i q u i d m i x i n g p r o b l e m s that c o u l d i m p a i r p e r f o r m a n c e . T h e p r o p e r o p e r a t i o n of a s p r a y d r y e r - s c r u b b e r also r e q u i r e s that a d r y p r o d u c t b e f o r m e d a n d s u b s e q u e n t l y r e m o v e d f r o m t h e gas stream. P i l o t tests h a v e s h o w n t h a t the p r o d u c t salts w i l l be d r y a n d c o l l e c t a b l e if t h e gas t e m p e r a t u r e at the d r y e r outlet is m a i n t a i n e d a b o u t 2 0 F a b o v e its d e w p o i n t . T h i s also tends to m i n i m i z e p l u m e f o r m a t i o n . T h e c y c l o n e collectors u s e d i n the p i l o t tests r e m o v e d 8 9 - 9 9 % of t h e p r o d u c t . A l t h o u g h this w a s excellent p e r f o r m a n c e b y m e c h a n i c a l collectors, p a r t i c u late e m i s s i o n standards w i l l r e q u i r e either r e p l a c e m e n t of the cyclones or a d d i t i o n a l c o l l e c t i o n devices i n series w i t h the cyclones. T h e system d e s i g n p r e s e n t l y f a v o r e d i n v o l v e s u s i n g cyclones to r e m o v e the b u l k of t h e p r o d u c t a n d a d d i n g a s m a l l electrostatic p r e c i p i t a t o r for final p a r t i c u l a t e r e m o v a l . T h e s o d i u m salts p r o d u c e d i n t h e s p r a y d r y e r - s c r u b b e r
14.
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Aqueous
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171
h a v e excellent r e s i s t i v i t y p r o p e r t i e s to p r o m o t e precipitation.
effective
electrostatic
It w a s o b s e r v e d d u r i n g the M o h a v e tests that the fine fly ash p a r t i c l e s e n t e r i n g the s p r a y d r y e r w e r e often t r a p p e d i n the c y c l o n e a l o n g w i t h the b u l k of the p r o d u c t salt, a p p a r e n t l y because of a g g l o m e r a t i o n w i t h the a t o m i z e d droplets i n the s p r a y d r y e r . T h u s , the d r y e r itself helps to m i n i m i z e e m i s s i o n of fine ash p a r t i c l e s w h i c h are n o r m a l l y difficult to r e m o v e e v e n w i t h a n electrostatic p r e c i p i t a t o r . N u m e r o u s samples h a v e b e e n t a k e n a n d extensive d a t a h a v e b e e n a c c u m u l a t e d o n the p h y s i c a l Table I. Inlet Flue Gas Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch014 T y p i c a l Scrubber System Performance Low Sulfur 300 400 0.03 ( d o w n s t r e a m of m a i n power p l a n t electrostatic precipitator) 14 Coal 3% 300 2200 2.0 (no p r i o r ash removal) Sulfur Coal
Properties
Temperature (F) S 0 concentrations (ppm) A s h content (grain/SCF)

2
H 0 content (vol
2
%)
10
Spray Dryer Operating Conditions Feed composition 4.4 20 (wt % N a C 0 ) 0.34 (0.70 l b F e e d rate 0.32 (0.12 l b Na CO /1000 SCF) (gal/1000 S C F ) Na CO /1000 SCF) 10 G a s pressure d r o p ( i n . 9 H 0 , including cyclone)
2 3 2 3 2 3 2
Exit Gas Properties T e m p e r a t u r e (F) D e w p o i n t (F) SO 2 concentration (ppm) Particulate loading (grain/SCF with cyclone)
155 134.5 40 ( 9 0 % r e m o v a l ) ~0.05 ( < 0.01 g r a i n / S C F w i t h electrostatic precipitator acc o r d i n g to m a n u facturer's g u a r a n teed specification) %) 6 12 17 62 1 2
155 132.5 130 ( 9 4 % r e m o v a l ) 0.2 (estimated 0.01 w i t h a d d i t i o n of p r e cipitator)
Product Composition Na C0 NaHC0 Na S0 Na S0 H 0 Ash

2 3 3 2 4 2 3 2
(wt
5 10 12 50 1 22
172
SULFUR
REMOVAL
AND RECOVERY
a n d c h e m i c a l p r o p e r t i e s of t h e p r o d u c t salts, b o t h u p s t r e a m a n d d o w n s t r e a m of t h e c y c l o n e . T h e s e d a t a are c o n s i d e r e d a d e q u a t e to specify, d e s i g n , a n d w a r r a n t p r o d u c t i o n c o l l e c t i o n systems c a p a b l e of l i m i t i n g emissions to less t h a n 0.01 g r a i n / S C F . T y p i c a l s c r u b b e r system p e r f o r m a n c e is g i v e n i n T a b l e I. I t w a s d e r i v e d f r o m test results, a n d it shows t w o casesone r e p r e s e n t i n g a p o w e r
Figure 6.
Typical ACP system plot arrangement
p l a n t s u c h as M o h a v e w h i c h b u r n s l o w s u l f u r w e s t e r n c o a l a n d t h e other r e p r e s e n t i n g a p o w e r p l a n t w h i c h b u r n s 3 % s u l f u r eastern c o a l . The m a j o r difference i n the t w o cases occurs because of t h e w a t e r v a p o r a n d t h e a s h content i n t h e i n l e t flue gas. T h e i n l e t w a t e r v a p o r content i n the M o h a v e case l i m i t s the a m o u n t of s o l u t i o n that c a n b e s p r a y e d i n t o t h e gas a n d t h e r e b y l i m i t s s u l f u r d i o x i d e r e m o v a l . T h e i n l e t ash content i n t h e s e c o n d case causes a s l i g h t l y h i g h e r a n d adds a significant b u r d e n to the p a r t i c u l a t e c o l l e c t i o n e q u i p m e n t . T h e h i g h p e r c e n t a g e of a s h i n t h e p r o d u c t w i l l also c o m p l i c a t e r e g e n e r a t i o n . B e n c h a n d p i l o t scale tests of the v a r i o u s steps i n A C P r e g e n e r a t i o n h a v e b e e n c o n d u c t e d s u c h as r e d u c t i o n , q u e n c h i n g , filtration, precarbonaThese t i o n , c a r b o n a t i o n , d e c o m p o s i t i o n , a n d h y d r o g e n sulfide s c r u b b i n g .
tests are c o n t i n u i n g i n t h e laboratories a n d the n e a r b y field test f a c i l i t y to o p t i m i z e t h e A C P r e g e n e r a t i o n system p e r f o r m a n c e a n d / o r to d e v e l o p n e w a n d better processing technology.
14.
BOTTS A N D G E H R I Engineering
Regenerative
Aqueous
Carbonate
Process
173
System
A n u m b e r of e n g i n e e r i n g studies h a v e b e e n c o n d u c t e d to e v a l u a t e the size, i n t e g r a t i o n a b i l i t y , cost, a n d interfaces of f u l l - s c a l e A C P systems. M o s t of this w o r k has b e e n d o n e i n c o n n e c t i o n w i t h p o w e r p l a n t i n t e g r a t i o n , b u t t h e results c a n be a p p l i e d to b o t h i n d u s t r i a l a n d p o w e r p l a n t s . F i g u r e 6 shows a p l o t p l a n for a n A C P system t h a t treats i n excess of 825,000 s t a n d a r d c u f t / m i n ( S C F M ) . T h e inlet sulfur dioxide concent r a t i o n of this gas is a p p r o x i m a t e l y 2200 p p m . or 0.027 l b / 1 0 B t u .
6
T h e system is d e s i g n e d
for a 9 5 . 5 % r e m o v a l a n d a n outlet p a r t i c u l a t e l o a d i n g of 0.01 g r a i n / S C F F i g u r e 7 is a p l a n v i e w of the s c r u b b e r i n s t a l l a t i o n w i t h t w i n s c r u b bers u s e d to treat the 825,000 S C F M . Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch014 T h e gas is r e m o v e d f r o m e x i s t i n g d u c t w o r k , c o n v e y e d to the t o p of the s c r u b b e r , a n d passed t h r o u g h the s c r u b b e r , cyclones, p r e c i p i t a t o r , booster fans, a n d b a c k to the e x i s t i n g stack. T h e e x i s t i n g d u c t i n g or the s c r u b b e r system, c a n b e b y p a s s e d d e p e n d i n g o n o p e r a t i n g a n d m a i n t e n a n c e cycles i n the p o w e r p l a n t . The scrubbers are a p p r o x i m a t e l y the largest m o d u l e size p r o p o s e d for either
I*-EXIST. COAL CONVEYOR EXIST. FLUE GAS DUCT AND STACK
SPRAY DRYER -EXIST. SOUTH ROAD
Figure 7.
Scrubber installation plan view
p o w e r or i n d u s t r i a l p l a n t s . T h e y are 52 ft i n d i a m e t e r a n d are m a d e of c a r b o n steel. F i g u r e 8 shows the s c r u b b e r i n s t a l l a t i o n stands 135 ft h i g h . W h i l e the e q u i p m e n t is o b v i o u s l y large, the costs associated w i t h these l o w energy s c r u b b e r systems are a c c e p t a b l y l o w . T h e t e c h n o l o g y is w e l l
174
7 ft 6 in. 21 ft DUCT 7 ft 6 in. 21 ft DUCT
SULFUR
REMOVAL
AND RECOVERY
OPERPT. EL. 131 ft 0 in.
16 ft 9 ft DUCT
NEW CONNECTION TO EXISTING (TYP 2 PLACES)!
ROTATE EXISTING ID FAN AS SHOWN EL. EXISTING ID FAN 17 ft 5-1/2 in. EL. 9 ft 6 in.
CONNECTION EXISTING (TYP 2 PLACES) SECTION A-A

T 0
ELECTROSTATIC PRECIPITATORS
Figure 8.
Scrubber installation elevation view
e s t a b l i s h e d , a n d materials s u c h as c a r b o n steel c a n b e u s e d because of t h e u n i q u e i n t e r n a l e n v i r o n m e n t of a s p r a y d r y e r - s c r u b b e r . T h e r e g e n e r a t i o n system associated w i t h , b u t d e c o u p l e d f r o m , t h e s c r u b b e r i n s t a l l a t i o n o c c u p i e s a p l o t of a b o u t 7 / 1 0 acre ( F i g u r e 9 ) . out. T h e system c a n p r o d u c e 17.7 t o n s / h r of s o d i u m c a r b o n a t e . It contains d u a l reducers a n d m u l t i p l e aqueous p r o c e s s i n g c o l u m n s t h r o u g h That
PRECARBONATION TOWERS PC-1 AND PC-2 SPENT ABSORBENT SYSTEM H-1b REDUCER R-1 \ CARBONATION TOWERS CT-1 AND CT-2 CARBONATE UNLOADING SYSTEM CARBONATE HANDLING SYSTEM H-3a
CONTROL HOUSE REDUCER R-2 AND MAINTENANCE BLDG. (25 ft 120 ft REDUCER AIR COMPRESSORS C-2a AND C-2b AIR PREHTR B-4 PROCESS GAS COMPRESSORS C-3a, C-3b, C-3c MAXIMUM)
Figure 9.
Regeneration
system plot
14.
Regenerative
Aqueous
Carbonate
Process
175
EL. 16 ft-0 in.
$8 * Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch014 Figure 10. Regeneration elevation
M 2 J
view
a m o u n t p r o v i d e s for p r o d u c t salt r e g e n e r a t i o n o n a c o n t i n u o u s basis w h e n t h e p o w e r p l a n t operates at f u l l c a p a c i t y o n 3 . 5 % s u l f u r c o a l . F i g u r e 10 shows a n e l e v a t i o n of this r e g e n e r a t i o n system. T h e largest e q u i p m e n t is associated w i t h the r e g e n e r a t e d carbonate h a n d l i n g a n d storage system. T h e r e d u c e r e q u i p m e n t , w h i c h is e l e v a t e d a b o v e the q u e n c h t a n k , is a b o u t 60 ft h i g h . T h i s p a r t i c u l a r regenerative A C P system i n c l u d i n g the C l a u s p l a n t r e q u i r e s a p p r o x i m a t e l y 2 % acres of l a n d , or a b o u t 300 s q f t / M w sq f t / 1 0 0 0 reliability. SCFM treated). T h e regeneration equipment can be (140 de-
c o u p l e d f r o m the s c r u b b e r system, y i e l d i n g h i g h o v e r a l l A C P system T h e d e c o u p l i n g is a f u n c t i o n of the surge c a p a c i t y w h i c h is Table II p l a c e d b e t w e e n the s c r u b b e r a n d the r e g e n e r a t i o n e q u i p m e n t .
shows the e x p e c t e d p e r f o r m a n c e f r o m this p l a n t . T h e t w o c o l u m n s i n d i c a t e the d e s i g n p e r f o r m a n c e a n d the w a r r a n t e d p e r f o r m a n c e . T h e p l a n t w i l l b e d e s i g n e d for s o m e w h a t better o p e r a t i n g p e r f o r m a n c e t h a n w i l l be w a r r a n t e d . H o w e v e r , e v e n the w a r r a n t e d p e r f o r m a n c e is s u b s t a n t i a l l y better t h a n m a n y other a v a i l a b l e systems, a n d a l l f e d e r a l standards are m e t or e x c e e d e d b y the system. Table II. A C P System Performance Warranty S 0 r e m o v a l " (%) S 0 missions ( l b / 1 0 B t u ) P a r t i c u l a t e emissions ( g r a i n / S C F ) E l e c t r i c a l power d e m a n d ( k w , 24-hr average) P e t r o l e u m coke ( t o n / h r )
2 2 6
a b
Design 95.5 0.25 0.01 7580 6.6
90 ( m i n i m i u m ) 0.55 0.02
6
9900 8
3.5 wt % sulfur coal. T o meet mass and opacity standards.
176 Economics
SULFUR
REMOVAL
AND
RECOVERY
A t h o r o u g h analysis of the c a p i t a l a n d o p e r a t i n g e c o n o m i c s w a s m a d e for the system d e s c r i b e d above. T h e basis for this estimate is s h o w n i n T a b l e I I I , a n d r e l a t i v e l y conservative assumptions h a v e b e e n m a d e for the cost of the v a r i o u s u t i l i t i e s , m a i n t e n a n c e , o p e r a t i n g s u p p l i e s , overh e a d , a n d c a p i t a l c h a r g e rate. T h e analysis w a s b a s e d o n d e s i g n i n g t h e p l a n t f o r the e q u i v a l e n t of 7000 h r / y r of f u l l l o a d o p e r a t i o n . T h e c a p i t a l costs, b r o k e n d o w n i n t o the gas i n t e r f a c e l o o p a n d the r e g e n e r a t i o n syst e m , are s h o w n i n T a b l e I V . T h e cost for the s c r u b b e r l o o p a n d its assoTable III. Total A n n u a l Cost Assumptions
O p e r a t i o n at f u l l p o w e r 7 0 0 0 hx/yr Natural gas$0.40/Mcf Coke$20/ton E l e c t r i c a l power c o s t 1 0 m i l l s / k w - h r Operation labor$10/hr M a i n t e n a n c e 3 % of c a p i t a l cost O p e r a t i n g s u p p l i e s 0 . 5 % of c a p i t a l cost Overhead P a y r o l l 4 0 % of l a b o r P l a n t 5 0 % of l a b o r , m a i n t e n a n c e , a n d supplies C a p i t a l charge r a t e 1 5 % / y r Table IV. Capital Cost Estimate U t i l i t y Systems for a 330-Mw Plant Using 3.5% Sulfur Coal G a s interface l o o p i n s t a l l e d Engineering and management Subtotal Regeneration system installed Engineering and management Subtotal Total $ 7,343,000 1,586,000 8,929,000 ( 2 7 / k w ) 9,201,000 2,917,000 12,118,000 $21,047,000 (36.8/kw) (63.8/kw)
c i a t e d e q u i p m e n t is a p p r o x i m a t e l y $ 2 7 / k w . T h i s i n c l u d e s a l l e n g i n e e r i n g , m a n a g e m e n t , e q u i p m e n t , c o n s t r u c t i o n , startup, a n d d e b u g g i n g . $36.80/kw. T h e reg e n e r a t i o n s u b s y s t e m is s o m e w h a t m o r e expensive a n d is estimated at T h i s cost is for r e g e n e r a t i o n associated w i t h h i g h s u l f u r f u e l . T h i s compares quite favorably with T h e t o t a l cost t h e n for the regenerative aqueous c a r b o n a t e process o n a n eastern u t i l i t i e s site is $ 6 3 . 8 0 / k w . the cost for n o n - r e g e n e r a t i v e l i m e a n d limestone systems, a n d the system has the a d v a n t a g e of b e i n g f u l l y regenerative. T a b l e V shows the utilities costs for this specific p l a n t site a n d c o n ditions. T h e largest o p e r a t i n g cost i n the u t i l i t y category is s u p p l y i n g T h e next largest expense is e l e c t r i c a l p o w e r , p e t r o l e u m c o k e at $ 2 0 / t o n .
14.
Regenerative Table V .
Aqueous
Carbonate
Process
177
Utility Costs 380 Mw Plant (mills/kw-hr)
Parameter E l e c t r i c i t y a t 10 m i l l s / k w - h r N a t u r a l gas a t 4 0 F / 1 0 0 Coke at $20/ton Cooling water Process w a t e r B o i l e r feed w a t e r Steam M a k e u p carbonate T o t a l u t i l i t y cost
0.230 0.039 0.400 0.0087 0.0136 0.0022 0.0114 0.0076 0.7125 With
w h i c h is to b e e x p e c t e d w i t h a n y s u l f u r d i o x i d e r e m o v a l system. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch014
r e g a r d to t h e coke r e q u i r e m e n t , one c o u l d d e s i g n this p l a n t to use c o a l as t h e r e d u c i n g agent i n t h e r e d u c e r at some p e n a l t y i n r e g e n e r a t i o n a n d filtration equipment. H o w e v e r , a n e t savings i n o p e r a t i n g costs c o u l d w e l l o c c u r because of t h e m a g n i t u d e of t h e costs. T h e other o p e r a t i n g costs associated w i t h t h e p l a n t i n c l u d e l a b o r , m a i n t e n a n c e , s u p p l i e s , p a y r o l l , p l a n t o v e r h e a d , c a p i t a l c h a r g e , etc. T a b l e V I s u m m a r i z e s u t i l i t y a n d m a t e r i a l costs f o r e a c h s u b s y s t e m , i.e., t h e gas a n d regenerative subsystems, a n d gives total operating costs. T h e costs a r e s o m e t h i n g less t h a n 1 m i l l / k w - h r f o r t h e gas interface syst e m a n d a b o u t 1.8 m i l l s / k w - h r f o r t h e r e g e n e r a t i o n system, o r a t o t a l o p e r a t i n g cost o f 2.8 m i l l s / k w - h r to p r o v i d e s u l f u r d i o x i d e r e m o v a l . N o c r e d i t w h a t s o e v e r has b e e n t a k e n f o r t h e s u l f u r p r o d u c e d , b u t t h e t o t a l o p e r a t i n g cost of t h e C l a u s p l a n t is i n c l u d e d . If o n e evaluates t h e cost effectiveness of s u c h a system b y l o o k i n g at f u e l costs as a f u n c t i o n of s u l f u r content a n d c o m p a r i n g t o t a l o p e r a t i n g Table V I . A n n u a l Operating Cost Estimate ($000) (17.7 tons Sodium Carbonate/hr, 7000 h r / y r ) Gas Interface Utilities and materials L a b o r and supervision at $10/hr M a i n t e n a n c e a t 3 % d e p r e c i a t i o n base S u p p l i e s a t 0 . 5 % d e p r e c i a t i o n base P a y r o l l overhead a t 4 0 % l a b o r a n d supervision P l a n t overhead a t 5 0 % l a b o r a n d s u p e r v i s i o n , m a i n t e n a n c e , a n d supplies C a p i t a l charge a t 1 5 % T o t a l ($000/yr) Total (mills/kw-hr) 303 100 268 44 40 206 1340 2301 0.99 Regeneration 1340 200 364 61 80 312 1820 4177 1.81 Total 1643 300 632 105 120 518 3160 6478 2.80
178
SULFUR
REMOVAL
AND RECOVERY
costs f o r the A C P system w i t h p o t e n t i a l savings i n f u e l costs, t h e result is q u i t e s u r p r i s i n g . F i g u r e 11 is a c u r v e f r o m Gas Turbine World of October 1972 t h a t shows f u e l costs as a f u n c t i o n of s u l f u r i n the f u e l . A l t h o u g h there is a great d e a l of scatter, i t c a n b e seen that F o s t e r - P e g g has p u t i n a c o r r e l a t i o n suggesting a b o u t a 350 p e r m i l l i o n B t u savings b y g o i n g f r o m 0 . 3 % s u l f u r f u e l to 2 % i n a n even l a r g e r savings. sulfur fuel. B e i n g a b l e to b u r n 3 . 5 % s u l f u r c o a l a n d s t i l l meet p o l l u t i o n standards p r o b a b l y w o u l d result Based on a conservative 3 5 0 / m i l l i o n B t u , the analysis s h o w n i n T a b l e V I I shows a 6V2 m i l l i o n d o l l a r / y r a n n u a l cost associated w i t h t h e p a r t i c u l a r p l a n t d e s i g n (as p r e s e n t e d i n T a b l e V I ) , a n 8.1 m i l l i o n d o l l a r f u e l savings, a n d a s u l f u r c r e d i t of $630,000. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch014 about T h e result is a n e t savings of 2.25 m i l l i o n d o l l a r s / y r or 1.0
m i l l / k w - h r , as o p p o s e d to t h e o p e r a t i n g loss u s u a l l y associated w i t h s u l f u r dioxide removal plants. Summary I n c o n c l u s i o n , this s e c o n d - g e n e r a t i o n s u l f u r d i o x i d e r e m o v a l process is n o w r e a d y f o r f u l l - s c a l e i n s t a l l a t i o n . I t promises to solve m a n y of t h e
D A T A = FOSTER-PEGG OCT. 1972 (FOR GAS TURBINE WORLD)
0CRUDE
83 80
60
48
AOl
20i\-
0 PERCENT S U L F U R
Gas Turbine World
Figure 11.
Fuel cost vs. sulfur content
14.
Regenerative
Aqueous
Carbonate
Process
179
Table V I I .
A C P C o s t Effectiveness 330 Mw Plant
A n n u a l o p e r a t i n g cost ( $ / y r , 0 0 0 ) A n n u a l o p e r a t i n g cost ( m i l l s / k w - h r ) F u e l savings ( $ 0 0 0 / y r ) S u l f u r v a l u e at $ 2 0 / t o n ( $ 0 0 0 / y r ) T o t a l credit ( $ 0 0 0 / y r ) T o t a l savings ( $ 0 0 0 / y r ) (mills/kw-hr)
6480 2.8 8100 630 8730 2250 1.0 Spehigh
p r o b l e m s associated w i t h past s u l f u r d i o x i d e s c r u b b i n g systems. c i f i c a l l y the A C P r e g e n e r a t i v e s y s t e m : 1. P r o v i d e s a n e c o n o m i c a d v a n t a g e b y a l l o w i n g the use of s u l f u r f u e l w h i l e p r o v i d i n g l o w s u l f u r d i o x i d e emissions 3. Eliminates maintenance plugging problems associated with
2 . E l i m i n a t e s s l u d g e p r o d u c t i o n a n d the r e l a t e d d i s p o s a l p r o b l e m scaling and
4. M i n i m i z e s t h e i m p a c t o n p l a n t r e l i a b i l i t y b y u s i n g a s i m p l e s c r u b b i n g scheme s o m e w h a t d e c o u p l e d f r o m the r e g e n e r a t i o n e q u i p m e n t
RECEIVED April 4, 1 9 7 4
15
Removal and Reduction of Sulfur Dioxides from Polluted Gas Streams
P. STEINER, H . JNTGEN, and K. K N O B L A U C H
Foster Wheeler Corp., Livingston, N . J. 07039
This new, second generation process was primarily designed to remove sulfur dioxide from polluted gas streams. front end of the process was developed by Forschung and operates as a sulfur dioxide Following the preferential The Bergbau
concentrator, adsorption of
placing the sulfur dioxide-containing a special carbon.
gases in contact with
sulfur dioxide, the special carbon adsorbent is regenerated by thermal treatment to yield a concentrated sulfur dioxide off-gas which is converted to sulfur in a coal bed by Foster Wheeler Corporation's sulfur 760F. Resox process. This process repre650sents a new way to achieve the desired reaction rate between dioxide and crushed coal at approximately
>"phe idea to use the various forms of coal to remove sulfur dioxide is not new and was described in an English patent as early as 1879 (I). However, massive research and development programs to develop commercially viable sulfur dioxide removal processes were not initiated until 80 years later, when ecological considerations forced public concern. The Bergbau Forschung-Foster Wheeler sulfur dioxide removal process was originally developed for the utility industry. However, the basic system can, and will, be used to meet the specific requirements of other industries as well. This second generation sulfur dioxide removal process consists of three basic steps. coke). The first step removes the sulfur dioxide from polluted gas streams by adsorption on carbon (activated The second step regenerates the adsorbent (coke), producing a gas stream with high sulfur dioxide concentration. The third step treats the sulfur dioxide-rich stream by reducing it to elemental sulfur. 180
15.
STEiNER E T AL.
Sulfur Dioxide
Removal and Reduction Regeneration
181
Sulfur Dioxide Removal and Adsorbent
Physical Chemistry and Process Technology of the Sulfur Dioxide Removal System. T h e s u l f u r d i o x i d e r e m o v a l system w a s d e v e l o p e d by B e r g b a u F o r s c h u n g i n E s s e n , W e s t G e r m a n y a n d is b a s e d o n a n d d e s i g n e d for a s p e c i a l a c t i v a t e d coke adsorbent. T h e a c t i v a t e d coke, t h e It has excellent s u l f u r most c r i t i c a l i n g r e d i e n t i n the system, is the result of a research a n d d e v e l o p m e n t p r o g r a m i n i t i a t e d i n the late 1950s. d i o x i d e a d s o r p t i o n , h i g h i g n i t i o n t e m p e r a t u r e , a n d g o o d p h y s i c a l strength. T h e b a s i c system consists of a g a s / s o l i d c o n t a c t i n g d e v i c e ( t h e a d s o r b e r ) a n d a regenerator ( t h e d e s o r b e r ) . W i t h i n t h e a d s o r b e r the a c t i by v a t e d coke moves d o w n w a r d i n the p l u g flow w h i c h is c o n t a i n e d Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch015
p e r m a n e n t l y fixed steel louvers o n the gas e n t r a n c e a n d exit sides of t h e unit. T h e p o l l u t e d gas stream is passed i n t h r o u g h the louvers, t h r o u g h the adsorbent, a n d out t h r o u g h louvers o n t h e opposite side of t h e a d sorber. T h e s u l f u r d i o x i d e c o n t a i n e d i n the gas stream is a d s o r b e d on the i n n e r surface of the a c t i v a t e d coke a n d is t h e n o x i d i z e d to s u l f u r i c a c i d i n the presence of the o x y g e n a n d w a t e r v a p o r w h i c h are also i n the p o l l u t e d gas ( 2 ) . C o i n c i d e n t a l l y , the a d s o r b e r f u n c t i o n s as a p a n e l b e d filter to r e m o v e p a r t i c u l a t e s e n t r a i n e d i n the gas stream. T h e s u l f u r i c a c i d content of the a c t i v a t e d c o k e increases as a f u n c t i o n of coke d w e l l t i m e i n the adsorber. T h e r e f o r e , the coke d i s c h a r g e d at the b o t t o m of the a d s o r b e r contains the highest possible a m o u n t of s u l f u r i c a c i d for the g i v e n c o n d i t i o n s a n d a d s o r b e r geometry. T h e adsorbent is regenerated after i t is d i s c h a r g e d f r o m the a d s o r b e r a n d is separated f r o m p a r t i c u l a t e s b y a v i b r a t i n g sieve. T h e r e g e n e r a t i o n is effected t h e r m a l l y b y h e a t i n g the s u l f u r i c a c i d - l o a d e d adsorbent i n a n inert atmosphere. T h e r e g e n e r a t i o n c o n d i t i o n s cause a d i r e c t i o n a l c h a n g e i n the d r i v i n g forces o f the reactions i n this system. T h e participants u n d e r g o a m o d i f i e d r e v e r s a l of t h e a d s o r p t i o n r e a c t i o n i n w h i c h the fixed c a r b o n of the adsorbent reduces the s u l f u r i c a c i d to s u l f u r d i o x i d e . T e c h n i c a l l y , the r e g e n e r a t i o n is c a r r i e d out i n a m o v i n g b e d reactor u s i n g s a n d as a d i r e c t heat c a r r i e r to heat the a d s o r b e n t to 6 0 0 - 6 5 0 C . T h e effluent gas of the r e g e n e r a t i o n contains 2 0 - 3 0 % v o l u m e as w e l l as w a t e r a n d c a r b o n d i o x i d e . to s u l f u r . Mechanism of Adsorption. T h e m e c h a n i s m of the s u l f u r d i o x i d e a d s o r p t i o n a n d o x i d a t i o n o n c a r b o n shows t h a t the s u l f u r d i o x i d e p i c k - u p c a n b e d i v i d e d i n t o three subsequent phases i n w h i c h phase c h a n g e is a f u n c t i o n of t i m e . I n phase one, t h e a d s o r p t i o n rate is c o n t r o l l e d b y t h e rate of s u l f u r d i o x i d e d i f f u s i o n i n t o the i n n e r surface of t h e adsorbent. A s the a d s o r p t i o n proceeds, the n u m b e r of locations a v a i l a b l e for a d s o r p sulfur dioxide b y It c a n b e f e d d i r e c t l y to
F o s t e r W h e e l e r s Resox process w h i c h converts the s u l f u r d i o x i d e content
182 t i o n declines, a n d finally most becomes occupied. to create vacancies It is necessary
SULFUR
REMOVAL
AND
RECOVERY
of the easily accessible
inner
surface
o n t h e i n n e r surface to a l l o w sulfuric acid interdependent
c o n t i n u e d a d s o r p t i o n . V a c a n c i e s , h o w e v e r , are c r e a t e d b y s u l f u r d i o x i d e o x i d a t i o n a n d t h e subsequent transport of t h e generated This to r e a d i l y accessible i n n e r pores. T h e r e f o r e , t h e a d s o r p t i o n rate is n o w
c o n t r o l l e d b y t h e rate of o x i d a t i o n a n d transport.
r e l a t i o n s h i p is c h a r a c t e r i s t i c of this phase o f a d s o r p t i o n . I n t h e t h i r d phase, t h e accessible i n n e r pores start to fill u p t o c a p a c i t y a n d , therefore, t h e transport rate approaches zero causing a n T h e conexcess o f s u l f u r i c a c i d to b u i l d u p s l o w l y o n the i n n e r surface. t i n u o u s presence of s u l f u r i c a c i d poisons a d s o r p t i o n a c t i v i t y declines. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch015 S i n c e t h e b u l k of the a d s o r p t i o n is a c c o m p l i s h e d i n the s e c o n d phase u n d e r stationary c o n d i t i o n s , t h e adsorbent w a s d e v e l o p e d to o b t a i n h i g h s u l f u r d i o x i d e - t o - s u l f u r i c a c i d c o n v e r s i o n rates f o r a l a r g e p o r t i o n of its i n n e r surface. T h e r e l a t i o n s h i p b e t w e e n p o r e structure a n d s u l f u r d i o x i d e a d s o r p t i o n is s h o w n i n F i g u r e 1. T h e o r d i n a t e is t h e t i m e , i n hours, after w h i c h 1 0 % of t h e i n l e t s u l f u r d i o x i d e w i l l pass t h r o u g h t h e c a r b o n w i t h out b e i n g a d s o r b e d . structure T h e m e a n p o r e d i a m e t e r of a d s o r p t i o n pores w a s produced from tested. bituminous coal w i t h a n d I n b o t h cases, t h e s u l f u r selected f o r t h e abscissa as t h e p a r a m e t e r t o c h a r a c t e r i z e t h e adsorbent ( 3 ) . Adsorbents w i t h o u t catalyst i m p r e g n a t i o n w e r e
t h e active centers, a n d t h e
Time of 10% Break Thraugh
with Catalyst
Average Diameter of Adsorption

Figure 1.
fjj
Sulfur dioxide sorption of various active carbons
15.
STEiNER E T AL.
Sulfur Dioxide
Removal and
Reduction
183
Reaction Parameters: / E*kca(/mol Reaction Rate .s X s-
far the format/on CO

/5
* 17 kcal/moi k * 10 min-'
0 s
2.Q\4
3
dV fNcm*\ dTL#.grdJ __
measured calculated m-SV/min
i.o Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch015
0.0+/
y 200 300 400 femperature Cc) Nonisothermal kinetics of thermal regeneration size 8A
Figure 2.
d i o x i d e a d s o r p t i o n increases i n i t i a l l y w i t h i n c r e a s i n g m e a n p o r e d i a m e t e r a n d t h e n declines after r e a c h i n g a m a x i m u m at a b o u t
a n d 7.2A, r e s p e c t i v e l y . T h e d a t a f u r t h e r i n d i c a t e that a n adsorbent w i t h catalyst adsorbs m o r e s u l f u r d i o x i d e a n d therefore that p o r e diameters are less c r i t i c a l . U n f o r t u n a t e l y , this difference i n performance is not sufficient to offset e c o n o m i c a n d process considerations w h i c h f a v o r a n
a d s o r b e n t w i t h o u t catalyst. T h e net result of the research a n d d e v e l o p m e n t w o r k is a n adsorbent for c o m m e r c i a l use, w h i c h is p r o d u c e d f r o m p r e o x i d i z e d b i t u m i n o u s c o a l a n d w h i c h has a p a r t i c l e d i a m e t e r of 9 m m , a hardness of over 9 0 % , an i g n i t i o n t e m p e r a t u r e over 4 0 0 C , a n d a s u l f u r d i o x i d e a d s o r p t i o n of 8 - 1 5 % Adsorbent Regeneration. (4). A t temperatures a b o v e 2 0 0 C a c t i v a t e d
c o k e c o n t a i n i n g s u l f u r i c a c i d undergoes t h e f o l l o w i n g r e a c t i o n : H S0
2
1/2C
> 1/2C0
H 0 +
2
S0
T o o b t a i n the n o n i s o t h e r m a l r e a c t i o n k i n e t i c s , the s u l f u r i c a c i d - c o n t a i n i n g coke as h e a t e d at a constant rate of 5 C / m i n a n d the v o l u m e of e v o l v i n g i n d i v i d u a l r e a c t i o n p r o d u c t s w a s m o n i t o r e d vs. the c h a n g e i n temperature. U n d e r the c o n d i t i o n s of this e x p e r i m e n t the r e g e n e r a t i o n r e a c t i o n starts a r o u n d 200 C a n d is p r a c t i c a l l y c o m p l e t e d at 450 C as i n d i c a t e d b y the e v o l u t i o n of the r e a c t i o n p r o d u c t s as s h o w n i n F i g u r e 2.
184
SULFUR
REMOVAL
AND
RECOVERY
T h e s l o w h e a t i n g rate u s e d i n this e x p e r i m e n t w o u l d b e i m p r a c t i c a l for a c o m m e r c i a l o p e r a t i o n as the regenerator vessel w o u l d be q u i t e large. C o m m e r c i a l l y , the r e g e n e r a t i o n heat is o b t a i n e d b y m i x i n g the adsorbent w i t h a h o t s o l i d . S a n d has b e e n f o u n d to b e a satisfactory s o l i d . A c c o r d i n g to the l a w s of n o n i s o t h e r m a l r e a c t i o n k i n e t i c s , the t e m p e r a t u r e r a n g e at w h i c h a g i v e n r e a c t i o n proceeds b e c o m e s h i g h e r as the h e a t i n g rate is i n c r e a s e d . 3. T h e l i b e r a t i o n curves of s u l f u r d i o x i d e for different h e a t i n g rates b e t w e e n 5 a n d 1 0 , 0 0 0 C / m i n are s h o w n i n F i g u r e T h e c a l c u l a t i o n s are b a s e d o n parameters e s t a b l i s h e d i n l a b o r a t o r y experiments a n d s h o w n i n F i g u r e 2. A t a n a p p r o x i m a t e d h e a t i n g rate of 5 0 0 C / m i n i n the s a n d regenerator, t h e m a x i m u m r e a c t i o n rate w o u l d b e expected at 5 2 0 C w i t h a n e n d p o i n t of 6 8 0 C . Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch015 k
3
dr
fiate of Heating = 5 10 50 /0*fx/O*/O
*I7 kcal/moi - Sx to* //min

4
5x/0 I0
C/min
100
ZOO 300
400
500
600
700
800
900
Temperature tC) Figure 3. Pilot Plant Liberation of sulfur dioxide for different heating rates
Testing
T h e process d e s c r i b e d here has b e e n tested for 2 yrs i n a c o n t i n u ously operating (5). p i l o t p l a n t processing over 100,000 actual cu
6
ft/hr
(ACFH)
D u r i n g 1969 the p i l o t u n i t processed 528
1 0 A C F of between
gas i n 6000 o p e r a t i n g h r . T h e d e s u l f u r i z a t i o n efficiency r a n g e d 60 a n d 9 5 % .
T h e s e differences w e r e c a u s e d b y d e l i b e r a t e changes i n
o p e r a t i n g parameters s u c h as the gas a n d c o k e residence times i n the adsorber, t e m p e r a t u r e of a d s o r p t i o n a n d r e g e n e r a t i o n , etc.
15.
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Sulfur Dioxide
Removal and Reduction
185
S i n c e the p i l o t u n i t a n d t h e d a t a o b t a i n e d f r o m i t are d e s c r i b e d i n n u m e r o u s p u b l i c a t i o n s o n l y some k e y c o n c l u s i o n s are m e n t i o n e d here. T h e p i l o t o p e r a t i o n e s t a b l i s h e d the t e c h n o l o g i c a l f e a s i b i l i t y of the process i n g e n e r a l a n d has s h o w n t h a t t h e assumptions, c a l c u l a t i o n s , a n d l a b o r a t o r y d a t a - b a s e d c o n c l u s i o n s c o n c e r n i n g p a r t i c u l a r features of the process s u c h as a d s o r p t i o n , r e g e n e r a t i o n at h i g h h e a t i n g rate, etc. are correct. D a t a o b t a i n e d d u r i n g the 2 yrs of o p e r a t i o n also has p r o v e d the econ o m i c a l v i a b i l i t y of the process. Reduction sulfur. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch015 of Sulfur Dioxide by Coal
T h e Resox process uses c o a l as a r e d u c i n g agent to p r o d u c e e l e m e n t a l It w a s d e v e l o p e d i n F o s t e r W h e e l e r C o r p o r a t i o n ' s J o h n B l i z a r d R e s e a r c h C e n t e r a n d is the result of a research p r o g r a m i n i t i a t e d i n the late 1960s. T h i s process is d e s i g n e d to r e d u c e the s u l f u r d i o x i d e i n a n off-gas stream to s u l f u r a n d to condense the s u l f u r p r o d u c t f r o m the gas stream. It is c a p a b l e of h a n d l i n g a w i d e range of i n l e t gas c o m p o s i t i o n s a n d does not r e q u i r e gas c l e a n i n g , d r y i n g , or dust r e m o v a l systems. C r u s h e d c o a l is the o n l y m a t e r i a l a n d the o n l y catalyst c o n s u m e d . T h e process r e p r e sents a n e w w a y to a c h i e v e the d e s i r e d degree of r e a c t i o n b e t w e e n s u l f u r d i o x i d e a n d c r u s h e d c o a l at temperatures as l o w as 600 C . T h e major process e q u i p m e n t consists of a reactor vessel a n d a s u l f u r condenser. I n the reactor vessel, s u l f u r d i o x i d e - r i c h gases react with c r u s h e d c o a l to y i e l d gaseous e l e m e n t a l sulfur. T h i s s u l f u r is c o n d e n s e d f r o m the gas stream i n the s u l f u r condenser. T h e high-purity l i q u i d sulfur effluent of the process is a n o n p o l l u t i n g b y - p r o d u c t . F o s t e r W h e e l e r C o r p o r a t i o n s efforts t o w a r d f u l l c o m m e r c i a l i z a t i o n of this process are e x t e n d e d i n the f r a m e w o r k of a three phase p r o g r a m of process research a n d b e n c h - s c a l e f e a s i b i l i t y studies, p i l o t p l a n t o p e r a t i o n , a n d large scale d e m o n s t r a t i o n . O n l y the conclusions d i r e c t l y p e r t a i n i n g to the process are discussed here. A d e t a i l e d d i s c u s s i o n of the m e c h a n i s m a n d k i n e t i c s of this r a t h e r i n v o l v e d system is b e y o n d the scope of this p a p e r a n d w i l l b e r e p o r t e d at a later date. Research and Bench-Scale Feasibility Studies. T h e r e a c t i o n b e t w e e n c a r b o n a n d s u l f u r d i o x i d e at e l e v a t e d t e m p e r a t u r e s is w e l l k n o w n a n d has b e e n u s e d for n u m e r o u s processes. F o r example, sulfur was produced at T r a i l , B r i t i s h C o l u m b i a f r o m 1935 to 1943 b y b l o w i n g s u l f u r d i o x i d e a n d o x y g e n into the b o t t o m of a coke-fired r e d u c t i o n f u r n a c e . C o k e w a s c h a r g e d at the t o p a n d ash w a s r e m o v e d o n a r o t a r y grate at the b o t t o m of the f u r n a c e . T h e hot z o n e of the f u r n a c e w a s k e p t at 1 3 0 0 C to m a i n t a i n r a p i d r e a c t i o n rates a n d s m o o t h o p e r a t i o n . Sufficient s u l f u r d i o x i d e was a d d e d to the gas to react w i t h the c a r b o n m o n o x i d e a n d c a r b o n oxysulfide c o n t a i n e d i n the r e d u c t i o n f u r n a c e off-gas. C o a l was con-
186
SULFUR
REMOVAL
AND
RECOVERY
s i d e r e d unsatisfactory as a r e d u c i n g agent because of
the
hydrogen
sulfide f o r m a t i o n . C a r b o n w i l l also react w i t h s u p e r h e a t e d steam at elev a t e d temperatures to y i e l d c a r b o n m o n o x i d e a n d h y d r o g e n . F o s t e r W h e e l e r C o r p o r a t i o n ' s research p r o g r a m w a s b a s e d o n the a s s u m p t i o n that w h i l e h i g h temperatures are necessary to o b t a i n a c o m m e r c i a l l y p r a c t i c a l r e a c t i o n rate w h e n s u l f u r d i o x i d e or steam reacts i n d i v i d u a l l y w i t h c o a l , the t w o reactions w o u l d i n t e r a c t s y n e r g i s t i c a l l y w h e n c o m b i n e d i n a single i n t e g r a t e d system. A s a result of this i n t e r a c t i o n , b o t h reactions w o u l d b e p r o m o t e d , a n d c o m m e r c i a l l y p r a c t i c a l rates for s u l f u r d i o x i d e r e d u c t i o n c o u l d be o b t a i n e d at s i g n i f i c a n t l y l o w e r t e m p e r a tures t h a n those r e p o r t e d i n the l i t e r a t u r e or u s e d c o m m e r c i a l l y . i n a separate research p r o g r a m . Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch015 T h e bench-scale study was conducted i n a small pilot plant designed for the r e a c t i o n of c r u s h e d c o a l w i t h s u l f u r d i o x i d e at c a r e f u l l y trolled conditions. conT h e i n l e t gas c o m p o s i t i o n , r e a c t i o n t e m p e r a t u r e , a n d A s i m i l a r b e h a v i o r f o r the c o a l gasification r e a c t i o n is n o w b e i n g s t u d i e d
gas residence t i m e w e r e selected as the i n d e p e n d e n t v a r i a b l e s f o r the study. T h e outlet gas c o m p o s i t i o n a n d r e a c t i o n rate w e r e m o n i t o r e d as dependent variables. S i n c e the gas residence t i m e , T h e r e l a t i o n s h i p b e t w e e n s u l f u r d i o x i d e c o n v e r s i o n a n d the w a t e r - t o s u l f u r d i o x i d e r a t i o is s h o w n i n F i g u r e 4. t h e r e a c t i o n t e m p e r a t u r e , a n d the d r y i n l e t gas c o m p o s i t i o n w e r e h e l d constant, i t is e v i d e n t that t h e r e a c t i o n rate increases w i t h the p a r t i a l
SO in -SO2out
z
X/O All other parameters constant
2
2
Ratio H 0
Figure 4.
to SO.
Mol. H ~4 Mol.S0
2 2
Relationship between sulfur dioxide conversion and the water-to-sulfur dioxide ratio
15.
STEINER
ET AL.
Sulfur Dioxide
Removal and
Reduction
187
Mot, product Mol* SO consumed

z
All otherparameters constant
I -
4 6
.5
"J
2 Z
/. H 0 Moi. SO
2
Ratio H 0 to S0
Figure 5.
Relationship between hydrogen sulfide selectivity and the water-to-sulfur dioxide ratio
pressure of w a t e r i n the system. T h e c h a n g i n g slope of t h e c u r v e shows the different degree of increase of the r e a c t i o n rate effected w h e n t h e w a t e r c o n c e n t r a t i o n of t h e system is i n c r e a s e d over different p r e v i o u s levels o f c o n c e n t r a t i o n . T h e w a t e r , c a r b o n d i o x i d e , s u l f u r d i o x i d e , n i t r o g e n gas, c a r b o n , a n d the n u m e r o u s other c o m p o u n d s r e s u l t i n g f r o m different c o m b i n a t i o n of the elements c o n t a i n e d b y the c o m p o u n d s a b o v e represent a c o m p l e x system. D e p e n d i n g o n t h e r e a c t i o n parameters, different r e a c t i o n routes reaction products. will d o m i n a t e t h e system a n d w i l l y i e l d different c o m p o u n d s as t h e m a j o r T h e recent research effort c o n c e n t r a t e d o n o b t a i n i n g e l e m e n t a l sulfur or h y d r o g e n sulfide as the p r i n c i p a l r e a c t i o n p r o d u c t s . I n g e n e r a l , i t w a s f o u n d that the s e l e c t i v i t y of the r e a c t i o n t o w a r d s hydrogen sulfide increases w i t h i n c r e a s i n g r e a c t i o n t e m p e r a t u r e s a n d T h e r e l a t i o n s h i p b e t w e e n h y d r o g e n sulfide selecw a t e r concentrations.
t i v i t y a n d the a m o u n t of w a t e r i n the system is s h o w n i n F i g u r e 5. N e a r l y a l l t h e sulfur d i o x i d e e n t e r i n g t h e process w a s c o n v e r t e d s e l e c t i v e l y to h y d r o g e n sulfide b e t w e e n 660 a n d 7 6 0 C . T h e process w a s also a p p l i e d to convert s u l f u r d i o x i d e to s u l f u r at l o w e r r e a c t i o n t e m peratures. A s s h o w n i n F i g u r e 6, w h e n 1 0 0 % of the s u l f u r d i o x i d e is c o n v e r t e d , 9 0 % reacts to f o r m e l e m e n t a l s u l f u r w h i l e 1 0 % y i e l d s different by-products s u c h as h y d r o g e n sulfide, c a r b o n oxysulfide, c a r b o n d i Lower temtime, sulfide, etc. N e a r l y 1 0 0 % s e l e c t i v i t y to s u l f u r c a n b e o b t a i n e d at l o w e r conversions c o r r e s p o n d i n g to l o w e r r e a c t i o n temperatures. peratures c a u s e d l o w e r conversions since t h e m a x i m u m contact
188
SULFUR
REMOVAL
AND
RECOVERY
Vsq*Converted to6
/00-i
All other parameters constant
H:
I
50
"I
1
60
Sfy Conversion %
70
SO
90
IO
SO tn
z
Figure 6.
Sulfur dioxide consumed vs. sulfur
produced
b a s e d o n e m p t y reactor v o l u m e , b e t w e e n s u l f u r d i o x i d e - c o n t a i n i n g gas a n d c a r b o n w a s fixed at 6 sec f o r a l l experiments. T h e v a r y i n g r e a c t i v i t y o f different coals u s e d i n this w o r k necessit a t e d different r e a c t i o n temperatures. T h e temperatures u s e d w e r e 5 5 0 7 0 0 C f o r b i t u m i n o u s coals a n d 6 5 0 - 8 0 0 C f o r a n t h r a c i t e coals. T h e results o b t a i n e d i n this phase of t h e p r o g r a m e s t a b l i s h e d process f e a s i b i l i t y a n d s h o w e d that t h e i n i t i a l assumptions c o n c e r n i n g process c h e m i s t r y a n d k i n e t i c s w e r e correct. Pilot Plant Operation. T h e pilot plant operation was the second phase o f t h e research p r o g r a m a n d w a s d e s i g n e d to d e l i v e r t h e d a t a necessary t o p l a n , b u i l d , a n d operate a c o m m e r c i a l size d e m o n s t r a t i o n p l a n t . I n o r d e r to a c c o m p l i s h these objectives, a p i l o t p l a n t of sufficient c a p a c i t y w a s c o n s t r u c t e d a n d o p e r a t e d f o r a n e x t e n d e d p e r i o d of t i m e . A d i a g r a m o f t h e p i l o t f a c i l i t y is s h o w n i n F i g u r e 7. T h e s u l f u r dioxide, carbon dioxide, nitrogen, a n d water were metered, blended, a n d b r o u g h t t o t e m p e r a t u r e b y a fired heater so that the m i x t u r e e n t e r e d the reactor at a t e m p e r a t u r e a n d c o m p o s i t i o n r e p r e s e n t a t i v e o f the off-gas f r o m t h e B e r g b a u F o r s c h u n g process. T h e reactor of 2 c u f t v o l u m e c o n t a i n e d a rice-size a n t h r a c i t e c o a l b e d w h i c h m o v e d d o w n w a r d s l o w l y
15.
STEINER E T A L .
Sulfur Dioxide
189
a n d c o u n t e r c u r r e n t to t h e gas stream.
T h e coal hopper located above
the reactor g r a v i t y f e d the system w i t h fresh c o a l as the b e d v o l u m e w a s d i m i n i s h e d b y the r e a c t i o n a n d b y t h e r e m o v a l o f spent m a t e r i a l . S a m p l e ports a r r a n g e d at q u a r t e r p o i n t locations a l o n g t h e v e r t i c a l reactor vessel p e r m i t t e d the gas c o m p o s i t i o n to b e m o n i t o r e d a t different reactor locations, r e p r e s e n t i n g different gas residence times. outlet, w e r e continuously monitored. T h e temperatures at e a c h o f these s a m p l e ports, as w e l l as at t h e i n l e t a n d t h e T h e effluent gas o f t h e reactor T h e t a i l gases l e a v i n g t h e vessel passed t h r o u g h t h e s u l f u r condenser.
s u l f u r condenser w e r e s a m p l e d a n d a n a l y z e d . A n u m b e r of i n d i v i d u a l p i l o t runs w e r e c o n d u c t e d at v a r i o u s process c o n d i t i o n s to d e t e r m i n e t h e cause a n d effect r e l a t i o n s h i p o f process p a Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch015 rameters s u c h as pressure, t e m p e r a t u r e , a n d residence t i m e o n t h e process behavior. A q u a n t i t y of 1200-1500 A C F H of s u l f u r d i o x i d e - c o n t a i n i n g gas w a s processed c o n t i n u o u s l y i n the p i l o t f a c i l i t y . T h e i n t e g r a t e d results o f these i n d i v i d u a l runs h a v e p r o v e d that t h e system is p r a c t i c a l f o r large scale operations a n d c a n treat a v a r i e t y of sulfur d i o x i d e - r i c h effluent gases. T h e c o m p l e t e d p i l o t test p r o g r a m has apparatus h a v i n g design d e m o n s t r a t e d t h a t 9 0 % o f the s u l f u r d i o x i d e i n a t y p i c a l f e e d gas c a n b e c o n v e r t e d to e l e m e n t a l s u l f u r i n a p r o t o t y p e features c o m p a t i b l e w i t h c o m m e r c i a l r e q u i r e m e n t s .
GAS SYNTHESIS
OFF-GAS TREATMENT
GAS COOLING
Figure 7.
Foster Wheeler Resox pilot unit
Commercial
Scale
Demonstrations
T h e first c o m m e r c i a l - s i z e d e m o n s t r a t i o n p l a n t was c o m p l e t e d i n e a r l y 1974 b y B e r g b a u F o r s c h u n g i n L u n e n , W e s t G e r m a n y . T h e p l a n t , s h o w n i n F i g u r e 8, is s u b s i d i z e d b y the W e s t G e r m a n g o v e r n m e n t . to process 5.3 1 0 s t a n d a r d c u f t / h r of gas.

6
I t is d e s i g n e d
T h i s gas is p a r t o f t h e
190
SULFUR
REMOVAL
A N D RECOVERY
Figure 8.
Bergbau Forschung
unit in West Germany
flue gas f r o m a 350 M W coal-fired b o i l e r of t h e Steag. T h e p l a n t consists of a n adsorber, regenerator, a n d a m o d i f i e d C l a u s u n i t to process t h e s u l f u r d i o x i d e - r i c h r e g e n e r a t i o n off-gas. C o n t i n u o u s o p e r a t i o n w a s s c h e d u l e d t o start i n A p r i l 1974. P a r a l l e l w i t h B e r g b a u F o r s c h u n g ' s efforts i n W e s t G e r m a n y , F o s t e r W h e e l e r C o r p . is c o n s t r u c t i n g t h e first d e m o n s t r a t i o n p l a n t i n t h e U n i t e d States. T h e p r o t o t y p e u n i t is b e i n g erected f o r G u l f P o w e r C o . i n C h a t t a hoochee, F l o r i d a a n d is s c h e d u l e d to b e c o m p l e t e d i n S e p t e m b e r 1974. Compared with the Bergbau F o r s c h u n g unit i n L u n e n , the Foster W h e e l e r p l a n t w i l l substitute t h e Resox process f o r t h e m o d i f i e d C l a u s u n i t a n d c o n s u m e c o a l i n s t e a d of n a t u r a l gas to r e d u c e t h e s u l f u r d i o x i d e r i c h regenerator off-gas. I n conclusion, w h e n sulfur dioxide must be removed from polluted gas streams a n d a c c u m u l a t e d i n some f o r m , r e d u c t i o n to e l e m e n t a l s u l f u r is t h e o p t i m u m f o r m f o r a c c u m u l a t i o n , a n d c r u s h e d c o a l is t h e least expensive r e d u c i n g agent. Literature Cited
1. British Patent 189 (1879). 2. Dratwa, H . , Jntgen, H . , Peters, W., Chem. Ing. Tech. Z. (1967) 39, 949965.
15.
STEiNER
ET
AL.
Sulfur Dioxide
191
3. Jntgen, H . , Knoblauch, K., Peters, W., Chem. Ing. Tech. Z. (1969) 41, 798-805. 4. Jntgen, H . , Knoblauch, K., Zndorf, D., Chem. Ing. Tech. Z. (1973) 45, 1148-1152. 5. Jntgen, H . , Knoblauch, K., Peters, W., " S O Removal From Flue Gases By Special Carbon 2," Kongr. Reinhalt. Luft, Washington, D . C . , 1970.
2
1974
16
Sulfur Dioxide Absorption and Conversion to Sulfur by the Citrate Process
L. KOROSY, Pfizer Inc., 235 E . 42nd St., New York, N.Y. 10017 H . L . G E W A N T E R , Pfizer Inc., 11 Bartlett St., Brooklyn, N.Y. 11206 F. S. C H A L M E R S , Arthur G. McKee and Co., 6200 Oak Tree Blvd., Cleveland, Ohio 44131 Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch016 S. V A S A N , Peabody Engineered Systems, 39 Maple Tree Ave., Stamford, Conn. 06906
The tion,
chemistry and
of the
citrate process has been and important
studied regenerahydrogen
through its principal functional steps (absorption, sulfur melting) aspects (oxidation and purging). process depends upon The action of complex and sulfur.
nonfunctional
sulfide on sulfur dioxide in solution to produce sulfur by this controlled interactions The citrate among a variety of sulfur-containing species including sulfite, bisulfite, thiosulfate, polythionates, ing greater than 95% molecule acts primarily as an efficient buffering agent allowsulfur dioxide removal from industrial sulfur. Process effiwhich The stack gases, high sulfur dioxide solution loading, and the recovery of high quality precipitated ciency is achieved by choosing operating conditions yield maximum absorption and regeneration efficiency. system will tolerate stoichiometric imbalances hydrogen absorbed sulfur dioxide fed to the reactors. and regenerant
between sulfide
' T ' h e citrate process for the recovery of elemental sulfur from sulfur dioxide emissions in waste gas was conceived by Bureau of Mines investigators at the Salt Lake City Metallurgy Research Center in their initial laboratory research reported in 1970 (J). This work led to a scale-up of the process to a 400 eu f t / m i n ( C F M ) pilot unit which began treating reverberatory furnace gas at a copper smelter in Arizona in November 1970. While a series of mechanical difficulties allowed only 192 In Sulfur Removal and Recovery; Pfeiffer, J.; Advances in Chemistry; American Chemical Society: Washington, DC, 1975.
16.
KOROSKY E T A L .
Citrate
Process
193
i n t e r m i t t e n t o p e r a t i o n of the d e m o n s t r a t i o n u n i t a n d g e n e r a t i o n of l i m i t e d e c o n o m i c a n d e n g i n e e r i n g d a t a o n the process, process c h e m i s t r y w a s established. the soundness (2). the unit, incorporating of the D e t a i l s of the process to this p o i n t
w e r e r e p o r t e d b y the B u r e a u of M i n e s i n J u n e 1971 B u r e a u assembled a second-generation laboratory
T o p u r s u e the n e e d e d c h e m i c a l a n d cost d a t a o n the process,
modifications d i c t a t e d b y the results of the earlier w o r k . T h i s was opera t e d as a p r o t o t y p e of a p i l o t p l a n t d e s i g n e d to treat 1000 C F M of 0 . 5 % s u l f u r d i o x i d e gas, w h i c h is n o w c o n s t r u c t e d a n d o p e r a t i n g at t h e B u n k e r H i l l l e a d smelter, K e l l o g g , I d a h o (3). to the P f i z e r h a d b e e n c o o p e r a t i n g w i t h the B u r e a u of M i n e s o n the process since its scale-up to the A r i z o n a p i l o t p l a n t . T h e c o m p a n y d e c i d e d Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch016 take a m o r e a c t i v e r o l e i n the i n v e s t i g a t i o n a n d d e v e l o p m e n t of
process w h e n the c o p p e r smelter d e m o n s t r a t i o n w a s c o m p l e t e d i n 1971. W o r k i n g closely w i t h the B u r e a u of M i n e s , Pfizer c o n s t r u c t e d a l a b o r a t o r y p i l o t u n i t i n w h i c h the v i a b i l i t y of the process w a s c o n f i r m e d . This was f o l l o w e d b y a t w o - p h a s e l a b o r a t o r y p r o g r a m c o n s i s t i n g of a n exhaustive s t u d y of p o t e n t i a l l y c o m p e t i t i v e a b s o r p t i o n systems a n d e l u c i d a t i o n of the process c h e m i s t r y . T h e first phase d e t e r m i n e d that the c i t r a t e system best m e t a l l of t h e c r i t i c a l r e q u i r e m e n t s for a n i d e a l s u l f u r d i o x i d e over a b r o a d c o n c e n t r a t i o n r a n g e , e.g., absorption medium, i n c l u d i n g t h e system's c a p a b i l i t y for efficient r e m o v a l of s u l f u r d i o x i d e the h i g h levels i n smelter waste gas, the s u l f u r d i o x i d e - l e a n stack gas e m i t t e d b y p o w e r p l a n t s , a n d t h e i n t e r m e d i a t e r a n g e r e p r e s e n t e d b y C l a u s p l a n t s . T h e results of the s e c o n d phase of the p r o g r a m , d e a l i n g w i t h the process c h e m i s t r y , forms the basis for m u c h of this p a p e r . A m a j o r step w a s t a k e n i n the d e v e l o p m e n t of the citrate process w i t h i n the i n d u s t r i a l sector w h e n , i n 1972, Pfizer Inc., A r t h u r G . M c K e e a n d C o . , a n d P e a b o d y E n g i n e e r e d Systems b e c a m e a w a r e of t h e i r m u t u a l interest i n the c i t r a t e p r o c e s s P f i z e r was a l e a d i n g m a n u f a c t u r e r of c i t r i c a c i d a n d a c h e m i c a l p l a n t operator, M c K e e e n g i n e e r e d a n d c o n s t r u c t e d process plants w i t h i n w h i c h the citrate process is a p p l i c a b l e for p o l l u t i o n control, and Peabody designed and manufactured pollution control equipm e n t a n d systems. I n late 1972 the three c o m p a n i e s a n n o u n c e d plans to the c o m m e r c i a l f e a s i b i l i t y of t h e citrate process. demonstrate objective The prime
was to generate h a r d e n g i n e e r i n g a n d e c o n o m i c d a t a . B a s i c a l l y , P e a b o d y was to f a b r i c a t e a n d assemble a s k i d - m o u n t e d 2000 S C F M u n i t to M c K e e ' s d e s i g n specifications w i t h Pfizer p r o v i d i n g c h e m i c a l expertise, c i t r i c a c i d , a n d i n i t i a l host o p e r a t i o n of the u n i t o n the p o w e r p l a n t i n t h e i r T e r r e H a u t e , I n d i a n a p l a n t site. S i n c e J u n e 1973, w h e n the T e r r e H a u t e u n i t
194
SULFUR
REMOVAL
AND RECOVERY
b e g a n o p e r a t i o n , i t has l o g g e d o v e r 1300 hrs of o p e r a t i o n a n d has p r o d u c e d m o r e t h a n 15 tons of s u l f u r . Chemistry of the Citrate Process
T h e c h e m i s t r y of the c i t r a t e process has b e e n c o n s i d e r e d to some extent i n recent B u r e a u of M i n e s p u b l i c a t i o n s (2,3). I n their early work o n t h e process, B u r e a u w o r k e r s b e l i e v e d the citrate i o n f u n c t i o n e d as a c o m p l e x i n g agent for s u l f u r d i o x i d e . S u b s e q u e n t w o r k has s h o w n , h o w ever, that the citrate i o n f u n c t i o n s p r i m a r i l y as a g o o d b u f f e r i n g agent w h i c h facilitates efficient e x t r a c t i o n of s u l f u r d i o x i d e f r o m stack gas, h i g h s u l f u r d i o x i d e s o l u t i o n l o a d i n g , a n d the r e c o v e r y of h i g h q u a l i t y p r e c i p i tated sulfur. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch016 A b s o r p t i o n . T h e s o l u b i l i t y of s u l f u r d i o x i d e i n w a t e r is l i m i t e d . dissolves a n d sets u p the e q u i l i b r i u m : S0 + H 0 * H S 0 2 3
It
H+
(1)
T h e s o l u b i l i t y c a n be i n c r e a s e d b y r e m o v i n g the h y d r o g e n ions f o r m e d . I n the c i t r a t e process this is a c c o m p l i s h e d b y t h e b u f f e r i n g a c t i o n of the v a r i o u s c i t r a t e species: Cit ~ +

3
H + <= H C i t 2
(2) (3) (4)
H
2
Cit " +
2
H+ < = > H Cit"

2
H Cit" +
H + <= H C i t
3
T h e s o l u b i l i t y of s u l f u r d i o x i d e i n aqueous solutions, S, c a n b e expressed as a f u n c t i o n of the p a r t i a l pressure i n the gas phase ( p ) , H e n r y ' s L a w constant ( H ) , the h y d r o g e n i o n c o n c e n t r a t i o n ( H ) , a n d the i o n i z a +
t i o n constants of sulfurous a c i d ( K i a n d K ) :
2
"
+w]
(5)
T h i s r e l a t i o n s h i p is p l o t t e d i n F i g u r e 1 for several a s s u m e d gas c o n c e n trations of s u l f u r d i o x i d e at 5 0 C . T h e g r a p h is a p p r o x i m a t e since m o l a l i t y a n d m o l a r i t y w e r e a s s u m e d e q u a l . A l s o p l o t t e d is the c o n c e n t r a t i o n of t o t a l s u l f u r d i o x i d e i n w a t e r vs. p H for u n b u f f e r e d solutions, R e a c t i o n 1. I n the b u f f e r e d r e g i o n to the r i g h t of this c u r v e , the s o l u b i l i t y increases, r a p i d l y a p p r o a c h i n g a 10-fold increase for each p H u n i t increase. T h u s , for a 1 0 0 0 - p p m gas the s o l u b i l i t y at p H 4.5 is 8.7 g/1., a p p r o x i m a t e l y 50 times that of w a t e r alone.
16.
KOROSKY E T A L .
Citrate
Process
195
.on.
in
<
oc . I
o.oi
2.0
3.0
P
j%
4.0
j 5.0
Figure 1. Calculated solubility of S0 in water solutions at 50C as a function of pH for various concentrations of S0 in a gas at 1 atm using Equation 5. The S0 + water curve shows the calculated pH vs. the S0 concentration at 50C for unbuffered solutions.
2 2 2 2
T h e p r a c t i c a l effects of p H o n s u l f u r d i o x i d e a b s o r p t i o n are s h o w n i n F i g u r e 2. F r o m this l a b o r a t o r y w o r k i t c a n b e seen t h a t i n the range s t u d i e d , a n increase of 0.17 p H u n i t reduces the s u l f u r d i o x i d e concent r a t i o n i n the vent gas b y a b o u t one-half. I n the citrate process's o p e r a t i n g range, a b o v e p H 4.0, the vent gas c o n t a i n e d less t h a n 60 p p m s u l f u r d i o x i d e , i n d i c a t i n g better t h a n 9 7 % a b s o r p t i o n for a 2 0 0 0 - p p m i n l e t gas. Absorption Reactions. is r e p o r t e d (4) I n p r a c t i c e the a b s o r b i n g s o l u t i o n contains Thiosulfate some t h i o s u l f a t e w h i c h is f o r m e d i n the r e g e n e r a t i o n step. to f o r m a c o m p l e x w i t h s u l f u r d i o x i d e :
196
SULFUR
REMOVAL
AND RECOVERY
3.4
3.6
P
3.8 OF ABSORBING SOLUTION
Figure 2. Laboratory absorption studies using a 2-in.-diameter packed column. The curve shows S0 concentration in the vent gas as a function of the pH of the absorbing solution for a 2000 ppm S0 -feed gas and a 0.5M citrate-feed solution.
2 2
H+
HSCV
S 0
2
S0 -S 0
2 2
- +
H 0
2
(6) evalu-
Based on spectrophotometric data, Battaglia a n d M i l l e r (5) a t e d the constant K * at p H 3.9 a n d 2 2 C , w h e r e , (H+) (H 0)

2
K*
(SQ -S 0 -)
2 2 3 2
( H S O r ) (S 0 -)
2 3 2
(7)
U s i n g t h e i r v a l u e for a 0 . 2 5 M t h i o s u l f a t e s a l u t i o n , a b o u t 2 % of t h e sulfur d i o x i d e is i n the c o m p l e x . T h u s the presence of t h i o s u l f a t e w o u l d be
16.
KOROSKY E T A L .
Citrate
Process
197
e x p e c t e d to a i d the a b s o r p t i o n of s u l f u r d i o x i d e s l i g h t l y . T h e effect w o u l d b e greater at l o w e r p H ' s . A f u r t h e r r e a c t i o n b e t w e e n bisulfite a n d thiosulfate c a n result i n the f o r m a t i o n of t r i t h i o n a t e : 4HS0 - +

3
S 0 ~ +
2 3 2
2 H + -> 2 S 0 - +
3 6 2
3H 0
2
(8)
T h e rate expression for this r e a c t i o n is r e p o r t e d ( 5 ) to b e : -d(HSO,-) dt
k(HS0 -)(S 0 ~) (H )
3 2 3 2 3 +
(9)
F r o m the r e p o r t e d v a l u e of the rate constant at 70 C , it is e s t i m a t e d that Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch016 for a p H of 4.0 a n d 0 . 2 5 M thiosulfate, the rate of bisulfite loss is v e r y low, 1% i n about 80 hrs. S i n c e the rate is p r o p o r t i o n a l to ( H ) ,
+ 3
the
r e a c t i o n w o u l d be m u c h m o r e significant at l o w e r p H ' s . Regeneration. T h e p r o d u c t s f o r m e d b y t r e a t i n g sulfur d i o x i d e s o l u hydrogen tions w i t h h y d r o g e n sulfide d e p e n d i n part o n the p H . W h e n
sulfide is a d d e d to a s o l u t i o n of s u l f u r d i o x i d e i n w a t e r , a c o m p l e x m i x t u r e is f o r m e d that i n c l u d e s p o l y t h i o n i c acids, t h i o s u l f u r i c a c i d , a n d c o l l o i d a l s u l f u r ( i n contrast to the c r y s t a l l i n e s u l f u r o b t a i n e d i n the citrate process ). T h i s is k n o w n as W a c k e n r o d e r ' s s o l u t i o n a n d has b e e n extensively s t u d i e d . T h e c o m p o s i t i o n varies w i t h the c o n d i t i o n s used. W i t h excess h y d r o g e n sulfide t h e final p r o d u c t is u l t i m a t e l y a p p r o x i m a t e l y 1 0 0 % phase C l a u s r e a c t i o n , the c h e m i s t r y is m o r e complex. S0 + 2 H S -> 3S +
2
sulfur
(6).
W h i l e the o v e r a l l s t o i c h i o m e t r y of the r e a c t i o n is the same as t h e gas
2H 0
2
(10) (7): (11)
I n n e u t r a l s o l u t i o n , almost 1 0 0 % thiosulfate is f o r m e d 4HS0 " +

3
2 H S - -> 3 S 0 " +
2 3 2
3H 0
2
T h e conditions of the citrate process at p H 4.0-4.5 f a l l i n t o a n i n t e r m e d i a t e range b e t w e e n the t w o cases c i t e d , a n d u n d e r these c o n d i t i o n s the r e a c t i o n of s u l f u r d i o x i d e w i t h h y d r o g e n sulfide falls i n t o t w o a p p r o x i m a t e l y separate phases. I n the first phase, i n the presence of a n excess of bisulfite, thiosulfate, a n d tetrathionate are f o r m e d b y the o v e r a l l reactions: 4HS0 ~ +
3
2 H S -> 3 S 0
2 2
- +
2H+ + 3H 0
2
3H 0
2
(12) (13)
3HS0 ~ +
3
H S +
2
H + -> S 0
4
- +
198
SULFUR
REMOVAL
AND RECOVERY
T h e t e t r a t h i o n a t e c a n r e a c t f u r t h e r to f o r m t r i t h i o n a t e a n d m o r e t h i o sulfate: S 0
4
- +
H S O 3 - -> S 0
3
- +
S 0
2
- +
H+
(14)
A s m a l l a m o u n t of s u l f u r m a y b e f o r m e d as i n R e a c t i o n 10. I n the s e c o n d phase the p o l y t h i o n a t e s a n d t h i o s u l f a t e r e a c t w i t h h y d r o g e n sulfide: S 0

4 2
- +
H S -> 2 S 2 O 3 2 2
S + 4S +
2
2H+ 3H 0
2
(15) (16) (17)
S 0
3
- +
2
3 H S -> S2O3 - +
2 2
S 0
2
- +
2H S +
2 H + -> 4S +
3H 0
I n a d d i t i o n there m a y be side reactions i n w h i c h t h i o s u l f a t e reacts w i t h the p o l y t h i o n a t e s to g i v e the next h i g h e r p o l y t h i o n a t e a n d sulfite, S 0 ~ +

3 6 2
e.g.: (18)
S 0
2
" -> S 0
4
- +
S0
T h e sulfite f o r m e d reacts w i t h h y d r o g e n sulfide to g i v e sulfur. S0 ~ +

3 2
2H S +
2
2 H + -> 3S +
3H 0
2
(19)
T h e r e a c t i o n of h y d r o g e n sulfide w i t h thiosulfate is m u c h s l o w e r t h a n w i t h the p o l y t h i o n a t e s a n d is rate d e t e r m i n i n g for the r e g e n e r a t i o n step. K e l l e r ' s d a t a ( 8 ) i n d i c a t e that i n the p H r a n g e o f 3.5 to 5.5 the rate is a p p r o x i m a t e d b y :
k(S 0 -)
2 3 2
3 / 2
(H+)
1/2
(20)
T h u s , b y a l l o w i n g the t h i o s u l f a t e c o n c e n t r a t i o n to b u i l d u p i n the system, t h e r e a c t i o n rate is i n c r e a s e d a n d s m a l l e r reactors c a n be used. T h e rate expression also shows that the r e a c t i o n is f a v o r e d b y a l o w pH. T h i s is the o p p o s i t e of the a b s o r p t i o n step w h e r e a h i g h p H is d e sired. T h e r e is, therefore, a n o p t i m u m p H for the process w h i c h balances the costs of the a b s o r p t i o n a n d r e g e n e r a t i o n steps. T h i s appears to b e i n t h e range b e t w e e n 4.0 a n d 4.5. I n F i g u r e 3 the r e g e n e r a t i o n reactions w e r e s t u d i e d b y m e a s u r i n g the concentrations of the reactants a n d the p r o d u c t s as a f u n c t i o n of t i m e i n contact w i t h h y d r o g e n sulfide. F o r phase one, as the bisulfite decreases, there is a s i m u l t a n e o u s b u i l d u p of p o l y t h i o n a t e a n d thiosulfate.
16.
KOROSKY E T A L .
Citrate
Process
199
Figure 3. Reaction of H S with absorbed S0 during the regeneration step. The curves show measured concentrations of reaction mixture components as a function of reaction time with H S at room temperature.
2 2 2
A s the bisulfite c o n c e n t r a t i o n approaches zero, the p o l y t h i o n a t e c o n c e n t r a t i o n levels off a n d s u l f u r p r e c i p i t a t i o n begins. T h e n as t h e p o l y t h i o n a t e reacts w i t h h y d r o g e n sulfide, its c o n c e n t r a t i o n begins to decrease w h i l e the thiosulfate a n d s u l f u r concentrations c o n t i n u e to increase. U n d e r t h e m i l d c o n d i t i o n s used, there w a s no a p p a r e n t r e a c t i o n of t h i o s u l f a t e or of the t r i t h i o n a t e p o r t i o n of t h e p o l y t h i o n a t e s to f o r m sulfur.
200
SULFUR
REMOVAL
AND
RECOVERY
W h i l e the c h e m i s t r y is c o m p l e x , the r e a c t i o n c a n be f o l l o w e d u s i n g o n l y t w o s i m p l e measurements: the p H a n d the thiosulfate content. Calc u l a t e d values are p l o t t e d i n F i g u r e 4 for a s i m p l i f i e d b a t c h r e a c t i o n i n w h i c h the h y d r o g e n sulfide reacts consecutively w i t h the bisulfite, p o l y
'
I I L
;
/
4
S
T MOSUL FA -
V -
liSULF \
LFUR
-\-^
)LYTHI O U A T E
.6 .8 1.0 12 MOLS H S / MOL

2
1.4 S0
2
1.6
1.8
2*0
ZA
Figure 4. Calculated variation of pH and thiosulfate during the regeneration step as a function of moles of H S reacted per mole of S0 initially present. H S is assumed to react consecutively with bisulfite, polythionate, and thiosulfate.
2 2 2
thionate, a n d thiosulfate. I n the first phase of the r e a c t i o n , as the b i sulfite is c o n s u m e d the thiosulfate l e v e l increases a n d the p H increases v e r y slightly. I n the first p a r t of the second phase, as polythionates are c o n v e r t e d to thiosulfate a n d s u l f u r p r e c i p i t a t i o n begins, the thiosulfate l e v e l continues to increase a n d a v e r y slight p H d r o p occurs. I n the last p a r t of the second phase, as thiosulfate reacts to f o r m sulfur, the thiosulfate l e v e l s t e a d i l y decreases w h i l e the p H increases. W h e n t w o moles of h y d r o g e n s u l f i d e / m o l e of sulfur d i o x i d e h a v e b e e n c o n s u m e d , the p H a n d thiosulfate c o n c e n t r a t i o n h a v e r e t u r n e d to
16.
KOROSKY E T A L .
Citrate
Process
201
the levels t h e y h a d before the a b s o r p t i o n step. R e g e n e r a t i o n is n o w c o m plete, a n d another c y c l e c a n b e g i n . A t this p o i n t the o v e r a l l s t o i c h i o m e t r y becomes the f a m i l i a r r e a c t i o n s h o w n e a r l i e r : S0 + 2 H S -> 3S +
2
2H 0
2
(10) hydrogen
I n a c t u a l p r a c t i c e i n a c o n t i n u o u s r e a c t i o n system, t h e d i t i o n s of p H a n d thiosulfate c o n c e n t r a t i o n .
sulfide a d d i t i o n rate m u s t be c o n t r o l l e d to o b t a i n the final reactor c o n I n this r e g a r d , F i g u r e 4 illustrates a n i m p o r t a n t feature of the c i t r a t e process. I t c a n b e seen t h a t , if s l i g h t l y m o r e or less t h a n t h e s t o i c h i o m e t r i c a m o u n t of h y d r o g e n sulfide is u s e d , the effect w i l l b e m e r e l y to cause s m a l l v a r i a t i o n s i n t h e p H a n d thiosulfate content of the l i q u o r r e t u r n e d to t h e a b s o r p t i o n step. Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch016 T h u s , the c o m b i n a t i o n of c i t r a t e b u f f e r i n g c a p a c i t y a n d thiosulfate c o n c e n t r a t i o n p r o v i d e s c a p a c i t y for s h o r t - t e r m overloads of either s u l f u r d i o x i d e or h y d r o g e n sulfide. T h e r e is no n e e d for p r e c i s e instantaneous adjustment of the h y d r o g e n sulfide flow rate to m a t c h exactly t h e i n s t a n taneous s u l f u r d i o x i d e a b s o r p t i o n rate. T h i s is i n contrast w i t h t h e gas phase r e a c t i o n w h e r e precise s t o i c h i o m e t r y m u s t b e m a i n t a i n e d at a l l times. Regeneration Step Theory. T h e r e a c t i o n of h y d r o g e n sulfide a n d s u l f u r d i o x i d e i n aqueous s o l u t i o n has b e e n s t u d i e d extensively as t h e W a c k e n r o d e r r e a c t i o n . T h e consensus of v a r i o u s w o r k e r s ( 9 ) is t h a t the first stage of the r e a c t i o n is the f o r m a t i o n of a n u n s t a b l e i n t e r m e d i a t e a c i d that f u r t h e r reacts to p r o d u c e t h e p r o d u c t s o b s e r v e d , p r i n c i p a l l y s u l f u r , t h i o s u l f u r i c a c i d , a n d p o l y t h i o n i c acids. T h e most p r o m i n e n t of the s u g gested i n t e r m e d i a t e s are s u l f o x y l i c a c i d ( S ( O H ) )
2
(JO) and thiosulfurous
acid ( H S 0 )
2 2 2
(11).
B o t h i n t e r m e d i a t e s h a v e schemes to e x p l a i n a l l of
the v a r i o u s p r o d u c t s f o r m e d . T h e m a j o r o v e r a l l reactions are g i v e n b e l o w . F o r m a t i o n of the i n t e r m e d i a t e s f r o m h y d r o g e n sulfide a n d s u l f u r dioxide : 2H S0

2
H S 0
2 2 5
+ +
H 0
2
(21A)
2 3
H S +
2 2
H S 0
2 2
-> S ( O H ) -> H S 0
2 2
H S 0
2
(21B) (22)
H S +
S0
F o r m a t i o n of t e t r a t h i o n i c a c i d , w h i c h appears to be the first stable product: S(OH) + H S 0

2 2
+ +
H S0
2
-> H S 0
2 4
+ +
2H 0
2
(23) (24)
H S 0
2 2
2H S0
2
-> H S 0
2 4
2H 0
2
202
SULFUR
REMOVAL
AND
RECOVERY
F o r m a t i o n of s u l f u r f r o m the i n t e r m e d i a t e s : S(OH) H S 0
2 2 2
+ +
H S -> 2S +
2
2H 0
2
(25) (26)
H S -> 3S +
2
2H 0
2
F o r m a t i o n of t h i o s u l f u r i c a c i d : H S +
2
H S 0
2 2
-> S ( O H ) H S 0
2 3
+ +
H S 0
2 2
(21b) (27) (28)
H S 0
2 4
H S0
2
H S 0
2 2
S + Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch016
H S0
2
-> H S 0
2 2
F o r m a t i o n of h i g h e r p o l y t h i o n a t e s : H S 0
2 4
H S 0
2 2
-> H S 0
2 5
H S0
2
(29) conditions
T h e s e same reactions o c c u r , b u t s o m e w h a t differently, u n d e r of t h e citrate process.
I n phase 1, w i t h the h i g h e r p H ' s u s e d , the s u l f u r f o r m e d b y R e a c t i o n 25 o r 26 w o u l d b e e x p e c t e d to react m o r e r e a d i l y to give greater a m o u n t of thiosulfate is f o r m e d ( 1 2 ) . r a t h e r tends to b e d e g r a d e d 14 a n d 27. I n phase 2, i n the absence of bisulfite, c h a i n b u i l d u p is p o s s i b l e , e.g. : S 0 ~
3 6 2
thiosulfate
b y R e a c t i o n 28. T h u s , s u l f u r f o r m a t i o n is r e d u c e d or e l i m i n a t e d a n d a A l s o i n phase 1, w i t h excess Reactions bisulfite, the p o l y t h i o n a t e c h a i n is n o t b u i l t u p as i n R e a c t i o n 29, b u t to t r i t h i o n a t e a n d thiosulfate,
+ +
S 0
2 2
" -> S 0
4
- + - +
S0 ~
3 2
(18) (30)
S 0 ~
4 6 2
S 0 ~
3 2
S 0
5
S0 ~
3 2
T h e sulfite f o r m e d w o u l d react w i t h excess h y d r o g e n sulfide to p r o d u c e s u l f u r d i r e c t l y f r o m the s u l f o x y l i c or t h i o s u l f u r o u s i n t e r m e d i a t e , R e a c t i o n s 25 a n d 26, w i t h o u t p o l y t h i o n a t e f o r m a t i o n . T h e o v e r a l l r e a c t i o n h y d r o g e n sulfide a n d sulfite w o u l d b e : S0 ~ +

3 2
between
2H S +
2
2 H + -> 3S +
3H 0
2
(19)
H o w e v e r , the p H is n o w m o r e f a v o r a b l e for r e a c t i o n of the p o l y thionates w i t h h y d r o g e n follows: S 0

4 2
sulfide (13,
14),
a n d tetrathionate reacts
as
H S -> 2 S 0
2 2
- +
S +
2H+
(15)
16.
KOROSKY
ET AL.
Citrate
Process
203
T h e p o l y thionates i n g e n e r a l r e a c t : S 0 - +
n 6 2
H S -> 2 S 0 - +
2 2 3 2
(n-3)S +
2H+
(31) R e a c t i o n 31
However,
with
t r i t h i o n a t e at t h e g i v e n
conditions,
y i e l d s o n e m o l e o f t h i o s u l f a t e a n d three moles o f sulfur. I n a d d i t i o n t h e r e a c t i o n rate increases i n t h e presence of thiosulfate. T h e s e suggest that the m a i n course of t h e r e a c t i o n w i t h h y d r o g e n sulfide p r o c e e d s t h r o u g h the i n i t i a l f o r m a t i o n of t e t r a t h i o n a t e : S 0 - +
3 6 2
S 0 - -> S 0 - +
2 3 2 4 6 2
S0 3 2
(18)
followed b y : Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch016 S 0 - +

4 6 2
H S -> 2 S 0 " +
2 2 3 2
S +
2H+
(15)
and S0 " +
3 2
2H S +
2
2H+ -> 3S +
3H 0
2
(19)
to give o v e r a l l t h e o b s e r v e d r e a c t i o n : S 0 - +
3 6 2
3H S -> S 0 ~ +
2 2 3 2
4S +
3H 0
2 8
(16)
F o s s (15) has p o s t u l a t e d a m e c h a n i s m f o r t h e f o r m a t i o n o f S f r o m p o l y thionates via t h e u n s t a b l e sulfanemonosulfonates as intermediates s i m i l a r could be formed b y to that p r o p o s e d b y D a v i s (16) f o r a c i d i f i e d thiosulfate solutions. I n t h e citrate process d i s u l f a n e m o n o s u l f o n a t e the attack of t h e H S " i o n o n tetrathionate. S 0 - +
4 6 2
H S - -> H S , O r +
S 0 "
2 3 2
(32) displacements of
T h e s u l f u r c h a i n w o u l d b e b u i l t u p b y consecutive thiosulfate b y d i s u l f a n e m o n o s u l f o n a t e : HS 0 " +

3 3
HS 0 - - HS 0 - +
3 3 4 3
S 0 ~ +
2 3 2
H+ H+
(33) (34)
HS 0 - +
4 3
H S 0 - -> H S 0 - +
3 3 5 3
S 0 ~ +
2 3 2 8
u n t i l t h e s u l f u r c h a i n w a s l o n g e n o u g h to f o r m S b y r i n g closure. HSioOr -> S +

8
S 0 - +
2 3 2
H+
(35)
T h e o v e r a l l s t o i c h i o m e t r y of t h e r e a c t i o n of thiosulfate w i t h h y d r o g e n sulfide is g i v e n b y :
204 S 0
2 2
SULFUR
REMOVAL
AND RECOVERY
- +
2H S +
2
2 H + -> 4S +
3H 0
2
(17)
T h i s s i m p l e e q u a t i o n is the result of a n u m b e r of c o m p l e x reactions w h i c h are discussed b e l o w . W h i l e t h i o s u l f a t e is stable i n n e u t r a l solutions, i n s l i g h t l y a c i d s o l u tions it decomposes s l i g h t l y a n d sets u p a n e q u i l i b r i u m S 0
2 3 2
(14): (36) A dis-
- +
H + <= H S O 3 - +
S (K =
.013 at 11C)
w h i c h stabilizes t h e s o l u t i o n a n d prevents f u r t h e r d e c o m p o s i t i o n .
p l a c e m e n t of the e q u i l i b r i u m to the r i g h t w i l l cause m o r e t h i o s u l f a t e to d e c o m p o s e . T h e use of a c i d to d o this has b e e n extensively i n v e s t i g a t e d . For Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch016 d i l u t e a c i d , t h e r e a c t i o n rate has b e e n s t u d i e d (17). The main p r o d u c t s w e r e r e p o r t e d to b e s u l f u r a n d sulfite w i t h o n l y s m a l l amounts of p o l y t h i o n a t e s . T h e t i m e of s u l f u r a p p e a r a n c e w a s m e a s u r e d , a n d b a s e d o n this the i n i t i a l r a t e of s u l f u r p r o d u c t i o n was expressed as : ^ = k(S 0 -)
2 3 2
3 / 2
(H+)
1 / 2
(37)
T h i s e q u a t i o n is of t h e same f o r m w h i c h w a s f o u n d to fit K e l l e r ' s later d a t a for the r e a c t i o n of h y d r o g e n sulfide w i t h thiosulfate, E q u a t i o n 20. A f t e r the a p p e a r a n c e of s u l f u r the r e a c t i o n w a s f o l l o w e d b y t i t r a t i o n , and the rate of sulfite p r o d u c t i o n w a s f o u n d to b e : ^ ~ = k(S 0 -) (H+)
2 3 2 2
d ( S
3 2
(38)
M e c h a n i s m s b a s e d o n t w o or m o r e consecutive reactions w e r e p r o p o s e d to e x p l a i n the o b s e r v e d rate d a t a (16,18). T h e s e w e r e the r e a c t i o n of t h i o s u l f a t e a n d b i t h i o s u l f a t e i o n to f o r m a c o m p l e x w i t h d i r e c t b r e a k d o w n to s u l f u r a n d the r e a c t i o n b e t w e e n the same t w o ions to f o r m d i s u l f a n e m o n o s u l f o n a t e ( H S 0 ~ ) , w h i c h reacts f u r t h e r .
3 3
As
n o t e d earlier, this last m e c h a n i s m was p r o p o s e d b y D a v i s . I n this
case the c h a i n b u i l d u p of the sulfanemonosulfonates is suggested to p r o c e e d b y successive d i s p l a c e m e n t s of sulfite b y t h i o s u l f a t e o n the u n s t a b l e intermediates. T h e sequence is as f o l l o w s : HS 0 - +
2 3
S 0
2
- - H S 3 O 3 - -> H S 4 O 3 -
+ +
S0 S0
(39) (40)
HS3O3until
S 0
2
H S 0 - -> S
9 3
HSO3-
(41)
T h e sulfite f o r m e d i n R e a c t i o n s 39 a n d 40 is r e m o v e d as bisulfite b y the a c i d present.
16.
KOROSKY E T A L .
Citrate
Process
205
R e a c t i o n b e t w e e n sulfanemonosulfonates w a s also p o s t u l a t e d to exp l a i n the f o r m a t i o n of p o l y t h i o n a t e s ( suifanedisulfonates ) as a side p r o d u c t i n this system. T w o molecules o f d i s u l f a n e m o n o s u l f o n a t e c o u l d g i v e pentathionate:
H S 3 O 3 + HS3O3-> S 0
5 2
H+
HS-
(42)
and
i n general HS 0 x 3
H S O r -> S
y
( x
_ " +
2
H+ +
HS-
(43)
S u l f u r isotope effects i n the a c i d d e c o m p o s i t i o n of thiosulfate also w e r e s t u d i e d ( 2 9 ) , a n d b a s e d o n these a s i m p l e b i m o l e c u l a r m e c h a n i s m w a s Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch016 favored. In contrast to the d i l u t e a c i d d e c o m p o s i t i o n of thiosulfate w h e r e t h e e q u i l i b r i u m a n d sulfite are a c t e d u p o n b y a c i d , this is a c c o m p l i s h e d i n the citrate process b y the r e a c t i o n of the various sulfite species h y d r o g e n sulfide. S0 In
2
with
- +
2H S +
2
2 H + -> 3S +
3H 0
2
(19)
this w a y the e q u i l i b r i u m of R e a c t i o n 36 is s h i f t e d , a n d the sulfite This
p r o d u c t s of c h a i n b u i l d u p i n Reactions 39, 40, a n d 41 are r e m o v e d . results i n the o v e r a l l e q u a t i o n : S 0

2 2
- +
2H S +
2
2 H + - 4S +
3H 0
2
(17)
Sulfur Melting. U n d e r t h e t e m p e r a t u r e c o n d i t i o n s u s e d i n the s u l f u r m e l t i n g step ( > 1 2 5 C ) there is some thiosulfate d e c o m p o s i t i o n . The r e a c t i o n consumes h y d r o g e n ions a n d forms s u l f u r a n d sulfate as p r o d ucts. T h e r a t i o f o u n d of 1.37 moles of s u l f u r f o r m e d p e r m o l e of t h i o sulfate r e a c t e d suggests that the m a i n f o r m of the d e c o m p o s i t i o n i n v o l v e s f o r m a t i o n of s u l f u r a n d bisulfite f r o m the thiosulfate, f o l l o w e d b y dec o m p o s i t i o n of the bisulfite ( 5 ) via t r i t h i o n a t e to sulfate. T h e sequence i s : S 0
2 2
- +
H + <= H S 0 - +
3
S 3H 0
2
(36) (8) 2H+ (44)
4HS0 - +
3
S 0
2
- + - +
2 H + -> 2 S 0
3
- +
S 0
3
H 0 -> S 0
2
- +
S 0
2
- +
to g i v e a n o v e r a l l r e a c t i o n : 3S 0 ~ +
2 3 2
2 H + -> 2 S 0
- +
4S +
H 0
2
(45)
206
SULFUR
REMOVAL
AND
RECOVERY
T h e d e c o m p o s i t i o n rate does not a p p e a r to b e a s i m p l e f u n c t i o n of the thiosulfate a n d h y d r o g e n i o n concentrations. R a t e expressions for the first t w o reactions i n t h e sequence w e r e n o t e d earlier, E q u a t i o n s 37, 38, a n d 9. A t the p H c o n d i t i o n i n the citrate process the reverse r e a c t i o n i n R e a c t i o n 36 also m a y b e a factor S o m e slight d e c o m p o s i t i o n (20). of citrate also occurs. T h e m a i n course
of this appears to be via acetone d i c a r b o x y l i c a c i d to f o r m gaseous p r o d uctsacetone, carbon dioxide, carbon monoxide, a n d water: C H 0
6 8 2 2 7
-*
(CH COOH) CO +
2 2
CO +
H 0
2
(46) (47)
( C H C O O H ) C O -+
(CH ) CO +
3 2
2C0
R a s e d o n t h e i r tests, the R u r e a u of M i n e s estimated (3) that, i n a continuous s u l f u r m e l t i n g system at 135 C , for e a c h ton of s u l f u r m e l t e d , a b o u t 3 lbs of sulfate w o u l d be f o r m e d a n d 0.7 lbs of citrate d e c o m p o s e d . Oxidation. D u r i n g the a b s o r p t i o n step some o x i d a t i o n occurs:
HS0 - + y 0
3 2
-> HSO4- <= H + + S 0 4 2
(48)
to b e concen-
T h e o x i d a t i o n rate decreases w i t h p H (21, 22) tration: -d(St) dt g(HSQ -)

3
a n d is r e p o r t e d (23)
i n v e r s e l y p r o p o r t i o n a l to the square root of the h y d r o g e n i o n
( +)i/2
H
(49)
C o p p e r a n d i r o n act as catalyst for the o x i d a t i o n . T h e results of some l a b o r a t o r y runs d e m o n s t r a t i n g t h e effect of p H a n d the o x i d a t i o n i n h i b i t i n g effect of citrate are g i v e n i n T a b l e I. T h e s e s h o w that i n g o i n g f r o m p H 4 to 5 i n the citrate system t h e o x i d a t i o n a p p r o x i m a t e l y doubles. I n a c o m p a r i s o n r u n , u s i n g a different a c i d , m u c h h i g h e r levels of o x i d a t i o n w e r e f o u n d . W h i l e c i t r i c a c i d does chelate the h e a v y metals that catalyze the o x i d a t i o n , this was not a factor i n the Table I. Acid Citric Citric Sulfosuccinic Sulfosuccinic Citric
a
Oxidation of Sulfur Dioxide D u r i n g Absorption" Cone. (M) 0.5 0.5 0.5 0.5 0.5 pH 4.0 5.0 5.0 5.0 5.0 Additive Oxidation (%) 0.40.5 0.81.0 5.66.0 5.66.0 0.15
2
EDTA Thiosulfate 0 . 3 M
2 2
Temperature = 50C. Inlet gas = 2,000 ppm S 0 , 3.5%
0 , remainder N .
16.
KOROSKY E T A L .
Citrate
Process
207
c o m p a r i s o n runs. T h i s c a n be seen f r o m the fact t h a t the a d d i t i o n of e t h y l e n e d i a m i n e t e t r a a c e t i c a c i d ( E D T A ) to the other a c i d d i d not i m p r o v e its a b i l i t y to i n h i b i t the o x i d a t i o n . T h e results also s h o w that the a d d i t i o n of t h i o s u l f a t e to the citrate f u r t h e r reduces o x i d a t i o n . T h e r e m o v a l of sulfate as the s o d i u m salt ( R e a c t i o n 4 8 ) requires the a d d i t i o n of a l k a l i to n e u t r a l i z e the h y d r o g e n ions also f o r m e d : H+ + S0
2
- +
Na C0
2
-> 2 N a + +
S0 ~ +
4 2
H 0 +
2
C0
(50)
Purging. I n a d d i t i o n to o x i d a t i o n , sulfate is present f r o m a n y s u l f u r i c m i s t r e m o v e d f r o m the i n l e t gas a n d thiosulfate d e c o m p o s i t i o n sources is s m a l l , the effect is c u m u l a t i v e a n d sulfate m u s t be Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch016 f r o m the system. T h i s is best d o n e b y d i v e r t i n g a p o r t i o n of t h e m a i n stream a n d c o o l i n g it to c r y s t a l l i z e G l a u b e r ' s salt, s o d i u m sulfate d e c a h y d r a t e . w i t h the s o l u b i l i t y d e c r e a s i n g greatly b e l o w about 3 0 C . mechanical refrigeration. Hydrogen Sulfide Generation. T h e regeneration reaction was disThus a reliable cussed earlier f r o m the s t a n d p o i n t of p r o d u c t s f o r m e d i n the r e a c t i o n of s u l f u r d i o x i d e solutions w i t h a d d e d h y d r o g e n sulfide. source of h y d r o g e n sulfide is m a n d a t o r y to i n s u r e u n i n t e r r u p t e d o p e r a t i o n of t h e citrate process. P o t e n t i a l sources of h y d r o g e n sulfide i n c l u d e d e m a n d generation, b y - p r o d u c t f r o m d e s u l f u r i z a t i o n of m a n u f a c t u r e d f u e l , a n d s e p a r a t i o n f r o m sour n a t u r a l gas. S e l e c t i o n of t h e most a p p r o p r i a t e source or c o m b i n a t i o n of sources for a p a r t i c u l a r citrate process a p p l i c a t i o n w i l l d e p e n d u p o n a v a i l a b i l i t y , logistics of t r a n s p o r t a t i o n , a n d c o m p e t i t i v e economics. T h e most r e a d i l y a v a i l a b l e source of h y d r o g e n sulfide often w i l l b e on-site g e n e r a t i o n b y c h e m i c a l synthesis a c c o r d i n g to d e m a n d . Such feedg e n e r a t i o n u s u a l l y w i l l r e q u i r e the r e a c t i o n of a n y r e d u c i n g agent h y d r o g e n sulfide. CH + 4S + 2H 0 - 4H S +
2 2
during purged
t h e s u l f u r m e l t i n g step. W h i l e the rate of sulfate f o r m a t i o n f r o m a l l these
T h e solu-
b i l i t y c u r v e of s o d i u m sulfate i n citrate l i q u o r is s i m i l a r to t h a t i n w a t e r This allows s o d i u m sulfate r e m o v a l to t a k e p l a c e at temperatures r e a d i l y a t t a i n e d b y
stock w i t h steam or w a t e r a n d some f o r m of s u l f u r to p r o d u c e d i l u t e
C0
(51)
E l e m e n t a l s u l f u r p r o d u c t f r o m the c i t r a t e process u n i t w o u l d b e a v a i l a b l e as a feedstock for s u c h a generator. S e v e r a l c o m m e r c i a l l y p r o v e d processes for m a n u f a c t u r i n g h y d r o g e n sulfide are a v a i l a b l e today. T h e s e g e n e r a l l y use either m e t h a n e or h y d r o gen as r e d u c t a n t , b u t other f u e l c o u l d b e s u b s t i t u t e d b y a p p l y i n g d e m o n -
208
SULFUR
REMOVAL
AND
RECOVERY
strated f u e l c o n v e r s i o n process technology. f r o m f u e l d e s u l f u r i z a t i o n operations w h e r e i t m a y be a v a i l a b l e .
B y - p r o d u c t h y d r o g e n sulfide production
a n d sour n a t u r a l gas
presents a p o t e n t i a l l y r e l i a b l e a n d i n e x p e n s i v e source for h y d r o g e n sulfide T h e logistics of t r a n s p o r t a t i o n of b y - p r o d u c t h y d r o g e n sulfide w i l l p l a y a n i m p o r t a n t p a r t i n the u l t i m a t e use of this m a t e r i a l . I n t r a - p l a n t transfers w i l l c o n t i n u e to be b y p i p e l i n e as c u r r e n t l y p r a c t i c e d i n p e t r o l e u m refineries a n d gas p l a n t s . I n t e r - p l a n t transfers for m o r e t h a n v e r y short distances w i l l l i k e l y i n v o l v e l i q u e f a c t i o n of the h y d r o g e n a n d m o v e m e n t b y t a n k trucks or t a n k cars. L i q u i d hydrogen sulfide has b e e n classified as a f l a m m a b l e compressed gas for s h i p m e n t i n b o t h t a n k t r u c k s a n d t a n k cars b y m e n t a l authorities b o t h i n the U n i t e d States a n d C a n a d a . Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch016 cars filled to a m a x i m u m d e n s i t y of 6 8 % . h y d r o g e n sulfide. Citrate Process Pilot Plant governsulfide
Department
of T r a n s p o r t a t i o n s p e c i a l p e r m i t s a u t h o r i z e use of t y p e 1 0 5 A - 6 0 0 W t a n k W i t h a c a p a c i t y of 13,500 g a l , these i n s u l a t e d tank cars w i l l h o l d a b o u t 30 short tons net w e i g h t of l i q u i d
T h e b l o c k f l o w d i a g r a m i n F i g u r e 5 indicates the p r i n c i p a l f u n c t i o n a l sections of the c i t r a t e process, c o r r e s p o n d i n g to the u n i t n o w p e r s p e c t i v e o n t h e process. operating i n T e r r e H a u t e . A b r i e f t o u r t h r o u g h these sections helps i n g a i n i n g a T h e 2 0 0 0 - S C F M gas stream b e i n g t r e a t e d i n the u n i t comes f r o m a coal-fired spreader stoker-type b o i l e r at 700 F w i t h 25,000 l b / h r steam-rated c a p a c i t y . G a s c o o l i n g , c l e a n i n g , a n d s u l f u r d i o x i d e r e m o v a l is by adiabatically cooling flue gas w i t h q u e n c h accomplished absorption water, passing into a
v e n t u r i - t y p e w a t e r s c r u b b e r to r e m o v e fly ash, f o l l o w e d b y acid.
of the s u l f u r d i o x i d e i n a n aqueous s o l u t i o n of s o d i u m citrate a n d c i t r i c T h e p i l o t p l a n t has d e m o n s t r a t e d the f e a s i b i l i t y of a c o m m e r c i a l p l a n t consistently to r e m o v e m o r e t h a n 9 5 % of t h e s u l f u r d i o x i d e i n the i n l e t gas. T h e p i l o t u n i t has o p e r a t e d for p r o l o n g e d p e r i o d s w i t h exit gas of 2 5 - 5 0 p p m s u l f u r d i o x i d e . T h e s u l f u r d i o x i d e - r i c h citrate s o l u t i o n i n the b o t t o m of t h e absorber is f e d b y l e v e l c o n t r o l t h r o u g h a steam-heated exchanger to a three-stage c o n t i n u o u s s t i r r e d t a n k reactor system c o u n t e r c u r r e n t to a flow of h y d r o g e n sulfide gas. F o r this i n s t a l l a t i o n the gas source is a tank of l i q u i d hydrogen sulfide. I n the reactor system, d e s i g n e d for 5 - m i n r e t e n t i o n t i m e or less i n e a c h of the three reactors, s u l f u r d i o x i d e is r e d u c e d to s u l f u r a n d citrate s o l u t i o n is regenerated. S u l f u r s l u r r y is p u m p e d to a sulfur s l u r r y surge d r u m a n d t h e n to the s u l f u r s e p a r a t i o n system. V a r i o u s a l t e r n a t i v e units
16.
KOROSKY E T A L .
Citrate
Process
209
for s e p a r a t i n g p r e c i p i t a t e d s u l f u r f r o m the s o l u t i o n are c u r r e n t l y b e i n g e v a l u a t e d i n c l u d i n g filtration a n d flotation u n i t s . A clear or n e a r l y clear l i q u o r is r e c y c l e d b a c k to t h e clear l i q u o i surge t a n k a n d t h e n b a c k to the a b s o r p t i o n system. W h i l e developing no the s u l f u r s e p a r a t i o n step, at times h i g h amounts of solids c o n t a i n i n g s u l f u r a n d a s h h a v e b e e n r e c y c l e d b a c k to the a b s o r p t i o n system w i t h problem.
MAKEUP CHEMICALS ( C ' T R I C A C I D , SODA ASH) GLAUBER'S SALT CRYSTALS
MAKEUP WATER
SODIUM SULFATE CRYSTALIZER
PRECIPITATED SULFUR SEPARATION
SULFUR MELT & DECANT
REGENERATION REACTION
REDUCING GAS (H S) GENERATOR

2
4
REDUCING AGENT (NATURAL GAS, ETC.)
Figure 5.
Citrate process flow diagram
T h e p r o d u c t f r o m the s u l f u r s e p a r a t i o n step is f e d as a s l u r r y i n citrate s o l u t i o n t h r o u g h a heater to raise the t e m p e r a t u r e a b o v e 125 C to m e l t t h e s u l f u r . L i q u i d phases are separated i n a decanter u n d e r pressure. T h e b o t t o m l a y e r is d r a w n off as h i g h q u a l i t y m o l t e n y e l l o w s u l f u r , a n d t h e c i t r a t e s o l u t i o n top l a y e r is d i s c h a r g e d to a flash d r u m at r e d u c e d pressure. C i t r a t e s o l u t i o n f r o m t h e decanter c a n b e b y p a s s e d a r o u n d or i n t o a v a c u u m c r y s t a l l i z e r w h e r e G l a u b e r s salt is r e m o v e d f r o m the s o l u t i o n b y c o o l i n g to a t e m p e r a t u r e w e l l a b o v e the f r e e z i n g p o i n t of w a t e r . r e n t d a t a i n d i c a t e t h a t less t h a n 2 - 3 % of n i t r o g e n oxide i n the i n p u t gas. A s a p r a c t i c a l m a t t e r , the i m p o r t a n t advantages of the system's c h e m i s t r y are that there is no c h a n c e t e r m overloads of p r e c i p i t a t i o n t a k i n g p l a c e i n the I n other a b s o r b e r a n d that the c i r c u l a t i n g s o l u t i o n has a h i g h c a p a c i t y for shortof either s u l f u r d i o x i d e or h y d r o g e n sulfide. w o r d s , as a l r e a d y stated i n the c h e m i s t r y d i s c u s s i o n , there is no n e e d for Curof t h e t o t a l s u l f u r d i o x i d e is
o x i d i z e d to sulfate. T h e a m o u n t d e p e n d s to a n extent o n the c o n c e n t r a t i o n
210
SULFUR
REMOVAL
AND RECOVERY
the h y d r o g e n sulfide flow rate to b e p r e c i s e l y a n d i n s t a n t a n e o u s l y a d j u s t e d to m a t c h t h e a b s o r p t i o n rate of s u l f u r d i o x i d e f r o m the flue gas. The citrate s o l u t i o n p r o v i d e s a d e q u a t e b u f f e r i n g c a p a c i t y w i t h resultant s l o w changes of process d e p e n d e n t v a r i a b l e s . T h i s effect is e x a c t l y the opposite of t h a t e n c o u n t e r e d i n a gas p h a s e d i r e c t r e d u c t i o n system, e.g., Claus r e a c t i o n , w h e r e precise s t o i c h i o m e t r y m u s t b e m a i n t a i n e d at a l l times. O p e r a t i o n of t h e u n i t has c o n f i r m e d b o t h the system c h e m i s t r y a n d expected s u l f u r d i o x i d e r e m o v a l efficiency. It has d e m o n s t r a t e d the i n h e r e n t s t a b i l i t y a n d tolerance of the system to s t o i c h i o m e t r i c i m b a l a n c e s b e t w e e n a b s o r b e d s u l f u r d i o x i d e a n d rgnrant h y d r o g e n sulfide f e d to the reactors. Economic Projection Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch016 Study
E c o n o m i c s for the citrate process, b a s e d o n a 200 M W p o w e r p l a n t , b u r n i n g 3 % s u l f u r c o a l , w e r e p r e s e n t e d last f a l l at the P u r d u e U n i v e r s i t y I n d u s t r i a l F u e l C o n f e r e n c e (24). D a t a c o m i n g out of T e r r e H a u t e w i l l costs s h o r t l y be t r a n s l a t e d to a n u p d a t e d e c o n o m i c p r o j e c t i o n o n the process. A n i m p o r t a n t c o n s i d e r a t i o n w h e n c o m p a r i n g citrate process to those of t h r o w a w a y processes, s u c h as non-regenerative l i m e s t o n e , is the h i g h cost of s u p p o r t i n g off-site f a c i l i t i e s for l i m e s t o n e h a n d l i n g a n d s l u d g e d i s p o s a l . T h e i m p a c t of waste d i s p o s a l expense o n o v e r a l l process costs is seen f r o m another source. t e c t i o n A g e n c y r e p o r t e d (25) I n m i d - 1 9 7 3 the E n v i r o n m e n t a l P r o o n t h e i r s t u d y of flue gas d e s u l f u r i z a t i o n Usually $ 5 - 1 5 / k W must be added
economics w h i c h c o m p a r e d ( T a b l e I I ) the c a p i t a l a n d a n n u a l i z e d o p e r a t i n g costs for a n u m b e r of processes. to c a p i t a l costs for waste d i s p o s a l f a c i l i t i e s . Table I I . Comparative Process Costs Comparative Process T h r o w a w a y ( C a p i t a l costs do not i n c l u d e disposal facilities u s u a l l y $ 5 - 1 5 / k W ) Double alkali L i m e scrubbing Limestone scrubbing Regenerable Citrate M g O (to S) W e l l m a n - L o r d (to S) Stone & W e b s t e r / I o n i c s (to S) Cat-Ox Capital ($/kW)
Process Costs A nnualized (mills/kWh)
24 1 35 > 36 ) 39 49 50 50 55
costs '
d
1.95 2.45 1.95 2.40 2.65 2.70 2.75
From (25). Basis 500 M W , 3.5% S coal, retrofit, 60% load, waste at $3/ton wet sludge, sulfur credit at $15/ton, particulate removal included.
16.
KOROSKY
ET Cited
AL.
Citrate
Process
211
Literature
1. George, D . R., Crocker, L . , Rosenbaum, T. B., Mining Eng. (1970) 22, (1), 75-77. 2. Rosenbaum, J. B., George, D . R., Crocker, L . , "The Citrate Process for Removing S O and Recovering Sulfur From Waste Gases," A I M E E n vironmental Quality Conference, Washington, D . C . , June 7-9, 1971. 3. Rosenbaum, J. B., McKinney, W . ., Beard, H . R., Crocker, L . , Nissen, W. I., "Sulfur Dioxide Emission Control by Hydrogen Sulfide Reaction in Aqueous SolutionThe Citrate System," U.S. Bur. Mines Rept. Invest. (1973) 7774. 4. Foerster, F., Vogel, R., Z. Anorg. Allg. Chem. (1926) 155, 161. 5. Battaglia, C. J., Miller, W . J., Photogr. Sci. Eng. (1968) 12, (1), 46. 6. van der Heijde, . B., Aten Jr., A . H . W., J. Amer. Chem. Soc. (1953) 75, 754. 7. Foerster, F . , Mommsen, E . Th., Chem. Ber. (1924) 57, 258. 8. Keller, J. L . , U.S. Patent 2,729,543 (Jan. 3, 1956). 9. Pollard, F . H . , Jones, D . J., Chem. Soc., Spec. Publ. (1959) 12, 363. 10. Schmidt, M . , "Sulfur in Organic and Inorganic Chemistry," A . Senning, E d . , 71-112, Marcel Dekker, Inc., New York, 1972. 11. Stamm, H . , Goehring, M . , Z. Anorg. Allg. Chem. (1939) 242, 413. 12. Barbieri, R., Faraglia, G., Gazz. Chim. Ital. (1962) 92, 660. 13. Blasius, E . , Kramer, R., J. Chromatogr. (1965) 20, 367. 14. Hansen, C. J., Chem. Ber. (1933) 66B, 817. 15. Foss, O., Acta Chem. Scand. (1961) 15, 1610. 16. Davis, R. E., J. Amer. Chem. Soc. (1958) 80, 3565. 17. Zaiser, E . M., L a Mer, V. ., J. Colloid Sci. (1948) 3, 571. 18. Dinegar, R. H . , Smellie, R. H . , La Mer, V . ., J. Amer. Chem. Soc. (1951) 73, 2050. 19. Agarwala, V., Rees, C. E., Thode, H . G., Can. J. Chem. (1965) 43, 2802. 20. Dinegar, R. H . , Smellie, R. H . , J. Colloid Sci. (1952) 7, 370. 21. Fuller, E . C., Crist, R. H . , J. Amer. Chem. Soc. (1941) 63, 1644. 22. Rand, M . C., Gale, S. B., Princ Appl. Water Chem., Proc. Rudolfs Res. Conf., 4th, Rutgers State Univ. (1965) 380. 23. Schroeter, L . C., J. Pharm. Sci. (1963) 52, 888. 24. Chalmers, F . S., Korosy, L . , Saleem, ., "The Citrate Process to Convert S O to Elemental Sulfur," Industrial Fuel Conference, Purdue University, West Lafayette, Indiana, October 3, 1973. 25. Rochelle, G. T., "Economics of Flue Gas Desulfurization," Flue Gas Symposium of the Environmental Protection Agency, New Orleans, L a . , May, 1973.
2 2
1974
INDEX
A
Absorbent flow rate 170 Absorber tank 127 Absorbers 58, 97 Absorption 57, 194 hydrogen sulfide 113 processes 5, 14, 192 reactions 195 studies 196 sulfur dioxide 130, 192, 199 oxidation during 206 surface selection 126 system 7, 159 tower 57 Acid mist 54 Acidic sites on alumina 88 Activated coke 181 Activation energies 81,82 Activity catalytic 65, 66, 87 of Jamaican red mud 65 of red bauxite 66 A C P system 172,175,179 Adsorbent regeneration 181, 183 Adsorption 181 on carbon 180 on ehromosorb-A 86 fixed-bed 11 of hydrogen sulfide 88 sulfur dioxide 86, 89 Afterscrubbers 17 Allied Chemical sulfur dioxide reduction technology . .5, 23, 24, 29 Alumina activated 84 acidic and basic sites on 88 catalysts . . . .61, 64, 67, 75, 78, 79, 83 Amine section 112, 119 Ammonia absorption process 14 recovery process 6 scrubbing process 16, 108 Aquaclaus process, Stauffer 13 Aqueous carbonate process, regenerative 164 phase, saturation of 147 scrubbing system 24 Arrhenius plots 81, 154 A S A R C O D M A absorption process 5 A S A R C O and Phelps Dodge Corp., elemental sulfur pilot plant of 35 Autothermal requirement 52
Base on catalysts, effect of 84 Basic sites of alumina 88 Basic species 131, 138 Basicity 79 catalyst 75, 84, 87 determination 86 of solution 137, 144 Bauxite 65, 75, 79, 84 Beavon sulfur removal process for Claus plant tail gas 13, 93, 96, 97, 98, 112 Bench-scale feasibility studies . . . . 185 Benzoic acid titration 86 Bergbau Forschung unit 190 Bicarbonator-crystallizer 168 Bisulfite 158, 197 Blister copper 49 Boiling media heat removal 46 Bureau of Mines citrate process . . . 13
Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ix001
C
Calcined dolomite 149 Calcite 147 Calcium -based sulfur dioxide scrubbing system 120,123 oxide-S02-S0 -C02-H 0 system 131,132 sulfite saturation of 133,140, 143 Canada, S C O T units in 117 Capital cost estimate utility systems 176 Carbon ( s ) active 182 adsorption on 180 dioxide 134, 135 monoxide ratios 63 monoxide, sulfur dioxide reduction with 60, 63 stability 37 Carbonate process, regenerative aqueous 164 Carbonate salts 141 Cafbonyl sulfide 62 Carboxylic acid salt catalyst . . . . 101 Catalysis 42,55 Catalyst(s) alumina 78, 79 basicity 75,84,87 bauxite 75 beds 57,60,61,96
3 2
215
216
Catalyst (continued) carboxylic acid salt 101 chemical and physical properties of 63 for Claus reaction 83, 84 cobalt-molybdenum 113 copper-alumina 67 copper low temperature shift . . . 69 double-bed 70 iron-alumina 61,64 iron oxide high temperature shift 68 Jamaican red mud 69 pellets 45 pretreatment of 79 single bed 65,69 sulfur dioxide reduction 42 temperature 71,72 Catalytic activity 65,66,87 converters, three-stage 76 reactor 44,94 reduction 25,60,63 Cation, effect of 83 Chromatographic firebrick ( chromosorb-A ) . . 78, 80, 81, 83, 86 Chromatographic separation of N2, H , S, H 0 , and S 0 78 Chromosorb-A ( chromatographic firebrick) 78,80,81,83,86 Citrate process, Bureau of Mines 13, 192, 194, 208, 209 Claus offgas treating ( S C O T ) process, Shell Ill plant 93,102,106,107 process 94, 111 reaction 64 activation energy for the . . . . 82 kinetic data for 80, 81 polarizing power at N a , L i , K , on 83 sodium catalysts for . .75, 83, 84, 87 reactivity 82 reactor system 26,41 sulfur plants 3,11,60 tail gas clean-up process 101 Coal high-sulfur 128, 149 limestone scrubbing 128 sulfur dioxide reduction by . . . . 185 Cobalt-molybdate on 7 -alumina catalyst 78,83 Cobalt-molybdenum catalyst . . . . 113 Coke, activated 181 Coke oven gas 4, 16 Combustor, fluidized-bed 149 Cominco process 6 Commercial design 95 lime-limestone flue gas scrubbing technology 120 plants 24,118 scale demonstrations 189
2 2 2 + + +
SULFUR
REMOVAL
AND
RECOVERY
Concentrating systems, sulfur dioxide 32 Condensation of sulfur vapor 41,76,185 Construction materials 54, 98 Contact section 56 Contamination of amine 119 Continuous smelting processes . . . . 31 Conversion 57 hydrogen sulfide 80, 104 for I F P unit 105 sulfur dioxide 192 Converter(s) gas, copper 48, 51 heat exchanger system 58 operations, cyclic copper 30 three-stage catalytic 76 Coolant 46 Cooling, gas 53 Cooling tower blowdown 146 Copper -alumina catalyst 67 blister 49 blows 50 converter gas 48,51 converter operations, cyclic . . . . 30 low temperature-shift catalyst . . 69 smelter 4,35,49 sulfides 49 Corrosion 45, 56 Cost effectiveness, A C P 179 fuel 176 investment 107 operating . .98, 107, 162,176, 177, 210 utility 176,177 Crystallizer, bicarbonator168 Cyclones 170
D
Davy Powergas 30, 49 Delay tank 127 Demisting stages 128 Desulfurization efficiency 184 Desupersaturation, reagent 127 Disc scrubber, flooded 121 Disulfanemonosulfonate 203 Desulfurization system, flue gas . . 30 Dissolution, solids 147 D M A absorption process, A S A R C O 5, 6 Dolomite limestones . . 145, 147, 149, 150 Doublebed catalysts 60,61,70 catalysis sulfuric acid plant . . . . 55 contact sulfuric acid process . . . 10 Dryer-scrubber, spray 164
Economics, process . . . .98, 110, 176, 210 Electric smelting furnace 9 Elastrostatic mist precipitators . . . . 54
INDEX
217 G
Gas ( es ) Claus plant tail coke oven compositions 93, 101 4,16 29, 30, 32, 37, 39, 40, 41, 70, 71 cooling 53 copper converter .48, 51 exhaust 69 feed 28, 102, 104, 105 flue (see Flue gas) 30 fluorine content of a 53 mixtures, sulfurous 68 natural 25, 38 purification 24, 52 ratio, liquid-to169 reactant gas 152 reduction of 33 reformed 37,38,44 roaster 24,31 scrubbing and cooling 53 shift reaction, water64, 95 smelter 5,31 stability, homogeneous 37 stream, head 42 streams, polluted 180 sulfurous 72 sulfur dioxide 158 tail (see Tail gas) volumes, process 33 waste 11 Gasification 15
Elemental sulfur pilot plant 35, 43 Emission(s) control systems 32 metallurgical 23 from sinter plants 16 sources 2 sulfur dioxide 2, 3 Energy, activation 81,82 Energy scrubber 124 Engineering, system 173 Equilibrium compositions, thermodynamic . . 67 condensation of sulfur vapor . . . 41 gas phase composition 40,41,68 Exhaust gas analysis 69 Exit gas composition 70,71
F
Feasibility studies 185 Feed gas considerations ..28,102,104,105 specifications 106 streams, sulfur dioxide 28 Feedstock 15 Film packing, wetted 121 Filter, froth 98 Filtration, panel-bed 150 Firebrick ( chromosorb-A ), chromatographic . .78, 80, 81, 83, 86 First-stage reactor 40 Fixed-bed adsorption process 11 catalysis 42 reactors 27,42 Flash smelting process 9 Flooded disc scrubber 121 Flooding points for high capacity packings 127 Flow rate, absorbent 170 Flow reactor 77 Flue gas 125,158 desulfurization system 30 regenerator 15 scrubbing technology, lime-limestone 120 Fluid catalytic cracking 4 Fluidized-bed combustor 149 Fluidized-bed roasting 23 Fluoride emissions 16 Fluorine content of a gas 53 Fly ash 125 Fossil fuel 35 Foster Wheeler Resox pilot unit . . 189 Froth filter 98 Fuel cost 176 Fuel, fossil 35 Furnace electric smelting 9 Kraft recovery 17 reverberatory 31 temperature 70
H
Head gas stream 42 Heat exchanger 44, 58 regenerator system, reactor- . . . 26 removal, boiling media 46 Helium 61 Hydrogen -carbon-oxygen-sulfur system . . 36 sulfide absorption 86,88,113 absorbed sulfur dioxide, with 199 concentration in feed gas . . 102, 104 conversion 80 generation 25,207 selectivity 187 -sulfur dioxide ratio in feed gas 105 Hydrognation 94 Hydrochloric acid 135 Hydrolysis reactions 94 Hydrotreating the feedstock 15
I
IFP ammonia absorption process . . . 1.^ 14 Claus tail gas clean-up process 100,101
218
IFP (continued)
SULFUR
REMOVAL
A N D RECOVERY
-150 process 108,109,110 -1500 process 101,102,104, 107 unit 105, 106 Inco oxygen flash smelting process 9 Industrial process sources of sulfur oxides 1 Industrial sulfur dioxide removal . . 164 Interstage absorber, Venturi-type . . 58 Investment costs 107 Iron -alumina bifunctional catalyst . .61,64 oxide high temperature shift catalyst 68 sulfides 49 Isothermal catalysts, single-bed . . 65
Mass transfer coefficients 128 Metallurgical emissions 23,30,31 Methane 38 Mist, acid 54 Mist precipitators, electrostatic . . . 54 process 16 Mitsubishi-JECCO lime scrubbing Molybdenum catalyst, cobalt78,83,113 Mud, Jamaican red 66, 69
on Claus reaction, polarizing power of 83 Natural gas 25,38 Nickel-containing pyrrhotite ore . . 23 Nippon Kokan scrubbing process . . 16 Nonferrous smelters 4 Nonisothermal catalysts 69 Nonisothermal kinetics 183
+
Na
Jamaican red mud
66, 69
K on Claus reaction, polarizing power of 83 Kinetic data for Claus reaction . . .80, 81 Kinetics of half-calcined dolomite with sulfur dioxide 149 Kinetics of thermal regeneration . . 183 Kraft recovery furnaces 17
+
Offgas treating ( S C O T ) process, Shell Claus Oil refineries, sulfur recovery in . . Onahama smelter Open-cycle scrubbing Operating cost estimate Operation controls Outokumpu flash smelting process Oxygen flash smelting process, Inco . . . . -to-sulfur dioxide ratio -sulfur system, hydrogencarbonIll 100 7 11 177 59 9 9 56 36
L
Laboratory development program 42 Lattice sulfur 62 Lead smelter 4,35 Lean-rich exchanger 114 L i on Claus reaction, polarizing power of 83 Lime scrubbing process, MitsubishiJECCO 16 -limestone flue gas scrubbing technology 120, 125, 130 limestone wet scrubbing 121 Limestone dolomite 145,150 flue gas scrubbing technology . . 120 magnesium content of 144 scrubbing, high sulfur coal . . . . 128 scrubbing, lime- (see Limelimestone scrubbing) Liquid-to-gas ratio 169 Liquid phase compositions . . . . 132, 137
+
pH 128, 134, 140, 200 Packed tower 124 Packing, high capacity 127 Packing, wetted film 121 Panel-bed filtration 150 Paper pulping industry 4 Parsons-Beavon process 112 Performance of IFP-150 process . . 110 Petroleum refineries 15 Phelps Dodge, elemental sulfur pilot plant of A S A R C O and . . 35 Phelps Dodge reforming process . . 44 Pilot plant 95 citrate process 208 costs of 47 elemental sulfur 43 Foster Wheeler Resox 189 operation 43, 45,188 testing 184 Plant design 51,95 Poisoning effect of water 65 Polarizing power of N a , L i , and K on Claus reaction 83
+ + +
M
Magnesia-base absorption system . . Magnesia-base pulping process . . . Magnesium basic species caused by content of limestone 140, salts 7 18 138 144 146
INDEX
219
Regeneration 197 adsorbent 181,183 step theory 201 subsystem 167 system 162,174 thermal 183 Regenerative aqueous carbonate process 164 Regenerator flue gas 15 Regenerator system, reactor-heat. . 26 Removal process for Claus plant tail gas, Beavon sulfur 93,96,98 sulfur dioxide ( see Sulfur dioxide removal ) sulfurous gases 72 Research feasibility studies 185 Reverberatory furnace 31,50 Roasters, gases from 24,31 Roasting fluidized bed 23
Polluted gas streams 180 Polythionates 198 Porasil 79 Precipitation of carbonate salts . . . 141 Precipitators, electrostatic mist . . . 54 Pressure, carbon dioxide 134 Pressure specification 39 Primary reactors 42, 44 Process capability 27 economics 98, 110, 176, 210 gas volumes 33 modifications 27 sources of sulfur oxides 1 technology 181 Pulp mills 17 Pulping process, magnesia-base . . . 18 Purging 55,207 Purification, gas 24 Purification system, wet 28 Pyrrhotite ore 23
Q
Quench section, reduction112
S
Salt(s) carbonate 141 catalyst, carboxylic acid 101 magnesium 146 Saturation of the aqueous phase . . 147 Saturation of calcium sulfite 140 S C O T process (Shell Claus offgas treating) . . . . 13, 111, 112,113,115 commercial plants 115,117, 118 operating requirements 114 performance testing and compliance 119 Scrubber energy 124 flooded disc 121 installation plan view 173 spray dryer 164 subsystem loop 167 system performance 171 Scrubbing ammonia 16, 108 aqueous 24 calcium based 120, 123 double alkali 16 gas < 53 high sulfur coal-limestone 128 lime-limestone 120, 122, 125, 130 Mitsubishi-JECCO lime 16 open-cycle 11 regenerator flue gas 15 Second-stage reactor 41 Shell Claus offgas treating ( S C O T ) process Ill gasification process 15 -and-tube heat exchanger 44 Shift catalysts 68,69 Shift reaction, water-gas 64, 95 Simulated solutions 134 Single-bed catalysts 65,69
R
Rate-controlling mechanisms . . . . 125 Rate studies 79,152 Reactant gas composition 152 Reaction orders 81 Reactor catalytic 44,94 Claus-type 26,41 first stage 40 flow 77 heat regenerator system 26 primary 42, 44 second-stage 41 Reagent 125, 127,128 Recovery as a function of design conversion, overall 106 furnaces, Kraft 17 process, ammonia 6 sulfur 100, 109, 111 dioxide (see Sulfur dioxide recovery ) Red bauxite 65 Red mud 66,69 Reducing agents 27 Reduction of gases, direct 33 process, Allied Chemical C o r p . . . 5, 29 -quench section 112 by reformed natural gas 38 sulfur dioxide ( see Sulfur dioxide reduction ) system, catalytic 25 Refineries, sulfur recovery in . . . 100, 109 Reformed gas 37, 38, 39, 44 Reforming process, Phelps Dodge 44
220
Single-stage reactor, fixed-bed . . . 27 Sinter plants 16 Slag 50 Smelter(s) copper 4,35,49 gases 5 lead 4,35 Onahama 7 zinc 4 Smelting furnace, electric 9 Smelting processes 8, 9, 31 Sodium base sulfite systems 18 carbonate 164 fraction of basic species caused by 138 hydroxide on catalysts for Claus reaction 83, 84 chromosorb A with and without 81 loading 82 sulfite-bisulfite system 158 Solids dissolution 147 Solvent stripper design 118 Sorption, sulfur dioxide 182 Sour water stripper 113 Spray dryer-scrubber 164 SRU (sulfur recovery units) . . .111, 114 Stack gas 130, 158 Stack sulfur dioxide concentration 103 Stauffffer Aquaclaus process 13 Steel mills 16 Stoichiometry 147 Stream ( s ) head gas 42 polluted gas 180 sulfur dioxide feed 28 Stretford process 95 Stripper design, solvent 118 Stripper, sour water 113 Sulfanemonosulfonates 205 Sulfate accumulation 56 Sulfite mills 17 Sulfite systems, sodium-base . . . . 18 Sulfreen process 12 Sulfur from Claus tail gas clean-up plants 102 coal, high 149 coal-limestone scrubbing, high . . 128 condenser 76,185 content, fuel cost vs 176 dioxide -absorbing species in solution 130 absorption and conversion to sulfur 192 adsorption 86, 89 analyzer 59 breakthrough 118 catalytic reduction of with carbon monoxide 60, 63 chromatographic separation of 78 concentrating systems 32
SULFUR
REMOVAL
A N D RECOVERY
Sulfur (continued) concentration 28,29,102 in a copper converter gas . . 51 inlet 27 minimum 52 reaction rate vs 152 stack 103 consumption 188 control systems 120 conversion 64, 186 feed streams 28 gas, concentrated 158 half-calcined dolomite with . . 149 hydrogen sulfide with absorbed 199 liberation of 184 liquid 162 natural gas with 25 oxidation of 206 in polluted gas streams 180 ratio, hydrogen sulfide-to- . . . 105 ratio, oxygen-to56 ratio, water-to186 recovery cost analysis of 162 cycle 18 process, Wellman-Lord . .30, 158 reduction catalysts 42,60 catalytic 60,63 by coal 185 dual-catalyst beds for . . . . 60 gas compositions 29 for metallurgical emissions, Allied Chemical 23 from polluted gas streams . . 180 to sulfur 35 technology roaster gas application 24 thermochemistry 36 reformed gas 37 removal vs. absorbent flow rate . . . 170 physical chemistry and process technology of . . 181 from polluted gas streams 180, 181 utility and industrial 164 scrubbing system, calciumbased 123 solubility of 195 sorption of active carbons . . . 182 to sulfur trioxide, conversion of 49 elemental 60, 162 lattice 62 load design 118 melting 205 oxides 1, 2, 3 pilot plant, elemental 35, 43 plants, Claus .3,11,160 production 43, 188 recovery 100, 109, 111 reduction of sulfur dioxide to . . 35, 192 removal process, Beavon . . . 93, 96, 98
INDEX
221 Trithionate Tubes, corrosion of . . . U U.S., S C O T units in 117 U.S., sulfur oxides emissions in . . 2, 3 Utility sulfur dioxide removal . . . . 164 Utility systems, capital cost estimate 176, 177 V Venturi-type interstage absorber . . 58 197 45
Sulfur (continued) system, hydrogen-carbonoxygen 36 trioxide 49,135 vapor 25, 41 Sulfuric acid gas cooling required for 53 manufacture of 5, 33 plants 4, 10, 48, 55, 162 process, double-contact 10 Sulfurous gases 68, 72 Surface selection, absorption 126 Surge tanks 162 System engineering 172
W Tail gas (es) 197 Claus plant 93, 101, 102, 107 Wackenroder's solution Waste gases, scrubbing of 11 treatment, approaches to 12 Water 135 Temperature balance maintenance 128 control 59 buildup 97 first furnace 70 chromatographic separation of . . 78 of Jamaican red mud catalyst . . 69 gas shift reaction 64, 95 second catalyst 71 poisoning effect of 65 specification 39 stripper, sour 113 sulfurous gas mixtures, effect of 68 -to-sulfur dioxide ratio 186 Tetrathionate 197 vapor 60, 64, 65, 66 Tetrathionic acid 201 Wellman-Lord sulfur dioxide Thermal regeneration 183 recovery process 30, 112, 158 Thermochemistry of sulfur dioxide Wet reduction 36 chemistry process 95 Thermodynamic equilibrium purification system 28 compositions 67 scrubbing, lime-limestone 122 Thiosulfate 195,200 Wetted film packing 121 Three-stage catalytic converters . . 76 Titration, benzoic acid 86 Tower, absorption 57 Tower, packed 124 Transfer coefficients, mass 128 Zinc smelters 4
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Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.

Sulfur Removal and Recovery

Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.fw001

Sulfur Removal and Recovery

Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.fw001

ADVANCES IN CHEMISTRY SERIES

Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.fw001

Library of Congress CIP Data

Advances in Chemistry Series

Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.fw001

not p u b l i s h e d elsewhere i n w h o l e or m a j o r p a r t a n d i n c l u d e reports of r e s e a r c h as w e l l as r e v i e w s since s y m p o s i a e m b r a c e b o t h types of p r e s e n t a t i o n .

Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.pr001

discussions present d e v e l o p m e n t s s u l f u r values as e l e m e n t a l s u l f u r .

i n n e w processes for r e c o v e r y of the

Process flowsheets for s e v e r a l a b s o r b in emission control are

Allied Chemical Corp. Morristown, N.J. October, 1974

Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001

T o u r i n g the past decade, the principal concern with control of sulfur L /

0.1 0.1 0.2 34.68

From Rf. 1. except as noted. Ref. 2.

SE M R A U Table II. Source

Publication Date: April 1, 1975 | doi: 10.1021/ba-1975-0139.ch001

H o w e v e r , i t seems c l e a r t h a t t h e greater p a r t of t h e refinery comes f r o m t h e c o m b u s t i o n heaters.

a c i d , a n d other s u c h sources are p r o b a b l y

T h e p u l p i n g processes ( p a r t i c u l a r l y sulfite) are most i n t e r e s t i n g because a p p l i e d to r e c o v e r y of s u l f u r d i o x i d e a n d s u l f u r f r o m the flue a n d process

A large p a r t of t h e p e r t i n e n t l i t e r a t u r e to 1970 o n c o n t r o l of s u l f u r oxides f r o m c o p p e r , l e a d , a n d z i n c smelters was r e v i e w e d b y the a u t h o r

i n t w o p r e v i o u s papers (9, 10).

T h e o u t p u t of r e l a t e d p u b l i c a t i o n s has and have first appeared devlop-

c o l l e c t i n g hoods a n d waste heat boilers to a l l the c o p p e r converters The Cominco process,

w h i c h uses a s o l u t i o n of a m m o n i a as the sulfur dioxide)

absorbent, has b e e n t r e a t i n g d i l u t e gases ( a b o u t 1 % (10, 22).

f r o m l e a d ore s i n t e r i n g m a c h i n e s o n a l a r g e scale for m o r e t h a n 30 y r T h e gases m u s t be c l e a n e d a n d c o n d i t i o n e d b e f o r e e n t e r i n g T h e r e a f t e r , the o r i g i n a l source of t h e gases is i m m a t e r i a l , the absorber.

I f i t is d e s i r e d to use a t h r o w a w a y process, t h e a m as a d o u b l e - a l k a l i system. This (26,

process for l e a c h i n g c o p p e r ores

to expect that a n y of t h e m s h o u l d be a p p r e c i a b l y , i f at a l l , less expensive

so the gas is p r e h e a t e d i n a T h e gas c l e a n i n g

T h e m a g n e s i u m sulfite is d e c o m p o s e d i n a r o t a r y k i l n i n t h e presence the r i c h k i l n gas stream ( 1 3 - 1 5 % sulfur dioxide)

T h e m a g n e s i a is r e t u r n e d to the a b s o r p t i o n process, a n d is sent to a s u l f u r i c

H e a t transfer a n d c o n t r o l are g o o d i n the e l e c t r i c H o w e v e r , electric

has b e e n p a r t i a l l y a l l e v i a t e d b y u s i n g i m p r o v e d hoods a n d w a s t e T h e flash smelter

H o b o k e n s i p h o n converters, the first u s e d i n the U n i t e d States s m e l t i n g a n d c o n v e r t i n g (51). f o r autogenous concentrate

T h e t o p - b l o w n r o t a r y converter, u s i n g o x y g e n , has b e e n a p p l i e d to n i c k e l It is a p p l i c a b l e to c o p p e r s m e l t i n g , b o t h s m e l t i n g a n d for m a t t e c o n v e r s i o n (49, flow 52). of off-gas that is r e a d i l y (49).

T h e means for r e d u c i n g the s u l f u r d i o x i d e emissions f r o m s u l f u r i c a c i d plants are a l r e a d y r e l a t i v e l y w e l l d e v e l o p e d .

Process Sources (62).

11 Applications now being made

o x i d e concentrations as l o w as 5 % gas c o l l e c t i o n systems. The conversion efficiencies of

b i s h i - J E C C O process has also b e e n a p p l i e d to a c i d p l a n t t a i l gases U n i t e d States.

b u t t h e g y p s u m b y - p r o d u c t w o u l d b e essentially a waste i n the

the r e d u c e d t e m p e r a t u r e , the c o n v e r s i o n e q u i l i b r i u m is i m p r o v e d , b u t the s u l f u r is r e t a i n e d o n t h e catalyst as a l i q u i d a n d m u s t b e r e m o v e d b y

Process Sources cycle.

13 I n the I F P process the C l a u s (typically a polyalkylene efficiencies

h o t inert gas i n a r e g e n e r a t i o n glycol)

r e a c t i o n takes p l a c e i n a h i g h - b o i l i n g solvent not affected.

c o n t a i n i n g a catalyst. C a r b o n y l sulfide a n d c a r b o n d i s u l f i d e are T h e p r o d u c t s u l f u r is d r a w n off as a l i q u i d . T h e so that n e i t h e r

of the S u l f r e e n a n d I F P processes are about 7 5 - 9 0 % , trations r e a c h e d w i t h some of the other processes.

consist of c o m b i n a t i o n s of p r e v i o u s l y u s e d a n d essentially c o n v e n t i o n a l S t r e t f o r d system r e p o r t e d l y of h y d r o g e n sulfide t h a n does a l k a n o l a m i n e scrubbing,

sorbent a n d d i r e c t l y p r o d u c i n g e l e m e n t a l s u l f u r . Processes of this t y p e w h i c h w a s d e v e l o p e d specifically (89). for C l a u s p l a n t t a i l gases, a n d the B u r e a u of M i n e s C i t r a t e process

a n d the costs for a t a i l g a s - t r e a t i n g system w i l l b e C o n s e q u e n t l y , r e d u c i n g the gas A major,

in removing and will now

l i m e s c r u b b i n g process o n a d e m o n s t r a t i o n i n s t a l l a full-scale system, h a n d l i n g 750,000 m N i p p o n K o k a n has d e v e l o p e d

gas/hr, on a new sintering double-

the M i t s u b i s h i process, l i m e w i l l p r e c i p i t a t e the s u l f u r oxides as w e l l as