A NOVEL SUPPORTED SORBENT FOR HOT GAS DESULFURIZATION

Aysel T. Atimtay
Lee D. Gasper-Galvin
James A. Poston
Morgantown Energy Technology Center
Morgantown, WV 26505
Keywords : D e s u l f u r i z a t i o n , supported Sorbents, Hot Gas Cleanup
INTRODUCTION

Integrated g a s i f i c a t i o n combined cycle (IGCC) system i s one of t h e most

promising power systems f o r producing e l e c t r i c a l energy from coal due t o the
noticeable improvement i n thermal e f f i c i e n c y t h a t it can provide. This advanced
power generating system involves t h e d i r e c t contact of hot coal-derived gases with
turbine blades.
I n order t o p r o t e c t the t u r b i n e s and r e l a t e d equipment from
corrosion and abrasion, it i s necessary t o clean t h e coal gas. Economical a s well
a s environmental requirements f o r advanced power generating systems mandate the
high-temperature removal of corrosive and abrasive compounds from coal gases such
a s sulfur and n i t r o g e n containing compounds, t r a c e metals, a l k a l i , residual
hydrocarbons, and p a r t i c u l a t e s .
Sulfur-containing compounds account, f o r most of
the acidic species formed during coal g a s i f i c a t i o n .
Hydrogen s u l f i d e , which is
t h e most abundant sulfur-containing compound i n coal gas, can react r e a d i l y with
the oxides of a l k a l i e a r t h and t r a n s i t i o n metals (1).
Westmoreland, e t a l . (2) reported t h e r e s u l t s of a thermodynamic screening of
the high temperature d e s u l f u r i z a t i o n p o t e n t i a l of 28 s i n g l e metal oxides by using
the f r e e energy minimization method. Also, k i n e t i c l i m i t s f o r ZnO, MnO, CaO, and
V,O, were reported by Westmoreland, e t a l . ( 3 ) f o r d e s u l f u r i z a t i o n reactions.
ZnO
showed a very favorable thermodynamic equilibrium with H,S ( 4 ) and iron oxide
showed easy r e g e n e r a b i l i t y with a i r . Results regarding s t r u c t u r a l changes i n the
pure ZnO sorbent a t high temperatures were reported by Ranade and Harrison ( 5 ) .
They showed t h a t s i n t e r i n g a c t u a l l y causes t h e p a r t i c l e t o shrink r a d i a l l y , thus
f o r the same number of p a r t i c l e s t h e surface a r e a a v a i l a b l e f o r reaction is
smaller. Also, z i n c metal produced by reduction of ZnO i n coal-gas v o l a t i l i z e s
above 1290F (699C).
Favorable p r o p e r t i e s of zinc oxide and i r o n oxide towards absorbing H,S were
combined a t t h e in-house research program of Department of Energy's Morgantown
Energy Technology Center.
The combined metal oxide sorbent, zinc f e r r i t e , was
shown to reduce H,S l e v e l s i n g a s i f i e r gases t o l e s s than 1 0 ppmv ( 6 ) . However,
zinc f e r r i t e has a temperature l i m i t a t i o n . The maximum operating temperature for
zinc f e r r i t e i s about 1200F (649" C ) . Focht, e t a l . ( 7 ) showed t h a t t h e sorbent
l o s t its pore volume during reduction, and subsequent loss of r e a c t i v i t y was
observed during s u l f i d a t i o n .
The sorbent a l s o showed a s u b s t a n t i a l amount of
d e c r e p i t a t i o n above 1200F (649C) .
Improvements i n t h e o r i g i n a l formulation have been attempted i n an e f f o r t to
An inorganic binder, bentonite, was
Overcome t h e l i m i t a t i o n s of zinc f e r r i t e .
added to zinc f e r r i t e . Thus, a sorbent with comparable r e a c t i v i t y and capacity to
t h e o r i g i n a l sorbent, but with a higher temperature limit than the o r i g i n a l zinc
f e r r i t e was obtained.
This sorbent can withstand temperatures up t o 1275'F
(691"C), which i s not very s a t i s f a c t o r y f o r high temperature f l u i d i z e d and
entrained bed g a s i f i e r s .
The need f o r developing a sorbent having b e t t e r p r o p e r t i e s ( d u r a b i l i t y and
r e a c t i v i t y ) than t h e o r i g i n a l or modified zinc f e r r i t e l e d researchers t o t r y
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other metal oxides. Various combination of metal oxides, such a s Zn, Cu, A l , T i ,
Fe, Co, Mo, and V were t r i e d a t Massachusetts I n s t i t u t e of Technology (MIT) and
and high
J e t Propulsion Laboratory ( J P L ) i n an e f f o r t t o develop a durable
capacity sorbent f o r removal of H,S from hot coal-derived gases ( 8 ) . Basically,
t h e sorbents t e s t e d were divided i n t o two groups: 1. Zinc-based sorbents, 2.
Copper-based sorbents.
Zinc-based sorbents included zinc f e r r i t e (ZF), zincCopper-based sorbents included
copper f e r r i t e ( Z C F ) , and zinc t i t a n a t e ( Z T ) .
Research r e s u l t s (8)
copper aluminate (CA) and copper-iron aluminate (CFA)
showed t h a t zinc-based sorbents were more promising than copper-based sorbents i n
t h e temperature range of 1000" 1350" F (538" 732C). One of t h e most promising
sorbents among t h e zinc-based sorbents was zinc t i t a n a t e (maximum operating
temperature of 1340'F (727C)). I t was found t h a t t h e TiO, phase helps t o s t a b i l i z e
t h e ZnO phase, and v o l a t i l i z a t i o n of Zn a t temperatures higher than 1290F (699C)
However,
has been reduced (about 1 w t % Zn i s l o s t i n 1000 hours of o p e r a t i o n ) .
TiO, does not absorb 4 s e f f e c t i v e l y . Therefore, t h e capacity of zinc t i t a n a t e is
lower than t h a t of zinc f e r r i t e due t o d i l u t i o n e f f e c t .

Extrudates of regenerable mixed metal oxide sorbents (copper-modif ied zinc

f e r r i t e , zinc t i t a n a t e , copper aluminate and copper-iron aluminate were t e s t e d i n
a high temperature-high pressure (HTHP) fixed bed r e a c t o r by Research Triangle
I n s t i t u t e (RTI) ( 9 ) . Reductions i n H,S concentration frem >10,000 ppmv t o < 1 t o
50 ppmv were achieved. The copper-modified zinc f e r r i t e sorbent reduced t h e H,S
concentration t o l e s s than 1 ppmv a t up t o 1100F (593C) with 20 % steam i n t h e
gas. The zinc f e r r i t e sorbent was a l s o t e s t e d i n t h e same r e a c t o r . Zinc t i t a n a t e
outperformed t h e other mixed metal oxide sorbents i n s t r u c t u r a l s t r e n g t h and
capacity a t steam l e v e l s a s low a s 5 % and temperatures a s high a s 1350F (732C).
However, entrained and f l u i d i z e d bed g a s i f i e r s which a r e p r e s e n t l y being developed
have o u t l e t temperatures a s high a s 1500F (816C) t o 1800F (982C). Furthermore,
f o r continuous d e s u l f u r i z a t i o n of a f u l l s c a l e g a s i f i c a t i o n stream, a f l u i d i z e d
bed sorbent system i n s t e a d of a fixed bed would improve t h e process e f f i c i e n c y
considerably by providing a means f o r continuous s o l i d s regeneration.
Zinc
f e r r i t e s i n t e r s a t temperatures higher than 1200F (649C). I t does not have
s u f f i c i e n t a t t r i t i o n r e s i s t a n c e t o withstand a f l u i d i z e d bed environment. Zinc
t i t a n a t e can withstand temperatures up t o 1350F (732"C), and has medium strength,
but t h e u t i l i z a t i o n i s low, i . e . 35 - 45 %. Therefore, novel sorbents a r e s t i l l
being sought
which w i l l show improved r e s i s t a n c e t o higher temperatures and
attrition.
Recently, copper manganate sorbents (bulk) a r e under study by
Electrochem Inc. ( 1 0 ) .
The objective of t h i s research i s t o develop a novel regenerable sorbent which
w i l l show improved r e s i s t a n c e t o higher temperatures and a t t r i t i o n . The p o t e n t i a l
advantages of supported sorbents, a s compared t o bulk sorbents, a r e higher surface
area, l e s s r e s i s t a n c e f o r d i f f u s i o n a l t r a n s p o r t , and higher temperature and
a t t r i t i o n resistance.
The sorbent i n v e s t i g a t e d i n t h i s study i s copper and
Results of s u l f i d a t i o n and
manganese oxides supported on SP-115 z e o l i t e .
regeneration experiments conducted using a simulated coal gas mixture a t
temperatures of 1000" - 1600F (538" - 871C) w i l l be reported.'
EXPERIMENTAL SECTION
Sorbent Preparation
The sorbents investigated i n t h i s study were prepared by a c o p r e c i p i t a t i o n
process. SP-115 z e o l i t e (1/8" extrudates, Union Carbide) was used a s t h e support.
SP-115 had t h e following c h a r a c t e r i s t i c s : SiO, > 99 % by weight, s u r f a c e area =
482 mz/g , crush s t r e n g t h = 6.6 kg/cm, pore diameter = 5.4 A". The c o p r e c i p i t a t i o n
process included : 1) Impregnation of t h e z e o l i t e with a s o l u t i o n of cupric
a c e t a t e and manganese a c e t a t e i n a r o t a r y vacuum evaporator, 2 ) Dehydration of t h e
sorbent i n a vacuum oven a t 158F (70C) and 0 . 1 inch Hg, 3) Calcination of t h e
sorbent i n a muffle furnace a t 1382F (750C) f o r 7 hours.
Three samples were
10.5

'

prepared with t h i s process (SPlCSM5, SP2C5M5, and SP2C9M1). The atomic absorption
spectrophotometer a n a l y s i s showed t h a t Cu and Mn loadings on t h e sorbent SPlC5M5
were 1.82 % and 1.64 % by weight, respectively. SP2C5M5 had 4.39 % by w t . Cu and
The corresponding values f o r SP2C9M1 were 5.15 % and 5.73 % by
6.11 % by w t . Mn.
weight, r e s p e c t i v e l y . The uncertainty i n t h e atomic absorption a n a l y s i s i s +1%.
Experimental
A schematic diagram of t h e experimental system i s shown i n Figure 1.
The
system consisted of a gas mixing system, a fixed bed reactor, a condenser and a
water knock-out p o t , a gas sampling system, and a t a i l - g a s cleanup System. Gases
were supplied from gas cylinders and t h e flow rates were monitored through mass
flow c o n t r o l l e r s . After t h e gases were mixed i n a manifold, they were fed i n t o
t h e fixed bed r e a c t o r . This gas mixture simulated the p a r t i a l l y quenched e x i t gas
of an air-blown KRW f l u i d i z e d bed c o a l g a s i f i e r which had t h e following molar
composition:
42.5 % N:, 11 % CO,, 1 2 . 5 % CO, 1 3 . 8 % H,, 1 % CH,, and 0.2 % H,S.
19 % &O i n t h e gas mixture was provided by adding a predetermined amount of water
i n t o the gas stream before it entered t h e reactor v i a a high pressure pump.

The reactor which consisted of a zirconia tube , with 0.875-inch inside

diameter and 12-inch length, was placed v e r t i c a l l y i n an e l e c t r i c furnace equipped
with graphite heating elements.
The furnace was water cooled.
The graphite
heating elements were l o c a t e d i n a helium atmosphere t o protect them from
oxidation. The temperatures of t h e gas a t t h e i n l e t and t h e center of t h e reactor
were measured by K-type thermocouples located along the c e n t r a l a x i s . T h e reactor
was designed t o withstand a pressure of 15 p s i g and a temperature of 3000F
(1649C). The sorbent sample was placed i n t h e center of t h e r e a c t o r and t h e bed
height was 2 inches. The gas l i n e s between t h e reactor o u t l e t and t h e condenser
i n l e t were heated v i a heating tapes and heavily i n s u l a t e d t o prevent the
The e x i t gas from t h e reactor
was
condensation of steam i n t h e gas l i n e s .
f i l t e r e d , cooled down i n t h e condenser, and sampled f o r gas analysis.
The t a i l
gas was s e n t through t h e absorbers t o remove t h e sulfurous gases before i t was
discharged t o t h e atmosphere.
The experiments consisted of a sequence of s u l f i d a t i o n and regeneration runs.
The reactor temperature was held constant during t h e s u l f i d a t i o n and regeneration
experiments. Reactor pressure was maintained a t 5 f 3 psig. Three temperatures
were t e s t e d : 1000, 1250, and 1600" F (538", 677", and 871C). The space v e l o c i t i e s
f o r the s u l f i d a t i o n and t h e regeneration runs were 2000 and 600 hr-', respectively.
Regeneration of t h e s u l f i d e d sorbent was conducted with a i r only and with a 50 8
a i r / 5 0 % steam mixture.
Breakthrough during s u l f i d a t i o n runs was defined a s 200
ppmv &S i n the e f f l u e n t gas. After t h e s u l f i d a t i o n run was stopped, t h e reactor
was purged with nitrogen f o r a t least 15 minutes. Regeneration was c a r r i e d out a t
t h e reaction temperature.
The regeneration cycle was stopped when t h e SOz
concentration of t h e e f f l u e n t gas was below 500 ppmv. The sorbents were subjected
t o f i v e sulfidation/regeneration cycles t o e s t a b l i s h s u l f u r sorption capacity and
regenerability.
Selected sorbent samples were analyzed f o r t o t a l weight, metal and sulfur
content, crush s t r e n g t h , s u r f a c e area,average pore diameter, pore volume, and pore
size d i s t r i b u t i o n both before and a f t e r reaction.
Gas grab samples obtained
A l s o Gas-tech
during experimentation were analyzed by gas chromatography.
precision gas d e t e c t i o n tubes were used t o determine t h e H,S and SO, concentrations
i n t h e i n l e t and o u t l e t gas streams.
RESULTS AND DISCUSSION

The effect of temperature on sorbent capacity i s shown i n Figure 2.

The H$
breakthrough curves i n d i c a t e t h a t t h e breakthrough times were 37, 45, and 45
minutes a t 1000F (538"C), 1250F (677'C), and 1600F (871"C), respectively.
The
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sorbent has g r e a t e r capacity a t 1250F (677C) and 1600F (871'C) than a t 1000F
(538C). However, t h e prebreakthrough H,S l e v e l s are lower a t 1000F (538C) and
1250F (677C) than a t 1600F (871C). Although t h e prebreakthrough H,S l e v e l i s
lower a t 1000F (538"C), t h e sorbent has more t o t a l capacity at t h e higher
temperatures.
Two runs were conducted a t 1250F (677C) with d i f f e r e n t samples from t h e same
batch of SPlC5M5 sorbent, t o e s t a b l i s h t h e extent of r e p r o d u c i b i l i t y of t h e
experimental method. Twelve d e t e c t o r tube readings of $S were taken, 5 min apart,
f o r each run.
The average difference between readings f o r t h e two runs was 30
ppmv. Thus, t h e experimental method appears t o be reasonably reproducible.
Two and one-half cycles
Sorbent regenerability was t e s t e d at 1250F (677'C).
were conducted with only a i r as t h e regenerant gas, and f i v e cycles were studied
Two c r i t e r i o n
using a 50 mole % steam/50 mole % a i r mixture f o r regeneration.
(1) a comparison of t h e
were used t o assess t h e r e g e n e r a b i l i t y of t h e sorbent:
H,S breakthrough curves, and ( 2 ) a comparison of t h e SO, o u t l e t curves during t h e
sulfidations.
When t h e sorbent was regenerated with a i r , t h e second and t h i r d s u l f i d a t i o n
breakthrough curves were somewhat s i m i l a r .
However, t h e prebreakthrough average
H,S o u t l e t concentration was approximately 50 ppmv less f o r t h e t h i r d s u l f i d a t i o n
than for t h e second s u l f i d a t i o n . Figure 3 shows t h e H,S breakthrough curves a f t e r
t h e sorbent was regenerated with steam/air. The curve f o r t h e f i r s t s u l f i d a t i o n
was not shown, a s t h e r e a c t o r bypass was a c c i d e n t a l l y l e f t open during t h e run.
The t h i r d through s i x t h s u l f i d a t i o n s , conducted with steam/air regeneration, gave
Thus, t h e steam/air regeneration appears t o give
s i m i l a r breakthrough curves.
b e t t e r regenerability than a i r regeneration.
Outlet SO, concentrations were compared f o r t h e second and t h i r d s u l f i d a t i o n s

(set I ) using a i r regeneration, with t h e second, t h i r d , and f o u r t h s u l f i d a t i o n s

( s e t 11) using steam/air regeneration.
After 15 min on-stream, set I showed
o u t l e t SO, concentrations between 500 and 600 ppmv. After t h e same period, set I1
yielded SO, concentrations ranging between 30 and 450 ppmv. These r e s u l t s indicate
t h a t more s u l f a t e was formed during a i r regeneration than during steam/air
regeneration.
This i s not unexpected, s i n c e t h e presence of steam reduces t h e
I n general, i f SO, i s
overall oxidative p r o p e r t i e s of t h e regenerant stream.
released i n l a r g e q u a n t i t i e s when reducing gases a r e introduced a f t e r oxidative
regeneration, t h i s indicates t h a t s u l f a t e s have been formed during t h e
regeneration.
The r e l e a s e of such sulfurous gases must be avoided during
I t has been suggested i n s t u d i e s on zinc f e r r i t e t h a t a clean
sulfidation.
reducing gas could be used for reductive regeneration of t h e sorbent a f t e r
oxidative regeneration, and p r i o r t o s u l f i d a t i o n .
However, t h e economics f o r
carrying out a reductive regeneration s t e p a r e poor, due t o t h e c a p i t a l cost of
additional vessels and t h e introduction of complications i n t o t h e o v e r a l l
operation of t h e system (11).
Although no carbonyl s u l f i d e was fed t o t h e r e a c t o r i n t h e simulated gas
mixture, appreciable concentrations were detected i n t h e o u t l e t gas during
s u l f i d a t i o n . The COS concentration was usually g r e a t e r than 50 ppmv, and often as
high a s 100-250 ppmv i n t h e o u t l e t gas.
It i s well known t h a t c e r t a i n zeolites
can catalyze t h e COS formation r e a c t i o n s . CO and CO, can react with H,S according
t o t h e following reactions (12):

+ CO,
$S t CO
H,S

COS t H,O

_ _ j COS t H,

temperatures between 440F (227C) and 1340F (727C). t h e thermodynamics of

reaction [21 a r e more favorable than those of reaction [ l ] . Figure 4 shows t h a t
Cos production became a minimum a f t e r about 30-40 min on-stream, and then

At

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increased. The i n i t i a l decrease i n COS may have been due t o reduced a v a i l a b i l i t y

of CO, because of t h e competing reactions i n which CO reduces copper oxides. The
l a t e r increase i n COS formation may have been caused by t h e k i n e t i c e f f e c t of
gradual heating of t h e sorbent bed with time on-stream.
The e f f e c t of increased
I t appears t h a t 1250'F
temperature on COS formation can be seen i n Figure 5.
(677'C) i s a more favorable temperature f o r COS formation than e i t h e r 1000F (538C)
o r 1500F (816C). The f i g u r e a l s o suggests t h a t COS production may increase with
t h e number of cycles; o t h e r d a t a which were c o l l e c t e d support t h i s conclusion.
The e f f e c t of a s i n g l e loading of t h e metal a c e t a t e s o l u t i o n versus a double
As expected, t h e double-coated
loading of t h e metals i s shown i n Figure 6.
sorbent, SP2C5M5, has a breakthrough time t h a t is nearly double t h a t of the
Thus, t h e capacity of t h e sorbent extrudates can be
single-coated SPlC5M5.
increased v i a m u l t i p l e loadings of t h e metal s a l t s .
Sorbents SP2C5M5 and SP2C9M1 were a l s o compared f o r t h e i r a b i l i t y t o remove H$
from t h e simulated c o a l gas mixture.
The second and t h i r d s u l f i d a t i o n s of each
The SP2C9M1 sorbent appears t o have greater
sorbent a r e shown i n Figure 7.
capacity than SP2C5M5 f o r H,S removal.
The s u r f a c e a r e a of t h e sorbent was determined before and a f t e r t h e reaction by
using t h e Langmuir adsorption method, with a maximum e r r o r of kl.5 %. The fresh
SP-115 z e o l i t e without metal coating had an average surface a r e a of 482 m'/g.
The
unreacted SPlC5M5 had an average surface area of 434 m'/g, with a metal loading of
1.82 w t % Cu and 1.64 w t % Mn. This suggests t h a t t h e presence of t h e metal has
caused some pore blockage.
After s i n g l e s u l f i d a t i o n s a t 1OOOT (538"C), 1250F
(677"C), and 1600'F
(871'C), t h e surface area decreased t o 379, 370, and 237 m'/g,
respectively.
The loss of surface a r e a under reaction conditions may be due t o
coalescence of pores of t h e z e o l i t e , o r t o a c e r t a i n e x t e n t , s i l i c i c acid
formation by r e a c t i o n of t h e z e o l i t e with high-temperature steam.
For a 5-cycle s e t of experiments on sorbent SP2C5M5, t h e u t i l i z a t i o n of sorbent
a t breakthrough f o r each of t h e f i r s t through f i f t h s u l f i d a t i o n s was,
These percent u t i l i z a t i o n s were
respectively, 20%. 7%, 7%, 13%, and 12%.
(1) t h e H,S breakthrough point was
calculated using t h e following assumptions:
200 ppmv H,S i n t h e o u t l e t gas, (2) t h e metal composition of t h e sorbent was 4.39
w t % Cu and 6.11 w t % Mn, a s determined by atomic absorption a n a l y s i s , (3) the
concentration of H,S i n t h e i n l e t gas was 2000 ppmv, and (4) t h e s u l f i d e d metals
The decrease i n
i n t h e sorbent were present only i n t h e form of C h S t MnS.
sorbent u t i l i z a t i o n a f t e r t h e f i r s t s u l f i d a t i o n was due t o incomplete
regeneration.
The increase between 7% and 12-13% may have been due t o random
v a r i a t i o n s . It i s p o s s i b l e t h a t t h e r e l a t i v e l y low u t i l i z a t i o n of t h e sorbent was
caused by i n e f f e c t i v e coating of t h e z e o l i t e pores, i . e . , t h e metals were
deposited i n s e v e r a l atomic l a y e r s on t h e o u t e r s u r f a c e of t h e extrudate, rather
than i n s i d e t h e pores. Or, even i f t h e pores were e f f e c t i v e l y coated, t h e r e may
have been s i g n i f i c a n t r e s i s t a n c e s t o d i f f u s i o n of H$ i n t o t h e pores.
Six d i f f e r e n t samples of t h e bed m a t e r i a l from t h e 5-cycle s e t performed with
SP2C5M5 a t 1250F (677C) and t h e 3-cycle s e t run with SP2C9M1 a t 1250F were
analyzed using atomic absorption. There was no conclusive evidence f o r loss of Cu
O r Mn g r e a t e r t h a n a few percent.
Thus, these metals do not appear t o undergo
appreciable v o l a t i l i z a t i o n under these conditions of s u l f i d a t i o n and regeneration.
The crush s t r e n g t h of t h e sorbent extrudates i s an important consideration for
p r a c t i c a l operation. Crush s t r e n g t h was determined by t a k i n g t h e average of the
f o r c e per u n i t l e n g t h of e x t r u d a t e required t o crush 15 extrudates; t h e range of
e r r o r f o r t h e s e t e s t s i s +20-35%, within t h e f i r s t standard deviation. The f r e s h
SP-115 z e o l i t e without metal coating had an average crush s t r e n g t h of 6.58 kg/an.
The crush s t r e n g t h f o r f r e s h SP2C5M5 and SP2C9M1 were 29.6 and 11.1 kg/an,
respectively. The metal coating makes t h e extrudates much stronger; p a r t i c u l a r l y
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the Mn appears to promote increased resistance to crushing. The average crush

strength of 6 samples from the SP2C5M5 bed, after 5 cycles, decreased by only 6%.
The average crush strength of 5 samples from the SP2C9M1 bed, after 3 cycles,
increased by 3%. Therefore, the crush strength of the zeolite was increased by
the metal loading, and essentially unchanged by reaction.
CONCLUSIONS
For the temperature range of 1000"-1600F (538"-871"C), the SP-115 zeolitesupported Cu/Mn oxides sorbent had more total capacity at 1250F (677C) and 1600F
(871C) than at 1000F (538C). Regeneration with a 50 mole % steam/50 mole % air
mixture was preferred over air regeneration, due to decreased sulfate formation in
the presence of steam. Further studies would be required to optimize regeneration
conditions, so that minimal. sulfate is formed during oxidative regeneration.
Appreciable amounts of COS were formed at 1250F (677"C), probably due to reactions
catalyzed by the zeolite; however, at 1500F (816C) the production of COS greatly
decreased. The sorbent containing Cu:Mn molar ratios of 9:l had greater capacity
for 4 s than those containing equimolar ratios of the metals. Sorbent utilization
with repeated sulfidation/regeneration cycles was low (513% for SP2C5M5). Surface
area of the sorbent decreased with metal loading and with reaction temperatures
between 1250F (677T) and 1600F (871C). It is uncertain whether the zeolite
pores had been effectively coated or plugged by the metal acetate solutions during
preparation.
There was little or no volatilization of the metals at 1250F
(677C). The SP-115 zeolite will require further testing to determine whether it
can withstand the highest temperatures (1250"-1600"F) (677"-871"C) for multiple
cycles.
REFERENCES
1. T. Kyotani, H. Kawashima, A . Tomita, A. Palmer, and E. Furimsky, " Removal of
H2S From Hot Gas in the Presence of Cu-Containing Sorbents," Fuel, 68, pp.74,
1989.
Westmoreland and D. P. Harrison, " Evaluation of Candidate Solids for
High-Temperature Desulfurization of Low-Btu Gases," Env.Sci.Tech., lo, pp. 659,
1976.

2. P. R.

" Comparative Kinetics of

High Temperature Reaction Between H2S and Selected Metal Oxides," Env.Sci.Tech.,
488, 1977.

3 . P. R. Westmoreland, J. B. Gibson, and D. P. Harrison,

11, pp.
4.

T. R. Rao and R . Kumar, " An Experimental Study of Oxidation of Zinc Sulfide

Pellets," Chem.Eng.Sci., 37, pp.987, 1982.

5.

P. V. Ranade and D. P. Harrison, " The Variable Property Grain Model Applied to
the Zinc Oxi'de-Hydrogen Sulfide Reaction," Chem.Eng.Sci., 3, pp. 1079, 1981.

6. T. Grindley and G. Steinfeld, " Development and Testing of Regenerable Hot CoalGas Desulfurization Sorbent," Report DOE/METC/16545-1125, 1981.
7. G. D. Focht, et al., " Structural Property Changes in Metal Oxide Hot Coal Gas
Desulfurization Sorbents," Report DOE/MC/21166-2163 ( DOE 86016041 ) , 1986.
8. M. Flytzani-Stephanopoulos, et al., "Detailed Studies of Novel Regenerable
Sorbents for High-Temperature Coal-Gas Desulfurization," Proceedings of the
Seventh Annual Gasification and Gas Stream Cleanup Systems Contractors Review
Meeting, DOE/METC-87/6079, Vol. 2, pp. 726, 1987.

9. S. K. Gangwal, et al., " Bench-Scale Testing of Novel High-Temperature

Desulfurization Sorbents," Proceedings of the Eighth Annual Gasification and Gas
109

Stream Cleanup Systems Contractors Review Meeting, DOE/METC-88/6092, Vol. 1, pp.

103, 1988.
1 0 . V . Jalan and M. Desai, " Copper-Based Sorbents For Hot Gas Cleanup,"
Proceedings of t h e Eighth Annual Gasification and Gas Stream Cleanup Systems
Contractors Review Meeting, DOE/METC-88/6092, Vol. 1, pp. 4 5 , 1988.
B i s s e t t , "Aspects of Fixed Bed G a s i f i c a t i o d F i x e d Bed Zinc F e r r i t e
Integration, " Ninth Annual Gasification and Gas Stream Cleanup Systems
Contractors Review Meeting, DOE/METC/PETC, June 27-29, 1989, Morgantown, WV.

11. L.

12. Chenistry of Rot Gas Cleafiup i n Coal Gasification and Combusr;ion, Morgantown
Energy Research Center, MERC/SP-78/2, 1978.

co +co*
H2

Distilled
Water
,Container

Fig. 1

Flow diagram of fixed bed reactor system

110

Tail

111