Professional Documents
Culture Documents
Optimization of the
In P a r t i a l Fulf illsnent
of the Requirement f o r the Degree Master of Science
BY
Yeong-Siarg Chang,
1
August 1984
A K O LD E E T C N WE GMNS
Wen-Jia Chen,
my
t h e s i s advisor, who suggested this topic and gave generously of h i s tirne and guidance during the course of t h i s study.
I am g r a t e f u l
t o Dr.
Robert
L.
Savage f o r h i s to this
constructive thesis.
criticisms
and useful
suggestions
support over the duration of this task. grateful for that. Finally,
I
I a more than m
wish t o express
deep gratitude t o my
parents f o r t h e i r encouragement and support which make t h i s studjr possible. This work is dedicated t o them.
TABLE O CONTENTS F
....................................... v LIST O FIGURES ......................................... v i F LIST O TABLES .......................................... i i F v 1.0 INTRODUCTION ........................................ 01
1.1 Coal Gasif'ication and the Flash Carbonization
Pee
2.0
3.0
4.0
......................................... 01 1.2 Econorni cs of the Flash Carbonization Process .... 05 1.3 Purpose of the Thesis ........................... 09 L I r n T J R E &'VIEW ................................... 10 2.1 Gasification Reaction ........................... 10 2.2 Equilibrium Computation ......................... 12 2.3 Overview of Optirmun Seeking Methods ............. 15 2.4 Overview of Experimental Designs ................ 18 OBJECTIVE FUNCTION .................................. 26 3.1 Assumptions ..................................... 26 3.2 Data and Parameters ............................. 28 3.3 Flnal Form of Objective Function ................ 29 OUTLINE OF OPTIMIZATION STKAmY .................... 32 4.1 A Sample Calculation of Response Value .......... 32 4.2 The Considerations of Optimization Strategy ..... 43
Process 4.3 F i r s t Order Design and Direction of Steepest
.......................................... 44 4.4 Second Order Design ............................. 46 5 0 REsULTS AND DISCUSSIONS ............................. 48 . 6.0 CONCLUSIONS ..........................................64 APPENDIX I ........................................ 65 REFFWSNCES .............................................. 66
Ascent
LIST OF FIGURES
..................................... 30
vii
LIST O TABLES F
........... 23 Table 2-2 Yatels Algorithm .............................. 25 Table 3-1-A Unit Cost of Feedstock and U t i l i t i e s ........ 31 Table 3-1-B Unit Varket Price of Products ............... 31 Table 4-1 Composition of Coal(Ohio Clarion 4A) .......... 37 Table 4-2 Calculation of Heat of Formation of Coal ...... 38
Constants(KP) of Selected Reactions Table 4-3 The Equilibrium Composition and Moles of Fach
..................................... 39 Table 4-4 Calculation of Heat of Reaction a t 1200K ...... 40 Table 4-5 Total Cost i n t h e Sample Calculation .......... 41 Table 4-6 Total Credit i n the Sample Calculation ........ 42 Table 5-1 Search on Stage-1 ............................. 53 Table 5-2 Search on Stage-2 ............................. 55 Table 5-3 Search on Stage-3 ............................. 57 Table 5-4 Search on Stage-4 ............................. 59 Table 5-5 Search on Stage-5 ............................. 6 1 Table 5-6 Search on Stage-6 ............................. 63
Component
Zxtensive
programs have
processes f o r the comnercial production of from coal, objective is o i l shale, t o replace tar sands,
o r biomass.(l)
exhausted or
Products can be varied t o include low-, gas, and raw materials f o r l i q u i d f u e l s , and petrochemlcal products.
high-Btu
such as gasoline,
It
methanol,
is a l s o
less
costly f o r chemical m u f a c t u r e ,
feedstock. sur,mrized by
c h a r a c t e r i s t i c s of
gasifiers
a r e the method of
supplying the heat, the gasifying medium and amount, and the reactor type. Once they a r e specified, the other dependent
characteristics such as the s t a t e of the s o l i d residue (dry o r slagging), the properties of the product
w i l l be
gas,
and t h e
gasification temperature
fixed.
There a r e three
and
dominates t h e
temperature d i s t r i b u t i o n , are a l l
supplying
d i r e c t method i s from t h e
t o s u p p l y oxygen
or air, of
is generated
combustion r e a c t i o n s an e x t e r n a l to supply
The i n d i r e c t steam or
method
applies
electricity,
gasification reactions.
The p o s s i b l e g a s i f y i n g steam.
reactions f o r
p r o d u c t i o n of
hydrogen r e s p e c t i v e l y .
It is .also
obvious t h a t t h e anount
a n d t h e k i n d o f h e a t i n g medium o r g a s i f y i n g medium i n f l u e n c e the three brief dependent c h a r a c t e r i s t i c s . of the In this of section, the a
description
characteristics
major
single-reactor,
g a s i f i e r s operate
with countercurrent
coal i s
It is
bottom s e c t i o n i s t h e i s burnt t o
renaining coal
supply heat
3
gasification zone. the dry-ash efficiency The s l a ~ i n g - a s hprocess is b e t t e r than process both in the tt- roughp put and i n thennal because of higher temperature operation. requirements, B y
reducing the
steam injection
the c a p i t a l
investment is reduced, and the process t h e m 1 efficiency i s increased. The pressurized gas FTier favors high methane to a significant overall process the gas w i l l be processed The disadvantages is that it
i n most cases,
requires a sized noncaking coal which increases the cost of coal. The reactor with a slowly downward moving bed is requires a However, large the
basically a low-throughput
device t h a t
number of g a s i f i e r s occupying a
large area.
Lurgi dry ash process is the only gasification process f o r which the technology has been commercialized. projects have applied this process Nqtural Gas. The Texaco and Shell-Koppers ( 5,6,7) processes 'The Sasol
t o produce Synthetic
closely
a high hydrogen t o
carbon monoxide r a t i o product gas and solves the problem of feeding coal i n t o a pressurized g a s i f i e r , t h e r m l inefficiency application %stman Co. of t h i s has i n operation. process but introducing a f o r the Tennessee acetic
The potential
is cons iderable
4
anhydride from co-al(8)
process,
the ,Ininimum
mount of s t e m f o r high thermal efficiency and produces a low hydrogen t o carbon monoxide r a t i o . entrained bed therefore, processes Both g a s i f i e r s a r e
both process u n i t s
energy i n the fonn of stean(Mangold, 1982, p.122), which can be u t i l i z e d i n a refinery o r chemical plant, used i n other applications.
A l l the g a s i f i c a t i o n processes discussed
but m y not be
to
convert
coal
totally
to
view,
it is extremely
from a k i n e t i c s
consideration.
it is impossible t o convert
the l a s t f i v e t o t e n
i s preferable t o use
i f both
a partial
Savage and Chen(9) a r e a c t i v e l y developing the Flash Carbonization process a t Ohio University f o r t h e concurrent production of synthesis gas and a low s u l f ur, char which
is s u i t a b l e f o r
low v o l a t i l e
along the Ohio River. Using an entrained bed reactor, oxygen and steam, along
with finely-&rounded coal(-40+100, -100+200, ?ksh No.), introduced from the top of the t o eighty percent systhesis reactor.
are
gas i s produced a t
Coal, oxygen, and steam a r e fed a t rates of 2.27Kg per hour, 5000c.c per ninute, and 2c. c. per minute respectively.
t ranging from 1 1 8 0 ~ o
in a s e r i e s
I n general, being an entrained bed system, has several advantages over the other
processes ( l o ) , m i n l y ; ( a ) the a b i l i t y coal, and (b) the product gas is f r e e of t a r s and Phenols. More importantly, the moderate temperature of (1100K-1500K) t o handle caking coal and low grade
a high temperature
( a ) t h e large
mounts of
energy(oxygen) required
to
The rigorous
economic analysis
of a
chemical process
c a p t i a l cost and t o t a l
the present
difficult
because the in
new
involves
uncertainties a n reliability
process rigorous a
operability,
es t i m t i o n is, theref ore, not necessary. quick calculation always meets the need Savage(9) has
Alternatively,
i n priliminary
design stages.
and operating cost of the Flash Carbonization process, based on the assumgtion of equilibrium yields. H also compared e
the production cost a t the experimental o p e r a t i w point with other coal gasification processes, and Koppers-Totzek process. The next step, followed by h i s work, i n economic such as, Texaco process
typical t o t a l
production
cost
analysis(l2)
contains plant
several items, direct production cost, fixed charges, overhead costs, administrative expenses,
and distribution
7
and marketing expenses. The first three items a r e sometimes The l a s t two items are so referred as manufacturing cost. called general expenses.
u t i l i t i e s cost(steam, e l e c t r i c i t y , f u e l , ref rigeration, water, etc. ) operating labor and supervision maintenance and repairs operating supplies laboratory charges catalysts and solvents For a given process o r a plant, raw materials and u t i l i t i e s
cost are the rmst i n f l u e n t i a l factors i n direct production cost. Therefore, the p r o f i t model can be simplified and
related t o the following factors: (a) the amount and the price of each product. (b) the m u n t and the cost of each raw material. ( c ) u t i l i t i e s cost. These three factors can be estimated i f the material and energy balance a r e known. In general, a kinetic model
should be used t o predict the material and energy balance at different operating conditions. the However, for high
temperature processes,
8
i s available. W w i l l use a thermodynamic equilibrium m d e l e calculations. is n a t u r s l l y Any p r o f i t model f o r a chemical and Chemical and
constrained by rules.
principles contraints
and economics
consist
of
mss
conservation and
therrmdynamics laws.
Gcononic constraints a r e t h e rules of The search f o r t h e rmxirnum prof it of how rnuch t h e constraints
give us
an explanation
influence t'ne prof it and operating point. The c h a r a c t e r i s t i c s of p a r t i a l g a s i f i c a t i o n i n Flash Since the is more
reaction heat-by
electricity
- is unknown.
and
char production
decreases energy required i n t h e reactor as well as heat waste i n the product stream;
it a l s o decreases
the
of themdynamic e q u i l i b r i a i n
This study
is t o
find a
auick estimation f o r t h e
since it
i s an
A
implementation
real world.
2 .o LITERATURE
m1w
changes of coal i n
drying,
a g a s i f i e r can be described by
pyrolysis, combustion, chemical
four categories:
and g a s i f i c a t i o n .
(dry)
----->
CH4
, C02
(2.2)
, Tar,
H S, Ha 0, e t c . ) 2
, CH4 , Tar)
-----> co2
50
1 1
G a s if'ication
Char +
5 0 ---- > co + 5
+H s + N
2
(2.5) 2 c ~ s h
Char + C02
-----> 2 C O + H 2 0 + %
N2
+H2S+ (2.6)
+ AS^
Char + 2H2
-----> CB4
Ash
+ H2 3 + H2
+ N2 +
(2.7)
data,
the
and summarized
i n Table 2-1. The overall reaction can be represented by the following equation:
aCoal + b02 + cH 2 0 ===== dCO + eH2 + f H 2 0 + gC02 + hCH4 + i H 2 S + jN2 + kChar + etc. (2.9)
Reactions involved
and constrained by stoichiometry, themdynamic equilibrium, k i n e t i c s , and transport Since t h i s is any gasif'ier concentrates r a t e s (~nass, energy, and m e n t u n ) . of the operating point i n t h e discussion equilibrium.
A
12
explanations and comparisons of the r e s u l t t o c o m e r c i a l and p i l o t plant data, Wei found a narrow f e a s i b l e operating by t h e m 1 balance t h e basis of and his
However,
studies is on t h e complete
2.2
Equilibrium Computation
A t the
present time,
there
i s no unifying model f o r
coal g a s i f i c a t i o n k i n e t i c s
because t h e e f f e c t s pyrolysis,
of
~nany
gasification
difference
in coals)
A s
themdynamic analysis is always a guide i n The information about chemical t o estimate The
a reaction allows us
calculation can be applied t o the design and analysis of the process. t e x t (14). l%ny examples were presented i n Shewood's
of yield f o r t h e f i r s t step i n assessing a Batchelder and Sternberg(l5) had a composition f o r Recently, suspension Wiser and
equilibrium
g a s i f i c a t i o n of
pulverized coal.
13
Kithany ( 16) investigated coal slurry- prepared a new c a t a l y t i c hydrogenation of
with
i n s hydrogen-donor solvent,
operating point of
g a s i f i e r is always operated under high Therefore, the overall performance determined approximately by Furtherimre, f o r an idealized
tanperature conditions.
stoichiometric constraints and mass conservation constraints f o r each principle reactions, the calculated equilibrium
.
are the
f o r the computation(l7)
a s e t of a r b i t r a r i l y
of the combustion of propane i n a i r by this method. equilibrium system contained ten gaseous constituents, o r without the formation of designed f o r a advantage of problem. So, solid carbon.
specific problem
special characteristics of
it
which s a t i s f y
the mass
spcifications, involved.
and a l l
t h e simultaneous
equilibria
A a l t e r n a t i v e method, n
system reaches its minimum value a t guilibriurn, t h e constraints of the material balance.
data, chanical p o t e n t i a l of each species, from spectroscopic constants p a r t i t i o n function of S tephanou and by
evaluating the
Baier ( 19)
equilibrium
d i s t r i b u t i o n of species
a l s o c i t e d some additional application, such as, calculation of the adiabatic flame temperature a t a and rocket motor performance calculations.
A NS AA
sgecified pressure
the 1950's f o r multipurpose application. Rased on the l a t t e r method, the program calculates the equilibrium canposition
is
described by
two
adiabatic constant pressure combustion properties, the (U,V) problem gives adiabatic constant volume or combustion (H,P), or
properties, (S,P),
the rocket
or (T,P),
where
S=E;ntropy,
15
Savage and Chen have applied it to calculate
equilibrium yields f o r the comparison with the experimental data. They found the experimental yields and the
canpositions of synthesis
of
of
an objective function.
engineering
optimization plays
an important r o l e f o r For
m a x i m profit
and t h e
possible technical aims might contain the maximum amounts of yield from a I n s p i t e of objectives, reactor o r a minimum s i z e of various kinds of a cooling tower. rnodels of
mathematical
the basic o p t i r m seeking methods a r e fixed. group of methods can be with high f o r an
objective
function
is s t i l l an a c t i v e f i e l d
Many
texts(21,22,23)
presented t h e
information of In
engineering problem.
broad categories:
16 These a r e applied t o two d i f f e r e n t types of objective m d e l s respectively. (Beveridge 1977, p. 26) The f i r s t type is a
mathematical model which is a s e t of a n a l y t i c a l expressions. The second type is the the so-called black-box model i n which input is detemined by
response t o a p a r t i c u l a r
optimum with a n a l y t i c methods, then, it might be solved ~ i t h nunerical methods.(Bveridge 1977, p.53)
W a r e not e
going t o are
review
a l l the
techniques
W e
optimum seekirg method i n t h e unconstrained multivariable problem. The review here w i l l be a basis f o r t h e s e l e c t i o n There are three
(a) u n i v a r i a t e search
The Univariate search sometLzes, is a kind of d i r e c t method;
it is a l s o called 'one
o r sectioning method1
(Beveridge 1977,
s t a r t i n g an i n i t i a l point and keeping k-1 of the k variables fixed a t some level, a mximm o r minirum value can be found along t h i s dimension. Therefore,
an e f f i c i e n t
singleThe
objective function is again optimized with another variable. The process continues : m t i l the successive change of
variables and object value is l e s s than a tolerance.(24) 'The disadvantage of univariant search is t h a t it is d i f f i c u l t t o be used i n a system containning a ridge or steep contours. The s t e p s i z e must not be kept too large because the process
my stop a t a n ~ n o p t i m l point.
The gradient vector is nor,ml t o the contour l i n e o r surface and indicates the direction of steepest ascent(or descent). The steps f o r t h i s method(Stocker, follows : ( a ) Select a t r i a l point. (b) Evaluate the gradient a t the current point and the 1980 p.180) a r e as
relationship of the changes of the x variable. ( c ) Decide s t e p s i z e and then move t h a t distance. (d) Determine the maximum o r minimurn point direction. ( e ) Check whether the o p t i m has been achieved. If along the
.
s t e p ( c ) and s t e p ( d ) , which
we have
an objective
is a
tetrahedron.
and passes
of gravity of
points. (Beveridge,
The purpose of
mona
bout the
designs have been introduced t o provide the l e a s t number of experimental trials. I n section (2.2)
only
significant.
In
t h i s study, method of
we are
i n many texts(25,26,27)
1Y
at two F a c t o r i a l Designs -- l e v e l s
A general f a c t o r i a l design is
t h e s e l e c t i o n of a fixed of
number
of
levels
for
each
number
of
varlables(factors) combinations.
In general,
more important by the following reasons: (Pox, 1978 p.306) ( a ) They require relatively few runs per' f a c t o r
composite d e s i g . ( c ) Through two l e v e l f r a c t i o n a l f a c t o r i a l design, number of runs can be decreased f u r t h e r . ( d ) The use of building blocks reduces the degree of the
complexity of the problem. ( e ) It is easy t o i n t e r p r e t the observations. I n general, t h e two l e v e l f a c t o r i a l design gives a There a r e a x 1954)
1967 p.271;
k x , 1978 p.510;
a t a time nethod.
are:
( a ) When i n t e r a c t i o n
effects
are
significant,
f a c t o r i a l design avoid leading wrong conclusions. For exanple, one f a c t o r a t a time w i l l be valueless when t h e response surf ace contains a ridge, but
20
f a c t o r i a l d e s i m my direction of
the axis of
improvement i s possible. (b) The discovery of f a c t o r dependence of a p a r t i c u l a r type provides the information i n connection with theoretical knowledge.
It is
the experimenter's
Fractional f a c t o r i a l design When a model contains more than three variables, f u l l factorial Fractional points designs a r e tedious the
and unmanageable.
1976 p. 454;
Orthogonal design
If we arrange
that
said t o be
orthogonal.
Composite d e s i ~
Response Surf ace Method The response surface method(24) has been selected with success design. Two survey a r t i c l e s , H i l l and Hunter(30), PFke(31), l i s t e d references t o those studies.
Belt
experinent
and Roder(32)
studied the
rapid
entrainment
carbonization of powdered coal under pressure i n a p a r t i a l hydrogen atmosphere f o r the production of low s u l f u r char. They established the relationship betrreen process variables m d char yield a s well a s q u a l i t y by response surface world the analysis.
It is
the application
of
c l e a r t h a t i n the r e a l
exact form of a
unknown.
function is not necessary because the m e d i a t e concerns f o r process design a r e questions such as(25)
( a ) What values of
22
this maximum,
interest? The response surface nethod has been applied t o answer these questions. One s t r i k i w application of the response surface method
i s 'Evolutionary 0peration1(EVOP).(33,34)
la process inf'ormation
should be
on how t o
experiments f o r t r u e t h e f u l l - s c a l e plant.
c a r r i e d out on
TABLE 2-1
H A OF REACTIONS ( k B : K A ) AND EQUILIBRIUJ'JI CONSTANTS( KP ) ET CL O SELFXTED @ACTIONS F
...........................................................
3eact ions
298K
700K
lOOOK
1500K
............................................................ ............................................................
Combustion
...........................................................
I-tR
-26.4
-26.4
-26.74
-27 75
Continued
24 Gasification
--->
H3+C02 KP -
0.07
0.15
0.20
0.28
.........................................................
H R
CO + 3H2 4 2 -49.26 -52.68 -53 87 -54 59
..............................................
14.83
--->CH +H 0 KP
1.15
-0.g6
-1-75
..........................................................
Source from Reference (1)
- - --
- --- -----
Temperature Unit
Oxygen
(wt%
St earn
(K)
T
>
(wt%)
H
T O H
(1)
(2)
(3) divisor
effect
- - + - +
8 4
ave
T
O
..........................................................
m i n effects: T , 0, H two factor interaction: TO, THY HO three factor interaction: T9H
3.1 As sumptions
A rigorous p r o f i t
i n chapter
One.
( a ) t h e a i i u n t and p r i c e of each product. (b) t h e amunt and c o s t of raw m t e r i a l s . ( c ) u t i l i t i e s cost. Once t h e amunt each product and cost of raw materials and t h e p r i c e of are specified, rigorous mss and energy
balances f o r each u n i t process and u n i t operation give us t h e mount of each product and t h e u t i l i t i e s cost.
w i l l also
Here, we
apply the simplified p r o f i t model f o r t h e Flash The necessary mass and e n e r w function of the Flash
objective
process have
c o s t of
recovery is
27 (d) N steam recovery system. o ( e ) E l e c t r i c i t y i s the only indirect heating source f o r coal gasification i n endothemic condition. gasifier ( f ) Operated i n isothermal condition at pressure. Figure 3-1.
(g) The products are under thermodynamic e q u i l i b r i m
1 atmospheric is show i n
condition.
'The
NASA
program
provided
the
equilibrium calculation.
NASA program,
Therefore,
it
char with
2.11.
aC v Hw 0 x N y S ,
calculation of heat of
calculation of
gas.
The necessary data and parameters are discussed i n t h i s section. Since cost and price a r e dependent on time, w e
and raw m t e r i a l s a r e
i n Table 3-1-B.
(1)N separation cost f o r char and product gas. o
29
After
t h e objective
function w i l l be
U l ,U2
= f (xl
X2
,X3)
+
y = z
E)
product gas c 1
,c
,c
'2jX3 : temperature x
1
HEAT
4
I I
\t/
............................................................
...........................................................
Feedstock Coal(0hio Clarion 4 A ) (Dry and Ash Free) Oxygen Stem Utility E l e c t r i c Power Source from Reference(9). $0.035 per IQih $15.00 per ton
Item
U n i t cost
...........................................................
..........................................................
Item Unit p r i c e ............................................................ Char Medim-BTU gas %Source from Reference(9). *Source from Reference(37). $14.00 per ton $5.30 per MM Btu
...........................................................
a r b i t r a r i l y s e l e c t 1 ton of dry and ash f r e e coal a s a basis t o c a l c u l a t e t h e necessary operating c r e d i t , and t h e profit-response value.
7-
cost,
the possible
Heat of formation of c o a l
--
( b ) Heating value of coal Frotn Dulongls formula(35), t h e heating value of coal can be expressed by:
Q (Btu/lb) = 14544
C + 62028
(H - 0/8)
+ 4050
where C, H, 0, element
.
formula and t h e elenent composition
Combining t h e
33
t a b l e (Table 4-1)
124.8 Kcal per g m l e dry and ash f r e e coal. ( c ) Heat of formation of coal a t 298K I n order t o calculate the heat coal, coal. of formation of
reactants a t 298K
The only unkno\m value i n t h e last equation is the Standard heat of formation of coal.
has been e s t i m t e d i n Page 32.
Heating value
Standard heats of
Table
(-126.88-(-124.8)
Kcal/gmle at 298K.
W arbitrarily e
rates
of
coal,
oxygen, steam s o t h a t the weight r a t i o of oxygen t o coal is 0.21127 and the weight r a t i o of stem to
coal i s 0.09726.
Molecular formula of coal, oxygen, and s t e m Pressure = 1 atm Temperature = 1200K The amount of coal = 1 The amount of oxygen = 0.21127 The amount of steam = 0.09726 (b) Output r e s u l t The output result for calculated equilibrium In
element balance of carbon t o g e t the t o t a l moles of carbon atorn i n fractions Therefore, of the system and the compounds t o t a l mole mixture.
carbon
i n the
/ 15.15 ( g / g m l e of coal)
The t o t a l mole f r a c t i o n s of
carbon
compounds
(Table 4-3).
=
0.653
.....................................
Once t h e t o t a l calculated,
moles of
is
be
t h e moles
estirrated and t h e r e s u l t i s indicated i n Table 4-3. Heat --of reaction -a t 1200K Heat of Heat of reaction = reaction at 298" a t 1200K
Each i t e m i n t h e r i g h t hand s i d e
of t h i s equation
Therefore,
It
i s an endot-hermic reaction i n t h i s
sample
calculation.
Note
f m
that
the
formula t o
calculate
sensible heat i s :
+A5
( ~ 52985 )/5
! 1 A;, I,
A3,
canponent a r e from data bank of the N S AA program. Cost, and - Credit, - P r o f i t Total c o s t i s indicated i n Table 4-5.
i s indicated i n Table
4-6.
The p r o f i t ,
value i s
equal t o t o t a l c r e d i t .minus t o t a l
which is $88.03 - $40.19 ( = $47.12) f o r one ton dry and ash f r e e coal i n t h i s sample calculation.
...........................................................
Component Weight % Molecular Weight Mole%
70.3
12
1
5 -86
503 0.45 0.086 0.15
H
0
5.3
7.2
16 14
N
S
12 . 4.8 11.O
32
Inert
.......................................................
Component Amount Standard Heat of F o m t i o n a t 298K
Reactants
Coal
...........................................................
Total
Products
Total
-125.88
39
Component
Mole Fraction
(By NASA program)
...........................................................
COS
3.583-04
37
...........................................................
40
TABLE 4 1 -1
...........................................................
Somponent Moles Standard Heat of Sensible Sensible Heat of Formation Heat Heat of Formation at 298K each a t 298K component Kcal/gmole Kcal
............................................................ ............................................................
input streams
gmol~? K c a l / @ ~ l eKcal
0 -137749 0 65972 -2.08 0 0 0 0 6602 5403 -57.598 -311201 0.539 2913.3 ............................................................ Total -448950 2913 3
coal
oqgen steam
............................................................
output strew
1200K
COS
37
-32.080
-1195
11.378
424
............................................................
Total
-656966
557313
TABLE 4-5
TOTAL COST I N THE SAMPLE CALCULATION
...........................................................
Itm
Amount
Unit cost
Conversion Fact o r
Cost
$
...........................................................
Feedstock Coal Oxygen Steam Utility 3lect Total 350 000 Kcal 0.035 $/kw-hr 0.0016222 kw-hr/Kcal
1 ton 0.21127ton 0.99726 t o n
2.2 klb/ton
19.67 40.91
......................................................... ..........................................................
TABLE 4-6
...........................................................
Itan Amount Unit Price Conversion Factor Credit
$
grm l e ..........................................................
Char Medium-Bt u 42496
14
$/ton
.000012 ton/gmole
7 .I4
Gas
Methane Carbon Monoxide
288
22976
variables
a r e assigned
i n the
x3)
where prof it y:
and experimental
provides a structure
f o r the
proposing
useful models
s t r a t e g i e s f o r gathering evidence useful and conjecture.' (b) It provides a basis whm we want f o r Evolutionary
f o r synthesis
Operation l a t e r ,
44
comnercial plant. ( c ) The s t a r t i n g point of the search is close t o one of the experimental points. optimum point. W assume it e
i s not f a r from the
steepest
i f the step
the direction w i l l
be meaningless. i n factorial
a variable s t e p
s i z e f o r open-ended
there was
probably
some distance
From calculus
point of view,
where
xO x
: a local point
: a neighborhood point around point xo : response of xo
yo y
Vy
*%
b2 b
+b3
)
*5
gradient a t y Table
determines the local slope of the surface. The least squares e s t i m t i o n of Because of
bo
is
occurs
i n the
Yatests algorithm
significant, then the f i t t i n g second degree equation w i l l be considered. I f some of main effects and interaction effects we m y discard the interaction t e r n and
a r e signiricant,
follow t h e direction of main effects. The next step i s t o search along the direction of steepest ascent. unbracketed search, For one dimensiorlal open ended o r
46
p.154 and Beightler 1979, p.190) has been used. reyuires t h a t This method
Sometimes, a l a s t two
the f i r s t three or the last three. has a bigger center objective value.
It depends on which s e t
Sooner o r
l a t e r it
It seem
w e a r e a f r a i d of
the small s t e p s i z e .
Therefore,
47
-points which allowed the quadratic e f f e c t s t o be detemined also.
A c e n t r a l composite design w a s formed i n t h i s study.
F i t t i n g a second order equation was possible. condition f o r finding the maximum on t h i s vanishing of the f i r s t derivative. f o r it
The necessary
equation w a s the
The s u f f i c i e n t condition
The -optimum operating point The r e s u l t s of t o 5-6. searching a r e displayed from Table 5-1 s i x stages. The f i r s t f i v e
steepest ascent based on a s t a r t i n g point (T=1180, 0=0.20127, H=0.09526) with objective value 46.56. an a r b i t r a r y 0.00007). increment Along t h i s direction (-16, 0.0134,
is taken t o be
where the
objective value
another two-level f a c t o r i a l design was new direction and the whole to 5-5. procedure
t o find a
repeated
i n Table 5-2
composite design. S t a r t i n g from an i n i t i a l point, e l e c t r i c charge was the f i r s t stage showed the feed
It
decreasing temperature and increasing the amount of oxygen. Besides, t o supply heat from e l e c t r i c i t y was not so
It costs $1.80 by e l e c t r i c i t y .
following one-dimensional
in
The point
seemed very close t o the maxium point along t h i s the difference between it
and
direction because
its
The second stage showed how oxygen and steatn affected the production of carbon monoxide and hydrogen after the t h e r m l l y neutral. Large amounts of
oxygen increased the production of CO from $36.78 t o $78.04, a l t h o u e the cost of oxygen increased from $8.51 t o $26.81. The one-dimensional search was ended where the excess oxygen reacted with CO and
3,
I n table 2-1,
.
temperature range
and H2
a t the
(1066-1166K).
because the
response
This
could be explained because the equilibrium constants of the main gas i f ication react ions were nearly constant a t the temperature range. (Table 2-1 )
The fourth stage showed how steam positively affected
the production
of H2
production of CO.
It was obvious t h a t
50
was a p p r o a c h i n g , p a r t l y b e c a u s e t h e i n t e r a c t i o n e f f e c t s were
important now a n d partly because no b i g difference
was
observed i n response values. The f i f t h s t a g e c o n f i r m e d a s t a t i o n a r y p o i n t was a r o u n d t h e p o i n t (T=1193, 0 = 0 . 7 2 1 0 7 , H=0.30049) main effects(0.12, 0.07, 0.95) -0.76, b e c a u s e two of t h e less than the
were
interaction effects(0.17,
-0.54,
0.33).
was t o o
small
s t a t i o n a r y p o i n t was m e a n i n g l e s s .
secondary e q u a t i o n
was f i t t e d
T* = 1 1 9 1
0* = 0.72841
H*
= 0.31384
The -q u a l i t y of
char
The optimum point thus obtained did not consider t h e quality of char. Suppose the minirrnun requirement of carbon content our search f o r optimization W assumed the weight e
The amount of ash
would be 0.12 ton if 1 ton of ash f r e e coal was reacted. order t o meet the requirement, unreacted i n char should be 0.12 corresponded t o a
O=O. 5199, H=O .13775).
In
point
i n the
second stage
calculation of
p r o f i t on those experimental
most i n f l u e n t i a l parameters i n t h e p r o f i t mode1,is the u n i t price of products and the u n i t cost of feedstock. W would e
l i k e t o c a l c u l a t e the objective values based on d i f f e r e n t u n i t prices and u n i t costs. case A and case B. Ve expressed them a s two cases,
following way:
the o p t i r m point
43.26
24.27
39.62
20.57
119.62 71.36
31.88
Note that the objective values were based on 1 ton dry and ash free coal.
All
were a t
1 atmosphere
pressure i n
isotherm1 condition.
Temperature
Unit
Oxygen
Steam
(K) T
(wt%)
0
(wt%>
1180
20
1200 1160
COST O F T C ) H y
$
CFEDIT OF
(CO
effect
ELECT
$
+
$
XYD)
$
CHAR
$
.............................................................
- - + - - + + + - - + + - + - + +
+ + +
46.56
18.61
-0.003 21.39
0.
17.33
0.003 19.67
....................................................
Continued
............................................................
direction: (-0.82 s t e p s i z e : -16 1.34 0.013426 0.04) 0.00007
----
COST O F
CREDIT O F
( CO
y
$
XECT
$
+ HYD)
$
C;&W
$
............................................................ .............................................................
0 1180 0.20127 1 1 1 6 4 0.21470 3 1131 0.24155 7 1066 0.29525 15 936 0.40265 0.09526 0.09533 0.09547 0.09575 0.09631 46.56 49.01 53.92 63.37 41.50 19.17 17.05 12.40 0.80
0.
19.03 32.81
(15-7) / (7-3)
z*
7
T: 1066,
The b e s t point:
0:0.29525,
H:O .09575
TABLE 5-2
SEARCH ON STAGE-2 P a c t o r i a l Design
Temperature Unit
Oxygen
Steam
(0
'T
(wtX>
0
(wt%)
1066
10
+
-
1076 1056
...........................................................
COST OF
cmn OF
(CO
y
$
effect
ELECT
SYD)
CHAR $
S $ $ .............................................................
- - - - + + + - - + + - + - + +
+
+ + +
52.06 62.69 51.62 52.66 54.25 52.48 0.22 1.89 0.76 0.59
64.49 -0.26
.............................................................
Continued
..........................................................
direction: (0. step size: 0 0.95 0.03195 0.30) 0.006
Z: t h e number of s t e p s f r ~ m r i g i n a l point o
............................................................
COST OF
y
cmrr
$
$
OF
CUR
OXY
$
(CO + rn)
.............................................................
0
1
1066 0.29525 1066 0.32720 1066 0.39110 1066 0.51990 1066 0.77550 1066 1.28670 1066 1.03110
3 7 15 31 23
26.81 78.04
0.
F i t t i n g points : Z=7, y=76.81; Z=15, y=91.30; Z=23, y=85.26 2nd-order model: y=47.29 + 5.342 The best point: T:1066
0.16Z
, Z*=16.60
H: 0.19563
0:0.8271
TABLE
5-3
........................................................
Tmperature Unit Oxygen S t earn
(K)
T
(wt%>
0
(wt%)
H
1066
20
lo86 1046
CS O OT F T O H
CREDIT O F
(CO
$
y
$
effect
ELECT
$
+ HYD)
$
C M
$
Continued
0.33
0.75) 0.0045
100 0.00325
Z: t h e number of s t e p s f r ~ m h e o r i ; ~ i n a l t points
SOST OF y
$
ELECT
CHaR
$
............................................................
The best point: T: 1166
0: 0.83035
H:0.20013
at Z = 1
Tmm
Factorial Design
5-4
SFACkl ON STAGE-4
..........................................................
Temperature Unit Oxygen Steam
(K)
T
(&%I
0
(wt%)
H
1166 10 1176
'T O H
Y
$
effect
(CO
HYD)
$
............................................................. ______-______-__-_----------------------------------------
- - + - - + + + -
- - +
+ - +
- + + + + +
Continued
-0.556 -0.01113
0.506) 0.01013
COST O F
CREDIT 9F
(CO + HYD)
$ $
Y
$
OXY
$
F i t t i n g points: Z=3, y=112.26; Z=7 y=117.08; Z = l l , y=116.98 2nd-order rmdel: y= 105.42 + 2.72
0.152
Z*=8.9
H: 0.29049
The b e s t point:
T: 1203
0: 0.73107
TABLE 5-5
SEARCH ON STAGE-5
F a c t o r i a l Design
...........................................................
Temperature Unit Oxygen
(wt%
0
Steam
(K) 'T
(wt%)
H
0.29049
0.01
0.30049 0.28049
..........................................................
COST OF T O H
y
$
C;IEDIT OF
(CO
$
effect
ELECT
$
kIYD)
............................................................ ------------_----__-_---------------------------.--__-_-_--__
- - + - -
0.
0.
+ +
0. 0. 0.21 1.95 0. 0.
- + -
+ +
+ + +
...........................................................
Continued
...........................................................
direction: (0. s t e p size:
0 0 . 0 0.52) 0.O1
SOST
OF
CREDIT OF
y
$
........................................................... ............................................................
0
1203 0.73107
0.29049
0. 0 . 0.
............................................................
The best point is a t : T: 1193 0: 0.072107
H 0.30049 :
.........................................................
Unit Center Condition Step Size Temperature (K)
T
Oxygen (wt%)
0
S te m
(wt%)
H
T O H
SOST O F CEiEDIT OF e f f e c t ELECT OXY (CO + FED) $ rt; $ $ $ ............................................................ - - - 112.40 115.53 0. 17.97 85-42 59.77 + - - 113.56 0.17 1.57 17.97 87.84 60.79 - + - 115.22 2.22 0. 19-53 90.45 59.77 + + - 117.35 0.97 0. 19.53 92.47 60.74 - - + 117.23 1.79 3.41 17.97 89.93 64.37 + - + 114.48 -1.98 17.97 92.47 6 . 4 6 9.04 - + + 116.92 -1.09 0. 19.53 89.89 63.36 + + + 117.06 0.48 19.53 90.41 63.51 0.
y
0.18 0.01 0.
0.
2.95 0.
0.
0 -a
3.36 1.69
0.
0.21
CONCLUSIONS
1. Based
on
thermodynamic
and
specified
economical
constraints, i.e.
a l o c a l optiinum
o p e r a t i n g p o i n t was f o u n d .
0.31384
w i t h t h o s e of we f o u n d t h e profit The than
of t h e optimum p o i n t
thermodynamically.
change of and t h e
on t h e q u a l i t y
of s o l i d p r o d u c t
would a l t e r t h e
optimum o p e r a t i n g
3. A
further
study
on
the
optimization
of
the
flash
i n t o account.
APPENDIX I
Coal, 2.27kg/h,
and
steam were
fed a t
rates
of
and 2 c.c.
water/m reapectiveljr.
Consider t h e feed coal contained 2.9 percent moisture and 11.5 percent ash. and ash Then, the feed r a t e of t h e moisture 0.971
f r e e coal w a s 2.27
0.885
which was
where P : pressure
, 1 atm
T : temperature, 298K
R : gas constant, 0.08205
V : v o l m e , 5 l i t e r s ( = 5000 c.c. )
t h e feed r a t e of steam was 2 c.c. water/m which was equal t o 0.12 kg/h. So, t h e r a t i o of oxygen t o coal = 0.39262/1.95069
=
0.20127 0.12/1.95069
t h e r a t i o of steam t o coal
= 3.0615
(1) Baughman,
G.
L.,
'Synthetic 1978.
R.
and Hicks,
E.
'Synthetic Fuels l ,
p. 145, 1982.
(3) Mongold,
'Coal
Liquefaction
and
Gasification
(5) Spinks,
A.,
J.
M.
Thorns a n d J .
Gibson
Chemistry1,
Philosophical Transactions of
Enera
Technology Review; 70' Noyes Data Co. (7 ) Energy Research and Development
'Handbook of Gasifiers and Gas Treatment System1, Dravo Co. p.20, 1976.
W.
and R.
(8) Coover, H.
C.
Hart,
'A
Chemical from Coalf, Chem. Eng. Frog., v.78, no. 4, p.72, 1982. (9) Savage, R. L. and W. J. Chen 'Process f o r the Concurrent Production of Volatile, Hydrogen, Carbon Monoxide and Low-
Y.
and T.
Z.
Chem.
Process Des.
D.
, McGraw-Hill,
Analysis of
p .147,
'A Stoichiometric
Coal
3asFfication1, Ind. Eng. Chem. Process Des. Dev., v.18, No* 3, ~055491979.
( 1 4 ) Sherwood, T. K. 'A Course i n Process DesignT, *TheM-I-T
Press, 1963.
(15) Batchelder H. K.
and J.
C.
Sternberg, lIhemdynamic
Study of Coal Gasification1, Industrial and Engineering Chemistry, v.42, no.5, p.878, 1950. (16) Wiser,
W.
H.
and S.
S.
Kithany,
'Equilibrium
T h e m d y n d c Correlations i n Coal Hydrogenation t o Gas Pipeline Gas l , Fuel V.57, p.485, 1978. (17) Zeleznik, F. J.
and S.
Chemical Equilibrium', Ind. No.6, p.27, Jun. 1968. (18) Kmdiner H. Complex
J.
and S.
R.
Rrinkley,
lcalculation of
Ind.
Q u i l i b r i m Relations l ,
and
%go
1950. S. E. and R.
W.
Stephanou,
Baier, Chemical
Free
, p. 19,
J.
and B. of
Complex
Composition, Rocket Perfornance, Incident and Reflected Shocks, and Chapman-Jouguet Detonations
N S Lewis AA
1977. Wilde,
tFoundations of Optimization' , Prentice 'Hall, 1979. (23) Wilde, 'Optimun Seek(24) Stoecker, W. F., Methods' Prentice Hall 1964. McGmw-
E.
P.,
Hunter,
I.,
Experiment
, Hafner
., p .27 1, 1967.
Analysis by S t a t i s t i c a l 1967.
(28) Box, G. E. P.
Response
Surfaces:
J.
and W.
G.
Methodology :
Literature
Survey l
Techno~netricsV.8, No.4, p.571, Nov. 1966. (31) Mead, R. and D. J. Pike, ' A Review of Response Surface Biometries,
Methodology from a B i m e t r i c Viewpoint1, V.11, No.31, p.803, Dec. 1975. (32) Belt, R.
J.
and M.
4.
Energy NeedsT, Advances i n Chemistry Series 127 Editor: R. M. Jimeson and R. S. Spindt, p.121, 1973. (33)Box,
G.
E.
P.
and N.
R.
Draper,
lEvolutionary
Operation1, John Wiley & Sons, Inc., 1969. (34) Box, G. E. P., 'Evolutionary m e r a t i o n :
A .mthod f o r
Increasing
Industrial 1954.
Productivity1,
Applied
L.,
'Fundamentals
of Flergy Production1,
John Wiley cSr Sons, p. 29, 1982. (36) Hunter, J. S. and T. for Computer H. Naylor, lExperhenta1 Designs Management
Simulation Experiments l ,
L.
andJ.
Gibson,
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Utilisation,