1

Optimization of the

Flash Carbonization Process

A Thesis Presented t o the Faculty

of the Engineering College of Ohio University

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

I would especially l i k e t o thank Dr.

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

N thanks a r e a l s o due D r . J. R. C o l l i e r and Dr. N. y

Dinos f o r t h e i r help during my stay i n Ohio University.

M wife, Huoy-Jen, has offered me her understanding and y

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

Figure 3-1 The Block Diagram of a Single-stage Gasifier

..................................... 30

vii

LIST O TABLES F

Table 2-1 Heat of Reactions(HR : Kcal) and Equilibrium

........... 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

1.1 Coal Gasification

Zxtensive

programs have

been undertaken t o develop synthetic fuels The

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

costly supplies of Coal gasification is fuels.

natural gas and petroleum-based fuels. a flexible

method f o r t h e production of synthetic

medium-,

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 ,

and more operable on lower

quality coals than coal liquefaction. Many g a s i f i c a t i o n processes have differences

i n mdes of

been developed with

operation and characteris t i c s of

the products produced. a

Each g a s i f i e r has been described f o r type of coal avaiable

as

s p e c i f i c application and the The three m i n

feedstock. sur,mrized by

c h a r a c t e r i s t i c s of

gasifiers

Probstein and Hicks(2),

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

t y p e s of r e a c t o r s : the entrained flow

t h e moving b e d , rzactor. The

t h e f l u i d i z e d bed, reactor type

and

heavily those are and

dominates t h e

temperature d i s t r i b u t i o n , are a l l

therefore, There direct

dependent c h a r a c t e r i s t i c s also two nethods The of

influenced. the heat:

supplying

indirect. where h e a t coal. source,

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

heating heat for

electricity,

gasification reactions.

The p o s s i b l e g a s i f y i n g steam.

media f o r Oxygen and the

g a s i f i c a t i o n a r e oxygen, a i r , h y d r o g e n , air are the s o u r c e s of oxygen i n the Hydrogen

reactions f o r

p r o d u c t i o n of c a r b o n monoxide. the source of h y d r o g e n f o r the

g a s and s t e a m a r e methane and

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,

direct-heat g a s i f i e r s is given. Lurgi processes(3,4) are

The d r y - a s h and s l a g g i n g - a s h moving bed p r o c e s s e s and p r i m a r i l y production of Synthetic Natural

t o be c o n s i d e r e d f o r t h e Gas(SNG). flow. Moving The bed

g a s i f i e r s operate

with countercurrent

coal i s
It is

i n t r o d u c e d downward t h r o u g h t h e upward f l o w i n g g a s e s . dried f i r s t , lower s e c t i o n . where t h e then devolatilized, The and

then gasified a t the c o m b u s t i o n zone for the

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

cantent yield and leads economy because,

i n most cases,

further at elevated pressure.

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

mnufacture e i t h e r low- o r medium-Btu synthesis gas i n a manner t h a t

is

closely

similiar t o the production of The 'Texaco

synthesis gas from petroleum f u e l residues. water s l u r r y injection system produces

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

applied it t o the production of

4
anhydride from co-al(8)

The Shell-Kogpers uses

process,

developed from Kopper-Totzek 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

i n high temperature operation,

require a high-temperature a costly technical problem. half of the available

both process u n i t s

heat exchanger which represents

A waste

heat b o i l e r m y give about

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

so f a r aim t o Though it gas frorn a difficult or

In

gasify completely t h e coal fed i n t o t h e gasif'ier.

i s possible

to

convert

coal

totally

to

thermodynamic point of expensive t o do practice,

it

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

percent of coal t o gas even under the rnost.favorable k i n e t i c condition. Therefore,

it

i s preferable t o use
i f both

a partial

coal g a s i f i c a t i o n process, products can be u t i l i z e d .

the gas and the s o l i d

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

i n d u s t r i a l and povJer plant use

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

A char with forty

of the original carbon,

together with a reactor.

gas i s produced a t

the botton of the

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.

Atmospheric pressure and temperatures 1450K were chosen of experiments.

t ranging from 1 1 8 0 ~ o
in a s e r i e s

f o r the operating conditions

Also, the residence times were varied. the process gasification

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

employed avoids - aisadvantages the

( >1500K) process such as ( l o ) :

a high temperature

( a ) t h e large

mounts of

energy(oxygen) required

to

maintain a high temperature condition, (b) t h e high cost i n r e f r a c t o r i e s and construction

material necessary i n the combustion zone,

( c ) the large m u n t

of energy l o s s i n product gas o r

high cost i n heat recovery system.

1.2 Econmics of the Flash Carbonization Process

The rigorous

economic analysis

of a

chemical process

includes detailed narket research, production cost estimation,

At

c a p t i a l cost and t o t a l

and other economic f a c t o r s . ( l l )

the present

stage economic evaluation f o r the Flash process

is rnany

Carbonization technology performance,

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.

shown the predesign capital

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

analysis is t o f i n d the best itself. In general,

operating point i n the process

the best or o p t i m operating point Net p r o f i t , by Total

implies that it w i l l yield a maxlmum p r o f i t . definition,

equals t o t a l income minus a l l expenses.

u income is the s m of each product amount multiplied by i t s

s e l l i n g price.
A A l l expenses are the t o t a l production costs.

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.

The first item is the dominating

A typical

factor i n evaluating the o p t i r m operating point.

list of d i r e c t production cost contains(Peters, 1968 p.192) r a w materials

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,

thermodynamic equilibrium model

4 t the

produces as good a prediction as the kinetic model. present stage,

no k i n e t i c model f o r the Flash Carbonization

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

f o r the profit chemical process physical physical

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

existing mrket syste~m.

will

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

Carbonization has raised a s e r i e s

of questions. which way

process is not energy s e l f - s u f f i c i e n t , economical i n supplying

reaction heat-by

electricity

( i n d i r e c t method) o r by oxygen ( d i r e c t method) The low temperature operation favors

- 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

production of syngas because t h e system.

of themdynamic e q u i l i b r i a i n

From t h e economical point of view, what i s t h e i n t h e Flash Carbonization f o r

optimal operating point

naxFinum prof it is not c l e a r .

1.3 Purpose of the Thesis

This study

is t o

find a

auick estimation f o r t h e

optimum operating point of Constrained considemtions, by both

the Flash Carbonization process. thermodynamic and economic

an objective function has been defined f o r

4n experimental design

the p r o f i t of each operating poigt.

i s used

a s an optinim seeking method of optimization i n the

since it

i s an
A

implementation

real world.

discussion on t h e search path of chedcal stoichiometry,

is given with the cornbination

equilibrium constant, The r e s u l t ,

and a t the the

reaction heats involved i n the system. o p t i r m operating point,

is cmpared with those of

experimental points using t h e same p r o f i t model.

2 .o LITERATURE

m1w

2.1 G a s i f i c a t i o n React ion

The principal chemical and physical

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 .

Each physical o r represented by the

transformation can be silnply

following equations : (bhngold, 1982, p . 132)

Drying Coal (high moisture)

---- > Coal

(dry)

Pyrolysis Coal (dry)

----->
CH4

Char + Volatiles (CO, H2

, C02
(2.2)

, Tar,

H S, Ha 0, e t c . ) 2

Combustion Combustible v o l a t i l e s (CO, H2

, 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)

In order t o discuss and apply the present main reactions i n a g a s i f i e r a r e simplified

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

i n a reactor a r e generally defined

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

a general analysis with on

syngas production, stoichiometry and

stoichiornetric analysis by Wei(l3).

of coal gasification has been made and g e m e t r i c

Through detailed vectorial

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

regian which is only limited stoichiometric constraints

However,

studies is on t h e complete

g a s i f i c a t i o n and thermal balance

which a r e d i f f e r e n t f r o n the assumption of t h i s study.

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

f a c t o r s (such as the mechanism of reaction, hydrodynamics, and the

gasification

difference

in coals)
A s

involved i n the reactions are not c m p l e t e l y understood. an a l t e r n a t i v e ,

themdynamic analysis is always a guide i n The information about chemical t o estimate The

t h e preliminary design work. equilibnun composition of

a reaction allows us

t h e t h e o r e t i c a l m s and energy balance f o r the system. as

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

I n a complex reaction such as coal gasification, information about the

equilibrium computation may provide upper boundary

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

synfuel technology. discussion of

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,

steam and hydrogen gas.

The potential application and

operating point of

the process w s found by estimating the a

equilibrium composition and heating value of product gas.

A entrainment n

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.

i n these g a s i f i e r s can be equilibrium considerations. o r a large reactor, supposed t o be I n a chemical

the residence tirne of coal particles is

long enough t o reach equilibrium condition. system, equilibrium constraint includes

stoichiometric constraints and mass conservation constraints f o r each principle reactions, the calculated equilibrium

cmpos i t i o n f u l f i l l s both constraints Two categories

.
are the

f o r the computation(l7)

equilibrium constant method and the f r e e energy minimization method.

The former aethod uses equilibrium constants t o

express certain species i n terms of chosen species

a s e t of a r b i t r a r i l y

Kandiner and Brinkley ( 18) had a calculation The with

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.

This method was

specific problem

and often took some the particular

special characteristics of
it

is necessary t o f i n d those compositions balance, the t o t a l presssure

which s a t i s f y

the mass

spcifications, involved.

and a l l

t h e simultaneous

equilibria

It seems tedious f o r a rnoderateljr complex system.

f r e e energy minimization method, t o t a l Gibbs f r e e energy of the subject t o

A a l t e r n a t i v e method, n

based on the f a c t t h a t the

system reaches its minimum value a t guilibriurn, t h e constraints of the material balance.

The necessary can be calculated canonical Oliver,

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

s t a t i s t i c a l thermodynamics. computed the

Baier ( 19)

equilibrium

d i s t r i b u t i o n of species

r e s u l t i n g frorn reacti-ng 5 moles of They

oxygen with 1 rnole of methane a t 873K by t h i s method.

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

cmputer progrm(20) has been developed s h c e

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

f o r any thermodynamic s t a t e which themdynamic parameters.

described by

two

The two thernodynanic paraneters the (H,P) problem gives

show the properties of the system,

adiabatic constant pressure combustion properties, the (U,V) problem gives adiabatic constant volume or combustion (H,P), or

properties, (S,P),

the rocket

problen uses (T,P), (H,P)

the detonation problem uses

or (T,P),

where

T=Temperature, V=Volu-;le, P=Pressure, Y=Enthalpy, U=Internal Energy.

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

(H2 and CO) gas approached the

r e s u l t s calculated from the NASA program.

2.3 Overview of 3ptir;wn Seeking iflethods

Optimization is the way

i-illnim values

of

finding t h e ~naxirnum o r I n chemical

of

an objective function.

engineering

optimization plays

an important r o l e f o r For

process evaluation, e i t h e r economically o r technically. example,

such economic improvement as m i n i m costs o r

i s required f o r a process design,

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

Which method o r what p a r t i c u l a r applied t o a specific

objective

function

efficiency and accuracy engineer.

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

optimization techniques f o r most general,

engineering problem.

optimization techniques can be c l a s s i f i e d i n t o two a n a l y t i c a l methods and numerical methods.

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

numerical computation, m experiment, o r a computer program. Sometimes a inathematical m d e l i s too coinplex t o f i n d a n

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

optimization the possible

techniques

W e

only concerned with

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

of an optimization technique i n t h i s study. methods summrized from most t e x t s .

(a) univariate search

( b ) s t e e p e s t ascent and ( c ) simplex method

(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

f a c t o r a t a time methodf p.355-363) By

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

variable search is necessary f o r t h i s type of search.

17 o p t i m l point Is substituted i n t o the function and the

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.

(-) steepest ascent b

It i s a kind of gradient method. ( k v e r i d g e , 1977 p.407)

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

not, return t o step(b) There a r e many variations of

.
s t e p ( c ) and s t e p ( d ) , which

depend on the chamcterization of the system.

18 (-) simplex ;nethod c

If

we have

an objective

function with k variables, For example,

( k + l ) points a r e necessary t o form a simplex. a simplex i n two dimensions dimensions

i s a t r i a n g l e and i n three The general direction of

is a

tetrahedron.

search m y be taken i n a direction away from t h e worst poht.

A new

point is then selected

along this direction the remaining

and passes

through t h e center 1977 p. 367)

of gravity of

points. (Beveridge,

[The search w i l l stop on a

The s t e p s i z e

region, where no knprovenent can be achieved. s h a l l be decreased t o s t a r t t'ne

search from there u n t i l the

desired accuracy i s reached f o r optirnurn.

2.4 b e r v i e w of Experimental Designs

The purpose of
mona

any experimental work is to understand Experinental

bout the

system being investigated.

designs have been introduced t o provide the l e a s t number of experimental trials. I n section (2.2)

only

the response kJe

values without experimental e r r o r have been considered.

have t o use a method derived from experimental designs t h a t

is applicable when experimental e r r o r is

significant.

In

t h i s study, method of

we are

considering an e f f e c t i v e experimental locating an

f i t t i n g response surface and of

optimum operating point. indicated

The basic experimental designs a r e and reviewed i n t h i s

i n many texts(25,26,27)

1Y

section as a basis of s o l u t i o n algorithm f o r t h i s study.

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.

and the experiments with a l l possible two l e v e l f a c t o r i a l d e s i g s a r e

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

studied. ( b ) \*en needed, they a r e e a s i l y augmnted t o form a

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)

f i r s t order equation t o represent l o c a l surface.

many texts(Davis,

1967 p.271;

k x , 1978 p.510;

comparing t h e two l e v e l f a c t o r i a l design with t h e one f a c t o r

a t a time nethod.
are:

I n general, the differences between them

( 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

identify it and give the the ridge so t h a t

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

helpful f o r f u t h e r experimentation. ( c ) For multivariables experimental design, factorial

design t e l l s exactly which factor and how . m y factors should be varied.

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.

f a c t o r i a l design i s needed f o r fewer design the nature of the

and enough i n f o r m t i o n about

response function we a r e exploring.

There a r e many examples

presented i n the well hewn textbooks (Davis,

1976 p. 454;

Orthogonal design
If we arrange

the levels of each f a c t o r i n such a way (when

that

the diagonal terms i n the normal equations vanished,

performing l e a s t square) would be

t h e design i s and the

said t o be

orthogonal.

The design matrix

calculation of e f f e c t s a r e shown i n Table 2-2.

Composite d e s i ~

Box and Wilson(24) o r i g i n a l l y introduced the concept i n

1951. design. Factorial design can be Therefore, augmented t o form composite

f i t t i n g a response surface i s possible Many examples are presented

with a second order equation. i n the paper. (28,29)

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

on locating the o p t i m point through

experinent

and Nead and

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

response function would be

unknown.

Also, the complete t h e o r e t i c a l mchanisms of nost I n f a c t , the exact

i n d u s t r i a l processes a r e not available.

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

a given s e t of inputs w i l l yield a

22

maximn o r reach a maximurn p r o f i t ?

( b ) What is the shape of

t h e response surface close t o regions of

this maximum,

o r over some specified

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)

The basic idea is plus The

la process inf'ormation

should be

run so as t o generate product

improve the product'. (34)

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.

optimum yields nust be

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

Gas Eieact ions

--->

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

0 0.20127 0.01 0.21127 0.19127

Center Condition Step Size

1180 20 1200 1160

0.09526 0.002 0.09726 0.09326

T O H

(1)

(2)

(3) divisor

effect

- - + - +

96.00 44.36 48.68

90.36 95.73 90.50

186.09 186.37 -3.27

372.46 -6.55 10.74

8 4

46.56 -1.64 2.69

ave

T
O

..........................................................
m i n effects: T , 0, H two factor interaction: TO, THY HO three factor interaction: T9H

3.0 OBJECTIVE FUNCTION

3.1 As sumptions

A rigorous p r o f i t

m d e l has Seen discussed

i n chapter

One.

A simplified one contains the following f a c t o r s :

( 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

Carbonization process. balances f o r the

objective

Carbonization assumptions : process

process have

been based on t h e following

( a ) Only a single-stage g a s i f i e r i s i n t h e system.

(b ) The operating

c o s t of

transmission machines (screw

feeder, pump, compressor) i s negligible. ( c ) The difference negligible. on the c r e d i t of heat

'

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

The block diagram of it

condition.

'The

NASA

program

provided

the

equilibrium calculation.
NASA program,

I n the data bank of the

there is no molecular fo m f o r char.

i s necessary t o replace

Therefore,

it

char with

Graphite carbon(C). The element form of coal, i.e.

Cv Hw 0, Ny S ,

a l s o replaces coal i n Reaction

2.11.

aC v Hw 0 x N y S ,

+ b02 + cH2 0 ====== dCO + eH2 +

+ kc + etc.

fH2 0 + gC02 + hCH4 + i H 2 S + j N 2

(h) applying Hessls law f o r the

calculation of heat of

reaction a t the reactiorl temperature.

( i )applying t h e ideal

gas law f o r the

calculation of

sensible heat content f o r each conponent of product

gas.

3.2 Data and Parameters

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

a r b i t r a r i l y referred them from the following reference.

cost and price --( j ) The u n i t cost of e l e c t r i c i t y

and raw m t e r i a l s a r e

shown i n Table 3-1-A.

( k ) The unit price of char and medium-Btu gas a r e shown

i n Table 3-1-B.
(1)N separation cost f o r char and product gas. o

(m) The price of product

composition of i t . gas here is content of it. physical and chemical data (n) Heat capacity only

should be varied with the However, the c r e d i t of product

calculated based on the heat

equations and heat capacity data bank of the N S PA

coefficients a r e f ran the prpgrun.

(0)

Heats of Formation a t 298K a r e shown i n Table 2-1. coal(0hio Clarion 4A)

is shown i n

( p ) Composition of Reference (9)

29

3.3 Final Form of Objective Furction

After

making the above assumptions,

t h e objective

function w i l l be
U l ,U2

= f (xl

X2

,X3)
+

y = z

1u 1 + Z 2 U 2 - ( c l + c 2 x 2 + c 3 x 3 y: prof it, response value

f : NASA program u1,u2

E)

: equilibrium mount f o r char and

product gas c 1
,c

,c

'2jX3 : temperature x
1

:unit cost of coal, oxygen, s t e m 3 : amount of oxygen and steam

: unit price of char and medium-Btu gas z19z2 E: cost of e l e c t r i c i t y

HEAT

4
I I

\t/

YIGURE: 3-1 THE BLOCK DIAGRAM OF A SINGLE-STAGE GASIFIEB

TABLE 3-1-A UNIT COST OF FEEDSMCK AND UTILITIFS

............................................................
...........................................................
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

$26.90 per ton

$3.50 p e r Lvl lb

...........................................................

UNIT !'hWKST PRICE O PRODUCTS F

..........................................................
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

...........................................................

4.0 OUTLINE O THE OPTIMIZATION STHAmY F

4.1 R SAMPLE CALCULATION O RESPONSE VALUE F

A calculation of response value

based on the objective section. ble

function i n Chapter Three is shown i n t h i s

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

--

(a) Molecular formula of coal

de derive composition the molecular table of formula from the element coal.(Table 4-1) The

molecular form is:

( 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

and S a r e weight f r a c t i o n of each

.
formula and t h e elenent composition

Combining t h e

33
t a b l e (Table 4-1)

t h e heating value of coal (Ohio which i s eqlal t o

Clarion 4A) i s 12880 Btu per l b ,

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

we have t o apply the combustion reaction of

Standard heat of Combustion per = p l e of coal

Higher heating value of 1 p l e of coal

The sum of heats o formation of f

The sum of heats of formation of products at 298K

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

f o r m t i o n of other component can be found i n many texts. Therefore,

is -2.08

Table

4-2 gives a d e t a i l calculation. of formation of coal

the standard heat

)

(-126.88-(-124.8)

Kcal/gmle at 298K.

The NASA -- program ( a ) Input data

W arbitrarily e

assume the flow

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.

Therefore, the input data f o r the

NASA program i n t h i s sample calculation are:

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

component d i s t r i b u t i o n i s l i s t e d i n Table 4-3. order t o convert each component,

mle f r a c t i o n i n t o mole basis of

w e have t o calculate the total

moles of the equilibrium mixture.

Here, w use the e

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

The t o t a l moles of carbon atom

= 1000000 (kg coal) = 65972 p l e

/ 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).
=

0.429 ( f o r C) + 0.003 ( f o r CH4 )

+ 0.219 ( f o r CO) + 0.00036 ( f o r C S ) O

+ 0.002 ( f o r C02 ) + 0.000014 ( f o r CS2 )

=

0.653

The t o t a1 moles of equilibrium mixtures The t o t a l moles of carbon atom

.....................................

The t o t a l mole f r a c t i o n s of carbon compounds

Once t h e t o t a l calculated,

moles of

equilibrium mixtures of each component can

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

Sensible heat of + react a n t s

Sens i b l e heat of products

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

is calculated i n t h e Table 4-4.

The heat of reaction at 1200K

Therefore,

= 350000 Ycal/ton coal

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

where Cp = heat capacity

R = gas constant

! 1 A;, I,

A3,

A4, A5 = parameters of each

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

Total c r e d i t response cost

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.

T B E 4-1 AL COMPOSITION O C O L (OHIO CLARION 4A) F

...........................................................
Component Weight % Molecular Weight Mole%

Mole% set C=l

70.3

12
1

5 -86
503 0.45 0.086 0.15

1 0*go5 0.078 0.015 0.026

H
0

5.3
7.2

16 14

N
S

12 . 4.8 11.O

32

Inert

TABLE 4-2 CALCULATION O HEAT O F R A I N O C A F F O M TO F O L

.......................................................
Component Amount Standard Heat of F o m t i o n a t 298K

Heat of Formation at 298K

Reactants

Coal

...........................................................
Total

Products

Total

-125.88

TABLE 4-3 THE ECJUILIBRIUM COME"G'SITION AND MOLES OF EACH COMPONFQJT

39

Component

Mole Fraction
(By NASA program)

...........................................................

mles (By calc.)

COS

3.583-04

37

............................................................ 101127 Total 9 999

...........................................................

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

15 $/ton 26 $/ton 3.5 $/klb

2.2 klb/ton

15.00 5 -49 0 .75

19.67 40.91

......................................................... ..........................................................

TABLE 4-6

TGTAL CREDIT I N A SAMPLE CALCULATION

...........................................................
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

Hydrogen 32688 Total

4.2 The Considerations of Optimization Strategy

Three independent objective function. i.e.

Y = f(xl,
X*,

variables

a r e assigned

i n the

x3)

where prof it y:

:weight r a t i o of Oxygen t o Coal

3 :weight r a t i o of Steam t o Coal

The 05jective function, defined i n Chapter Three, showed
A

i t s complex calculation involved the NASA prograrn. combination of optimization technique

and experimental

design method is used t o determine objective function.

the optimal value of the

The following considerations influence

the selection of step s i z e and direction f o r optimization.

(a) Experimental design

provides a structure

f o r the

investigator I s learning process (36) said ' A prior

Hunter and Nay l o r f u l l use of and

successful learning requires the knowledge

in

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 ,

t o search an optimum operating point on a

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

e I f it is, w a r e interested a l s o i n the

l o c a l surface f o r those experimental points. The s t a r t i n g point is a r b i t r a r i l y taken t o be close t o Two

the operating p o h t reported by Savage. (APPENDIX I ) l e v e l f a c t o r i a l design gives us a direction of However,

steepest

ascent and a l o c a l surf ace picture. s i z e is Therefore, desim. too big, a

i f the step

the direction w i l l

be meaningless. i n factorial

smll s t e p s i z e is always used

Once the direction is determined,

a variable s t e p

s i z e f o r open-ended

search is employed t o f i n d the optimwn I f the s i z e i s too big, we

If the s i z e

point along the given direction.

might mlss the best point along t h e direction.

is too small, w e might have an unefficient search.

4.2 F i r s t Order Design and Direction of Steepest Ascent

A t the beginning point of the investigation,

there was

probably

some distance

from the maximum.

From calculus

point of view,

the local c h a r a c t e r i s t i c s of the surface can

be represented by i t s gradient, i.e.

where
xO x

: a local point
: a neighborhood point around point xo : response of xo

yo y
Vy

: response of x : gradient vector a t x

Rewrite Equation f o r three independent variables a s :

Y=bo

+bl *xl +b2

= (b

*%
b2 b

+b3
)

*5

gradient a t y Table

5-1 shows how the two level f a c t o r i a l design

determines the local slope of the surface. The least squares e s t i m t i o n of Because of
bo

is

the average of a l l eight responses.

the orthogonality of each independent variable,

is the change t h a t

the coefficient b response when x

occurs

i n the

i s changed by one unit.

Yatests algorithm

gives a rapid calculation of effects,

main effects m y be checked by higher

The significance of order interactions. of experimental I f it is

They are supposed t o be negligible because errors.

Curvature effects w i l l be checked also.

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

the method of Swam (Beveridge 1977,

46
p.154 and Beightler 1979, p.190) has been used. reyuires t h a t This method

the design points would be chosen t o have a u n t i l reaching a

s t e p s i z e double t h e i r previous points

point where no f u r t h e r progress seem l i k e l y . point points.

is necessary i n the

Sometimes, a l a s t two

region between the

O f the four equally spaced values, we s e l e c t e i t h e r

the f i r s t three or the last three. has a bigger center objective value.

It depends on which s e t

Having carried out an open ended search and defined the

optimum within a bracketed region, w may f i t a second order e p o l y n d a l curve w n g t h i s region and locate the best point f o r t h i s curve by i n t e w o l a t i o n . Other one dimensional

searchs in a limited region, such as, Fibonacci search, e t c , a r e not considered.

4.4 Second Order Design

Sooner o r

l a t e r it

would becotne c l e a r t h a t t o f i t a l o c a l surface

is not

f i r s t degree equation representing a possible. t h i s method. Besides,

no f u r t h e r progress can be obtained by t h a t a near stationary region is

It seem

reached and f i t t i n g a second degree equation is necessary. SomtFmes,

w e a r e a f r a i d of

the stationary point caused by t o double or t r i p l e the

the small s t e p s i z e .

Therefore,

s t e p s i z e is necessary around t-his region.

A two l e v e l f a c t o r i a l design was augmented with f u r t h e r

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

is t o calculate the Hessian matrix o r t o transform

t h e equation t o canonical form.

5.0 RESULTS AND DISCUSSIONS

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

W divided them i n t o e a direction

stages included search.

change and an one-dimensional

Each one-dimensional search consisted an open-ended In Table 5-1, a two-level direction of

search and a close-ended search.

f a c t o r i a l design was f i r s t used t o f i n d the

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

SignFficant irnprovernents were observed along t h i s

(2=7)

direction u n t i l the point was 63.37. used Then,

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

The l a s t stage was a

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

the doininating f a c t o r because

m u n t of oxygen was sm11. was c l e a r t h a t

The system was endothermic.

the direction of steepest ascent was toward

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

49 economical as by oxygen. oxygen, costs $0.50. The heat, supplied by 0.02 kg

The

It costs $1.80 by e l e c t r i c i t y .

following one-dimensional

search was ended a t a point

in

which the system was close t o t h e m 1 neutral. (y=63.37)

The point

seemed very close t o the maxium point along t h i s the difference between it
and

direction because

its

succeeding point w s two times the difference I ~ t w e e nit and a

i t s preceding point.

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

systern was around

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,

these two combustion

reactions only produced H2 0 and C02

.
temperature range

The t h i r d stage showed how temperature affected the production of

CO

and H2

a t the

(1066-1166K).

The temperature e f f e c t s seemed constant a t

( 1166-1566K)

the temperature range

because the

response

value had not been changed much ($108.63-107.37)

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

and oxygen inversely affected the

a stationary point

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).

One p o s s i b l e m i s t a k e we c o u l d if the step size

h a v e i n o p t i m i z a t i o n was and, therefore, the

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 .

So, t o i n c r e a s e t h e s t e p From t h e c o m p o s i t e by l e a s t square

s i z e was n e c e s s a r y f o r t h e s i x t h s t a g e . desidn, method.

secondary e q u a t i o n

was f i t t e d

By v a n i s h i n g t h e 1 s t d e r i v a t i v e , t h e optimum p o i n t was xl* = - 0 . 0 7 4 1 x2* = 0 . 2 4 4 7 6 x3* = 0 . 4 4 5 By t r a n s f o r m i n g t h e c o d e d v a l u e i n t o a b s o l u t e v a l u e , we g o t

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

i n char c as 50 weight percent,

would be stopped a t the other point.

percent of ash content i n coal w a s 0.11.

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

t h e r n i n i m carbon amount ton also. This number (T=1066,

point

i n the

second stage

The com~arisons With the same p r o f i t model, w compared the r e s u l t s e

It simply

with t h e e x p e r i i ~ n t a lpoints reported by Savage. means that w applied the e

sane objective function f o r the points. The

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,

Case A was the one we already agplied Case 9 j u s t included

f o r the search of the optimm point. the modification of

the Table 3-1-A and Table 3-1-B i n the

following way:

unit cost of coal = 25 $/ton

unit price of &ar = 25 $/ton
unit price of inedium-Btu gas = 4.0 $/MMBtu

Now, w can see the objective values of e

the o p t i r m point

were always bigger than those of experimental points.

The Experimental points

The optinnun point

prof it ($ ) case A case B

50.54

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.

TABLE 5-1 SEARCH ON STAGE-1 F a c t o r i a l Design

----

Temperature
Unit

Oxygen

Steam

(K) T

(wt%)
0

(wt%>

Center Condition Step Size

1180
20

0.20127 0.01 0.21127 0.19127

0.09526 0.002 0.09726 0.09326

-

1200 1160

COST O F T C ) H y
$

CFEDIT OF
(CO

effect

ELECT
$

+
$

XYD)
$

CHAR
$

.............................................................

- - + - - + + + - - + + - + - + +
+ + +

46.00 44.36 48.68 47.05 46.07 44.43 48.75 47.12

46.56

18.61

30.05 30.64 31.73 32.36 30.35 30.94 32.03 32.66

46.07 46.62 46.07 46.63 46.37 46.93 46.37 46.94

7.41 7.38 7.21 7.18 7.38 7.34 7.18 7.14

-1.638 20.89 2.685 16.85 0.008 19.18 0.07 19.09

-0.003 21.39
0.

17.33

0.003 19.67

....................................................
Continued

Open-ended he-dimensional Search

............................................................
direction: (-0.82 s t e p s i z e : -16 1.34 0.013426 0.04) 0.00007

Z: the number of s t e p s from o r i g i n a l point

~ ~

----

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.

31.39 32.26 33.65 34.10

46.53 46.29 45.66 43.46

7.27 7.15 6.94 6.66 7.21

19.03 32.81

Close-ended One-dimensional Search

%cause (63.37-41.50) / (63.37-53.92)

(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%)

Center Condition Step Size

1066
10

0 29525 0.01 0.30525 0.28525

0 09575 0.006 0.lo175 0.08975

+
-

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

0. 2.40 0. 0.45 1.07 3.70 0. 1.75

32.09 33.80 33.48 35.27 32.85 34.60 34.24 36.07

42.55 43.47 42.53 43.46 43.40 44.34 43.38 44.33

6.86 6-75 5.68 6.56 6.76 6.65 6.55 6.46

51.85 -0.36 64.14 0.26

64.49 -0.26

.............................................................
Continued

Open-ended One-dimensional Search

..........................................................
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

0.09575 0.10175 0.11375 0.13775 0.18575 0.28175 0.23375

63.37 65.97 69.56 76.81 91.30 55.66 85.26

7.68 8.51 10.17 13.52 20.16 33.45

34.10 36.78 42.11 52.82 73.97 62.52

43.46 43.57 44.69 46.35 49.70 43.52 49.80

6.66 6.32 5.62 4.23 1.46

0.

3 7 15 31 23

26.81 78.04

0.

Slose-ended One-dimensional Search

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

SMCH ON STAGE-3 Factorial Design

........................................................
Tmperature Unit Oxygen S t earn

(K)
T

(wt%>
0

(wt%)
H

Center Condition Step Size

1066

0.82710 0.01 0.83710 0.81710

0.19563 0.006 0.20163 0.18963

20
lo86 1046

CS O OT F T O H

CREDIT O F
(CO
$

y
$

effect

ELECT
$

+ HYD)
$

C M
$

Continued

Open-ended One-dimens i o n a l Search

d i r e c t i o n : (5.02 step size:

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
$

CREDI'I' O F (CO + HYD)

$ $

ELECT

CHaR
$

Close-ended One-dimensional Search

............................................................
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

Center Condition Step Size

1166 10 1176

0.83035 0.01 0.84035

0.20013 0.01 0.21013 0.19013

1156 0.82035 ...........................................................

SIiEDIT O F

'T O H

Y
$

effect

(CO

HYD)
$

............................................................. ______-______-__-_----------------------------------------

- - + - - + + + -

106.91 108.29 107.51 107.62 109.63 109 75 107.46 107.54

108.08 0.42 -1.11 -0.328 1.013 -0.323 -1.077 0.308

89 74 90.98 91.14 91.39 91.22 91 49 90 43 90.65

53.47 53.87 53 44 53.70 54099 55.28 54.60 54.77

- - +
+ - +

- + + + + +

Continued

60 Open-ended One-dimensional Search

direction: (0.211 step size:

-0.556 -0.01113

0.506) 0.01013

Z: t h e number of s t e p s from t h e o r i g i n a l points

COST O F

CREDIT 9F
(CO + HYD)
$ $

Y
$

OXY
$

Close-ended One-dimensional Search

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

Center Condition Step S i z e

1203 10 1213 1193

0.73107 0.01 0.74107 0.72107

0.29049
0.01

0.30049 0.28049

..........................................................
COST OF T O H
y
$

C;IEDIT OF
(CO
$

effect

ELECT
$

kIYD)

............................................................ ------------_----__-_---------------------------.--__-_-_--__

- - + - -

116.89 117.70 117.87 118.38 4 6

118.18 0.12 0.07 0.17 0.95 -0.54 -0.76 0.33

0.

90.21 90 92 91.92 92.42 91.73 92.46 91.66 91.83

61.13 61.44 61.14 61.43 62.68 63 .OO 62.41 62.56

0.

+ +

0. 0. 0.21 1.95 0. 0.

- + -

118.54 118.28 118.35

+ +

+ + +

...........................................................
Continued

Open-ended One-dimensional Search

...........................................................
direction: (0. s t e p size:
0 0 . 0 0.52) 0.O1

Z: the number of s t e p s from o r i g i n a l point

SOST

OF

CREDIT OF

y
$

ELECT STEhVI (CO + HYD)

$ $
$

........................................................... ............................................................
0

1203 0.73107

0.29049

119.21 119.41 119.35

0. 0 . 0.

2.24 2.32 2.47

92.21 92.10 91.46

62.07 62.74 53.80 65.56

1 1203 0.73107 0.30049 3 1203 0.73107 0.32049

7 1203 0.73107 0.36049 118.52

0.61 2.78 90.04

Close-ended One-dimensional Search

............................................................
The best point is a t : T: 1193 0: 0.072107

H 0.30049 :

63 TABLE 5-6 SEARCH ON STAGE-6

.........................................................
Unit Center Condition Step Size Temperature (K)
T

Oxygen (wt%)
0

S te m

(wt%)
H

T O H

1193 30 1223 1163

0.72107 0.03 0.75107 0.69107

0.30049 0.03 0.33049 0.27049

CXAR $

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

0.73 0.57 0.12

0.

0.18 0.01 0.
0.

............................................................ augmented points t o make composite design ............................................................

a 0 0 117.62 -a 0 0 117.49

2.95 0.
0.

0 116.45 O 114.54 0 0 a 118.68 0 0 -a 114.61 0 0 0 119.46 0

9

0 -a

3.36 1.69
0.

0.21

18.75 18.75 19.70 17.80 18.75 15.75 18.75

92.61 89.79 91.01 88.62 91.21 88.95 91.73

63.18 61.92 61.91 62.68 64.86 59.86 62.68

0. 0.18 0. 0.42 0. 0.38 0.05

a:1.215 from 3eference(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 .

T e m p e r a t u r e = ll9lK Weight r a t i o of oxygen t o c o a l = 0.72841 Weight r a t i o of s t e a n t o c o a l

2 . Comparing t h e p r o f i t
=

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

t h e e x p e r i m e n t a l p o i n t s r e p o r t e d by Savage, complete gasification of coal led more

partial gasification the contraints

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

economical pararneters point.

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

c a r b o n i z a t i o n p r o c e s s s h o u l d i n c l u d e a n o r e r i g o r o u s mass and e n e r g y b a l a n c e and c a p i t a l c h a r g e s . of s h o r t r e s i d e n c e t i m e of Also, t h e n a t u r e be t a k e n

the process should

i n t o account.

APPENDIX I

Coal, 2.27kg/h,

oxygen, 5000 c.c./m,

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

equal t o 1.95069 kg/h.

W a l s o applied t h e i d e a l gas law e

t o c a l c u l a t e t h e feed r a t e of oxygen on weight basis:

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.

Fuels Data Handbook1,

Cameron mgineers Inc. (2) Probsteh R.

F.

and Hicks,

E.

'Synthetic Fuels l ,

McGraw-Hill Book Co.

p. 145, 1982.

(3) Mongold,

'Coal

Liquefaction

and

Gasification

Technologies l , Ann Arbor Science p. 229, 1982.

( 4 ) Anderson, L. L. and D. A. Tillman, 'Synthetic Fuels from

Coal l , Wiley-interscience, p. 45, 1979.

(5) Spinks,

A.,

J.

M.

Thorns a n d J .

Gibson

'New Coal the Royal

Chemistry1,

Philosophical Transactions of

Society of London p.112, 1981. (6) Nowacki,

P.,

'Coal Gasification Processes,

Enera

Technology Review; 70' Noyes Data Co. (7 ) Energy Research and Development

p.254, 1981. Administration,

'Handbook of Gasifiers and Gas Treatment System1, Dravo Co. p.20, 1976.
W.
and R.

(8) Coover, H.

C.

Hart,

'A

Turn i n the Road:

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-

Low-Sulfur Char by Flash Carbonization of

Coal1, Int. J . Hydrogen Energy V.7, No.9, p.717, 1982.

67 Volatile, Low-Sulfur Char by Flash Carbonization of

CoalT, I n t J. Hydrogen Energy V.7, No. 9, p. 717, 1982. (10) Wen,

C.

Y.

and T.

Z.

Chaung Ehtrainment Coal

Eng.

Gasification Modeling', Ind. Dev. V.18, No.4, p.684, 1979. et.al,

Chem.

Process Des.

(11) Alain Chauvel,

'Manual of Economic Analjrsis of

Chemical Process', 1978. (12) Peters, M. S. and K.

I n s t i t u t e Francais du Petrole p.3,

D.

Timnerlnaus, 'Plant @sign and

Economics f o r Chemical Engineers 1968. (13) Wei,

J.

, 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.

Gordon lcalculation of Corilplex m d Eng. Chemistry, V.60,

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

68 Chemistry, v.42, no.5, p.850, (19) Oliver, R. 'Calculating

C.,

1950. S. E. and R.
W.

Stephanou,

Baier, Chemical

Free

Energy Minimizationt, 1962. McBri.de,

Engineering, Feb. (20) Gordon, S. Calculation

, p. 19,
J.

and B. of

'Computer Program f o r Chemical Equilibriui

Complex

Composition, Rocket Perfornance, Incident and Reflected Shocks, and Chapman-Jouguet Detonations

N S Lewis AA

Research Center 1971. (21) Beveridge G. E. G. and R. S. Schechter, 'Optimization: p.26,

J.

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