1 Optimization of the Flash Carbonization Process
A Thesis Presented to the Faculty of the Engineering College of Ohio University
In Partial Fulf illsnent of the Requirement for the Degree
Master of Science
BY
YeongSiarg Chang, August 1984


1
ACKNOWLEDGEMENTS
I would especially like to thank Dr. WenJia Chen, my thesis advisor, who suggested this topic and gave generously of his tirne and guidance during the course of this study.
I am grateful to Dr. Robert L. Savage for his constructive criticisms and useful suggestions to this thesis. Ny thanks are also due Dr. J. R. Collier and Dr. N.
Dinos for their help during my stay in Ohio University.
My wife, HuoyJen, has offered me her understanding and
I am more than
support over
the duration
of this task.
grateful for that. Finally,
parents for their encouragement and
I
wish to express
a deep gratitude
to my
support which make this
_{s}_{t}_{u}_{d}_{j}_{r} _{p}_{o}_{s}_{s}_{i}_{b}_{l}_{e}_{.}
This work is dedicated to them.
Pee
TABLE OF CONTENTS 
v 
LIST OF FIGURES 
vi 
LIST OF TABLES 
vii 
1.0 
INTRODUCTION 
01 

1.1 Coal Gasif'ication and the Flash Carbonization 

_{P}_{r}_{o}_{c}_{e}_{s}_{s} 
01 

1.2 Econorni cs of 
the Flash Carbonization Process 
05 

1.3 Purpose of the Thesis 
_{0}_{9} 

2.0 
LIrnTJRE &'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 

_{3}_{.}_{0} 
_{O}_{B}_{J}_{E}_{C}_{T}_{I}_{V}_{E} _{F}_{U}_{N}_{C}_{T}_{I}_{O}_{N} 
_{2}_{6} 

_{3}_{.}_{1} 
_{A}_{s}_{s}_{u}_{m}_{p}_{t}_{i}_{o}_{n}_{s} 
26 

3.2 
Data and Parameters 
28 

3.3 
Flnal Form of Objective Function 
_{2}_{9} 

4.0 
OUTLINE OF OPTIMIZATION STKAmY 
32 

4.1 A Sample Calculation of Response Value 
_{3}_{2} 

4.2 
The Considerations of Optimization Strategy 
_{4}_{3} 
4.3
First Order Design and Direction of Steepest
v
_{A}_{s}_{c}_{e}_{n}_{t}
44
4.4 Second Order Design 
46 

_{5}_{.}_{0} 
_{R}_{E}_{s}_{U}_{L}_{T}_{S} _{A}_{N}_{D} _{D}_{I}_{S}_{C}_{U}_{S}_{S}_{I}_{O}_{N}_{S} 
_{4}_{8} 
6.0 
CONCLUSIONS 
64 
_{A}_{P}_{P}_{E}_{N}_{D}_{I}_{X} I 
65 

REFFWSNCES 
66 
LIST OF FIGURES
Figure 31 The Block Diagram of a Singlestage _{G}_{a}_{s}_{i}_{f}_{i}_{e}_{r}
30
vii
LIST OF TABLES
Table 21 Heat of Reactions(HR _{:} _{K}_{c}_{a}_{l}_{)} _{a}_{n}_{d} _{E}_{q}_{u}_{i}_{l}_{i}_{b}_{r}_{i}_{u}_{m}
Constants(KP) of Selected Reactions 
23 

Table 22 
Yatels Algorithm 
25 
Table 31A Unit Cost of Feedstock and Utilities 
31 

Table 31B Unit Varket Price of Products 
31 

Table 41 Composition of Coal(Ohio Clarion 4A) 
_{3}_{7} 

Table 42 Calculation of Heat of Formation of Coal Table 43 The Equilibrium Composition and Moles of Fach 
38 

Component 
39 

Table 44 Calculation of Heat of Reaction _{a}_{t} 1200K 
40 

Table 45 Total Cost in the Sample Calculation 
41 

Table 46 Total Credit in the Sample Calculation 
42 

_{T}_{a}_{b}_{l}_{e} _{5}_{}_{1} _{S}_{e}_{a}_{r}_{c}_{h} _{o}_{n} Stage1 
53 

Table 52 Search on Stage2 
55 

Table 53 Search on Stage3 
57 

Table 54 Search on Stage4 
59 
Table 55 Search on Stage5
_{T}_{a}_{b}_{l}_{e} _{5}_{}_{6} _{S}_{e}_{a}_{r}_{c}_{h} _{o}_{n} _{S}_{t}_{a}_{g}_{e}_{}_{6}
61
_{6}_{3}
Zxtensive
processes for
1.1 Coal Gasification
programs have
been
undertaken to
develop
synthetic fuels
the comnercial production of
from 
coal, 
oil 
shale, 
tar 
sands, 
or biomass.(l) 
The 
objective is 
to replace 
exhausted or 
costly supplies 
of 
natural gas and petroleumbased
a flexible
Products can be varied to include low, medium, highBtu
gas,
methanol, and petrochemlcal products. It is also less
and more operable on lower
quality coals than coal liquefaction.
Many gasification processes have been developed with
differences in mdes of operation and characteris tics of
the products produced. Each gasifier has been described for
fuels.
Coal gasification is
of synthetic
method for
the production
fuels.
and raw materials for liquid fuels,
such as gasoline,
_{c}_{o}_{s}_{t}_{l}_{y} _{f}_{o}_{r} _{c}_{h}_{e}_{m}_{i}_{c}_{a}_{l} _{m}_{u}_{f}_{a}_{c}_{t}_{u}_{r}_{e}_{,}
a specific application
and the
type of
coal avaiable
as
feedstock. 
The three 
min 
characteristics of gasifiers 

sur,mrized by 
Probstein and 
Hicks(2), 
are the method 
of 
_{s}_{u}_{p}_{p}_{l}_{y}_{i}_{n}_{g} _{t}_{h}_{e} _{h}_{e}_{a}_{t}_{,}
_{r}_{e}_{a}_{c}_{t}_{o}_{r} _{t}_{y}_{p}_{e}_{.}
characteristics such as the state
the gasifying medium and amount, and the
Once they are specified, the other dependent
of the solid residue (dry
or 
slagging), 
the properties of the product 
gas, 
and the 

gasification temperature 
will be 
fixed. There 
are three 
types
The reactor type heavily
dominates the temperature distribution, therefore, those
and
the entrained flow rzactor.
of
reactors:
the
moving bed,
the
fluidized bed,
dependent characteristics 
are 
all 
influenced. 
There 
are 

also 
two 
nethods 
of supplying 
the 
heat: 
direct 
and 
indirect. 
The 
direct 
method 
is 
to 
supply oxygen 
or air, 

where 
heat 
is 
generated 
from 
the 
combustion reactions 
of 

coal. 
The 
indirect 
method 
applies 
an external 
heating 

source, 
steam 
or 
electricity, 
to 
supply 
heat 
for 

gasification 
reactions. 
The possible 
gasifying 
media 
for 

gasification 
are oxygen, 
air, 
hydrogen, 
steam. 
Oxygen 
and 

air 
are 
the 
sources 
of 
oxygen 
in 
the 
reactions 
for 
the 
production
of
carbon monoxide.
Hydrogen
gas
and
steam are
the 
source 
of 
hydrogen 
for 
the production 
of 
methane 
and 

hydrogen respectively. 
It 
is .also 
obvious 
that 
the anount 
and 
the kind 
of heating 
medium 
or gasifying medium influence 

the 
three dependent characteristics. 
In 
this section, 
a 
brief
description
of
the
characteristics
of
the
major
singlereactor, directheat gasifiers _{i}_{s} given.
The dryash and slaggingash Lurgi processes(3,4) are
moving bed processes and primarily to be considered for the
production of Synthetic Natural Gas(SNG). Moving bed
gasifiers operate with countercurrent 
flow. 
The 
coal 
is 

introduced downward through 
the upward flowing 
gases. 
It 
is 

dried 
first, 
then devolatilized, and 
then gasified 
at 
the 

lower 
section. 
The bottom 
section 
is 
the combustion zone 

where 
the renaining coal 
is burnt 
to 
supply 
heat 
for the 
3
gasification zone. The sla~ingashprocess is better than the dryash process both in the tt roughp put and in thennal
efficiency because of higher temperature operation. By
reducing the steam injection
investment is reduced, and the process them1 efficiency is
methane
cantent yield and leads to a significant overall process
economy because, in most cases, the gas will be processed
further at elevated pressure. The disadvantages is that it
requires a sized noncaking coal which increases the cost of
coal. The reactor with a slowly
basically a lowthroughput device that requires a large
number of gasifiers occupying a
the
gasification process for
downward moving bed is
requirements, the capital
increased. The pressurized gas FTier favors high
large area.
However,
Lurgi dry ash
process is the only
which the 
technology has been commercialized. 
'The Sasol 

projects have applied this process 
to produce 
Synthetic 
Nqtural Gas.
The Texaco and ShellKoppers ( 5,6,7) processes
mnufacture either low or mediumBtu synthesis gas in a
manner that is closely similiar to the production of
synthesis gas from petroleum fuel residues. The 'Texaco
water slurry
injection system produces
hydrogen to
and solves the problem of
a high
carbon monoxide ratio product gas
feeding coal into a pressurized gasifier, but introducing a
therml inefficiency in operation. The potential for the
considerable . Tennessee
application of this process is
%stman Co. has applied it to the production of acetic
4
anhydride from coal(8).
developed from KopperTotzek process, uses the ,Ininimum
mount of stem for high thermal efficiency and produces a
low hydrogen to carbon monoxide ratio. Both gasifiers are
entrained bed processes in high temperature operation,
The
ShellKogpers
process,
therefore, both process units require a hightemperature
heat exchanger which represents a costly technical problem.
A waste
energy in the fonn of stean(Mangold, 1982, p.122), which can
be utilized in a refinery or chemical plant, but my not be
used in other applications.
All the gasification processes discussed _{s}_{o} _{f}_{a}_{r} _{a}_{i}_{m} _{t}_{o}
gasify completely the coal fed into the gasif'ier. Though it
a
difficult or
consideration. In
practice, it is impossible to convert the last five to ten
is possible to
coal
thermodynamic point of
expensive to do it from a kinetics
heat boiler
my give about
half of
the available
convert
totally
to
gas
frorn
view,
_{i}_{t} is extremely
percent of coal to gas even under the rnost.favorable kinetic
condition.
coal gasification process, _{i}_{f} both the gas and the solid
products can be utilized.
Savage and Chen(9) are actively developing the Flash
Carbonization process at Ohio University for the concurrent
production of synthesis
char which
along the Ohio River.
plant use
and a low sulf ur, low volatile
Therefore,
it
is preferable to use
a partial
gas
is suitable for
industrial and povJer
Using an entrained bed reactor, oxygen and steam, along
5
with finely&rounded coal(40+100, 100+200, ?ksh No.), _{a}_{r}_{e} introduced from the top of the _{r}_{e}_{a}_{c}_{t}_{o}_{r}_{.} _{A} _{c}_{h}_{a}_{r} _{w}_{i}_{t}_{h} _{f}_{o}_{r}_{t}_{y}
to eighty percent of the original carbon, together with a
produced at the botton of the reactor.
Coal, oxygen, and steam are fed at rates of 2.27Kg per hour, 5000c.c per ninute, and 2c. c. per minute respectively.
Atmospheric pressure and temperatures ranging from 1180~to
1450K were chosen for the operating conditions in a series
of experiments. Also, the residence times were varied.
In general, being an entrained bed system, _{t}_{h}_{e} _{p}_{r}_{o}_{c}_{e}_{s}_{s}
gasification
processes (lo), minly ;
has several advantages over the other
systhesis gas is
(a) 
the ability 
to handle caking coal 
and low 
grade 
coal, and 

(b) 
the product gas is free of tars and Phenols. 
More importantly, the moderate temperature (1100K1500K)
employed
avoids the

aisadvantages
( >1500K) process such as (lo) :
of
a high
temperature
(a) 
the large mounts of energy(oxygen) required to 
maintain a high temperature condition, 

(b) 
the high cost in refractories and construction 
material necessary in the combustion zone,
(c) the large munt
of
energy loss in
product gas or
high cost in heat recovery system.
1.2 Econmics of
the Flash Carbonization Process
The rigorous economic analysis of a chemical process
and total
includes detailed
narket research,
captial cost
production cost estimation,
and other economic factors.(ll)
At the present 
stage 
economic evaluation for 
the 
Flash 
Carbonization 
process 
is difficult because the 
new 

technology involves 
rnany uncertainties 
in process 
performance, operability, an reliability . A rigorous estimtion is, theref ore, not necessary. Alternatively, a
quick calculation always meets the need in priliminary design stages. Savage(9) has shown the predesign capital
and operating cost of the Flash Carbonization process, based
He also compared
the production cost at the experimental operatiw point with
other coal gasification processes, such _{a}_{s}_{,} Texaco process
and KoppersTotzek process. The next step, followed by his work, in economic
_{a}_{n}_{a}_{l}_{y}_{s}_{i}_{s} is to find the best operating point in the process
itself. In general, the best or optim operating point
on the assumgtion of equilibrium
yields.
implies that it will yield a maxlmum profit. Net profit, by definition, equals total income minus all expenses. Total
_{i}_{n}_{c}_{o}_{m}_{e} _{i}_{s} _{t}_{h}_{e} sum of each product amount multiplied by its _{s}_{e}_{l}_{l}_{i}_{n}_{g} _{p}_{r}_{i}_{c}_{e}_{.} All expenses are the total production costs.
A typical total production cost analysis(l2) contains several items, direct production cost, fixed charges, plant
overhead costs, administrative expenses, and distribution
7
and marketing expenses. The first three items are sometimes referred as manufacturing cost. The last two items are so called general expenses. The first item is the dominating
factor in evaluating the optirm operating point. list of direct production cost contains(Peters,
A typical
1968
p.192)
raw materials
utilities cost(steam, electricity, fuel,
ref rigeration,
water,
etc. )
operating labor and supervision
maintenance and repairs
operating supplies
laboratory charges
catalysts and solvents
For a given process or a plant, _{r}_{a}_{w} _{m}_{a}_{t}_{e}_{r}_{i}_{a}_{l}_{s} _{a}_{n}_{d} _{u}_{t}_{i}_{l}_{i}_{t}_{i}_{e}_{s}
cost are the rmst influential factors in direct production
cost. Therefore, the profit model can be simplified and
related to the following factors:
(a) 
the amount and the price of each product. 
(b) 
the munt and the cost of each raw material. 
(c) 
utilities cost. 
These three factors can be estimated if the material and
energy balance are known. In general, a kinetic model
should be used to predict the material and energy balance at
different operating conditions. However, for high
temperature processes,
4t the
present stage, no kinetic model for the Flash Carbonization
thermodynamic equilibrium model
produces as good a prediction as the kinetic model.
the
8
is available. We will use a thermodynamic equilibrium mdel
for the profit calculations. Any profit model for a chemical process is naturslly constrained by chemical and
physical principles and economics rules. Chemical and
physical contraints
therrmdynamics laws. Gcononic constraints are the rules of
_{e}_{x}_{i}_{s}_{t}_{i}_{n}_{g} _{m}_{r}_{k}_{e}_{t} _{s}_{y}_{s}_{t}_{e}_{~}_{m}_{.} The search for the rmxirnum prof it
will give us an explanation of how rnuch the constraints
influence t'ne prof it and operating point.
The characteristics of partial gasification in Flash
Carbonization has raised a series of questions. Since the
process is not energy selfsufficient, which way is more
economical in supplying reaction heatby electricity
(indirect method) or by oxygen (direct method) _{} is unknown.
operation favors
decreases energy
as heat
The
and
consist of mss conservation and
low temperature
char production
as well
required in
the reactor
waste in the product stream;
it also decreases the
production of syngas because of themdynamic equilibria in
the system. From the economical point of view, what is the
Flash Carbonization for
naxFinum prof it
optimal
in the
operating
point
is not clear.
1.3 Purpose of the Thesis
the
optimum operating point of the Flash Carbonization process.
Constrained by both thermodynamic and
considemtions, an objective function has been defined for the profit of each operating poigt. 4n experimental design
economic
This
study
is
to
find
a
auick estimation
for
is
implementation of
discussion on the search path is given with the cornbination
of chedcal stoichiometry, equilibrium constant, and reaction heats involved in the system. The result, at the
the
experimental points using the same profit model.
optirm operating point, is
used
as
an
optinim seeking optimization
method
in
the
since
real
it
is
an
A
world.
cmpared
with
those of
2 .o LITERATURE m1w
2.1 Gasif ication Reaction
The principal chemical and physical changes of coal in
a gasifier can be described by four categories: drying, pyrolysis, combustion, and gasification. Each physical or
chemical transformation can be silnply represented by the
following 
equations : (bhngold, 
1982, p. 132) 
Drying 
Coal (high moisture)  > Coal (dry)
Pyrolysis
Coal (dry) > Char + Volatiles
(CO,
H2
CH4
, Tar,
H
2
Combustion Combustible volatiles
_{(}_{C}_{O}_{,}
S, 
Ha 
0, 
etc.) 
_{H}_{2} 
_{,} _{C}_{H}_{4} 
_{,} Tar) 
> co2
_{+} _{5} _{0}
, C02
(2.2)
11
Gasif'ication
Char
+ 5 0  > co + 5
_{+} _{H}
2
_{s} _{+} _{N}
2
c~sh(2.5)
Char + C02 >2CO+H20+% +H2S+ 

N2 
+ 
AS^ 
(2.6) 

Char + 2H2 > CB4 + H2 
3 + H2 S + N2 
+ 

Ash 
(2.7) 
apply the present data, the
main reactions in a gasifier are simplified and summarized
in Table 21. The overall reaction _{c}_{a}_{n} be represented by the
following equation:
In order
to discuss and
aCoal + b02
+ cH
2
0 =====
dCO + eH2
+ fH2
0
hCH4
+ iH2
S + jN2
+ kChar + etc.
+ gC02
+
(2.9)
Reactions involved in a reactor are generally defined and constrained by stoichiometry, themdynamic equilibrium, kinetics, and transport rates (~nass,energy, and mentun).
Since this is 
a general analysis of the operating point in 

any gasif'ier 
with 
syngas production, 
the discussion A 

concentrates 
on 
stoichiometry 
and 
equilibrium. 
stoichiornetric analysis of coal gasification has been made
by
Wei(l3).
Through
detailed
vectorial
and
gemetric
12
explanations and comparisons of
pilot plant
data,
Wei
found a
the result to comercial and
operating
narrow feasible
regian which is only limited
stoichiometric constraints. However, the basis of his studies is on the complete gasification and thermal balance
by them1 balance and
which are different fron the assumption of this study.
2.2 Equilibrium Computation
model for
coal
factors (such as the mechanism of pyrolysis, gasification reaction, hydrodynamics, and the difference _{i}_{n} coals) involved in the reactions are not cmpletely understood. As
an alternative, themdynamic analysis is always a guide in
the preliminary design work. The information about chemical equilibnun composition of a reaction allows us to estimate the theoretical mass and energy balance for the system. The
calculation can be applied to the design and analysis of the process. l%ny examples were presented in Shewood's
text (14). In a complex
equilibrium computation may provide information about the upper boundary of yield for the first step in assessing a
synfuel technology. Batchelder and Sternberg(l5) had a discussion of equilibrium composition for suspension
gasification of pulverized coal. Recently, Wiser and
At the
present time,
there
is no unifying
effects
gasification
kinetics
because the
of
_{~}_{n}_{a}_{n}_{y}
reaction such as coal gasification,
13
Kithany ( 16) investigated a new catalytic hydrogenation of
coal slurry prepared in s hydrogendonor solvent, with
steam and hydrogen gas. The potential application and
operating point of the process was found by estimating the
equilibrium composition and heating value of product gas.
An entrainment gasifier is always operated under high
tanperature conditions. Therefore, the overall performance in these gasifiers can be determined approximately by
equilibrium considerations. Furtherimre, for an idealized
or a large reactor, the residence tirne of coal particles is
supposed to be long enough to reach equilibrium condition.
In a chemical system, equilibrium constraint includes
stoichiometric constraints and mass conservation constraints
for each principle reactions, the calculated equilibrium
cmposition fulfills both constraints. Two categories for the computation(l7) are the
equilibrium constant method and the free energy minimization
method. The former aethod uses equilibrium constants to
express certain species in terms of a set of arbitrarily
calculation
chosen species . Kandiner and Brinkley ( 18) had a
of the combustion of propane in air by _{t}_{h}_{i}_{s} method. The
equilibrium system contained ten gaseous constituents, with
or without the formation of solid carbon. This method was
some
designed for a specific problem
advantage of special characteristics of the particular
problem. So,
which satisfy the mass balance, the total presssure
and
often
took
it is necessary to find those compositions
spcifications, and all the simultaneous equilibria
involved. It seems tedious for a rnoderateljr complex system.
An alternative method, free energy minimization method, based on the fact that the total Gibbs free energy of the
system reaches its minimum value at guilibriurn, subject to
the constraints of the material balance. The necessary
data, chanical potential of each species, can be calculated
from spectroscopic constants by 
evaluating the 
canonical 
partition function of statistical thermodynamics. 
Oliver, 
Stephanou
equilibrium
moles of
oxygen with 1 rnole of methane at 873K by this method. They also cited some additional application, such as, calculation of the adiabatic flame temperature at a sgecified pressure
distribution of
and
Baier ( 19)
computed
the
species
resulting frorn reacting 5
and rocket motor performance calculations.
developed shce
the 1950's for multipurpose application. Rased on the latter
A NASA
cmputer progrm(20)
has been
method,
for
themdynamic parameters.
show the properties of the system, the (H,P) problem gives
adiabatic constant pressure combustion properties, the (U,V) problem gives adiabatic constant volume combustion properties, the rocket problen uses (T,P), or (H,P), or
where
S=E;ntropy,
T=Temperature, V=Volu;le, P=Pressure, Y=Enthalpy,
U=Internal Energy.
described by two
the program calculates
thermodynamic
the equilibrium canposition
is
any
state which
The two thernodynanic paraneters
(S,P),
the detonation problem uses
(H,P)
or (T,P),
15
Savage
and
Chen
have
applied
it
to
calculate
equilibrium yields for the comparison with the experimental data. They found the experimental yields and the
canpositions of synthesis (H2 and CO) gas approached the
results calculated from the NASA program.
2.3 Overview of 3ptir;wn Seeking iflethods
Optimization 
is the 
way 
of 
finding the 
~naxirnum or 

iillnim 
values 
of 
an objective 
function. 
In chemical 
engineering , optimization plays an important role for process evaluation, either economically or technically. For
example, such economic improvement _{a}_{s} _{m}_{i}_{n}_{i}_{m} costs or
maxim profit is required for a process design, and the
possible technical aims might contain the maximum amounts of
yield from a reactor or a minimum size of a cooling tower.
In spite of various kinds of mathematical rnodels of
objectives, the
Which
be
applied to a specific objective function with high
for an
efficiency and accuracy is still an
basic optirm
what particular
seeking methods
group of
are fixed.
method or
methods can
active field
engineer.
Many texts(21,22,23) presented the information of
optimization techniques for most engineering problem. In
general, optimization techniques can be classified into two
broad categories:
analytical methods and numerical methods.
16
These are applied to two different types of objective mdels
respectively. (Beveridge 1977,
p. 26)
The first type
is
a
mathematical model which is a set of analytical expressions.
The second type is the socalled blackbox model in which
the response to a particular input is detemined by
numerical computation, m experiment, or a computer program.
Sometimes a inathematical mdel is too coinplex to find an
optimum with analytic methods, then, it might be solved ~ith
nunerical methods.(Bveridge
1977, p.53)
optimization
techniques _{.}
optimum seekirg method in the unconstrained multivariable
problem. The review here will be a basis for the selection
of an optimization technique in this study. There are three
methods summrized from most texts.
only concerned with the possible
We
are
not
We
going to
are
review
all
the
(a) univariate search
(b) 
steepest ascent and 
(c) 
simplex method 
(a) univariate search
is
sometLzes,
p.355363) By
the k variables
fixed at some level, a mximm or minirum value can be found
starting an initial point and keeping k1 of
or sectioning _{m}_{e}_{t}_{h}_{o}_{d}_{1}_{.}
The
Univariate search
a
kind of
direct
method;
it is also called 'one
factor at a time methodf
(Beveridge 1977,
along this
variable search is necessary for
dimension.
Therefore,
an
efficient
single
The
this type of search.
17
the
objective function is again optimized with another variable.
The process continues :mtil the successive change of
variables and object value is less than a tolerance.(24) 'The
optiml point Is
substituted
into
the function
and
disadvantage of univariant search is that it is difficult to
be used in a system containning a ridge _{o}_{r} _{s}_{t}_{e}_{e}_{p} _{c}_{o}_{n}_{t}_{o}_{u}_{r}_{s}_{.}
The step size must not be kept too large because the process
my stop at a n~noptimlpoint.
(b) steepest ascent

It is a kind of gradient method. (kveridge, 1977 p.407)
The gradient vector is nor,ml to the contour line or surface
and indicates the direction
The steps for this method(Stocker, 1980 p.180) are as
follows :
of steepest ascent(or descent).
(a) 
Select a trial point. 

(b) 
Evaluate the gradient at the current point and the 

relationship of the changes of the x variable. 

(c) 
Decide step size and then move that distance. 

(d) 
Determine the 
maximum or 
minimurn point along the 
direction. 

(e) 
Check whether 
the optim has been achieved. If 
not,
return to step(b) .
There are
depend on the chamcterization of the system.
many variations of
step(c) and step(d), which
18
(c) simplex ;nethod
variables,
(k+l) points are necessary to form a simplex. _{F}_{o}_{r} _{e}_{x}_{a}_{m}_{p}_{l}_{e}_{,}

If
we have
an objective
function
with k
a
dimensions
simplex in
is
two dimensions
a
tetrahedron.
is
a triangle
The
and in
three
of
general direction
search 
my be 
taken in a direction away from the worst 

poht. 
A new 
point is then selected 
along this direction 
and passes through the center of gravity of the remaining
points. (Beveridge, 1977 p. 367) [The search will stop on a
The step size
search from there until the
region,
where no knprovenent
can be achieved.
shall be decreased to start t'ne
desired accuracy is reached for optirnurn.
2.4
berview of Experimental Designs
The purpose of any experimental work is to understand
mona bout the system being investigated. Experinental
designs have been introduced to provide the least number of
experimental trials. In section(2.2) , only the response
values without experimental error have been considered. kJe
have to use a method derived from experimental designs that
is applicable when experimental error is significant. In
this study, we are considering an effective experimental
method of fitting response surface and of locating an optimum operating point. The basic experimental designs are
indicated in many texts(25,26,27) and reviewed in this
1Y
section as a basis
of solution algorithm for this study.
Factorial Designs at two levels A general factorial design is
number of levels for each of a number of
possible
two level factorial desigs are
combinations.
varlables(factors)
_{t}_{h}_{e} _{s}_{e}_{l}_{e}_{c}_{t}_{i}_{o}_{n} _{o}_{f} _{a} _{f}_{i}_{x}_{e}_{d}

and
the experiments
with all
In general,
more important by the following reasons: (Pox, 1978 p.306)
(a) 
They require relatively few runs per' factor 
studied. 

(b) 
\*en needed, they are easily augmnted to form a 
composite desig. 

(c) 
Through two level f ractional factorial design, _{t}_{h}_{e} 
number of runs can be decreased further. 

(d) 
The use of building blocks reduces the degree of 
complexity of the problem. 

_{(}_{e}_{)} 
It is easy to interpret the observations. 
In general, the two level factorial design gives a
first order equation to represent local surface. There are
many texts(Davis, 1967 p.271; kx, 1978 p.510; ax 1954)
comparing the two level factorial design with the one factor
at a time nethod. In general, the differences between them
are:
(a) When interaction effects are significant,
a
factorial design avoid leading wrong conclusions. For exanple, one factor at a time will be valueless when the response surf ace contains a ridge, but
20
factorial
desim
my
identify it
and
give
the
direction of the axis of 
the 
ridge 
so 
that 

improvement is possible. 

(b) 
The discovery of factor _{d}_{e}_{p}_{e}_{n}_{d}_{e}_{n}_{c}_{e} _{o}_{f} _{a} _{p}_{a}_{r}_{t}_{i}_{c}_{u}_{l}_{a}_{r} 

type provides the information 
in connection 
with 

the experimenter's theoretical knowledge. 
_{I}_{t} _{i}_{s} 

helpful for futher experimentation. 

(c) 
For multivariables experimental 
design, factorial 
design 
tells exactly 
which 
factor 
and how 
.my 
factors should be varied. 

Fractional factorial design 

When a model 
contains more than three 
variables, 
the 
full factorial designs are tedious and unmanageable.
Fractional factorial design is needed for fewer design
points and enough informtion about the nature of the
response function we are exploring. There are _{m}_{a}_{n}_{y} examples
presented in the well hewn textbooks (Davis, 1976 p. 454;
Orthogonal design
_{I}_{f}
_{w}_{e} _{a}_{r}_{r}_{a}_{n}_{g}_{e}
the levels of each factor in
such a way
that
the
diagonal
be
terms in
the
would be
performing least square)
said
to
orthogonal.
The
normal
vanished,
equations
matrix
(when
the design is
and
the
design
calculation of effects are shown in Table _{2}_{}_{2}_{.}
Composite desi~
Box and Wilson(24) originally introduced the concept in
1951. 
Factorial design can be 
augmented to form composite 
design. 
Therefore, fitting a response surface is possible 
with a second order equation. _{M}_{a}_{n}_{y} _{e}_{x}_{a}_{m}_{p}_{l}_{e}_{s} _{a}_{r}_{e} _{p}_{r}_{e}_{s}_{e}_{n}_{t}_{e}_{d} in the paper. (28,29)
Response
has been selected with
success on locating the optim point through experinent
design. Two survey articles, Hill and Hunter(30),
_{a}_{n}_{d} _{N}_{e}_{a}_{d} _{a}_{n}_{d}
PFke(31), listed references to those studies.
studied the rapid entrainment
carbonization of powdered coal under pressure in a partial
Surf ace Method
The response surface method(24)
Belt
and
Roder(32)
hydrogen atmosphere for
They established the relationship
the production of
low
sulfur char.
betrreen process variables
md char 
yield as 
well as 
quality by the application 
of 

response surface 
analysis. 
It 
is clear that in the real 
world the exact form of a response function would be
unknown. Also, the complete theoretical mchanisms of nost industrial processes are not available. In fact, the exact
function is not necessary because the mediate concerns for process design are questions such as(25)
_{(}_{a}_{)} _{W}_{h}_{a}_{t} _{v}_{a}_{l}_{u}_{e}_{s} _{o}_{f} a given set of inputs will yield a
22
maximn or reach a maximurn profit?
(b) What is the shape of
the response surface close to
this maximum, 
or over 
some specified 
regions of 
interest? 
The response surface nethod has been applied to answer these
questions. One strikiw application of
is 'Evolutionary 0peration1(EVOP).(33,34) The basic idea is
the response surface method
la process should be 
run so 
as 
to 
generate 
product 
plus 

inf'ormation 
on 
how 
to improve 
the 
product'. (34) 
The 
experiments for true
the fullscale
plant.
optimum yields nust be
carried out on
TABLE 21
HEAT OF REACTIONS ( kB : KCAL ) AND EQUILIBRIUJ'JI CONSTANTS ( KP )
OF SELFXTED @ACTIONS
3eactions 
298K 
700K 
lOOOK 
1500K 

Combustion 

ItR 
26.4 
26.4 
26.74 
27 75 
Continued
24
Gasification 

Gas Eieactions 

> H3+C02 
KP 
HR 

_{C}_{O} _{+} _{3}_{H}_{2} 
>CH +H 0 KP
4
2
0.07 
0.15 
0.20 
0.28 
49.26 
52.68 
53 87 
54 59 
14.83 
1.15 
0.g6 
175 
Source from Reference (1)
Unit
Temperature
(K)
        
Oxygen
(wt%>
_{S}_{t}_{e}_{a}_{r}_{n}
(wt%)
T 
0 
H 

Center Condition 
1180 
0.20127 
0.09526 

Step Size 
_{2}_{0} 
_{0}_{.}_{0}_{1} 
_{0}_{.}_{0}_{0}_{2} 

+ 
1200 
0.21127 
0.09726 

 
1160 
0.19127 
0.09326 

TOH 
Y 
(1) 
(2) 
(3) 
divisor 
effect 
 
96.00 
90.36 
186.09 372.46 
8 
46.56 ave 

+ 
 
 
_{4}_{4}_{.}_{3}_{6} 
95.73 
_{1}_{8}_{6}_{.}_{3}_{7} 
6.55 
4 
1.64 
T 
 
+ 
 
48.68 
_{9}_{0}_{.}_{5}_{0} 
3.27 
10.74 
4 
2.69 
O 
min effects: T, 0, H two factor interaction: TO, THY HO three factor interaction: T9H
One.
3.0
A rigorous profit
OBJECTIVE FUNCTION
3.1
Assumptions
mdel has Seen discussed
in chapter
A simplified one contains _{t}_{h}_{e} _{f}_{o}_{l}_{l}_{o}_{w}_{i}_{n}_{g} _{f}_{a}_{c}_{t}_{o}_{r}_{s} _{:}
(a) 
the aiiunt and price of each product. 

(b) 
the amunt and cost of 
raw mterials. 
(c) 
utilities cost. 
Once the amunt and cost of raw materials and the price of
each
balances for each unit process and unit operation give us
rigorous _{m}_{s}_{s} and energy
product
are
specified,
the mount of each product and the utilities cost. Here, we will also apply the simplified profit model for the Flash Carbonization process. The necessary _{m}_{a}_{s}_{s} and enerw
balances
for
the
objective
function
of
the
Flash
Carbonization 
process 
have 
been based 
on 
the 
following 
assumptions _{:} 

process 
(a) Only a singlestage gasifier _{i}_{s} _{i}_{n} the system.
(b )
The operating cost of transmission machines (screw feeder, pump, compressor) is negligible.
(c)
The difference on the credit of heat ' recovery is negligible.
27
(d) 
No steam recovery system. 
(e) 
Electricity is the only indirect heating source for 
coal gasification in endothemic condition. 

gasifier 
(f ) Operated in
isothermal condition at
1 atmospheric
pressure. 
The 
block diagram 
of 
it 
is show 
in 
Figure 31. 
(g) The products are under thermodynamic equilibrim
the
data bank of the
condition.
'The
NASA
program
In the
provided
equilibrium calculation.
NASA program,
Therefore,
Graphite carbon(C).
there is no molecular fom for char.
is necessary
to replace
char with
The element form of coal,
_{i}_{.}_{e}_{.}
it
Cv Hw 
0, 
Ny 
S, 

2.11. 

aC 
H 
0 
N 
S, 
vwxy 
fH2
0 + gC02
,
also replaces coal in Reaction
+ b02
+ cH2 0 ======
S
+ jN2
dCO + eH2
+ etc.
+ hCH4
+ iH2
+ kc
+
(h) applying Hessls law for the
(i)applying the ideal
calculation of heat of
reaction at the reactiorl temperature.
calculation of
sensible heat content for each conponent of product
gas law for the
gas.
3.2 Data and Parameters
The necessary data and parameters are _{d}_{i}_{s}_{c}_{u}_{s}_{s}_{e}_{d} _{i}_{n} _{t}_{h}_{i}_{s} section. Since cost and price are dependent on time, we
arbitrarily referred them from the following reference.
 cost and price (j) The unit cost of
electricity
shown in Table 31A.
and raw mterials are
(k) The unit price of
in Table 31B.
char and mediumBtu
gas are shown
(1) No
separation cost for char and product gas.
(m) The price 
of product 
should be varied with 
the 

composition of it. 
However, 
the credit of product 

gas here is 
only 
calculated 
based on 
the 
heat 
content of 
it. 

physical and chemical data   

(n) Heat capacity equations 
and heat 
capacity 

coefficients are f ran the data bank prpgrun. of the 
NPSA 
(0) Heats of Formation at 298K are shown in Table 21.
(p) Composition of Reference _{(}_{9}_{)}_{.}
coal(0hio Clarion 4A)
is
shown in
29
3.3 Final Form of Objective Furction
After
making
function will be
the above
assumptions,
the
objective
Ul
y
=
,U2
z
y:
=
f
(xl
9
+Z2U2
X2

, X3)
(cl
u
11
+c2x2 + c3x3
prof it, response value
+ E)
f:
u1,u2
NASA program
: equilibrium mount for char and
product gas
c
,c
,c
123
:unit cost of
coal,
oxygen,
: amount of oxygen and steam
_{'}_{2}_{j}_{X}_{3}
x 1 : temperature
stem
_{z}_{1}_{9}_{z}_{2} : unit price of char and mediumBtu gas
E:
cost of
electricity
HEAT
4
I
I
\t/
YIGURE: 31 THE BLOCK DIAGRAM OF A SINGLESTAGE GASIFIEB
TABLE 31A
UNIT COST OF FEEDSMCK AND UTILITIFS
Item
Feedstock
Coal(0hio Clarion 4A) (Dry and Ash Free) Oxygen
Unit cost
$15.00 per ton
$26.90 per ton
Stem 
$3.50 
per Lvl 
lb 
Utility 
Electric Power
Source from Reference(9).
$0.035 per _{I}_{Q}_{i}_{h}
UNIT !'hWKST PRICE OF PRODUCTS
Item 
Unit price 

Char 
$14.00 
per ton 
% 

MedimBTU 
gas 
$5.30 
per MM Btu 
* 
%Sourcefrom Reference(9). *Source from Reference(37).
4.0 OUTLINE OF THE OPTIMIZATION STHAmY
4.1 R SAMPLE CALCULATION OF RESPONSE VALUE
_{b}_{a}_{s}_{e}_{d} _{o}_{n} _{t}_{h}_{e} _{o}_{b}_{j}_{e}_{c}_{t}_{i}_{v}_{e}
ble
arbitrarily select 1 ton of
to calculate the necessary operating cost, the possible
credit, and the profitresponse value.
Heat of formation of coal
function in Chapter Three is
dry and ash free coal as a basis
A calculation of response value
shown
in this
section.

7
(a) Molecular formula of
coal
de derive the molecular formula from the element
composition table of coal.(Table 41) The
molecular form is:
(b) Heating value of
coal
Frotn Dulongls 
formula(35), 
the heating value 
of 

coal can be expressed by: 

Q (Btu/lb) 
= 14544 * C 
+ 62028 * 
(H  0/8) 

+ 4050 * S 

_{w}_{h}_{e}_{r}_{e} _{C}_{,} _{H}_{,} _{0}_{,} and S are weight fraction of 
each 

element . 
Combining the
formula and the
elenent composition
33
table (Table 41) , the heating value of coal (Ohio
Clarion 4A) is 12880 Btu per lb,
which is eqlal to
124.8 Kcal per gmle dry and ash free coal.
(c) Heat of formation of coal at 298K
In order to calculate the heat of formation of
coal, 
we have to apply 
the combustion reaction of 
coal. 
Standard heat of 
Higher heating 

Combustion per 
= 
value of 
1 ple 
ple of coal 
of coal 
The sum of heats The sum of heats
= of formation of _{p}_{r}_{o}_{d}_{u}_{c}_{t}_{s} _{a}_{t} _{2}_{9}_{8}_{K}

of
formation of
reactants at 298K
the last equation is the
Standard heat of formation of coal. Heating value
has been estimted in Page 32. Standard heats of
The only unkno\m value in
formtion of other component can be found in many
texts. Table 42 gives a
Therefore, the standard heat of formation of coal
is 2.08 (126.88(124.8) ) Kcal/gmle at 298K.
detail
calculation.
 The NASA program
(a) 
Input data 

We 
arbitrarily 
assume 
the flow 
rates 
of 
coal, 

oxygen, steam so that the weight ratio of oxygen to 

coal 
is 0.21127 and the 
weight 
ratio of 
stem to 

coal is 0.09726. Therefore, the input data for the 

NASA program in this sample calculation are: 

Molecular formula of coal, oxygen, and stem Pressure = 1 atm 

Temperature = 1200K 

The amount of 
coal 
= 
1 

The amount of 
oxygen = 0.21127 

The amount of steam = 0.09726 

(b) 
Output result 
The
output
result
for
calculated
equilibrium
component distribution is listed in Table 43. In order to convert mle fraction into mole basis of
each
moles of
component,
we
have to
calculate the
Here,
total
we use the
the equilibrium mixture.
element balance of carbon to get the total moles of
carbon atorn in the system and the total mole fractions of carbon compounds in the mixture. Therefore,
The total moles of
carbon atom
= 1000000 (kg coal) /
= 65972 ple
The
15.15
total
mole fractions
(g / gmle of coal)
of
carbon
compounds
Heat of

(Table 43).
= 0.429
(for C) + 0.003
(for CH4 )
+ 0.219
(for CO) + 0.00036
(for COS )
+ 0.002
= 0.653
(for C02 ) + 0.000014
(for CS2 )
The tot a1 moles of
equilibrium mixtures


The total moles of
The total mole fractions of
carbon atom
carbon compounds
Once the total
calculated, the moles of
estirrated and the result is indicated in Table 43.
moles of
equilibrium mixtures
each
component can
is
be
reaction
at 1200K

_{H}_{e}_{a}_{t} _{o}_{f}
_{r}_{e}_{a}_{c}_{t}_{i}_{o}_{n} _{=}
at 1200K
Each item in
is calculated in the Table 44.
Heat of
reaction 
at 298"
Sensible
_{h}_{e}_{a}_{t} _{o}_{f}
react ants
the right hand side
The heat of
reaction _{a}_{t} 1200K
Sensible 

+ 
heat of 
products 

of 
this equation 
Therefore,
It
= 350000 Ycal/ton
coal
is
an
endothermic
calculation.
reaction
in
this
sample
Cost,

fm
Note sensible heat is :
that
the
formula
to
calculate
+A5 * (~5 2985 )/5 where Cp = heat capacity
R = gas constant
!I1, A;,
A3,
A4,
A5 = parameters of
each
canponent are from data bank of
the NASA
program.
Credit,
and Profit

Total credit
is indicated in Table 46. The profit, response value is equal to total credit .minus total cost
for one ton dry
which is $88.03 
Total cost is indicated in Table 45.
$40.19
(= $47.12)
and ash free coal in this sample calculation.
TABLE 41
COMPOSITION OF COL (OHIO CLARION 4A)
Component 
Weight% 
Molecular 
Mole% 
Mole% 
Weight 
set C=l 

C 
70.3 
12 
586 
1 
H 
5.3 
1 

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