Computers and Chemical Engineering Vol. 7, No. 5, pp.

645-661, 1983

0098 1354/83 $3.00+ .00

1983 Pergamon Press Ltd.

Printed in Great Britain.

PROCESS OPTIMIZATION:
A COMPARATIVE CASE STUDY
LORENZ T. BIEGLERt and RICHARD R. HUGHES*
Chemical Engineering Department and Engineering Experiment Station, University of WisconsinMadison, Madison, Wl 53706, U.S.A.
(Received 1 February 1982)

Abstract--Four recently developed algorithms were tested on a realistic propylene chlorination process simulation. All four are based on successive quadratic programming and
interface easily with most sequential modular simulation packages. Using SPAD for simulation, optimal cases were obtained in as few as 29 simulation-time equivalents. The paper
includes model details, reactor kinetics, and algorithm performance.
Scope Our previous papers [1-3] describe four algorithms developed for efficient optimization
of sequential-modular simulation models. Each algorithm was tested extensively on a simple
flash process to determine optimal tuning parameters and to study algorithmic performance.
All four algorithms are" based on the Successive Quadratic Programming (SQP) algorithm
of Powell[4] and use a BFGS update to develop the quadratic matrix. The methods differ in
the strategies used for the three basic steps: function evaluation, gradient evaluation, and
formulation of the quadratic program.
The first algorithm, Quadratic/Linear Approximation Programming (Q/LAP)[1] requires
a converged process flowsheet for each function evaluation. Gradients are calculated by
construction of linear models for each flowsheet module. These are then assembled into a large
sparse linear system which is perturbed in lieu of the actual process model, to obtain the
gradient in decision-variable space. This gradient is the basis for the next quadratic program.
Infeasible Path Optimization of Sequential Modular Simulations (IPOSEQ)[2] converges
and optimizes simultaneously. Function evaluations and gradient evaluations are performed
by simple (non-iterative) passes through the calculation sequence. Tear equations (the
difference between guessed and calculated stream elements) are linearized and included as
equality constraints in the quadratic program. The dimensionality of the gradient and the
quadratic program is increased to include the decision variables and the tear (guessed recycle
stream) variables. Implementation is very simple; for most modular simulators, IPOSEQ
merely requires the substitution of an optimization "block" for the recycle convergence
algorithm.
The last two algorithms[3] are feasible variants of IPOSEQ. The Complete Feasible
Variant (CFV) and Reduced Feasible Variant (RFV) algorithms use the same gradient
calculation strategies as IPOSEQ, but require converged flowsheets for each function
evaluation. CFV, like IPOSEQ, includes tear equations in the quadratic program while RFV
calculates reduced gradients and solves the smaller quadratic program that Q/LAP uses.
Convergence is accelerated because the quadratic programming solution yields good starting
values for the tear variables, either directly (in CFV) or through the reduced gradients (in
RFV).
Here, we present a comparative study of these four algorithms on a realistic problem--the
design of a process for direct chlorination of propylene. The simulator used was again
SPAD [5], as installed on the Univac 1100/82 at the University of Wisconsin. Special modules
were added to handle the reaction kinetics and the HCI scrubber.
Conclusions and significance--The nine-variable model was successfully optimized by each of

the four algorithms. From a starting point design which showed a net value added of
1010.13 $/hr, the following results were obtained:
Algorithm

STE

Optimum ($/hr)

RFV
CFV
IPOSEQ
Q/LAP

28.83
28.74
45.29
61.18

1609.97
1609.92
1609.84
1600.55

*Author to whom correspondence should be addressed.

fPresent address: Carnegie-Mellon University, Pittsburgh, PA 15213, U.S.A.
645

LORENZT. B1EGLERand RICHARDR. HUGHES

646

(STE or Simulation Time Equivalents is the ratio of the CPU time for optimization to that
for simulation.)
Comparison of the optimal points shows that there is an optimal "ridge" along the lower
reaction temperature bound, in the space of the other three variables which influence the
reactor kinetics.
The results suggest that, if numerical perturbation must be used for gradient calculation,
then the feasible variant algorithms, CFV and RFV, are the best SQP methods for
optimization of sequential-modular models.
PROCESS EXAMPLE
The process chosen for this comparative study is the
synthesis of allyl chloride, a valuable intermediate in
the manufacture of epoxy resins and glycerine[6].
The flowsheet adopted (Fig. 1) is an elaboration of
the example described by Hughes[7]. It uses the
reaction scheme and separation sequence from published process descriptions[6,8], with an added
quench loop to reduce carbon deposition in the
reactor effluent transfer line and cooler. The plant
scale is set by using a fresh propylene feed rate of
100 lb-mole/hr. This results in an allyl chloride production of about 34 million lbs/yr at a stream factor
of 95%.
This process, modeled on a sequential modular
simulator, requires the ordering and solution of
thousands of unit operations, physical property, and
mass and energy balance relationships. The optimization of such a system can clearly be termed a
large-scale optimization problem.

A block diagram of the simulation of this process

on SPAD [5] is given in Fig. 2. For the most part, this
uses standard SPAD unit modules, as follows:
CMP--Single-stage polytropic compressor
DIS---Shortcut distillation (Fenske-UnderwoodGilliland)
HCB--Process cooler
HHB--Process heater
MIX--Adiabatic mixer
PMP--Process pump
SPL--Stream splitter (mechanical)
ZWB--Iterative convergence via Wegstein procedure.
Two special modules were developed: UU1 for the
reactor; and UU2 for the scrubber-drier. Details of
these models are given in the following process
description.
In the example process, propylene feed at 60F and

Vent

O-[]

NaOHHz
SO~r I ~" I

Propylene 171o

J__I J ll n"

Water80

Feed

60

PREHEATER

674o
Chlorine
80

COOLERr~O-I~ I=

[]

"

2:30

800 661 ~ , .

l
20~

aq.HCI(32%w)
L

Feed

@..L

~-~

Ally,Chloride
N

/ ~

116

Direct Chlorination of
Propylene
- Decision Variables
~'-~- Constraints
[~o - psia'~ Conditions
F J at RFV
Optimum

~Chlorides_> 99mol %}
es

I10
Fig. 1. Process flowsheet.

Process optimization: a comparative case study

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Fig. 2. Propylene chlorination: SPAD simulation.

200 psia is mixed with a recycle stream which is

mostly unconverted propylene. The combined gaseous feed is then preheated and fed directly into the
reactor with make-up chlorine at 80F. The principal
(and desired) reaction is substitution by chlorine to
produce allyl chloride:

(3). Values for the heats of reaction and the constants

Aj, Bj are given in Table 1. The table also lists values
of the kj's at several reaction temperatures.
The kinetics of this reaction system are seriesparallel:
+ CI2

C12 + CH2~-~CH-CH3 -~ CH2=CHCH2CI + HCI.(1)

Other restrictions that yield less desirable byproducts are the addition of chlorine, to form
1,2-dichloropropane:
C12 -F-CH2--CHCH3 -~ CH2CHC1CH2CI

CH2--CHCH 3

CH2=CHCHI + HCI

kl

k 2 ~ Cl2
CH2CHCICH2CI

ka~X~+ C12
CHCI--CHCH2CI + HCI.

(2)

and further chlorine substitution in allyl chloride, to

yield 1,3-dichloropropene:
C12 + CH2--CHCH2C1 ~ CHC1--CHCH2CI + HC1. (3)
Rate expressions for reactions (1) and (2) are given by
Smith[9]; these were derived from the data of Groll
& Hearne[10]. Further analysis of these data led to
a rate expression for reaction (3). All three reactions
are exothermic and have overall second-order,
Arrhenius-type kinetics, of the form (forj = 1, 2, 3):
rj = kjp?Pa2

(4)

kj = Aj exp[ - Bj/(Tx + 459.69)].

(5)

where

Here, ,p? is the partial pressure of propylene for

reactions (1) and (2) and of allyl chloride for reaction

The desired product, allyl chloride, is an intermediate

in the series reaction. This would normally call for a
plug-flow reactor, to keep the allyl chloride away
from the inlet with its high chlorine concentration.
However, the system is highly exothermic and the
rate constants in Table 1 suggest that high temperatures favor reaction (1) vs reaction (2). This is
confirmed by Smith's analysis[9], based on reactions
(1) and (2) alone; his Figs. 5-8 indicates a much better
product for stirred-tank reactors. Thus, the reactors
actually used promote back-mixing; they are really
flame reactors[11], although the residence times are
longer--about one-tenth of a second. To prevent
excessive loss of allyl chloride via reaction (3), the
process uses a high propylene/chlorine ratio, with
recycle of unconverted gases. A high ratio also reduces the rate of coke build-up on the reactor internals.
Based on these considerations, we model the reactor (in special subroutine UUI), as a gas-phase
continuous stirred tank reactor (CSTR). The design

LORENZ T. BIEGLERand RICHARD R. HUGHES

648

Table 1. Reaction constants for propylene chlorination

Reaction
Stoiehiometric Coefficient%
1.
2.
3.

HC~

4.
5.
6.

C385C~
C3H6C~2
C3H4C 2

Substitution
(j=l)

Addition
(j=2)

Sec'y. Subst.
(if3)

+1
-1
-1
+1

0
-1
-1
0

1
-1
0
-1

+1
0
-I

+1

vij

C2
C3H6

0
0

Heats of Reaction
-AHj (BTU/Ib-mol)

4,800

79,200

91,800

Kinetic Coefficients
f 1b-tool" ]
AJlkr
3_a-Sj j
Bj(*R)

Rate Constants,
~(Ib-mol/~rat

..7

206,000

4 . 6 x 108

13,600

3,430

0.55
4.23

0.46
0.77

18.55

1.12

21,300

ft3-atm 2)

600*F
800*F
IO00*F

0.86
20.95
212.24

Conversion to SI Units:
K =

(*R)/1.8

J/mole = 2.326

variables are the propylene/chlorine ratio in the feed

(q), the reactor temperature (Tx), and the reactor
volume (Vx). (Another possible variable is the reactor
pressure (Px), but, in the present model, this is set
arbitrarily to make the pressure-molal flow product
of the effluent equal that of the combined feed.)
The reactor calculation begins by setting the
combined-feed component flows, F~,--adjusting the
make-up chlorine to match the specified propylene/
chlorine ratio, q = F i / F 3. The effluent flows, Ei, can
then be defined from the stoichiometric coefficients
(v~) (Table 1) and the reaction extents (Xj):
Ei = F i + ~ v ~ ;

i=1,6.

(6)

The reaction extents are obtained from the kinetic

Eqs. (4) and (5) with usual CSTR and ideal-gas
partial pressure assumptions:
X j = Vxrj = V,,kj(Px/14.7)2E~,EJE2r;

j = 1,3 (7)

where
ET = ~ ei = FT-- x~

(8)

(BTU/lb-mol)

and (for the present results)

(9)

Px = P F F r / E T

In the reactor model, the simultaneous solution of

Eqs. (6)-(9) is done by iteration. For this calculation,
Eq. (7) are transformed, with the use of (6), to:
6=_x, -

v),P~(e,

x,

Xg(F:

X, -

X~ -

X~)/E~

(10)
X 2 = (kJkOX ~

(11)

k3X,(e, + X,)
)(3 = k3Xl + k l ( F 3 - X~ -- )(2)"

(12)

Now X~ is adjusted iteratively by the secant method

until 6 < e( ~ 10-4). For each assumed X~, the equation order is (11), (12), (8), (9), (10). After closure,
Eqs. (6) are used to fix the Ei values. Finally, by heat
balance, the necessary feed preheat temperature is
calculated.
The reactor effluent is mixed with a quench stream
and the combined stream further cooled to 50F. The
stream is then fractionated in a 14-plate distillation

Process optimization: a comparative case study

column to separate synthesis gases from the heavier
chlorinated hydrocarbons. The vapor overhead is
scrubbed and dried to remove the HCI, and a fraction
vented to prevent build-up of impurities. The remainder is then recompressed before mixing with the
feeds. The bottoms from the column is split to form
the quench and product streams. The quench is
pumped and cooled to 20F before mixing with the
reactor effluent, and the product is sent to a 14-plate
finishing column to separate allyl chloride from the
heavier dichlorides.
The HCI scrubber is a gas-liquid countercurrent
absorption tower. Water enters the top at 80F and
leaves as boiling 32wt% hydrochloric acid[12]. In
addition to absorbing 99.9% of the HCI, the scrubber
also absorbs the following compounds (if present):
Max % wt, dry basis in
aqueous 32% HCI
Chlorine
Propylene
Allyl chloride
1,2-dichloropropane

0.1
0.1
0.3
0.7

These values were estimated by Hughes[7] from

handbook solubility data. The scrubbed gas is then
dried with caustic or sulfuric acid to remove any
water vaporized in the scrubber.
The special scrubber-drier unit subroutine UU2
calculates a scrubber mass balance based on the
above solubilities. This yields the component flows
for the scrubber outlet gas and the hydrochloric acid,
on a dry basis. Then an energy balance assuming
effluent acid at its boiling point yields an outlet
temperature for the gas. No calculations are made for
the drier; at the low gas temperatures expected, water
vapor carryover is too small for any significant heat
effect.
In this preliminary optimization study, it was
desirable to keep the computation time for simulation
as short as possible. Accordingly, simplified physical
property correlations were used, with vapor-liquid
equilibrium data fitted to Antoine equations. Vapor
pressure data for 1,3-dichloropropene were estimated
by comparing boiling points and vapor pressures of
chlorinated hydrocarbon homologues. Although
these physical property correlations may yield inaccurate flash and enthalpy calculations, the effect of error
is minimized by the choice of design variables-temperatures, pressures and split fractions--and by
the use of an objective function which is affected
mainly by reactor kinetics.

OPTIMIZATION PROBLEM AND PROCESS DESIGN

RESULTS

To optimize a process design, the preferred objective is usually the venture profit or venture worth.
However, for this process, the product and feed
values are high and the plant is fairly simple and
relatively inexpensive. Thus the objective function
can be approximated as the net value added, i.e. the
sales return less the feed costs. This is fortunate, since
SPAD has only limited capabilities for estimating
capital and utility costs.

649

The prices used for raw materials and products are

given in Table 2. The last column (net value added)
is calculated by adjusting for stoichiometric feed
requirements and by-product HC1. With these values
the following objective function was established, and
used in all the calculations.
Max ff ---22.17(AC) + 12.48(DCP) + 10.06(DCP-)
(13)
If the product rates are in lb moles/hr, ~b has units
of S/hr.
(Note that the coefficient of DCP= does not agree
with Table 2. This is a numerical error which was
found after the optimization calculations were completed. It does not really invalidate the comparative
study, so there has been no attempt to repeat the
calculation).
The nine decision variables and three constraints
for the optimization are listed in Table 3. This table
also summarizes the optimization results. Tables 4
and 5 provide additional details for the best design
found--the RFV optimal point. The temperatures
and pressures for this design are also shown in
Fig. 1.
In Table 3, the Q/LAP results are somewhat disappointing, although the best point obtained is a
marked improvement over the starting point. The
best points for the other three methods--IPOSEQ,
CFV, and RFV--are within a range of 13 /hr of each
other. However, the design variable values differ
considerably, especially those for the propylene/
chlorine ratio(r/), the reactor volume (Vx) and the
compressor outlet pressure (Pc) (which directly controls the reactor pressure). The optimum apparently
lies on a "ridge" in variable space; along this ridge,
different values for these three variables result in the
same product yields, and, thus, the same objective
value. This can also be seen by straightforward inspection of the kinetic expessions. The other reactor
variable, the temperature (Tx), seeks its lower bound
of 800F. The present CSTR model finds a better
yield structure at low temperatures, and the cost of
the high recycle required is not recognized in the
objective functions.
This neglect of costs also permits the choice, for the
separation system, of a low column pressure (Ps),
high recovery factors (fLx, fHx) and high recycle
quench (fe)" These all result in slight improvements
in product recovery, even though they mean a
relatively-large, low-temperature, high-reflux column. The allyl chloride content of the recycle, small
as it is, also drives the vent fraction (f~) to its lower
bound. An implied assumption of the objective, Eq.
(13), is that the remaining components in the vent
have a net added value of zero, i.e. are priced the
same as the feed, so the allyl chloride content alone
provides the incentive to reduce the vent. This is not
really an adequate decision criterion for the vent,
which really exists to prevent build-up of undesirable
trace impurities. To handle this properly, the impurities should be included in the feeds, and the
reactor and separation units should allow for this
presence. However, without such improvements, the
only solution is to fix a .reasonable lower bound.
Table 3 lists three problem constraints. The first
tests the need for a recycle compressor. If this con-

LORENZ T. BIEGLER and RICHARD R. HUGHES

650

Table 2. Raw material and product prices

Price at Plant Limit*

Net Value
Added

Compound

As Quoted

$/ib-mol

HC

$ 3 5 / t o n (36 B~ )

0.96

C2

$145/ton

5.15

C3H6

21 / i b

8.84

A l l y l c h l o r i d e (AC)

46 e / l b

Dlchloropropane (DCP) I
Dichloropropene (DCPffi)~

$/ib-mo]
Note**

35.20

22.17

1.35/gal if

126.47

12.48

~ 50% unsaturated

{22.13

4.91

*For C 2 and C.H.

J o' price is cost delivered to plant. For products p price
is net to plant, excluding marketing costs. For dichlorides, marketing
costs have been taken as 50% of quoted market price of $2.70/gai.
**Stolchiometrlc by-product credits added to C3 chloride values.

straint were active, and remained active when the test

value (now 10psi) was lowered to zero, the compressor could be eliminated. However, this is physically unlikely and would probably mean there is an
error elsewhere in the simulation. The second constraint enforces high purity in the chlorinated hydrocarbon product stream. A third constraint is needed
to guard against a simulation problem in the reactor
block. Here we force the reactor inlet temperature to
be no less than 90F; certain combinations of the
reactor design variables may calculate a temperature
that is unrealistically low due to the high heats of
reaction. Constraints (1) and (3) remained inactive
throughout all of the optimization calculations. The
second constraint was active at least sometime during
the optimization on Q/LAP, IPOSEQ and CFV. A
fourth constraint that could have been added would
have assured that the production of dichloropropene
was greater than that of dichloropropane as required
by the product price in Table 2. This was not in the
original model forumlation and was not added because the requirement was satisfied in all of the
optimization calculations.
In retrospect, constraints (1) and (3) were really
unnecessary. More significantly, some of the variables should not have been included in the optimization. The simple objective function of Eq. (13)
does not properly evaluate the effects of the column
variables and the split functions. Thus the process
conclusions with respect to these variables are not
realistic; a large low-pressure, low-temperature separation column is probably not justified. However, as
an optimization study, the present model is quite
valuable. It is apparent that all four of the optimization methods adjusted to nine variables in a
manner consistent with the chosen objective function,
and the process characteristics. In the remainder of
this article, we discuss the relative performance of the
methods on the nine-variable model.

OPTIMIZATION PERFORMANCE

Q /LAP (Quadratic/Linear Mpproximation Programming)

The progress of the Q/LAP optimization is shown in
Fig. 3, and significant base points along the path are
presented in Table 6. An objective function improvement of $590.42/hr was obtained after nine new
base points and 313.2 sec of CPU time. For this calculation, the convergence tolerance was 10 _3 and the
perturbation factor 10 -2. The fifth variable was scaled
to make the corresponding objective function derivative fall between 1 and 10; for the other variables, the
scale factors were adjusted to yield derivatives between 10 and 100[1].
This performance was quite efficient, but the algorithm failed to find a declared optimum. After reaching the last point and resetting the Hessian matrix, a
line search failure terminated the algorithm. The final
point also violated the purity constraint by 0.18~. In
search of better results, several changes of scale and
perturbation sizes were tried, but these were in vain.

IPOSEQ (Infeasible Path)

Here, the convergence block (ZWB in Fig. 2) was
replaced with an optimization block, and both optimization and convergence advanced with each pass
of the calculation loop[2]. The tear variables are
included with the design variables, and tear equations
are present as equality constraints. Because the column and outlet compressor pressure determined the
stream pressures for both loops, the pressure tear
variable was not included in the optimization problem.
Several scale factors were tried for this algorithm.
The most successful run stopped at an optimum of
$1609.84/hr in 231.816CPU seconds and 39 iterations. A perturbation factor of 0.01 was used and the
Kuhn-Tucker error at the optimum was $.012/hr.

Process optimization: a comparative case study

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Process optimization: a comparative case study

653

Table 5. Propylene chlorination---optimal design----equipment summary

Columns

Separator
No. of trays -actual
-theoretical
Reflux ratio (L/D)
Diameter, ft
Max sup. gas tel. -ft/see
At gas density
-ib/ft 3
Pressure, psia
-top
-bott
Temp, F
-top
-bott

Finishing Column

14
i0

14
i0

.037
6.0
2.38
0.21
20
25
-51.7
36.3

.406
2.0
2.81
0.19
14.7
19.7
114.0
109.9

Heater
Rx Freheater

S.C. Reboiler

F.C. Reboiler

19,365
135.1
674.1

2,904
36.3
36.3

1,108
109.9
109.9

Duty, HBTU/hr
Proe. strm-*F -in
-out
Coolers
Quench
Duty, MBTU/hr
Proc. strm-*F -in
-out

126
38
20

Effl. Cooler
32,951
661
50

S . C . Condenser
1,014
-51.7
-72.0

F.C. Condenser
265
114.0
109.2

Rotating ~[aehines

Compressor
Pressure, psfa
Temp, *F

-in
-out
-in
-out

Inlet flow
Inlet density-lb/ft 3
Brake Horsepower

18
88.8
44.2
171. 2
4743 CFM
0.1497
1335

The scale factors were chosen so that the initial

objective function derivatives had absolute values
between 10 and 100.
The IPOSEQ stepwise performance is not really
comparable to the other algorithms; each iteration
requires much less CPU time, and the objective
function does not increase monotonically, since the
convergence requirements also affect the path. Thus,
in Fig. 4, we show both the progress of the objective
function and the reduction of the tear equation
residuals. Table 7 presents design variable and inequality constraint values for iterations with
significant changes. Note, however, that only the last
two sets given in the table represent feasible designs.
Until iteration 24, the residual errors in the equalities
are excessive.

CFV (Converged Feasible Variant)

This algorithm required only 147.118 CPU sec and
20 iterations. It terminated at an optimum of
1609.925/hr with a Kuhn-Tucker error of 3.10 -3
S/hr. Again, the scales were chosen so that the initial
objective function derivatives had absolute values
between 10 and 100. A perturbation factor of 10 -2
with a convergence tolerance of 10- 3 was chosen. The

quench Pump
27
100
36.3
38.2
39.6 GPH
65.49
5.2

progress of this optimization can be seen in Fig. 3.

Design variable movement is shown in Table 8.
As seen in the table, movement for the first six base
points is fairly rapid, and comes close to the optimum. The remaining points are fairly close together
and show very little objective function improvement.
At each iteration, the quadratic programming step is
now searching for a point which more closely satisfies
the tear equations. Since the convergence block has
already satisfied these equations within a certain
tolerance, the work of the optimization algorithm is
in vain. Better termination procedures are needed for
the algorithm.

RFV (Reduced Feasible Variant)

The RFV algorithm required 12 base points and
147.605 CPU sec. The algorithm stopped after a line
search failure at a base point with an objective
function of 1609.97 $/hr and a Kuhn-Tucker error of
$0.82/hr. The perturbation factor and convergence
tolerance were 10 -2 and 10 -3 , respectively and, the
scale factors were chosen so that the initial objective
function derivatives had absolute values between 10
and 100. RFV made very rapid progress for the first
five base points. Later, however, only small steps

654

LORENZ T. BIEGLER and RJCHARD R. HUGHES

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were taken until the algorithm terminated with a line

search failure (Fig. 3). Table 9 lists the changes in
design variables over the course of this optimization.
Compared to CFV, the Reduced Feasible Variant
method seems to take larger steps, but requires more
time per new base point because of more function
evaluations per line search. Also, since tear variables
and their bounds are included in the CFV optimization step, smaller steps are taken per base point.
Though this reduces movement of the algorithm, it
also prevents extrapolation to a region where the
quadratic approximation is invalid. The RFV algorithm, like CFV, also calculates good starting guesses
for tear variables, but care must sometimes be taken
if these can become negative.
COMPARISON AND EVALUATION

Table 10 summarizes the results obtained with the

four algorithms on this problem. The two feasible
variant algorithms had the best performance. Their
CPU times and objective values are almost identical,
although CFV required more base points than RFV.
A simulation at the best point required
5.119 CPU sec. Thus, the feasible variant algorithms,

CFV and RFV, required less than 29 STE's (Simulation Time Equivalents) for a complete optimization. IPOSEQ, the infeasible path algorithm,
required 45.3 STE's because it used more iterations
and gradient calculations.
The performance of the Q/LAP algorithm is somewhat disappointing; it required more CPU time than
the others and terminated prematurely. The excessive
CPU time can be explained by the bookkeeping
required in the modeling and condensation steps and
the large number of flowsheet evaluations per line
search. The latter problem, as well as the line search
failure, are due to errors in the gradients from the
modeling step. Combination of linear approximations for a sequence of highly nonlinear modules
may result in a poor approximation of the combined
result. Also, the error introduced by convergence
calculations makes the choice of an appropriate
perturbation factor difficult.
Consider the initial, unscaled objective function
derivatives compared in Table 11. Here, a perturbation factor of l0 -2 and convergence tolerance
of l0 3 is used to calculate the Q/LAP and RFV
gradients. (By definition, the reduced gradient for

Table 10. Summary of propylene chlorination

Algorithm

Best Point

CPU time (see)

Iterations

Total STE's*

Q/LAP

1600.55

313.200

10

61.18

IPOSEQ

1609.84

231.816

39

45.29

RFV

1609.97

147.605

12

28.83

CFV

1609.92

147.118

20

28.74

it

Based on the simulation time at the best point, - 5.119 sec.

Table 11. Unsealed gradient comparison at the starting point

Unscaled Derivative Values

Variable
1 ~

q/LAP
-27.99

RFV (and reduced CFV)

-27.6

2 T

-0.4323

-0.432

3 V

2.350

2.356

-.06539

-.06395

-.1272

-.08191

P
S

q
V

7 P

-10731.9
-2524.8

-8207.46
0.4737

LK

-1885.69

511.05

fHK

-1944.27

972.47

Process optimization: a comparative case study

CFV is equivalent to the R F V gradients.) Note that
the first six gradient elements compare reasonably
well in sign and magnitude. The last three elements
differ greatly in magnitude and are of opposite signs.
The difference in the derivatives for the component
recoveries (elements 8 and 9) is due to the column
nonlinearities introduced when perturbing a heavy or
light
key
recovery
from
0.98,
say,
to
(1.01)(0.98) = 0.9898. The effect of this perturbation
is less severe on the tear equation responses than on
the output streams of the separator. Thus, the effect
of these design variables is smoothed when using
feasible variant algorithms.
This explanation also applies to element 7, the
derivative of the compressor outlet pressure, but we
should also consider the pressure perturbations in
Q/LAP. In the feasible variant algorithms, the pressure of the tear stream is not perturbed because it is
fixed within the loop by the design variables. With
Q/LAP, pressure must be perturbed in order to define
thermodynamically the inlet and outlet streams for
each module. The pressure relationships within modules are either nonlinear, as in the reactor block, or
of the unit response-no response type. Consider a
simple mixer block where the outlet pressure is the
lowest inlet pressure. Now, if two or more low
pressure streams have pressures close to each other,
perturbing one causes the wrong stream to have the
lower pressure and leads to erroneous model
coefficients and gradients. Because the compressor
pressure also determines the reactor pressure after
passing through a mixer block, the error in the
derivative for this variable is compounded by the
pressure effect on the nonlinear reactor kinetics.
Acknowledgements--The authors express appreciation for
the support of the Paul A. Gorman Fellowship from the
International Paper Company Foundation (for L.T.B.) and
of the Engineering Experiment Station of the University of
Wisconsin-Madison.

Aj
Bj
Ei
Er
Ep

Fi
Fr
fLx
fnK

NOMENCLATURE
premultiplier for rate constant kj; lb-mol/(hr-ft3-atm2)
Arrhenius temperature factor for rate constant, kj, R
flow of component i in reactor effluent, lb-mol/hr
total flow of reactor effluent, lb-mol/hr
flow of reactant in reactor effluent, lb-mol/hr
j = 1,2 - reactant is propylene q
= 3 - reactant is allyl chloride]
flow of component i in combined reactor feed, lbmol/hr
total flow of combined reactor feed, lb-mol/hr
fractional recovery of light key (C12) to sepn. column
tops
fractional recovery of heavy key (AC) in sepn. column
bottoms

fq
f~,
j*
kj
Pc
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Pcl2
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fraction of sepn. column bottoms split to quench

fraction of dry gas split to vent
key component for reaction j
rate constant for reaction j, lb-mol/(hr-ft3-atm2)
compressor outlet pressure, psia
reactor feed pressure, psia
compressor inlet pressure, psia
separation column top pressure, psia
reactor pressure, psia
partial pressure of CI2 in reacting mixture, atm
partial pressure of reactant in mixture, atm
[ j = 1,2- reactant is propylene 1
= 3 - reactant is allyl chlorideJ
reaction rate for reaction j, lb-mol/(hr-ft3)
reactor preheater outlet temperature, F
temperature of reacting mixture, F
reactor volume, ft 3
extent of reaction j, lb-mol/hr
residual error (Eq. (10)), lb-mol/hr
closure test value for 6, lb-mol/hr
propylene/chlorine ratio in combined reactor feed
stoichiometric coefficient for component i in reaction
j (neg. for reactants, pos. for products)
objective function = net value added, $/hr
REFERENCES

1. L. T. Biegler & R. R. Hughes, Approximation programming of chemical processes with Q/LAP. Chem.
Engng Prog. 76-83 (Apr. 1981).
2. L. T. Biegler & R. R. Hughes, Infeasible path optimization with sequential modular simulators. Comput.
Engng (in press).
3. L. T. Biegler & R. R. Hughes, Feasible path optimization with sequential modular simulators." Comput.
Engng (in press).
4. M. J. D. Powell, A fast algorithm for nonlinearly
constrained optimization calculations. Presented at
1977 Dundee Conf. on Numerical Analysis (1977).
5, R. R. Hughes, R. K. Malik & L. T. Biegler, SPAD--simulator for Process Analysis and Design. Engng Expt.
Sta. Rep. No. 52. University of Wisconsin-Madison
(1981).
6. A. V. Hahn, The Petrochemical Industry. McGraw-Hill,
New York (1970).
7. R. R. Hughes, Optimization methods for block simulation. Proc. VI lnteramerican Cong. of Chem. Engng,
Caracas, Venezuela (1975).
8. A. W. Fairbairn, H. A. Cheney, & A. J. Cherniavsky,
Commercial scale manufacture of allyl chloride and
allyl alcohol from propylene. Chem. Engng Prog. 43(b),
280 (June, 1947).
9. J. M. Smith, Chemical Engineering Kinetics, 2nd Edn,
pp. 212-231. McGraw-Hill, New York (1970).
10. H. P. Groll & G. Hearne, Halogenation of hydrocarbons. Ind, Engng Chem. 31(12), 1530 (1939).
11. H. F. Rase, Chemical Reactor Designfor Process Plants.
Vol. I, pp. 464-471. Wiley, New York (1977).
12. C. F. Oldershaw, L. Simenson, T. Brown & F. Radcliffe,
Absorption and purification of hydrogen chloride from
chlorinated hydrocarbons. Chem. Engng Prog. 43(7),
371 (1947).