Conclusions

SUBSCRIPTS

Combined bubble and foam fractionation operates successfully, with good stripping and enriching ratios obtainable.
However. the incremental advantage of the elongated bubble
section is small, a t least for the present system.
Increasing the reflux ratio increases the degree of enrichment. Increasing the rate of gas flow improves the degree of
stripping but decreases the degree of enrichment. Location of
the feed inlet can be important under certain circumstances.

Nomenclature

C = solute concentration in liquid and collapsed foam

streams, molarity
D = tops flow rate, ml.,min.
F = feed flow rate. ml.,mn.
G = gas flow rate. ml./min.
h = height above gas bubbler, cm.
Q = collapsed (air free) overhead flow rate, ml.,min.
R = reflux ratio
T I * = bottoms flow rate, ml., min.

=
=
=

tops
feed
bottoms

literature Cited

(1) Bikerman, J. J., Foam, p. 2, Reinhold, N e w York, 1953.

(2) Brunner, C. A , , Lemlich, R.. Ind. Eng. Chem. Fundammtals
2, 297 (1963).
(3) Lemlich, R., Lavi, E., Science 134, No. 3473, 191 (1961).
(4) Leonard, R . .4.,
Lemlich. R., A.1.Ch.E. J . : in press.
(5) Rubin, E. E., Gaden, E. L.? Jr., New Chemical Engineering
Separation Techniques, H. M. Schoen, ed., Chap. 5, Foam
Separation, p. 319, Interscience, New York, 1962.
RECEIVED
for review September 20, 1963
ACCEPTED
July 20, 1964
b-ork supported by U. S. Public Health Service Research Grant
WP-16 1.

PROCESS OPTIMIZATION BY
NONLINEAR PROGRAMMING
C A R L O S W .

D I

B E L L A A N D W I L L I A M

F. S T E V E N S

.Yorthroestern CniLerszty, Euanston, Ill.

A recently proposed nonlinear programming technique i s used to optimize a continuous chemical process.
The problem i s to extremize a nonlinear criterion function, F(x,), subject to nonlinear constraints, G,(x,) = 0,
1 5 j 2 n; 1 5 i 5 rn
n. The method consists of finding a feasible solution, and then applying the
linear programming algorithm to the linearized mathematical model around successive feasible solutions
until an optimum i s reached. The example solved i s of sufficient complexity to demonstrate the value of
this method for chemical process optimization.

<

HE first step in the design of a chemical plant is the steadyTstate

optimization of the system. Optimization means
the process of finding the optimum-i.e.,
the best set of
variables a t Lvhich to run the plant. everything considered.
Optimization is not a new concept, since chemical engineers
have been trying to find the best design values since the first
plant \vas built. However, the classical technique has been
little more than calculating a few trial-and-error solutions and
choosing the best one. Pilot plants have been used not only
to gather data but also to find the best operating conditions.
Because of the relatively large time required to reach steady
state. it is hardly possible to explore completely a system of
even a fe\v variables. Simulation by analog computer reduces
the time required to reach steady state. But if a system consisting of five independent variables \Yere to be explored over
tenth range intervals: 105 separate runs would be required.
Considering 4 minutes a run to reach steady state, record data,
and reset pots. this \vorks out to nearly 4 man-years of experirner.tation. incluaing analysis of d a t a !
The above techniques are known as simultaneous search
techniques: -411 of the experiments are run in a batch; then
the data are collected and examined. A more efficient procedure would be a sequential or adaptive search. This implies that the results obtained from all previous experiments are
used to plan the subsequent ones.

16

l&EC PROCESS DESIGN A N D DEVELOPMENT

The impetus for the development of sequential search techniques in chemical engineering design is largely due to the increased availability and reliabilit). of knowledge concerning
physical and chemical phenomena. Growing familiarity with
the capabilities of digital computers has increased their use for
optimization calculations. Reliable chemical and physical
data permit the construction of mathematical models which are
sufficiently trustworthy in many cases. High-speed computers
enable sequential search iterations to be carried out in seconds.
Although both the mathematical model and the computer routine are formidable tasks. they must be knit together by suitable optimization techniques. Fortunately, such techniques
are becoming increasingly available. having been developed
mainly by mathematicians working in the areas of operations research and management science.
Optimization is onl>-one step in the process of arriving a t an
engineering decision. If the optimization is to be done
analytically. a t least two preliminary steps are necessary.
First: the engineer must develop a mathematical model of his
system. incorporating all that is known about the process into
the resulting expressions. Second: he must select a measure of
effectiveness, Lvhich is to be minimized or maximized by means
of the optimization procedure. Both steps require an intimate knokvledge of the system under study and its relation to
the rest of the company or the economy as a whole.

Mathematical

G,(xl",. . . .x,")

Let

We shall assume that the problem is completely deterministic

a n d , therefore, is amenable to analytical solution. Mathematically. the nonlinear optimization problem for a complex
chemical plant design may be represented in the following
form.
Maximize

aF

X?)

. . . .x,)

(1)

Subject to

Gr

(XI,

Lj

x2,

....x n )

xj

0
j

5; C;

1, 2, . . . .rn

w,

(11)

(X,

X,")

AYj

(12)

Now Equations 5, 6, and 7 may be rewritten as folloi+s

Maximize
n

(2)

1, 2, . . . .n

. . . bl")

(9)

ax5

and
F(X1,

(XI",.

L'l, a constant

F - F" =

(3)

W3Axj
1-1

Subject to

and
.x3

2 0

(4)

where F ( x , ) is the objective function (also known as the

criterion function or cost function) to be extremized
and is generally nonlinear.
G,(x,) are the constraints and are also generally non2 , for
linear. T h e equality sign could also be
some or all of the m relations; usually m < n in the
case of equality constraints.
L , and C, are the lower and upper limits, respectively,
on the variable x i . These limits arise from the
physical limitations of equipment and materials.

and

s>

Discontinuities that may arise in any physical situation may

be handled by smoothing over or by penalty functions. They
are not considered in this report. Convergence of the optimization procedure to a global optimum is assured only under
the very restrictive qualifications that all constraints are convex
and the objective function is concave. If these conditions are
satisfied. it is impossiblt to end u p in any place where the objective function cannot be improved by moving in a feasible
direction (except a t the (optimum). In practice, few real problems meet these conditions. Most real systems are well behaved. however. a n d can be solved by multiple starting points
and engineering judgment.

Now let A*x, = .Ix, when AX, 2 0, and A - x j = -Atl \rhen

AX] 5 0. Although this step essentially doubles the number of
variables to be considered, it is necessary because the linear
programming algorithm will handle only variables Ivhich are
greater than or equal to !zero. Substituting in Equations 13
a n d 14 the problem becomes
Maximize

Subject to :
n
]

=1

Now restrictions of the following form may be added.

Nonlinear Programminsg Method

Griffith and Stewart ( 7 ) have presented the following technique for solving the nonlinear programming problem as given
in Equations 1, 2. 3. a n d 4 by using a linear programming
technique sequentially. T h e problem is first linearized in the
region about some initial approximation of x j by expansion as a
Taylor's series. ignoring terms of higher order than linear.
T h e linearized problem then becomes
Maximize

= F(Xl0... . . . X n " )

a n d M , is the maximum distance x j is allowed to move before

reapproximating the problem. If any variable Y ] is close to its
upper limit LT3, then (C; - xj0) will be approximately zero
a n d A+x, will be small. T h e same reasoning holds for Y . Y ~
when ( x j o - L j ) is close to zero.
Equations 16, 17, 18, 19. a n d 20 now define a system which
can be solved by linear programming. After going through the
AT2, linear programming routine. x j 3 is changed to . x I o
4-xj a n d the routine is repeated until no further_
change
in x j is
.
indicated. This is the optimum.

Subject to

G , (.xl0,. . . ..no)

Chemical Process Example

i
L,
and

x,

5 u,

l,..m

j=l,..n

(7)

T h e design problem optimized in this report was first proposed by Williams and O t t o ( 3 ) . T h e Williams plant contains
many of the characteristics of a typical chemical design problem
a n d is realistic enough so that a steady-state optimization has
meaning.
VOL. 4

NO. 1

JANUARY

1965

17

T,

MCHANGER

REACTOR

Fp,*

DISTILLATION

HEAT

g-

CSTR

cooling
water

&

DECANTER
COLI"

Lc

I
I

I
Icwiing

Figure 1 shows a simplified block diagram of the process.

T h e plant is to manufacture 40 million pounds of chemical P
per year. T h e plant consists of a perfectly stirred reactor, a
heat exchanger, a decanter, and a distillation column in series.
There is recycle from the column reboiler to the reactor.
T h e chemical reaction kinetics are complex. There are
three second-order irreversible reactions.
1. A
2. C
3. P

+B
+B
+C

-+
-+

C reaction coefficient, k l
P
E reaction coefficient, k?
G reaction coefficient, ka

Reactants A and B are fed separately to the reactor in pure

form. Components C a n d E are intermediates and/or byproducts. They have no sales value but may be disposed of as
plant fuel. By-product G is a heavy oil which must be disposed of as a waste material. T h e reaction coefficients may
be expressed in the Arrhenius form:

kt
where

F,,

- 0.1 FRE -

Fp = 0

3.

Material balance on component E

4.

Material balance on component P

5.

Material balance on component -4

= AIexp(--B,,'T)

X 109/hr., wt. fraction

12,000O Rankine (based on A or B)
2.5962 X 10I2/hr., wt. fraction
15,000 Rankine (based on B)
9.6283 X lOl5,'hr.) wt. fraction
20.000' Rankine (based on C)
Z' = temperature (variable), O Rankine

A1

Gn

= 5.9755

F.4

B1 =
A? =
B2 =
AS =
BS =

6.

In addition the rate of reaction is negligible below 120' F.,

and undesirable decomposition occurs above 220' F., SO that
the reactor temperature is constrained.
580 _< T

680

Rankine

0 (26)

(27)

(28)

Material balance on component B

F , L
FR - F p - F ,
~

7.

+ F,

Material balance on component C

(21)

Steady-State Balances

T h e following constraint equations are derived by making

independent material balances across the system, by a constraint on separation efficiency in the distillation column, and
by the definition of FR.

8.

Material balance on component G

(29)

1, Over-all material balance

G1

FA

+ FB -

FO

- Fp

- F,

(22)

2. Constraint on the separation efficiency of the distillation

column (azeotrope formation)
18

l&EC PROCESS DESIGN A N D DEVELOPMENT

F,

0
(30)

T h e objective function is expressed as per cent return on investment.

% return

Table I. Initial Approximation, Improved Approximation,

and Optimal Solution

F = 100 18400(0.30Fp 0.0068FD 0.02FA - 0.03Fb - 0.01FG) - 2.22FR (0.124)(8400)(0,30Fp f 0.0068FD) - 60 V p ] t

=

600 V p

Variable

(31)

Thus. the mathematical model of the \Cilliams plant agrees

with the nonlinear optimization problem description of Equations l : 2 > 3, and 4. T h e number of variables, n: is 1 2 : FA!
FB2F , ? FG, FRAI
F R B , FRcl FR,,
F R p . F R s V : and 7.
The
number of equality constraints, rn: is 9. T h e reader interested
in the complete development of the objective function is referred to \Villiams original paper.

FA
FB
FD
Fc
FRA
FRB
FRC
FRE
V

FR
FRP
T

7;return

Initial
Guess
10.000
40,000
20.000
5,000
6,000
35,000
10.000
15.000
150
100.000
6,000
61 0
3 x 109

Improzed
Initial Guess

Optimal
Solution

11,540
31 -230
36.010

13.546
31,523
36 6g7
3,609
18,187
60.915
3,331
60.542
60
157,391
10,817
656
100
72 75

2.010

8.820
39.910
2.360
31.660
223
92.640
7 890
610
1 2 x 104
=18

Units
Lb./hr
Lb./hr.
Lb./hr.
Lb./hr.
Lb. /hr.
Lb. /hr.
Lb /hr.
Lb./hr,

cu. ft.

Lb./hr.
Lb./hr.
O Rankine
c
/C

Method of Solution

T h e Williams plant problem is optimized by applying a

modified steepest descent technique to the constraints, and then
using a linear programming technique to improve the value of
the objective function. First a n .arbitrary set of values is
picked for the variables.. Then the steepest descent routine is
applied in order to bring the variables .close to satisfying the
set of constraint equations. T h e objective function and the
constraints are linearized next, a n d the objective function is
improved in a small region about the set of variables by the
method of linear programming. T h e variables are changed
and the entire process is repeated.
In the steepest descent routine, we are concerned only with
improving the initial guess. ( x 1 O > . , .xl2)> to the equality constraint sct: G,(.ul,.. x , ? ) i= 1 . . . .9>and the objective function is
ignored for the time being. T h e steepest descent method may
be formulated mathematicallv as a problem of minimizing the
sum of the squares of the residual errors-i.e.,
Given
G,

G,
Find a set of

Y]

(XI

. . . . XI?)

1, . . . .9

(32)

such that
9

Gt2 =

:=

(33)

,=l

Obviously. if a set of x I can be found to satisfy Equation 33,

this set \\ill also satisfv the constraint equations. Now the
slope of S is determined in respect to each variable. T h e n
each variable is given a small increment proportional to a n d
opposite to its slope. T h e slopes are evaluated as follows.

T h e steepest descent technique is generally considered to be

one of the better methods available for solving simultaneous
algebraic equations ( 2 )
Actually, in the problem a t hand, it is not necessary to use
the steepest descent technique. Sound engineering judgment
\+auld give a n initial guess which is close enough to satisfying
the constraints so that ihe linearizing a n d linear programming
methods could be applied directly.
A Fortran I1 program was written for a n I B M 709 computer.
T h e program applied the methods of steepest descent a n d
linear programming to Equations 21 through 31 which define
the \Villiams system. The initial guess chosen for a starting
point is given in Table I T h e value of S i s very high, which indicates a poor initial g,uess. T h e poor guess was chosen to
show the convergence of the method T h e steepest descent

program was used to decrease S to approximately lo4, a t which

point the linear programming program was applied. It was
found that a set of variables which yielded a value of S of this
order of magnitude differed from a true solution by no more
than + l % .
In view of the poor precision of most measuring
devices below this figure, it was decided that the linear programming program could be applied to a solution set with
this error. T h e improved initial guess also i s given in Table I.
T h e value of the reactor temperature, T,was he13 constant
Lvhile applying the steepest descent method because of the
relatively narrow limits imposed on T.
It was found that S could be held to lo3 or less by the proper
choice of the negative costs associated with the artificial
variables added to the linear programming tableau, and by
choosing rather small values of M , [Equation 181. This increases the amount of computer time required but has the advantage that every linear programming solution has meaning.
T h e final per cent return was found t o be 72.757,. T h e
complete solution is given in Table I. There were strong indications that the objective function could be improved further. T h e amount of improvement of the objective function with each iteration was decreasing, however, and any increases in the objective function would be a t the expense of
progressively larger amounts of computer time. Furthermore,
the solution was tending toward an area where the very high
throughput in the reactor could cause pumping costs to be
higher than estimated and could make temperature control
difficult.
There are 12 variables in the problem. But for the linear
programming routine this number must be doubled to prevent
dealing with negative variables. There are nine artificial
variables contributed from the nine equality constraints,
and there are 12 slack variables from the upper- a n d lowerbound inequality constraints. Thus there are 45 variables and
21 equations in the linearized linear programming matrix.
T h e Simplex method was used to solve the linear programming
problem and required about 11 seconds per pass, exclusive of
write-out and compiling time. Approximately 600 passes
through the linear programming routine were made between
the improved initial guess and the optimal solution. Much
time was used in exploring the computational intricacies of
the method. Any efficiently programmed routine would
locate the optimum in a small fraction of the time actually
used.
Conclusions

T h e optimization technique studied was found to be a rapid

method for finding a n improved solution vector. T h e method
VOL. 4

NO. 1

JANUARY

1965

19

produced intermediate nonoptimal solution vectors a n d corresponding values of the objective function. I t would be of
great value in both the design and operation of a chemical
plant. In design, variations in uncontrollable parameters
such as raw material costs, product price, etc., could be considered a n d a design with complete flexibility produced. When
the plant is actually operating and a change in one or more of
the parameters is encountered, it is necessary to change only
those values in the program and then reoptimize.
T h e method presented is simply another variation on the
many organized sequential search techniques proposed recently. As such, it is susceptible to the same shortcomings of
other methods-namely,
more than one extremum, concave
constraint space, convex objective function, etc. Fortunately, in most real systems, these problems are nonexistent or can be handled easily by multiple starting points.
T h e advantages of the method lie in the speed of solution, the
relative ease of programming, and, most importantly, its ability
to handle nonlinear equality constraints. Although many
nonlinear programming methods have been proposed in recent years. very little investigation has been made of their
relatiLe computational efficiency or practical worth. T h e
present paper is a step in the desired direction, presenting a
new combination of two known methods and indicating the
practical use of the combined method.
Nomenclature

A,

= Arrhenius reaction rate pre-exponential factor for ith

B,

= Arrhenius reaction

FA

reaction
rate exponential factor for ith
reaction
flow rate of reactant A to reactor, Ib./hr.

flow rate of reactant B to reactor? Ib./hr.

flow rate of portion of column bottoms sent to plant
fuel?Ib./hr.
flow rate of G from decanter (to waste), lb.,'hr.
flow rate of product P from column, 40 million 1b.j
year = 4763 lb.;hr.
flow rate of A from reactor, lb.,'hr,
flow rate of B from reactor, lb.,'hr.
flow rate of C from reactor, lb., hr.
flow rate of E from reactor, lb.;hr.
total flow rate from reactor, lb./hr.
flow rate of P from reactor. lb.;hr.
reaction coefficient of ith reaction
lower limit on j t h variable
maximum distance t i is allowed to change in each
linear programming iteration
molecular weight of B: 100
molecular weight of C: 200
molecular weight of G. 300
molecular weight of E , 200
error criterion; sum of squared residuals
reactor temperature, O Rankine
upper limit on j t h variable
reactor volume, cu. ft.
density of reactor solution, 50 lb.,'cu. ft:

literature Cited

(1) Griffith, R. E., Stewart, R. A , , .Mana,Tement Sci'.7 , 379-92

(July 1961).
(2). Naphthali, L. M., "Iteration Methods for Non-linear Equations," Preprint 145, A.1.Ch.E. AMeeting,Chicago, December
1962.
(3) LYilliams, T. J.! Otto, R. E., A.I.E.E. Trans. 7 9 (Communications and Electronics), 458-73 (November 1960).

RECEIVED
for review Xovember 26, 1963
ACCEPTED
February 3, 1964

F U N D A M E N T A L S T U D I E S ON A N O D I C
PROTECT ION
Carbon Steel in Sulfuric Acid
Z

F0 R 0 U L I S

General Engineertng Diviszon, Esso Research and Engineering Co., 'Madison. .V. J .

The anodic polarization behavior of carbon steel in sulfuric acid was investigated b y potentiostatic techniques in acid concentrations from 0.5 to 96.4% H2S04 and in the temperature range - 1 .O" to 88" C. An
increase in acid concentration up to approximately 50 to 60% leads to a displacement of the polarization
curve toward more cathodic potentials and higher currents. A further increase up to 96.4% HzS04 displaces
the polarization curve toward more cathodic potentials and lower currents. An increase in temperature displaces the polarization curve toward higher currents, and decreases the passive potential range. Particular emphasis was placed on interpretation from an engineering viewpoint of the anodic polarization
parameters such as critical current, passive current, etc., as affected b y changing acid concentration and temperature.

anodic passivation of metals and alloys, although known

T f o r many years, has only recently been applied commercially to solve certain corrosion a n d contamination problems
(6, 8. 72).
This report presents the results of a program initiated to
evaluate the feasibility of using anodic protection with a
commercial carbon steel in various sulfuric acid concentrations.
T h e results of a previous laboratory program on anodic passivation of Alloy 20 in H2SOawere presented in another report
(3).
HE

20

l&EC PROCESS DESIGN A N D DEVELOPMENT

Experimental

T h e experimental technique used has been described (<?).

T h e material used to prepare the test electrodes was a commercially available carbon steel (1020).
Results and Discussion

TVhen the potential of the anode with respect to the reference

electrode is plotted against the current flowing between the
cathode and anode using the potentiostat, a polarization curve