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Polymer-Plastics Technology and Engineering


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Simulation and Optimization of an Industrial Nylon 6 Reactor: A Review


Aatmeeyata & Santosh K. Gupta
a a a

Department of Chemical Engineering, Indian Institute of Technology, Kanpur, 208 016, India Version of record first published: 22 Aug 2006

To cite this article: Aatmeeyata & Santosh K. Gupta (1998): Simulation and Optimization of an Industrial Nylon 6 Reactor: A Review, Polymer-Plastics Technology and Engineering, 37:2, 201-239 To link to this article: http://dx.doi.org/10.1080/03602559808006921

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P0LYM.-PLAST. TECHNOL. ENG., 37(2), 201-239 (1998)

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SIMULATION AND OPTIMIZATION OF AN INDUSTRIAL NYLON 6 REACTOR: A REVIEW


AATMEEYATA and SANTOSH K. GUPTAT

Department of Chemical Engineering Indian Institute of Technology Kanpur, 208 016, India

Abstract
An industrial semibatch Nylon 6 reactor has been modeled and then optimized. The model developed accounts for most of the important physicochemical phenomena present, like heat transfer, vaporization, polymerization, and so forth. Five parameters are present in the model, which are tuned using data from the industrial reactor under one set of operating conditions, producing one grade of the polymer (using initial water concentration, [W],,, of 3.45 wt%). The tuned model is found to predict the behavior of the reactor for two other operating giving confidence in the model. conditions ([W], = 2.52% and 4.43%), The optimization involves the minimization of two objective functions, namely the reaction time, tf, and the concentration of the undesirable cyclic dimer in the product, [Cz], The final monomer conversion, convt. and the degree of polymerization of the final product, k n l . are constrained to lie at values currently obtained for the three different cases. The (constant valzre of the) jacket fluid temperature, T,, is one of the control variables, whose optimal value is to be ascertained. The pressure history, p ( t ) ,in the reactor, which can be manipulated through the vapor release rate, VAT),is the other optimizing variable. Initially, the shape

* Mahila Mahavidyalaya, BHU, Varanasi, 22 1005, India.


t To whom correspondence should be sent.

201
Copyright 0 1998 by Marcel Dekker. Inc

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of the pressure history is selected to be similar to that used currently, and p ( t ) is described in terms of four constants, pmax, S, and tf (tf is t,., Optimal values decided by the attainment of the desired value of pnf). ofp,,,, t,., S, and T, are obtained using the sequential quadratic programming (SQP) method to give the Pareto set (set of equally optimal or noninferior points). An adapted Nondominated Sorting Genetic Algorithm (NSGA) is then used with the optimal results from the SQP study to obtain improved multiobjective Pareto optimal solutions for the three grades of Nylon 6 , using the continuous variable, V d t ) ,and the value 7', as the optimizing variables. The solutions obtained are better than those obtained using the SQP technique with the shape of p ( r ) fixed a priori. A decision-maker can select the best operating condition from among these equivalent optimal points on the Pareto set, based on considerations which are usually nonquantifiable. The methodology used here can be used for studying other industrial reactors as well. Good mathematical models accounting for all the physicochemical aspects operative in a reactor (and which have been preferably tested on industrial data) are a prerequisite for such optimization studies.

INTRODUCTION
The field of polymer reaction engineering has matured considerably since Flory ( 1) first postulated the equal-reactivity hypothesis (now associated with his name) in 1936, based on the early experiments of Haywood (2), Bhide and Sudborough (3), and other workers ( ) Several experimental studies 4. followed this work and the rate constants of the main reactions were evaluated for important polymerizations using data obtained in small glass ampoules under isothermal conditions. In the late sixties, the emphasis shifted and the rate constants of important side reactions were evaluated using newly developed analytical techniques like high-performance liquid chomatography gas chromatography, spectroscopy (ultraviolet, nuclear magnetic resonance, infrared), and so forth (5,6). In addition, several chemical engineers entered the field and started to study complex polymerizations [e.g., polypropylene (7,8), polyphenylene oxide (9), polyimides (lO,ll), and so on], as well as reported work on various aspects of heat and mass transfer. Studies on the optimization of ideal reactors started to appear in the open literature to obtain interesting qualitative justifications of existing industrial reactors. For example, it was found that one should use high concentrations of water initially in the polymerization of E-caprolactam, followed by removal of water to very low levels, in order to minimize the reactiodresidence times for Nylon 6 polymerization (1 2,13) while producing polymers of number-average chain

SIMULATION AND OPTIMIZATION OF NYLON 6 REACTOR

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lengths, P,~, around 150. Only in the late eighties and early nineties were of studies reported in the open literature on the simulation and optimization of industrial polymerization reactors with plant data appearing in slightly disguised forms. These include the work of Hamielec and co-workers (14) and Kiparissides et al. (15) on low-density polyethylene (LDPE) reactors, as well as our own work (16,17) on Nylon 6 systems. This paved the way for several industrially relevant and useful studies [e.g., development of commercially available software packages for the design of polymerization reactors such as POLYRED (18), optimal control of polymerization systems (19), simulation and optimization of industrial reactors (16,17,20), and so forth]. It is this last topic which is the focus of this article. We first review our work on the modeling and simulation of an industrial semibatch Nylon 6 reactor in India, and then discuss its optimization. The latter leads to better operating conditions for this reactor. Some improvements have, indeed, been achieved in the concerned industry on the basis of our studies.

MODELING AND SIMULATION


The semibatch reactor (16,17,21) which has been modeled and optimized in the present study is shown schematically in Fig. 1. The reactor is a jacketed

Condensing

vapor at Tj

Condenso

Stirrer

FIG. 1. Schematic representation of the industrial semibatch Nylon 6 reactor.

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vessel equipped with a low-speed anchor or ribbon agitator for mixing the reaction mass. A liquid mixture of caprolactam, C1,and water, W (along with other inert additives like Ti02, etc.), is heated by condensing vapors at a in constant temperature, Ti, the jacket. Polymerization takes place in the liquid reaction mass as its temperature, T , goes above 220C, and some water and caprolactam vaporize. The pressure, p , above the liquid reaction mixture is manipulated by a control valve which releases the vapor mixture of nitrogen (inert), monomer, and water to a condenser at a prescribed rate of V , (moVh). This helps maintain a desired pressure history, p ( t ) , in the reactor. The pressure history, p ( t ) ,used presently [all present or current values are termed as reference (ref)] is shown schematically in Fig. 2 (curve marked "ref"). The following dimensionless variables are being used in this study:

FIG. 2. Schematic pressure histories for the semibatch reactor. Curve (ref): current industrial practice; (opt): pressure history for optimization (SQP) purposes.

SIMULATION AND OPTIMIZATION OF NYLON 6 REACTOR

205

n=

P - Po
Pmax,ref -

PO

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T G -

$,ref

where PO, the initial pressure, is 1 atm. pmax.ref maximum pressure used is the currently, and +,ref is the reaction time used currently. Their values are not being provided for proprietary reasons. The operation of the reactor at present can be described in terms of five stages or zones (see Fig. 2, curve ref). In the first stage, the reaction mass is heated gradually to about 250-270C. During this time, the control valve is kept closed ( VT = 0) and the pressure is allowed to build up to a desired, maximum value, pmax,ref. stage 2, the valve opens and releases vapor at In such a rate that the pressure remains constant at pmax,ref a short period of for time, t, ,ref. In the third, fourth, and fifth zones, the control valve is operated such that the pressure drops linearly (at different rates), finally reaching a value slightly above atmospheric, to prevent leakage into the reactor at the end of the fifth stage. By this time, the polymerization is complete, and the contents of the reactor are emptied for further processing (cooling to below the melting point of Nylon 6, hot water extraction, pelletizing, etc.). The and values of rc.ref, kref, the slopes of the p versus t curves in zones 3 , 4 , and 5 could differ for the three sets of operating conditions (corresponding to three initial water concentrations, [W],, of 2.52%, 3.45%, and 4.43% by weight) used at present to produce three different grades of polymer. The control variables, u, are thus observed to be [W],,, TI, andp(r) [or V d t ) ] . A detailed mathematical model is developed first, with afew model parameters tuned using one set of industrial data (for [W], = 3.45%) to get the best-fit values of these parameters. The model of the semibatch Nylon 6 reactor accounts for the following features: heat transfer from the jacket fluid to the reaction mass, vaporization of water and ecaprolactam from the reaction mass, build up of pressure and maintenance of a prescribed pressure history above the liquid reaction mass in the reactor, change in the viscosity of the reaction mixture during polymerization and its effect on the heat and mass transfer rates, and the various reactions leading to the formation of the polymer and side products. The reaction scheme, shown in Table 1 (13,22-24), is comprised of three major reactions (Reactions 1, 2, and 3) and two important side reactions (Reactions 4 and 5). The reactions are known to be autocatalytic and reversible. The rate and equilibrium constants for the reactions of Table 1 are given

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TABLE 1 Kinetic Scheme for Nylon 6 Polymerization


____ ~______

1. Ring opening

c , + w +s,
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2. Polycondensation

ki

k{ = k I I K I

s, + sm3. Polyaddition

h
k$=k2lK2

s,,, + w
k3

s, + C , + s.+
kj= kVK3

4. Ring opening of cyclic dimer

c, + W+S,
5. Polyaddition of cyclic dimer

k4

k; = k4jK4

s. +c2F=====+S"+
k; =k s / K s

ks

0
C,: H-N+CH,),-C

II

(monomer: e-caprolactam)

O H C,: H-N<CH2),-[C-N<CH2)51,_
I

II I

I1
1-C
I

(cyclic oligomer)

S,: H-[-N<CH,),C-],-OH

I/

(polymer: nylon 6 )

W: H,O

in Table 2. These are based on results from a series of experiments carried out by Tai and co-workers (5,13,25-29) using a nonlinear regression analysis. The model (17,30-34) is described by a set of 15 state variables, x ( = [ x , , x2, . . . , xI5lT). Equations for these can be written easily using mass and energy balances and by obtaining moments of the polymer chain-length distribution; they can be written in the following general form:
dx,
-

dt

=fi(x,u), i

1 , 2, . . . , 15

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TABLE 2 Rate and Equilibrium Constants"

k , = kp +k:[-COOH] = A : exp( - Er, RT) 4; t ~ p - E:, RT)[-COOH] = kp + k : + (


"=I

1 ([SJ)
U -

K,=exp[(AS,-AM,
,=I,?.

TI K].

.5

E P
A; (kg2 m o l - ' h - ' )
I)

AS,
(J mol-'

A: (kg mol- I h -

I)

(J rnol - I )

E; (J rnol

AH; (J mol-I)

K-')
-3.2991 x 10'
lo3 lo'

1
10'

10'

lo4
lo4
lo5

z <
- 3.9496x 10' 2.9068 x loo

lo4
10''

10' 10'" 10"'

5
Q)

2 3 4
10'

5.9874 x lo5 1.8942 x 2.8558 x lo9 8.5778 x 10' ' 2.5701 x lo* 4.3075 x 1.21 14 x 1.6377 x 2.3307 x 3.01 10 x 7.8703 x 8.6504 x 8.4148 x 1.5652 x 8.5374 x

8.3198 x 9.7389 x 9.5606 x 1.7577 x 8.9141 x

104 lo'

lo4

lo4

8.0268 x -2.4883 x - 1.6923 x -4.0176 x - 1.3263 x

lo4 L O ' lo4

-6.0166 x 10'

2.4384~ loo

n 2

Data from Refs. 13 and 24.

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where x and u are the vectors of the state and the control variables. The exact equations are given in Ref. 17. The ODE-IVPs (ordinary differential equations-initial value problems) in Eq. (2) along with the associated algebraic equations for the properties, and parameters, can be integrated using the D02EJF subroutine of the NAG library for any given u ( t ) and initial conditions. This subroutine uses Gears technique for integrating sets of stiff ODE (35). The rates of vaporization of monomer and water (R,.,,,,R,.,,,) are described using the activity coefficients, y. of the monomer ( m )and water (w). These have been related to the monomer , conversion, x (or conv), using

where (see Nomenclature section for definitions)

Also, the inside-film heat transfer coefficient, h , , is written as

h, (kJ/h m2 K)

href

[q (Pa.s)lo.

Values of the five (constant) parameters, p ( = [ P m o , Pmf, P d , Pwf, href])? have been obtained by curve-fitting one set ([W], = 3.45%) of industrial data (entire temperature history, pressure history in zone 1 of Fig. 2 and the final value of k,,) under reference conditions using the Box (36) complex technique. The optinial parameter values are given in Table 3 (case a). Figures 3 and 4 (curve a) show the model results (17) for the dimensionless temperature and pressure [defined in Eq. (l)] as a function of the dimensionless time, T,for the reference conditions. Fairly good agreement between industrial data and simulation results is observed, both for the entire temperature history as well as for the pressure history in zone 1. The computed values of p , at T , = 1 (t = is 151.76, which agrees well with the industrial value of 152.5 for the product. It is seen, however, that the predicted temperatures in zones 3-5 are consistently higher (a similar disagreement is observed for the other two values of [W], also).

SIMULATION AND OPTIMIZATION OF NYLON 6 REACTOR TABLE 3 Parameter Values Used for Generating Results Shown in Figs. 3-8

209

Values of parameters for Parameter


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ES a AH3
PI
a
Pmo
Pmf

Case a
8.4148 X lo4 -1.6923 X lo4 1.32789 0.156224 1.33774 0.163764 109.9952

Case b
7.5733 x 104 -1.5231 X lo4 1.3791 0.2 1.6331 0.184 107.7931

Units J/mol J/mol


-

PZ P,
P4

Pmo

=Pa
= href

As in Table 4

P5

These values are not obtained by the Box complex method. Source: Ref. 17.

Next, we explored whether we could improve the agreement between the predicted values of I(?) in zones 3-5 and the industrial points, without worsI7 ening the agreement in r ( ) (zone 1) and in IJ., ( T = 1). This could be acheved only by changing some of the other parameters (than p in Table 3) used in our model (17). These correlations and parameters had been compiled from the literature and were used to generate Figs. 3 and 4 (case a), even though some disagreements and questions on their applicability to Nylon 6 systems have been reported. For example, Tai et al. (25) have reported variations of the parameters in Table 2 characterizing the rate and equilibrium constants as the initial water concentration is changed. Similarly, the parameters used to estimate the mass transfer coefficients have been developed on systems having far lower viscosities than encountered in Nylon 6 reactors. A parametric sensitivity study was camed out by varying several parameters one at a time around their reference values (by about ? 30%) and observing the effects on I(T), n(?)(zone l), and p, ( T = 1). We also evaluated the importance of the different individual terms in the energy balance equation at different values of T , using the reference values of the parameters. On the basis of these exploratory studies, it was decided to try out lower values of E ; and ( - A H 3 ) , two of the parameters which influence the r3(- A H 3 ) term in the energy balance equation. Use of E'; = 0.9E!& and ( - A H 3 ) = 0.9( led to fairly good agreement in I(?) but worsened the fit between predicted and observed values of n ( ~ ) (zone 1) and of p, (7 = 1). These effects could be compensated for by retuning the values of p. The Box (36) complex method was tried again for the [W], = 3.45% case, and the best-fit values of the new parameters are given in Table 3 as case b. The

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agreement between model results and industrial data for the [W], = 3.45% run is seen from Figs. 3 and 4 (case b) to be much better than for case a. These values are then used to predict (withoutfurther tuning) the results for the other two values of [W], for which industrial data are available. Figures 5-8 (case b) show the agreement to be good. The corresponding values of p , (T = 1) for case b are given in Table 4,and these agree well with the + industrial values. This confirms that the model accounts for most of the important physicochemical phenomena which play an important role in the reactor. Some additional interesting simulation results using the parameter values for case b are shown in Figs. 9-14 (curves marked current). Figure 9 shows the three pressure histories being used currently for the three different values of [W],; Fig. 10 shows the dimensionless temperatures for these cases.

1.2

Regions

[W

lo

: 3.4s

1.

o Industrial data

---Madel

results

FIG. 3. Variation of the dimensionless temperature, 8,with dimensionless time, 3.45 mass %. Circles show industrial data. Curves show model results using the best-fit values of the parameters as given in Table 3 (cases a and b). Current conditions used. (From Ref. 17.)
T, for [W], =

SIMULATION AND OPTIMIZATION OF NYLON 6 REACTOR


1.:

21 1

Regions
-1fi++-4-+-5-

1.I

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0I .

0.1

04 .

ri

t w 10 = 3.45 v.

---Model

o Industrial

data results

0.2

0
02
0.5
K

0.6

0.8

1.0

FIG. 4. Variation of the dimensionless pressure, n, with dimensionless time, 7, for [W], = 3.45 mass %. Notation same as in Fig. 3 . (From Ref. 17.)

These two diagrams are the same as the individual plots shown earlier. Figure 11 (current) shows how the monomer conversion increases sharply at about T - 0.2 to almost its final value for the three values of [W],. A sharp increase in monomer conversion occurs in zone 2. Figure 12 (current) shows how p , increases in two stages to its final value for all three feed water concentrations. The initial (up to T - 0.2) sharp rise in p, is associated with the polyaddition reaction (note that this is associated with almost the enfire consumption of the monomer to near-equilibrium values; see Fig. 1I), whereas the later increase in p, (T > 0.5) is associated with the polycondensation reaction (with little further change in the monomer concentration). The polydispersity index (PDI) attains a value of 2.0 for T above about 0.24. Figure 13 shows the gradual buildup of the cyclic dimer concentration for the three feed water concentrations. It may be pointed out that Figs. 12 and 13 show the compounded effects of changing [W], as well as the pressure history. What is

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interesting is that the final, near-equilibrium value of the monomer conversion is relatively insensitive to these two operating parameters. Figure 14 (current) shows how V , varies with time. V , shows local maxima in two regions-the first near T - 0.2 when the control valve opens for the first time (zone 2), and the second time during 0.4 < T < 0.6 (zone 4 .The latter is associated ) with a relatively sharp decrease in It is interesting to mention that the concentration of the inert falls sharply to negligible values after T - 0.2. By this time, the vapor space has a preponderance of water. In fact, the [W](T) history looks quite similar to the n ( ~ ) history.

n.

OPTIMIZATION
With a good reactor model available, the stage is now set for optimizing its performance. The function, which is usually minimized (or maximized) for

1.0 -

a
b--oo-

0.8 [ W 10
Q)

:2.52

*/*

0.6

o Industrial data

7.

FIG. 5. Variation of the dimensionlesstemperature, 8, with dimensionlesstime, for [W], = 2.52 mass %. Parameters ofTable 3 are used to generatesimulationresults (current conditions) for cases a and b. Circles represent industrial data. (From Ref. 17.)

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1.01

tW

lo = 2 . 5 2

'/a

o Industrial data

1.o
T

FIG. 6. Variation of the dimensionlesspressure, II,with dimensionless time, 7, for [W], = 2.52 mass %. Notation same as in Fig. 5. (From Ref. 17.)

a polymerization reactor, is the weighted average of a few individual objectives, I;, selected, for example, from among (a) concentration of unreacted monomer in the product, (b) concentration of undesirable side products, (c) reaction time, (d) deviation of the number-average chain length ( , and/or p) polydispersity index (PDI), from desired values, and so forth. The scalar objective function, I , could, thus, be written as Min I =
Ut ()

2 wiri[x(+),tf]
i

In Eq. (6),w iis the weightage factor associated with the individual objective function, Ii,and $is the (final) reaction time. The optimal histories (or profiles) are usually generated using a variety of constraints [e.g., the reaction temperature being limited between an upper and a lower bound (to ensure single-phase polymerization), etc.].

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Computation of the optimal temperature trajectories, u t ) , of the type de( scribed in Eq. (6) is relatively simple, but there is considerable subjectivity on the values assigned to the weightage factors, wi. Mathematically,the most important drawback of this approach is the possibility of losing certain optimal solutions (37,38) irrespective of the weightage factors used in the (overall) scalar objective function, I. In recent years, the area of vector optimization has come into prominence in polymer engineering. In this, the objective function, I, is a vector comprised of the individual objective functions, I,. This is a very powerful approach and leads to better decision making by a designer because it helps narrow down the optimal choices considerably. This method has its roots in management science and resource management and is referred to as multiobjective decision making or optimization. It not only overcomes the disadvantages associated with scalar optimization but also offers additional

0.2

0.4

0.6
T

0.8

1.o

T,

FIG. 7 Variation of the dimensionless temperature, 0, with dimensionless time, . for [W], = 4.43 mass %. Notation as in Fig. 5. (From Ref. 17.)

SIMULATION AND OPTIMIZATION OF NYLON 6 REACTOR

215

IWI, = 4 . 4 3 %
l .
0

Industrial data

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FIG. 8. Variation of the dimensionless pressure, ll,with dimensionless time, T, for [W], = 4.43 mass %. Notation same as in Fig. 6. (From Ref. 17.)

TABLE 4 Number-Average Chain Lengths of Product Under Different Conditions

WIO
(mass %) 2.52 3.45 4.43
Source: Ref. 14.

Industrial 156.0 152.5 150.625

Computed (case a) 155.53 151.76 150.62

Computed (case b) 155.957 152.234 150.146

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AATMEEYATA AND GUPTA

1.0

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0.0

0.6

I =
0.4

02 .

0.0

0.2

0.4

0.6
t / tf, ref

0.8

1.0

FIG. 9. Variation of the dimensionless pressure with time for the current (using parameters of Table 3, case b) and optimal (SQP, preferred solution) cases, for three grades of Nylon 6. (From Ref. 17.)

advantages of being able to deal with usually incompatible and nonquantifiable effects like pollution, quality, and so forth. Because most optimization problems in polymer reaction engineering often deal with such objectives, multiobjective function optimization offers excellent prospects for use in the optimal design and operation of these reactors. We have optimized the operation of the industrial semibatch Nylon 6 reactor, using multiobjective function optimization. Multiobjective function optimization is usually executed in two stages-an objective or mathematical stage followed by a subjective or decision-making stage. In the mathematical stage, a Pareto set is generated. This is a set of equivalent (noninferior) optimum points, such that upgrading any one objective function leads to simultaneous worsening of at least one or more other objective functions. The points on the Pareto set satisfy all the constraints of the problem-mass and energy balance equations [usually in the form of ordinary differential equations (ODES) for well-

SIMULATION AND OPTIMIZATION OF NYLON 6 REACTOR

2 7 1

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mixed reactors], end-point constraints (e.g., product having a desired value of pn),and so forth. The second stage is slightly more subjective in nature and involves the decision-maker to identify the best of the optimal points on the Pareto set, using his judgment (or additional information not incorporated in the generation of the Pareto, and usually not easily quantifiable). It is obvious that the Pareto set generated in the first stage helps channelize the thinking of the decision-maker in a better manner because it restricts his choice substantially. Several methods have been described in the literature on the generation o f the Pareto set. O f these, the simplest and the most commonly used is the -constraint approach. In this (37,38), we select any one objective function and minimize it while constraining the remaining objectives to have some preassigned values, ej. Thus, the original multivariable optimization problem described by

00 .

00

0.2

04

0.6
t t f,ref

0.8

1.0

FIG. 10. Variation of the dimensionless temperature with dimensionless time for the current (using Table 3, case b values) and optimal (SQP, preferred solution) cases, for three grades of Nylon 6. (From Ref. 17.)

218

AATMEEYATA AND GUPTA

-O

L
-

0.8-

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0 .-

vl L a l
C
U 0

0.6-

0.0

02 .

04 .

06 .
1 t f, ret

0.8

1.0

FIG. 11. Model results for monomer conversion for three values of [W], (using case b parameters of Table 3). Current as well as optimal (SQP, preferred solutions) values shown. (From Ref. 17.)

Min I[x(tf), 91 = Min [ l ~ [ x ( t , ) , Iz[x(tf), +I, . . . , Ir[x(rf),9 1 91, 1


W)
u(r)

(74

subject to (s. t.): all constraints [e.g., mass and energy balances, end-point constraints, maximum and minimum values on u(t), etc.] (7b) is transformed into the following simpler problem: Min l i [ X ( t f ) ,
U(f)

91

s. t.:
IJXQ),

9 = E j ; ;= 1, 2, . . . , r ; ; f i 1 all other constraints [listed in Eq. (7b)l

The solution of the problem described in Eq. (8) gives a single point on

SIMULATION AND OPTIMIZATION OF NYLON 6 REACTOR

219

the Pareto set. The complete Pareto surface can be generated by varying ej over their entire range, qmin E ~ , The ~values of E ~ or E ~~ can, be~~ to ~ . , ~ obtained by the solution of the following two still simpler problems:
ej,max -

Max
u(0

lj[x(tf>,

9 1

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s. t.:

all constraints in the original problem [Eq. (7b)l

and

qmin Min Zj[x($), $1 =


u(0

s. t.:

t w lo :I.

0.4
t / t f ,ref

08 .

FIG. 12. Model results for p,,,(~) for three feed water concentrations using Table 3, case b parameter values. Current as well as optimal (SQP, preferred solutions) values shown. (From Ref. 17.)

220

0.04

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0.03

I w lo ; / .
2.52

AATMEEYATA AND GUPTA

for FIG. 13. [ C 2 ] ( 7 ) three feed water concentrations. Notation as in Fig. 12. (From Ref. 17.)

all constraints in the original problem [Eq. (7b)l

(lob)

Each point on the Pareto set has an optimal history, ~ ( t ) , associated with it. These are generated simultaneously while obtaining the solutions of the problem described in Eq. (8), using various techniques (e.g., dynamic programming, iterative dynamic programming, Pontryagin's principle using firstor second-order techniques, genetic algorithms, etc.). Two objective functions are selected in this study for minimization: (i) The dimensionless reaction time, tf/tt.rrf,where the total reaction time, r f , is determined by the time required for the degree of polymerization, kn, reach a value, p,,.,,f,being manufactured currently in the to industrial reactor (this is why +is not really an optimization variable). This ensures the quality of the product in terms of its physical properties. (ii) The nondimensional concentration of the undesirable cyclic dimer in the polymer produced (i.e., we minimize [C2]f/[C2]f.ref). cyclics The

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cause problems in polymer processing and hot water extraction is used to remove them (24). Because this operation is expensive and energy intensive, minimization of the final cyclic dimer concentration are is important. It is to be noted that and [CZILref constants and their inclusion in the individual objective functions (due to proprietary reasons) does not influence the results of the study. The optimization problem being solved in the present study is, thus, described by Min I = [ I , , I2IT
u(r)

where

to'

I
0.2

I-

0.0

1 0.6
'tf,ref

06 .

0.8

1.O

FIG. 14. Vr as a function of Fig. 12. (From Ref. 17.)

for three values of [W],. Notation same as in

222
1

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= - tf
@,ref

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convf = convf,ref

(1 1 4

mass and energy balance equations [Eq. (211 any additional physical limits on the control variables

(110 (llg)

The above two-objective optimization problem has been solved using the two techniques described below.

Optimization Using Sequential Quadratic Programming (20)


In this first study, the shape of the pressure history, p ( t ) , is constrained to have a certain form (similar to that used currently), as shown schematically by the curve marked opt in Fig. 2. p ( t ) is completely described by four t,, S , and 9 (see Fig. 2). These constitute parameters (constants), namelyp,,, four of the five optimization or control variables (these are not functions of time). The fifth optimization variable is the jacked fluid temperature, Tj. Solutions of the optimization problems described in Eqs. (8)-(10) are obtained using the sequential quadratic programming (SQP) technique (39,40). Each point obtained in the Pareto set corresponds to a set of optimal values of these five parameters. The precise optimization problem solved using this approach, is summarized as follows:

s. t.:

convf

convJref

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223

mass and energy balance equations (Ref. 17) additional limits puts on control variables:
Pmax

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1.0

Pmax.ref

05-

1.0

Smax.ref

0.8703

563K

<
-

1.0

This optimization problem is solved using the E04UCF code of the NAG library using the E-constraint approach [Eq. @)I. Figure 15 shows the Pareto set obtained for [W], = 3.45%. This diagram shows that as the value of one objective function, +/kref,decreases (improves), the other one increases (worsens). The curve in Fig. 15, thus, has the characteristics of a Pareto set. S, The corresponding optimal values of the control parameters, pmax, t,, and TJ (in dimensionless form), corresponding to the different points (circles) of the Pareto in Fig. 15, are shown in Figs. 16-19 (circles). Some amount of scatter is observed in Figs. 16-19, but the optimal values of T j show a smooth decrease as increases. In fact, some adjacent values of the optimal control parameters fluctuate wildly, even though the Pareto itself is quite smooth. This creates problems in the use of our optimization results in industry and needs further study. We found that changes in values of pmax, and t, S, around their optimal values lead to relatively small changes in the values of and [C21d[C2]href. This suggests that we can obtain smoothened curves for the operating (control) parameters (instead of the fluctuating points shown by circles in Figs. 16-19) and still be quite close to Pareto solutions. These suboptimal solutions would have more use in industrialpractice and are shown in Figs. 15-19 by smooth curves (20). Suboptimal (smoothened) Pareto solutions were also generated for the two other grades of polymer being produced currently in the industrial reactor, using [W], of 2.52% and 4.43%. These correspond to a different set of values The of convhref,kn,ref9 and Smax,ref. smoothened Pareto sets are given in Fig. 20. The optimal values of the operating parameters, pmax/pmax,ref, S , tc/tf,ref, and Ti, these cases are available in Ref. 20. It is to be noted that one can for

224
I

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--A

------____
IU

____________

010
0.1

0.5

0.6
tf

0.7
t f, ref

0.8

0.9

1.0

FIG. 15. Pareto set (SQP) for [W], = 3.45%, JL,,,,~ = 152. Circles show exact Pareto points; curve shows the smoothened, suboptimal Pareto. Utopia (U) and preferred solution (0)shown. (From Ref. 20.)

achieve substantial improvements (lower [C&, lower +) in the operation of the industrial reactor in all three cases studied herein, merely by effecting simple changes in the operating variables in the industrial reactor. As indicated earlier, a decision-maker can now select a preferred solution from among the equivalent optimal points on the Pareto. A common technique to identify the preferred solution is to choose it as a point nearest (geometrically) to a point called the utopia. The latter is the point whose coordinates are the two limiting solutions [Eqs. (9) and (lo)]. The utopia, obviously, is unattainable and represents an ideal. Figures 15 and 20 show the utopias ( U ; )as well as the preferred solutions (0;). The variation of several important reactor/product characteristics as a function of time for the optimal preferred solutions shown in Fig. 20 are shown in Figs. 9-14. It is interesting to note from Fig. 12 that optimal operation (preferred solution) leads to a vanishing of the intermediate plateau in the

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kn(r)plots. Also, it is found that pn does not attain its final value, Fn,ref, asymptotically for the optimal cases, and, so, better control of the emptying operation of the reactor is required to prevent the overshoot of k n . Such control should not pose much of a problem these days. Figure 10 shows that the temperature histories, T(r), for the optimal solutions differ from what is currently practiced, because of differences in the rates of vaporization necessitated by the different pressure histories shown in Fig. 9. A substantial lowering of both the undesirable cyclic dimer in the product as well as the reaction time is achieved under optimal conditions, as observed in Fig. 13.

Optimization Using Genetic Algorithm (41)


An important assumption in the optimization study using SQP is that the curve describing the optimal pressure versus time is forced to take a certain predetermined shape and is, therefore, described by constant values of the

1.01

I
[WI, = 3 . 6 5 -/.

08 .

I
t f 1 f,ref t

FIG. 16. Optimal values of the dimensionless maximum pressure for the different cases shown in Fig. 15. [W], = 3.45%. (From Ref. 20.)

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0.5 0.4

0.6
tt

0.8

1.0

tt ,ref
=

FIG. 17. Optimal Islopel for the different cases shown in Fig. 15. [W], (From Ref. 20.)

3.45%.

parameters, pmax, f,., and tf. This prevents the consideration of a large range S, of other pressure histories having other shapes, which could possibly be better in terms of optimality. The most apt control (or optimizing) variables would be p ( t ) [or V T ( f ) ]and TI rather than pmax, t , , and TI. Unfortunately, the S, use of p ( t ) as the optimizing variable requires the use of an entirely different set of techniques for solution [e.g., Pontryagins minimum principle, dynamic programming, genetic algorithm (GA), etc., as applied to continuous variable problems]. These techniques are not easy to implement and are associated with severe numerical problems. This was precisely the reason why we had to abort our inirial attempts at solving the continuous-variable optimization problem described by Eq. ( l l ) , and study the much simpler problem [Eq. (12)] with p ( t ) described by a few (constant) parameters. With the solution of the simpler problem using the SQP technique now achieved, we can attempt to solve the more difficult optimization problem, using the solutions of the former as initial guesses (required in almost any of the continuous-variable optimization techniques, so that they converge to the true optimum). We have recently (41) solved the more general, continuous-variable optimization

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problem [Eq. (1 l)] using V d t ) (a history) and Tj (a value) as the control variables, and using an adapted version of the GA (42-46). This recently developed search technique mimics the biological process of evolution and is extremely robust. Some details are presented below. It may not be possible to satisfy both the end-point constraints given in Eqs. (1Id) and (1 le) simultaneously using an arbitrary choice of V d t ) and 7',. To take care of this, the integration of the model equations [Eq. (2)] is terminated at the point where conv = convf.ref.This denotes the point tp The value, pnf,of p, at this point is incorporated in the first objective function, ZI,in the form of a penalty function with weightage factor, w l :

Minimization of II leads to an increase in the production capacity of the industrial plant (through t'q,,,,) while giving preference to solutions satisfying (along with convf = convf,ref).The second the requirement, pnf = pnVref objective function, I*, is chosen similarly as

0.1 5

0.10
L

tW1, = 3 . 4 5 '1.

a l

e
Y

\
U
CI

0.05 oQQ4
W

-oo%-aooooo

O O - ' ? l

' '

I J , '

'

' '

FIG. 18. Optimal tcltf,ref the different cases shown in Fig. 15. [W], = 3.45%. for (From Ref. 20.)

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0.4

0.6
t f /tf,ret

0.8

1.0

FIG. 1 . Optimal jacket temperature for the different cases shown in Fig. 15. 9 [Wl0 = 3.45%. (From Ref. 20.)

The use of penalty functions involving pnf in both the objective functions, and the use of the condition convf = convf,,f to stop the integration of the state variable equations, ensures that we obtain optimal solutions where are and [C2]f/[C2]f,ref minimized while ensuring convf = convf,refas well as p n f = pflTIef. precise mathematical statement of the optimization problem The solved using GA is, thus, given by Min I
T,.Vdn

= [ I , , I2IT

where

SIMULATION AND OPTIMIZATION OF NYLON 6 REACTOR


2

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convf = convLref mass and energy balance equations any additional physical limits on the control variables

0.10

0.4

06 .
t f tf,ref

0.8

1.0

FIG. 20. Smoothened Paretos (SQP) for the three grades of Nylon 6 produced presently. Utopia and preferred solutions shown along with limiting solutions. Values of pnfand convf,,er differ for the three cases.

230
0.24

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[W],,% 3.45
9

5.52
4.43

0.22
0.2

I I

-. .. ----

..
.
I

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c N

f! 0.18

2. 0.16 c
4

..\\
..\
0,

.. ..
.-.. .. M 2 .0

0.14
0.12

._ ... .-. - . _ _ .._ . . _ _ . .

0.1 I

.\ \ .

.. ..

..
1

._ - - _ ...
1
I

0.08

FIG. 21. Comparison of the three Paretos (NSGA) with the Pareto (SQP) for [W], = 3.45% obtained by Sareen and Gupta (20). Preferred solutions indicated by 0 2 ,0 3 , and O4 for [W], = 2.5270, 3.45%, and 4.43%, respectively. (From Ref. 41.)

The solution of the two-objective optimization problem described in Eq. (15) is obtained using the nondominated sorting genetic algorithm (NSGA) (42) adapted by us (41) so as to apply for control variables which are continuous functions of time, t. Details of this adapted NSGA are available in Refs. 42-46. In this intelligent search technique, a population of several solutions (chromosomes involving a set of binary numbers) are first generated using a random-number generator. The (two) objective functions are evaluated for each of these, and then the chromosomes are classified into several fronts based on the concept of dominance [42-461. The chromosomes are then mated pairwise to give sturdier (improved) offsprings (solutions). The procedure continues until the best solutions (constituting the Pareto) remain in the population. There is no need to use the e-contraint approach in this case. In order to obtain Pareto solutions using the adapted NSGA, we have to first select upper and lower limits of each of the N,, control variables, uj?y and uj?p, k = 1, 2,. . . , Nga (Nga digitized values of the history, VT/VT,,,,,ref), as well as of the jacket fluid temperature, and TJmin. was It found that these (slightly restricted) search windows for VTIVT,max,ref and

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T j were necessary, and that very large search domains on these two control variables led to severe computational problems with no Pareto solutions being obtained. Because the earlier multiobjective optimization study (20) using SQP gave us an optimal VTIVT,max,ref history and an optimal value of Tj, we selected the windows of these control variables around these previous solutions (20) as
I1.6(

VT

vT

VT,max.ref 2o

at corresponding values of fI9. The subscript 20 indicates values obtained in Ref. 20. The window for TJ was taken as 220C 5 T j 5 270C. It was found that the window for VTIVT,max,ref at tlrf = 0 had to be widened beyond that given in Eq. (16) before solutions could be obtained. Any further increase in reduces the number of Pareto points the width of the window for VT/VT,max,ref obtained (without any change in the optimal solutions), and no further widening of the width of the window was attempted.

1.2

~owdrlimits o upperlimits +
Rcf.20
r,=0.45-

1 -

L .

08 .

>

E C; 0.6

r,=0.54-. - . . K 9.65- -- I

.
04 .

FIG. 22. Dimensionless vapor release rate histories for [W], = 3.45%, for three points (tflq,,,, = 0.45,0.54,0.65) on the Pareto (NSGA) optimal set. 0and denote the lower and upper limits of the window used in this study; 0denotes the optimal values of VT/VT,max,ref obtained in Ref. 20. (From Ref. 41 .) as

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8.530 .
t. .
520

. .

510

500
490 0.4

1
1

0.5

0.6 If

0.7

0.8

0.9

f,ref

FIG. 23. Jacket fluid temperaturescorresponding to different points on the three Paretos (NSGA) shown in Fig. 21. (From Ref. 41.)

The Pareto sets obtained for three water concentrations, [W], = 2.52%, 3.45%, and 4.43%, are given in Fig. 21, along with the preferred solutions [obtained as in the earlier case (20)]. It may be added that the values of [C2]f,.ref different for the three cases, and +.ref is the same. The Paretos are obtained in the present case indicate superior performance compared to that obtained earlier. This indicates that freezing of the shape of the pressure history during optimization [as in our SQP study (20)] does not give the best optimal solutions, because the search space gets limited by this procedure, a drawback that does not exist in the more general study using NSGA. Each point on the Pareto sets in Fig. 21 corresponds to a different VTIVT,max,ref history as well as T J .Three of these histories (for +/$ref = 0.45, 0.54, 0.65 on the Pareto for the reference case of [W], = 3.45%) are shown in Fig. 22. Figure 23 shows the optimal values of T,, corresponding to the Paretos for all three values of [W],. Figure 24 shows the optimal history of VTIVT,max,ref the three preferred solutions. It is observed that the vapor for release rate is finite at the beginning in the case of the NSGA-generated optimal solutions, in contrast to the current operation (see Fig. 14). Also, the maximum value of the optimal vapor release rate is lower. It must be ensured that the values of V , indicated in the beginning can, indeed, be attained (the

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pressure inside the reactor may not be high enough). Figure 24 shows that higher vapor release rates are required for higher values of [W],. Figure 25 shows the variation of the dimensionless pressure, n, with dimensionless time for the preferred solutions (02-04). Much lower pressures are required as compared to the current operation. Also, the pressures are lower than suggested for the optimal (preferred) solutions obtained by SQP. The variation of some of the other variables at the preferred optimal solutions obtained by the NSGA technique are quite similar (qualitatively) to the results shown in Figs. 10-13 and are available in Ref. 41.

CONCLUSIONS
In this study, a systematic simulation of an industrial semibatch Nylon 6 polymerization reactor was first carried out, taking into consideration the vaporization of water and a monomer. A very general computer package was prepared to solve the set of differential equations obtained from the mass and energy balance equations. A set of best-fit values of five curve-fit parameters (in the equations for the activity coefficients and the heat transfer coefficient) was obtained using industrial data on T(f),p ( t ) (zone l), and b,,(+) for one

0.5

0.45

'
[W1,,96

2.52 __

3.45 ... . . .

4.43 - - - -

11

0.2

0.4

0.6

0.8

FIG. 24. Dimensionless vapor release rate histories for the preferred solutions (NSGA) for [W], = 2.52%, 3.45%,and 4.43%.

234
1.2
1

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0.8

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06 .
0.4

0.2

f.ref

FIG. 25. Dimensionless pressure histories used currently to produce three grades of Nylon 6 , using different values of [W],. Optimal histories correspondingto points, O;, in the Pareto optimal solutions (NSGA) also shown. Arrows indicate the values of qtr,rer the three [W],. Values 2, 3, and 4 on the arrows indicate [W], = 2.52%, for 3.45%, and 4.43%,respectively. (From Ref. 41.)

value of the initial feed water concentration. Model results were found to agree well with industrial data for two other operating conditions for which industrial data were available, thus justifying the use of our model for studies on optimization and control. Multiobjective Pareto optimal solutions were then generated for producing the three different grades of polymer. Initially, the shape of the pressure history was fixed (so as to be described by pmax, S, and q) and optimal f,, values of pmax, S, and T, obtained for each of the points on the Pareto set. fc, Operating conditions were generated corresponding to the preferred optimal solutions for all three initial water concentrations. These optimal solutions obtained using the SQP technique were then used to generate the window of VAT) in which the optimal history had to be searched using the evolutionary technique, NSGA. It was found that improved optimal solutions were obtained using the second approach, as the constraints associated with freezing the shape of the pressure history were not present. The optimal solutions have been implemented on the industrial reactor and have led to substantial improvements in the operation. However, better control of the reactor is necessary under the suggested operating conditions, because the product is not a near-equilibrium material.

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An important assumption in the present study was the incorporation of only two reactions (Nos. 4 and 5 ) involving the undesirable side product (viz. C2). It is well known (13,22-24) that reasonable amounts of higher cyclic oligomers, Cj, C4, . . . , C6, and so on are formed during the reaction, and these, also, need to be extracted out by hot water. The values of the kinetic parameters associated with the reactions involving the higher cyclic oligomers were not known precisely, and so these reactions had to be omitted in our study. However, recently, we (47) have modeled the rates of formation of the higher cyclic oligomers and have obtained correlations for the rate constants associated with these reactions [using some experimental data (26,29) on the concentrations of C3-C6]. Future optimization studies should possibly use this more general kinetic scheme.

NOMENCLATURE
Frequency factor for ith reaction in the absence (0) and in the presence (c) of catalytic effect (kg/mol/h or kg2/moI2/h) Monomer conversion (= ) x , Caprolactam (i = 1) and cyclic dimer ( i = 2) Degree of polymerization of polymer product ( = ,un) Activation energies for the ith reaction in the absence (0) and in the presence (c) of catalytic effect (J/mol) Mass of liquid in reactor at time t (kg) Heat transfer coefficient of liquid (inside) (kJ/m2/h/K) Constant coefficient in Eq. ( 5 ) Enthalpy of ith reaction (J/mol) Vector of objective functions, Znl; m = 1, 2 Forward rate constant of ith reaction Reverse rate constant of ith reaction Equilibrium constant for ith reaction Number-average molecular weight Weight-average molecular weight Number of zip values which GA generates Number of chromosomes in the population Preferred solutions for ith case ( i = 2, 3, 4 indicating [W], = 2.52%, 3.45%, and 4.43%) Pressure (kPa or atm) Parameter vector Polydispersity index Net forward rate for ith reaction (mol/kg/h) Gas constant (J/mol/K) Rate of vaporization of monomer and water at time f (mol/h) Slope (absolute value) of pressure versus time plot during the third stage in reactor being optimized (atm/h)

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rnin Urnax u P , k 7 P.k

u i

Linear n-mer Entropy change for the ith reaction (J/moVK) Time (h) (h) Time for which pressure remains constant at pmax Total reaction time (h) Temperature (K) Jacket fluid temperature (K) Lower and upper bounds on jacket fluid temperature Vector of control variables, [ u p ( [ ) , T J ] Value of control variable ( VT/VT,rn,,,r,,)g~ the end of the X.th at time interval in the ith chromosome Lower and upper bounds on control variable at the end of kth time interval Utopia for ith case (i = 2, 3, 4 indicating [W], = 2.52%, 3.45%,and 4.43%) Rate of vapor release from reactor (moVh) Weightage factors Water Vector of state variables, x, Monomer conversion (= conv)

Greek Letters
Pi
Yi

5i

rl

0
p k
t4I

n
7

Constant coefficients in Eq. ( 3 ) Activity coefficient of i Total mol of m (i = l), M' (i = 2), or both ( i = 3) vaporized until time t (mol) Viscosity of liquid mixture (Pa.s or poise) Dimensionless temperature [Eq. (l)] kth moment of the chain length distribution ( k = 0, 1, 2, . . .); = ~Ys,I (mol/kg) Number-average chain length ( sp 1 /pol Dimensionless pressure [Eq. ( 1)I Dimensionless time [Eq. (l)]

C,"=,

Subscripts/Superscripts
c,

f
j,J
WZ

Catalyzed Desired value Final (value for the product) Jacket Monomer

SIMULATION AND OPTIMIZATION OF NYLON 6 REACTOR

237

max
min

0
ref
! f

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Maximum value Minimum value Feed conditions Reference (value used in industrial reactor currently) Value at t = tf Water

Symbols

[I

Concentrations (mollkg mixture)

Other terms as defined in Refs. 17, 20, and 41.

ACKNOWLEDGMENT
The work described here has been partly funded by a grant from the Research Center, Gujarat State Fertilizers Co. Ltd., Vadodara, India.

REFERENCES
1. P. J. Flory, Molecular size distribution in linear condensation polymers, J. Am. Chem. Soc., 58, 1877-1885 (1936). 2. P. C. Haywood, Reactivity of alkyl iodides with sodium benzoyloxides and the effect of temperature on such reactions, J . Chem. Soc., 121, 1904-1921 (1922). 3 . B. V. Bhide and J. J. Sudborough, Esterification, J . Indian Inst. Sci., 8A, 89-127 ( 1925). 4. P. J. Flory, Principles of Polymer- Chemistry, Comell University Press, Ithaca, NY, 1953. 5. K. Tai, H. Teranishi, Y. Arai, and T. Tagawa, The Kinetics of Hydrolytic Polymerization of E-Caprolactam, J . Appl. Polym. Sci., 24, 21 1-224 (1979). 6. K. F. ODriscoll and J. Huang, The rate of copolymerization of styrene and methyl methacrylate-I. Low conversion kinetics, Eur. Polym. J.,25,629-633 (1989). 7. S. Floyd, K. Y. Choi, T. W. Taylor, and W. H. Ray, Polymerization of olefins through heterogeneous catalysis-111. Polymer particle modelling with an analysis of intraparticle heat and mass transfer effects, J . Appl. Polym. Sci., 32, 2935-2960 (1986). 8. P. Sarkar and S. K. Gupta, Modeling of propylene polymerization in an isothermal slurry reactor, Polymer, 32, 2842-2852 (1991). 9. S. T. Kuberkar and S. K. Gupta, Simulation of polyphenylene oxide reactors, Polymer, 37, 1243-1256 (1996).

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