Modeling of Poly(Ethylene Terephthalate) Reactors: 5.

A Continuous PrepoIy merizat ion Process

K. RAVINDRANATH and R. A. MASHELKAR
Polymer Engineering Group
Chemical Engineering Dicision
National Chemical Laboratory
Pune 411008, Indiu

A mathematical model for the continuous prepolymerization

of BHET to PET, carried out in a series ofstirred tank reactors,
has been developed. The influence of process and operational
variables on productivity, as well as the side-product formation
(which controls the product quality), have been studied in a
range as close to industrial practice as possible. The overall
conclusions concerning the productivity profile, a s well as
some side products, appear to be substantiated from the availa-
ble data in the open literature. The results of the mathematical
model have been used to highlight the key process and opera-
tional variables that are likely to give the best productivity and
product quality in industrial practice.

INTRODUCTION EG, water, methanol, diethlyene glycol [DEG], and

n the first paper in the series (I), we undertook mod-
I eling of the direct esterification process, which is the
first stage in the manufacture of polyethylene tereph-
thalate. We shall now investigate, in depth, the second
stage, where the continuous prepolymerization of the
product emerging out of the esterification train, con-
sisting mainly of bis 2-hydroxyethyl terephthalate
[ BHET], is undertaken. Modeling of this stage has not
been undertaken previously in the literature. We shall
focus our attention mainly on the influence of process
and operational variables on the change of degree of
polymerization and also on the formation of side prod-
ucts, which critically affect the product quality.
PREPOLYMERIZATION PROCESS
A typical process flow diagram for continuous prepo-
lymerization process is shown in Fig. 1 . The feed for
prepolymerization reactor [R-2011 is the product
emerging out of the transesterification, or ester-
ification reactor. The feed contains mainly bis
2-hydroxyethyl terephthalate [BHET] and ethylene
glycol [EG]. If the transesterification, or esterification
process, is not complete, then (depending upon the
process) the feed will contain methyl e n d groups and
acid e n d groups.
In the continuous prepolymerization process, the
ketones.
During the prepolymerization process, the viscosity
of the reaction mass is small [=40 PI as compared to
that in the polycondensation reactor [ 4 , 0 0 0 PI, since
the degree of polymerization [DP] obtained in the pre-
polymerization is around 20 to 30. Therefore, a special
design for the agitation system is not usually provided
at this stage.
For developing a mathematical model for the contin-
uous prepolymerization process, it is necessary to know
whether the process is mass-transfer-controlled or
kinetically controlled. As will be seen later, the main
reaction involves equilibrium polycondensation accom-
panied by the removal of volatile EG from the reaction
mass. Some authors (2-8) modeled the later stages of
polycondensation reaction [over D P of 501 and showed
that diffusional factors play an important role in this re-
VACUUM
b P
GLYCOL
R-20 1 R-202 R-203

feed is passed through a fixed number of reactors. For

simplicity, only three reactors are shown in Fig. 1. The
product from one reactor will be the feed for the next
reactor. In industrial practice, prepolymerization reac-
tors are operated under vacuum [lo-25 torr]. The va-
pors emergingout of the reactor are condensed and sent
for purification. The condensate contains mainly

POLYMER ENGINEERING AND SCIENCE, JULY, 1982, Vol. 22, No. 10 619
 K . Racindranath and R. A. bfashelkar

gion. Aneja (9),Yokoyama, et a1 (lo), pointed out that, in Transesterification reaction:

the beginning of polycondensation reaction [below D P
of 301, reaction mass resembles a boiling liquid, and the
reaction rate is the controlling step. Simple considera-
e O O C H 3 + HOCHzCH200C
Em E, --e 1\

tion will indicate that diffusional factors become impor-

tant when the following inequality is satisfied:

Rate of chemical reaction >> rate of mass transfer + CH30H (3)

Expressing this inequality in terms of a kinetic constant
M
Polycondensation reaction:
and an overall mass transfer coefficient, we have

Here, k ; can be considered as an equivallent first order

polycondensation rate constant. kL is the mass transfer
coefficient, and a is the interfacial area per unit vol- + HOCHzCHzOH (4)
ume. Approximate calculations indicate that k , a would EG
be on the order of 10-2s-1;k; values, on the other hand,
would be on the order of s-'. Therefore, in the ini- Side reactions leading to the formation of acetaldehyde,
tial stages of polycondensation [below IIP of 301 the DEG, and acid end groups:
influence of diffusional factors may not play an impor-
tant role. We have made another assumption, that the -OOCH~C O k,\
H ~H
individual reactors are fully mixed. In industrial prac- E,
tice, reactors are agitated by turbine agitators. As indi-
cated earlier, when the D P changes from 1.5to 20, the -0OCH + CH3CH0 (5)
viscosity would change from a few cP to approximately A
El-
40 P. The mixing times under such cortditions (esti-
mated from the data provided by Chavan and
+ HOO H
~ O O C H ~ C H ~ CH~CH~OH &,
Mashelkar (11)) would be far smaller in comparison to EY EG
the time in which an appreciable extent of reaction -0OCH + HOCHzCH20CH2CH20H
might take place in a prepolymerization reactor. The as- Er DEG
sumption of complete mixing in each individual reactor (6)
thus appears to be quite reasonable. k e
2 e O O C H 2 C H 2 0 H 6, O O H +
-
E, Er
REACTION SCHEME ~ O O C H ~ C H ~ O C H ~r. C H (7)
~ O H
Various reactions occur in the prepolymerization pro- I5 DEG
cess. These mainly include a polycondensation reaction
and side reactions leading to the formation of DEG,
water, acetaldehyde, acid end groups, and vinyl end Esterificdtion reactions:
groups. Ravindranath and Mashelkar (12-14) have dis-
cussed, in detail, all the above reactions while model- e O O H + HOCH2CHzOH k7

ing the semibatch ester interchange reactor, a continu- E,. EG kdK4

ous transesterification process, and a semibatch
e O O C H zCHzOH + H 2 0 (8)
prepolymerization process. To study the influence of
E, W
unreacted dimethyl terephthalate [DMT] left in the
transesterification process on the prepolymerization
process, in the present model we have also included
transesterification reaction and ester interchange reac-
tion. Various reactions considered in the present model
are given below. - O C H 2 CH200C-@
e O + H20 (9)
Z W
Ester interchange reaction:

k Degradation of diester groups:

- O C H 3 + HOCHzCHzOH G=&
e O
E, EG k l K
+OOCH~CH~OOC+
- - --L
z
~ ) - C O O C H ~ C H ~ O H+ C H ~ O H (2) e -O O H + CH2 = C H O O C e (10)
E, M Ec E,
620 POLYMER ENGINEERING AND SCIENCE, JULY, 7982, Vol. 22, No. 70
 Modeling of Poly(Ethy1ene Zerephthulate) Reactors: 5 . A Continuous Prepolynlerizution Proces.s

Polycondensution of vinyl end groups: Figi - F,g + p2V[- RI + R3 - R7] - F,g" = 0

(18)
-0OCH = CH2 +
E 1( E, Fiz' - F,z + p 2 V [ R Z+ R3 + Rs - Rg + R,o] = 0
(19)
-k, f p-2 0 0 C H 2 C H 2 0 0 C - @ - + C H 3 C H 0 Fie',. - Foe,. 4- p 2 V [ R 4+ R5 + R6 - R7 - & + R9] = 0
Z A
(20)
( 11 )
In writing E9s 2 to 3 , it is assumed that methyl end F ~ W '- F,w + p2V[R7 + Rn] - F,wU = 0 (21)
groups of DMT and half-esterified DMT will react at Fig*' - F f,g* + p 2 ~ [ +
~ 5~~1 = o (22)
the same rate, and hydroxyl end groups of EG and half-
esterified EG will react at different rates. Acid end Fie\ - F,,e, + p 2 V [ R g - R l o ] = 0 (23)
groups formed in reactions 5 to 7 will react with E G and pZV[R4 + R,,] - F'U' = 0 (24)
E,, as shown in reactions 8 and 9. Further, reactions 8
and 9 represent the influence of terephthalic acid p 2 V [ R l + R2] F,mU = 0
- (25)
[TPA], added in the beginning of prepolymerization Here, Fi and F , represent the input and output flow
process on the course of the reaction. Vinyl e n d groups rates of prepolymerization mass, and F , is the flow rate
formed in the degradation of diester groups [see Eq ofvapor leaving the reactor. gv,w', u', and m'represent
101, can react with E,, as shown in reaction 1 1 , or they the concentration of EG, water, acetaldehyde, and
can lead to a complex mixture of end products. Because methanol in the vapor, respectively; em,e,, z , e,., w , and
of the lack of reliable kinetic data, the reactions forming e , represent the concentration of the respective species
complex mixtures, cyclic oligomers, and other side re- (as shown in the reaction scheme with capital letters) in
actions are not considered in the present work. How- the output. Quantities with superscript i represent the
ever, they can always be included within the framework input concentrations. g and g* are the concentration EG
of this model when more reliable data are available. and DEG. p and V are the density and volume of the
DEG and EDEGcan react with Em, E,, and E,, as in the reaction mixture. R , - Rlo represent the reaction rates
case of E G and E,. For simplicity, these reactions are for reactions 2 to 11. These are given as
not shown in the above reaction scheme. Further, the
reaction of EDEGin E , involves four polycondensation R, = k 1 [ 2 e m g- e,m/K1]
reactions:
R2 = k2[e,e, - 2zm/K2]
E, + E, + EG2 (12)
R3 = k3[e,2 - 4zg/K,]
E, + ED,, S Z* + EG (13)
R4 = he,
Eg + ED,, S Z + DEG (14)
R5 = 2k5e,g
EDF;, + EDEG $ Z * + DEG (15)
R6 = k6e;
where Z* represent the polymer repeating unit incorpo-
rated with the DEG molecule. Because of the complex- R7 = k7[2e,g - e,wIK,]
ity of the reactions between EDEGand E,, and because of R8 = kn[ece, - 2zwIKJ
the lack of kinetic data, we have calculated total DEG
(free DEG and DEG incorporated in polymer chain) in R9 = k , z
the present work rather than calculating the two values
Rlo = kneoev (35)
separately.
Here, k , to kS, k, to k , are second-order rate constants,
MATHEMATICAL MODEL FOR CONTINUOUS and k,, k , are first-order rate constants. K , - K , are
PREPOLYMERIZATION PROCESS equilibrium constants. It is assumed that the reactivity
of vinyl end group and hydroxyl end group is the same.
Prepolymerization reaction mixture contains mainly
The critical temperatures of acetaldehyde and metha-
EG, DEG, water, and linear polymer molecules having
nol are 188C and 240C respectively. Therefore, the
methyl, hydroxyl, carboxyl, and vinyl end groups. We
concentration of acetaldehyde and methanol in the re-
shall use the equal reactivity hypothesis, implying that
action mixture is assumed to be approximately zero.
the functional group reactivity is independent of the
Equation 22 is written for the total amount of DEG
polymer chain length. Then, the mass balance equation
formed (i.e., free DEG and DEG incorporated in the
for ideal steady-state, continuous-stirred tank reactor
polymer chain). The reactivity O f EDEC and E , were con-
[CSTR] can be written as
sidered approximately to be the same. Hence, the dis-
Fieh - Fnem + p 2 V [ - R1 - R,] = 0 (16) appearance of EG by reaction represented in E9 6 is not
included in E9 18, and the disappearance ofE, by reac-
Fie; - Foey
tion represented in Ey 7 is considered only once in E q
+ p 2 V [ R I- R2 - 2R3 - R4 - R, - R, + R7 - Rn - R l o ] 17.
=o We have an additional relationship. For a constant
(17) reactor volume, V, the following relation will hold

POLYMER ENGINEERING AND SCIENCE, JULY, 1982, Vol. 22, No. 10 62 1

 K . Ravindranuth and R. A . Mashelkar
Fi = F,, + F, (36)
For solving Eqs 16 to 36, concentration of each species
in the vapor phase must be known. They are related to
the species concentrations in the liquid phase through
Eq 37.
Concentration o f j th
component in the vapor = -
X-
jP:'
phase [mol/Kg] 2
XjMjPj*
1
M j , Xj, and Pj represent the j th component molecular
weight, mole fraction, and vapor pressure, respec-
tively. While writing Eq 37, it is assumed that the vapor
above the melt is ideal and Raoult's law is valid. It is
also assumed that physical equilibrium exists between
the components in the liquid phase and in the vapor
phase. Then, the total pressure PT will be the sum of the
partial pressure; therefore:
P T; &;
- +p,xu.+
P%
a' + m'
PT a" + mu + g c + w' __.-
HovenKamp (15) pointed out the limitation in using
Raoult's law and has advocated the use of the Flory-
Huggins (16)theory for calculating the concentration of
volatile species in the vapor and in the liquid. Using the
Flory-Huggins theory, the partial pressure of volatile
components pj will be given by
p j = Pj*vje1+X
where c j is the volume fraction ofthejth volatile compo-
x
nent, and is the solvent polymer interaction parame-
x
ter. The value of is taken approximately as 0.5 in the
present work. Usng Eys 39 to 40, the concentration of
volatile species in the vapor phase can be calculated.
Concentration o f j th
2) .p .*
component in the vapor = J J L
phase [mol/Kg] UjMjPj*2 (37)
I Number of reactors
The total pressure P T will be the sum of the partial pres-
sures; therefore:
It may be noted here that accurate vapor-liquid equi-
librium data are not available in the literature in this
case when a monomeric species [BHET] undergoes po-
lymerization only to a moderate degree, forming (at
best) a high oligomeric species. However, it is expected
that the Eqs 38 and 41 will provide upper and lower
bounds on the reactor performance.
The concentration of methanol in the reaction mix-
ture is zero. Therefore, em, e,,, and g* can be calculated
by knowing the species concentration of e,, g, z , e, and
w . In the absence of methyl e n d groups, the values ofem
and m, will be zero. Equations 1 7 to 21 and E q 38 or 41
will be solved for obtaining e,, e,, z , g, and ZGfor a given
set of input parameters. The governing equations were
nondimensionalized by normalizing the flow rates with
the input flow rates and the concentrations with the in-
622
put terephthalate units' [-OOC-COO-, referred
to as ] concentration. The governing equations are
nonlinear in nature. The method suggested by Brown
(17)was used for solving these equations. Good initial
guess values are a prerequisite for convergence. There-
fore, an objective function consisting of the sum of
L.H.S. o f E q s 1 7 t o 2 1 a n d E y 3 8 o r 4 1 wasforrned. This
objective function was then minimized with respect to
(37) the variables using the multivariable optimization tech-
nique proposed by Box (18).The guess values obtained
were then used for solving governing equations with
Brown's method. Using the mathematical model devel-
oped in the foregoing governing equations were solved
to obtain
DP in each reactor having different residence
times.
Amount of side products formed such as DEG,
acetaldehyde, water, acid e n d groups, and vinyl
-1
e n d groups.
In order to obtain the above information, we need in-
formation about
the kinetic parameters k, - k, as a function of tem-
perature, catalyst type and concentration,
equilibrium constants viz. K , to K 5 ,
vapor pressure data of water and EG.
Ravindranath and Mashelkar (12-14)have discussed the
available information on the pertinent kinetic, thermo-
dynamic, and physicochemical data. Kinetic parameter
(39) values and equilibrium constants used in the present
work are tabulated in Table 1.
The numerical computations were carried out for the
following processing and operating variables.
Initial DP 1.5
Catalyst concentration 0.025%
[Sb203] [by weight]
Temperature 240"C, 260"C, 280C
Reactor pressure 20 Torr
1, 3, 6
Total residence time 2h
Please note that the catalyst concentration has been as-
sumed to be constant in all the computations. Further,
the density of the reaction mixture was assumed to be
approximately 1 kg/L. The feed for prepolymerization
process is assumed to have the following species con-
centrations nondimensionalized with respect to the
moles of repeating units).
Hydroxyl e n d group 1.332
Diester group 0.334
EG 0.302
The feed conditions chosen here are very close to those
encountered in industrial practice.
RESULTS AND DISCUSSION
It will be recalled that the objective of the present
work was to examine the influence of pertinent process
and operational variables on the performance of the re-
actor. The computations were run essentially in the
range of operational and process variables that was com-
monly employed in industrial practice.
POLYMR NG/NR/NGAND SC/ENC, IULY, 1982, Vol. 22, No. 10
 Modeling of Pol!y(Ethyleiie Terephthulute) Reacfors. 5 . A Contiiiuous Pre~ol!/i7i"ri~utioi~
Proces 5

Table 1. Kinetic Parameters Used in This Work

Acetal Diester
Ester Trans- Poly- dehyde DEG Esteri- Esteri- group
inter- esteri- conden- for- for- fica- fica- degra-
change fication sation mation mation tion tion dation
Reaction Es 2 Eq 3 Eq 4 Eq 5 Eq 6-7 Eq 8 Eq 9 Eq 10

Activation
energy 15.0 15.0 18.5 29.8 29.8 17.6 17.6 37.8
kcal/mol
Frequency
factor, 4.0 . lo4 2.0. 104 6.8. l o 5 4.16.lo7* 4.16.10' 1.04.106 1.04.lo6 3.6.10''
Umol-min
Equilibrium 0.3 0.15 0.5 - - 2.5 1.25 -
constant
* units are In min-'

The comparisons of the predictions obtained in the
present work were done with certain proprietary indus-
trial data that were available with us, and these appear
to be quite satisfactory. In addition, there were some
overall indications available from the published litera-
ture that gave us confidence that the predictions were
adequatc. For instance, Ellwood (19) has shown that,
with a train of reactors operated at 15 to 25 torr pressure
and 245 to 270C temperature, it was possible to accom-
plish a change in D P from 1.5 to 25 within a residence
time of 2 h. Our computations, approximately in the
same range, showed a similar DP change.
It might be remarked here that detailed data are not
available as regards the byproduct formation. How-
ever, the industrial data (20) show that DEG formed
will be approximately of the order of 2 percent for the
conditions enumerated above, which is in fair agree-
ment with our predictions (which ranged from about 1.5
to 2.5 percent). Unfortunately, no quantitative compar-
ison is possible with industrial data at this stage.
Single Reactor Case: Influence of Residence Time and
Temperature
As discussed earlier, there is some uncertainty con-
cerning the phase equilibrium in the PET melt in terms
of the validity of Raoult's law (E4 38)vs. the Flory Hug-
gins theory ( E q 4 1 ) . Therefore, computations were run
This can be explained mechanistically as soon as one re-
alizes that the reaction leading to the formation of DEG
( E 4 6 and 7) is favored in the initial stages due to the
high hydroxyl end-group concentration in the begin-
ning of the reaction. Such a behavior is substantiated
qualitatively from the recently published work by
Hornof (21). His data show that most of the other link-
ages were formed during the first 30 min of polycon-
densation and that only a slow increase was observed
thereafter.
It is seen from Fig. 3 that the'trends for formation of
acetaldehyde are similar to those in the case of DEG.
Again, the degradation reactions leading to the forma-
tion of acetaldehyde are promoted in the initial stages
(see E 4 5 ) .Interestingly, increased reactor temperature
appears to enhance the formation of acetaldehyde;
therefore, the product quality might suffer. One has,
therefore, to be careful while taking advantage of the
improved productivity in terms of enhanced rate of DP
rise, as shown in Fig. 2 .
F i g u r e 4 shows the change of acid end groups with the
residence time and temperature. It is again seen that
acid end group concentration increases rapidly in the
RAOULT'S LW
- - - - - __ FLORY-HUGGINS THEORY

with both these equilibrium relationships and data

presented for both. Figure 2 shows the predictions ob-
12 -
tained in a single reactor. For the purpose of compari-
son, in the subsequent discussion, we shall be pre-
senting all the results only for the case where Raoult's
law will be assumed to be valid; the qualitative conclu-
sions in both the cases, as regards the relative influence
of process and operational variables, were similar.
Figure 2 shows the obvious conclusion that, with an
increase of residence time and with an increase in tem-
perature, the D P continuously increases. However, the
temperature cannot be increased continuously, since
many degradation reactions are promoted at higher
temperatures (see later).
Let us examine the influence of residence time and 0 I
0.5
I
1.5
1
2
.
0 I
temperature on the formation of different side prod- RESIDENCE T I M E h
ucts. Figure 3 shows that the extent of DEG rises at a Fig. 2 . Effect of residence t h e on the rute of DP rise f o r ii .sirtg/e
rapid rate in the initial stages, then the rise tapers off. reactor.

POLYMER ENGINEERING AND SCIENCE, JULY, 1982, Yo/. 22, No. 10 623
 K . Ruvindranath and R. A . Mashelkar
RESIDENCE T I M E , h
Fig. 3. Effect of residence time and tcJmperatureo n the formu-
tion of acetaldehyde [-] untl DEG [---I f o r u single reuctor.
i li!
,
b'
I,
0 I 1 0
0 0.5 10 1 5 2-0
RESIDENCE T I M E , h
Fig. 4 . Effect cflresideiice time und teniperuture c'11theforntu-
tion ofucid end groups [-] a n d water [---I f o r n sin& reactor.
beginning from zero and levels off at higher residence
time. The initial rapid rise in acid end groups arises due
to the high hydroxyl end group concentration in the ini-
tial stages (see Eqs 5 to 7 ) .
Again, there is indirect evidence that shows that such
predictions are, indeed, valid. For instance, Cefelin
and Malek showed that, during solution poly-
condensation of BHET at 260C, the acid end groups
rose rapidly in the first half-hour to a very lhigh value;
then there was a decrease in the acid end-group concen-
tration. Of course, the acid end groups might undergo a
further increase if the degradation reaction were al-
lowed to proceed for much longer times, as was done by
624
Cefelin and Malek (22). It is thus seen that the trends
predicted by the model calculations are at least qualita-
tively verified.
Figure 4 also shows that the extent of water formation
increases as the temperature and the residence time are
increased.
Influence of a Number of Reactors in Series
Industrial practice is to use a train of CSTRs. Com-
mercially, two or three CSTRs are used. In order to see
the influence of the number of reactors used in the
series, we ran computations by keeping the same cumu-
lative residence time of 2 h for the entire train.
Figure 5 shows the effect of an increase in the number
of reactors on change of DP. As the number of reactors
is increased, higher D P is reached. It is well-known that
an approach to plug flow behavior is made as the nurn-
ber of reactors in a series is increased. Our observation
is thus consistent. It might be remarked here that, in
spite of the advantages to be gained by increasing the
number of reactors, this number cannot be increased
indefinitely in industrial practice due to the considera-
tions of increased, fixed capital cost.
Figure 6 shows the influence of the number of reac-
tors used on the side-products formation. It is noticed
that the extent of DEG and water formed goes up,
whereas the extent of acid end groups and acetalde-
hyde goes down.
Influence of Temperature Distribution
Industrial practice is to provide a certain temperature
distribution in different reactors. We wanted to exam-
ine the effect of maintaining such a distribution for a
train of CSTRs comprising three reactors. Table 2 shows
the influence of maintaining a temperature distribu-
tion. The first three cases correspond to the mainte-
nance of equal temperatures in all the reactors. The
fourth case corresponds to the maintenance of a temper-
- 260.C
_ - _ _ _ 280'C
_
40
0
/
0
32 - /
/
/
n
0 24-
16 -
0 1 2 3
NUMBER OF REACTORS
Fig. 5. Effect of the number of reactors on the rate of DP rise
POLYMER ENGINEERING AND SCIENCE, JULY, 1982, Vol. 22, No. 10
 Modeling of Poly(Ethy1ene Terephthalate) Reactors: 5 . A Continuous Prepolynierizotion Proce.s.r.

the minimization of different side-products. For in-

3.c stance, comparison of cases 2 and 4 shows that the for-
mation of DEG, acetaldehyde, and water is reduced,
whereas the extent of vinyl end group and acid end
2.5 group is increased in case 4 in comparison to that in case
2.
Effect of Residence Time Distribution
0
1- 2 . 0 Although the industrial practice is to maintain the
0
E same residence time, we wanted to examine the effect
v)
I-
of maintaining a residence time distribution in the train
V
2 1-5
of CSTRs. Table 4 shows the results. It is seen that pro-
0
rc
file of increasing residence time in consecutive reactors
P might be preferred, since it helps in increasing the pro-
W
0 ductivity marginally with very little change in
v) i.a
byproducts.
Influence of Presence of Unreacted DMT and TPA
0.5 In the first paper in this series, we have described
the process of esterification of TPA with EG. The feed
to the prepolymerization train of reactors modeled in
0 this work is, essentially, a product emerging out of the
f 2 3 4
first stage. It is, therefore, instructive to inquire as to
NUMBER OF REACTORS what effect the unreacted TPA in the feed stream might
Fig. 6. Effect of the number of reurtors on the fomzution of side have on the performance of the reactor. Ravindranath
products. Solid symbols, [-] 260C; open synibols, [---I 280C : and Mashelkar (13)have modeled the process ofcontin-
(@, 01 ncetuldehyde . l o 2 [m,01 DEG . l o z , [V,71 w a t e r . lo2,
[ A , A] acid end groups . lo3, [ O , 01 vinyl end groups . lo4. uous transesterification of DMT with EG. Feed to the
prepolymerization train could, therefore, emerge from
ature distribution of 240, 260, and 280C in the three this as well, so the influence of the presence of a certain
consecutive reactors. Note that the residence time in all amount of unreacted DMT or TPA on the productivity
the reactors is kept the same. of the prepolymerization train, and also the side-
When we examine the influence of such a tempera- product formation therein, was also examined.
ture distribution, it is found that there is an advantage There is an additional incentive to examine the in-
to be gained by maintaining a temperature profile of fluence of the presence of unreacted TPA. Busot (23)
the kind shown in case 4. It would, therefore, appear shows that the continuous addition of TPA at the pre-
that a gradual rise in temperature in the train of reactors polymerization stage results is increased productivity
is to be preferred from productivity viewpoint. and product quality, especially as regards color. Plants
It is quite interesting to see from Table 3 that there is using this concept might, therefore, practice a deliber-
also a considerable benefit to be obtained as regards ate addition of TPA.
Table 5 shows the results, where we have compared
Table 2. Effect of Maintaining a Constant Temperature and a the results, for case 1, where the feed stream has D P =
Temperature Distribution on Productivity Profile 1.5 but no unreacted DMT or TPA; case 2, where the
feed stream has DP = 1.5and 10percent TPA; and case
Reactor temp
C DP 3, where the feed stream has DP = 1.5 and 10 percent
Case R-201 R-202 R-203 R-201 R-202 R-203 unreacted DMT.
As is clearly seen, there is an enhancement in D P
1 240 240 240 4.67 8.97 13.87
2 260 260 260 6.38 14.00 23.24
when a certain amount of unreacted TPA is present. But
3 280 280 280 8.62 21.56 38.31 D P reduces if there was an unreacted DMT. Mechanis-
4 240 260 280 4.67 11.60 25.78 tically, this is obvious, since the rate constant for esteri-
fication polycondensation reaction [see E q 91 is high
Table 3. Effect of Maintaining a Constant Temperature and a for TPA as compared to polycondensation reaction-rate
Temperature Distribution on the Formation of Side Products constant [kJ, thus enhancing the productivity. In the
(conditions the same as in Table 2) case of DMT, the reverse will be true. Table 5 shows the
Side products formed influence on side-products formation due to the pres-
[mol/@] ence of unreacted raw material from the first stage. The
Acetal- Acid end Vinyl end presence of unreacted TPA and DMT in the feed helps
dehyde Water groups groups in reducing the extent of side-products formation, ex-
Case . lo3 DEG . lo3 . lo3 . 105 . 105
cepting formation of water, which is quite considerable
1 3.76 6.04 8.81 1.oo 1.56 in the case ofTPA. It is obvious from E q 8 and 9 that the
2 7.92 9.36 16.05 1.30 7.77 esterification reaction leading to water formation can
3 15.66 13.72 27.90 1.77 24.65
4 7.32 7.54 13.36 1.65 13.90
be expected to be promoted. The same is true about the
vinyl end groups.

POLYMER ENGINEERING AND SCIENCE, JULY, 1982, Vol. 22, No. 10 625
 K . Ravindranath and R. A. Mashelkar

Table 4. Effect of RTD in Prepolymerization Process for a Prescribed Temperature Distribution

Side products Imol/Ol

Residence time
distribution [h] DP Acetal- Acid End Vinyl End
dehyde Deg groups Water groups
Case R-201 R-202 R-203 R-201 R-202 R-203 . lo3 ' 103 . 10 ' 102 . 104
1 0.5 0.5 1 4.1 9.7 26.8 8.00 7.78 1.68 1.43 1.70
2 0.666 0.666 0.666 4.7 11.6 25.8 7.32 7.54 1.65 1.336 1.39
3 1 0.5 0.5 5.6 11.6 23.5 6.82 7.34 1.65 1.26 1.24
4 0.5 1 .o 0.5 4.1 12.6 24.7 7.22 7.6 1.64 1.332 1.237

Table 5. Effect of Presence of Unreacted DMT or TPA on Productivity and on the Side-Products Formation Rate (R-201 = 240"C, R-202 ==
260"C, R-203 = 280C)

Side products formed

[moll01
DP Acetal- Acid end Vinyl end
dehyde DEG Water groups groups
Case R-210 R-202 R-203 .lo3 ,103 ,103 .1OJ ,105

FEED 4.67 11.60 25.78 7.32 7.54 13.36 1.65 13.90

[DP = 1.51
FEED 4.77 12.33 27.71 5.82 5.04 266.40 8.00 14.52
[DP = 1.5
+ 10% TPA]
FEED 3.92 8.55 15.95 6.16 5.72 10.46 0.78 7.13
[DP = 1.5
+ 10% DMT]

Comparison Between a Batch Reactor and a CSTR
Although the continuous process is currently replac-
ing the batch process to a large extent, the batch process
has some advantages, especially on a smaller scale, and
is still in practice. It is, therefore, desirable to under-
take a comparison of the performance of a batch reactor
with a CSTR. Ravindranath and Mashelkar (14) have
modeled the prcpolymerization process using batch
system. Their data were used for the sake of compari-
son. The comparisons were done between a hatch with a
cycle time of 1 h, a single CSTH with a residence time of
creased, the plug flow behavior is reached, and the
governing equations for the performance prediction of a
plug flow reactor become the same as that of the batch
reactor when the cycle times and the residence times
are considered equivalent.
Interestingly, it is seen that, in the case of batch reac-
tor, DP is considerably higher than in the case of a
single CSTR. This can be appreciated when one realizes
that the extent of backmixing can play a very significant
role at high levels of conversion. For instance, DP of 7.7
1;s. 24.89 signifies an extent of conversion based on end

1 h, and a train of six CSTRs with a cumulative resi- groups of 87 and 96 percent, respectively. Thus,
dence time of 1 h (see Table 6). backmixing affects the reactor performance very
Some interesting observations emerge from such significantly in this region. Approach to plug flow be-
comparisons. As the number of CSTRs is increased, the havior, therefore, enhances the DP considerably.
reactor performance approaches that of a batch reactor The trends observed on the side-products formation
when the residence time and batch cycle times are are interesting. It is seen that the extent of acetalde-
equated. As the number of CSTRs in a train is in- hyde, water, and acid end group formation is less,
Table 6. Comparison of the Results for a Semibatch and a
whereas the extent of DEG and vinyl end groups forma-
Continuous Prepolymerization Process (Temp = 26O0C,batch tion is more in the case of a batch reactor, when com-
cycle time = 1 h, residence time = 1 h) pared with a CSTR. It may be remarked that the various
products emerge as the result of a complex set of reac-
Single
batch Single tions described in E q 2 to 11 and, therefore, the effect
reactor CSTR Six CSTRs observed is cumulative, arising out of this complexity of
net work.
DP 24.89 7.70 18.51
Acetaldehvde . lo3. 4.48 6.22 5.14 CONCLUSION
mollQ
DEG . 103. 9.43 8.02 8.98 In the foregoing, we have developed a mathematical
moll0 model to examine the performance of the continuous
Water . lo2, 1.25 1.26 1.26
moll0
prepolymerization process. Wherever possible, we
Acid end groups. lo3, 1.45 1.64 1.49 have compared the results of the investigation with the
mol/Q data available in the literature. There appears to be a
Vinyl end groups. lo4, 0.53 0.32 0.46 qualitative agreement between the model predictions
moll@
~
and the reported observations.

626 POLYMER ENGlNEERING AND SCIENCE, JULY, 1982, Vol. 22, No. 10
 Motleling of Pol;y(EfhyleneZerephthulute) Reuctors: 5. A Continuous Prepolynierization Process
It would be very desirable to undertake a rigorous
optimization. Presently, in view of the fact that there
are somc uncertainties in the kinetic, thermodynamic,
and other physicochemical data, and that there has
been no previous model at all to simulate the continu-
ous prepolymerization, it was thought desirable to ex-
amine the plant performance at discrete values of pro-
cess and operational variables, so that an improved
understanding of the influence of key variables could
be obtained. The results of this model decidedly focus
on these aspects.
NOMENCLATURE
a =concentration of acetaldehyde in vapor,
mol/kg
a =interfacial area, cm-
e,, c,, e,,e, = concentration of acid, hydroxyl, methyl,
and vinyl e n d groups, respectively, equiv/kg
(superscript i indicates input concentration)
Fi, F , , F,. = input, output, and vapor flow rates, re-
spectively, kg/min
g, g, g = concentration of ethylene glycol in output,
input, and vapor respectively, molikg
g* =concentration of DEG, mol/kg
kl-k3, k,-k, = second order rate constants, Wmol-min
k,, k, =first order rate constants, min-
k, =an equivalent first-order polycondensation
rate constant, s-l
kL =mass transfer coefficient, cm/s
K I - K , =equilibrium constants
mu =concentration of methanol in output, mol/kg
Mi =molecular weight o f j t h species, kgimol
Pj =partial pressure o f j t h component, torr
PT =total pressure, torr
P*,,iP*,. = vapor pfessure of ethylene glycol and water,
respectively, torr
P,* =vapor pressure of j t h species, torr
Rl-Rlo =reaction rates, mol/L-min
Vj =volume fraction o f j t h component
V =volume of the reaction mixture, L
w , mi, =concentration of water in output, input, and
W L vapor, respectively, mol/kg
POLYMER ENGINEERING AND SCIENCE, JULY, 1982, Vol. 22, No. 10
Xj =mole fraction of j t h species in the liquid
z, zi =concentration of diester group in output and
input, respectively, equiv/kg
P =density of the reaction mixture, kg/L
X =solvent polymer interaction parameter
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