Chemical EngineeringScience.Vol.41. No. 4, pp. 1031-1038,1986. oOOSr2509/86$3.00 + 0.

00
Printedin Great Britain. @ 1986.Pergamon PressLtd.

A MATHEMATICAL MODEL FOR THE PRODUCTION OF LOW DENSITY POLYETHYLENE IN A TUBULAR REACTOR

P. P. Shirodkar and G. 0. Tsien

Mobil Chemical Company

Research & Development
P. 0. Box 240
Edison, NJ 08818

ABSTRACT

A computer model was developed to simulate LDPE free radical polymerization at high pressure in
either one- or two-zone tubular reactors. The model comprises a set of non-linear differential
equations baaed on theoretical polymerization kinetics applied to a known reactor heat transfer
profile. The predicted conversion and temperature profiles agreed with actual plant data within
10%. Calculated molecular weight distribution parameters were similar to measured data. The
model is also capable of handling short and long chain branching. The sensitivity of reactor
output and product molecular properties to various process variables, i.e., initiator systems,
initiator injection modes, reactor jacket and ethylene inlet temperatures, reactor pressure, and
ethylene split ratio can be projected using this model. Key features of the development of this
model and several typical examples will be discussed.

KEYWORDS

Polymerization; ethylene; tubular reactor; polyethylene; free radical; mathematical model; high
pressure.

INTRODUCTION

Polyethylene has been manufactured by the high pressure process for over 50 years. But the
challenge of developing a cohesive understanding of the process is still active as witnessed by
the survey of the more recent literature <Agrawal and Han, 1975; Chen, Vermeychuck and Ehrlich,
1976; Donati and co-workers, 1982; Goto and co-workers, 1981; Lee and Marano, 1979; Luft and
Seidl, 1981; Gupta and co-workers, 1985; Takahashi and Ehrlich, 1982; Nigam and co--workers, 1983;
Yoon and Rhee. 1985). The high pressures (>2000 bars) and temperatures (>250°C) make it
difficult to obtain accurate kinetic constants using small scale laboratory experiments. Thus,
one has to rely on published literature for kinetic data. Unfortunately, there is very little
agreement between the various publications. The lack of data is not limited to the kinetic
parameters. It is also evident in the transport and thermodynamic properties of
ethylene/polyethylene mixtures at elevated temperatures and pressures, thus precluding any
accurate description of the heat transfer process. Being fully aware of the limitations, we set
out to develop a computer model that would assist us in scale-up and process development efforts
related to the production of polyethylene by the free radical polymerization process in the
tubular reactor. This paper gives an outline of our attempts at meeting these goals.

MODEL DESCRIPTION

The model is based on the following widely accepted kinetic scheme for free radical polymerization
of ethylene: initiation; propagation; termination by combination, disproportionation; chain
transfer to monomer. polymer, transfer agents; and short chain branching reaction.

1n addition to the species balance associated with the above reaction scheme, we also include a
heat balance for an idealized tubular reactor. In reality, the above kinetic scheme would result
in an infinite number of balance equations. However, a finite set of closed form equations is
obtained by using generating functions as outlined by Lee and Marano (1979). The mass and heat
balance equations that result from this analysis are in the form of stiff non-linear ordinary
differential equations. The stiffness characteristic is a result of the wide disparity in the
rates of the various kinetic steps.

The equations are solved by the GEAR routine designed for stiff differential equations. The bulk
of the computer programming effort, which is done In APL, is concerned with the definition of the
function and its Jacobian, as follows:

El - Fi(Y1. Y2......YN, t)
dt

i = 1, 2,......N
t = residence time

1031
1032 P. P. SHIRODKAR and G. 0. TSIEN J-2

where Yi represents the various unknowns such as monomer, initiator, radical, polymer,
temperature and moments of the radical and polymer distribution. The specific forms of the
function Fi and the reaction mechanism on which they are based are discussed in the Appendix.

The Jacobian of the functions is a matrix with the elements defined by

The differential equation solver is the basic unit of the computer model and is used in various
reactor configurations and initiation injection systems. The only variations are in the initial
and boundary conditions associated with changes in the reactor inlet temperatures, peroxide type,
reactor configuration (1 or 2 zones), or peroxide injection location. The output from the
computer simulation consists of two matrices. One representing the profiles of temperature,
concentration of various species (e.g., monomer, initiator(s), radical, polymer, and chain
transfer agent(s)) concentration and also the various moments of the radical and polymer chain
length distribution. The second matrix deals with the profiles of conversion and polymer
properties (e.g., En, k_fw,e&n, SCB/lOOOC and LCB/lOOOC).

To simulate actual plant operating modes, the computer model includes such features as: specified
peak temperature, its location, and/or constant molecular weight. The desired values are achieved
by a trial and error adjustment of the peroxide concentration, inlet temperature, and modifier
concentration, respectively. In view of the large computational time required for the solution of
the ODE's, the half-interval method provides the best algorithm for the implementation of the
trial and error procedure.

In the following section we will discuss specific applications of the computer model in a
production environment.

RESULTS AND DISCUSSIONS

The computer model was applied to simulate the effects of process variables on the performance of
a two--zone reactor. Good agreements between computed and production data are apparent, as shown
in the examples which will follow.

Before we proceed with specific examples, however, it is worthwhile outlining the reaction
process. It is initiated at the beginning of the tubular reactor by injection of an Initiator
mixture (oxygen and peroxides) suitable for the temperature. The reaction proceeds rapidly and
almost adiabatically to a peak temperature at which the initiators and radicals are nearly
depleted. Thereafter, cooling occurs in the reactor, the monomer conversion ceases and the
molecular characteristics of the product remain unchanged. For a two-xone reactor, the reaction
mixture from the first zone is mixed with fresh monomer before entering the second sane for
further reaction. The ratio of fresh monomer feeds <i.e., first zone to second zone>, is referred
to as the split ratio.

Figs. 1 and 2 show the effect of changing inlet temperature on reactor conversion as computed by
the model and observed in production under similar process conditions. Other than the difference
in the inlet temperature, the peak temperatures, peak positions and product quality were
maintained constant in the two cases by adjusting the initiator concentrations and the modifier
concentration. The computed temperature profiles and conversions agree with actual data within
10%. There was no change in short chain branching for the two cases. In both Figs. 1 and 2 the
changing slope during the reaction portion Is due to the mixture of peroxides.

Fig. 1 Simulation of two--zone LDPE reactor under low

inlet temperature (1) and high Inlet temperature <2)
Key: ooo - Data; - Computed Profile
J-2 Production of polyethylene

FINAL CONVERSION
CURVE COMPUTED ACTUAL
(1) 28.8 28.2
(21 25.2 28.3

20 40 80 80 20 40 80 80 100

PERCENT OF ZONE LENGTH

Fig. 2 Effect of inlet temperature on reaction conversion;
low inlet temperature (1) and high inlet temperature (2)

Figure 3 shows the effect of varying low temperature peroxide initiator concentrations with the
inlet temperature unchanged. It is observed that with the increase in the initiator
concentrations, the peak position moves forward shortening the reaction part and lengthening the
cooling part. This leads to a corresponding decrease in conversion, as shown in Fig. 4. The peak
temperature, however, is relatively insensitive to initiator concentration.

1.0 II
0 20 40 80 80 100
-.3 13
24 28 28 30 32 34 38

PERCENT OF ZONE LENGTH PEAK POs.ITION, PERCENT ZONE LEN0-r”

Fig. 3 Effect of initiator concentration on Fig. 4 Effect of peak temperature position

the temperature profile at constant inlet temperature on
reactor conversion

Temperature and pressure variation influence the rates of the individual chemical reactions and
thus, the product molecular structure. Chain transfer, short chain branching and long chain
branching are enhanced by higher temperature and/or lower reaction pressure. Figures 5 and 6 show
the effect of pressure on polymerization in a two-zone tubular reactor. Two resins of identical
melt index, produced under similar temperature profiles but different pressure, are compared. The

Fig. 5 Simulation of two--zone reactor under low (1) and

high (2) reactor pressures: o - Data, - Model
 1034 P. P. SWTRODKAR and G. 0. TSIEN J-2

Fig. 6 Effect of pressure on molecular properties;

<I) low and (2) high pressure

computed temperature profiles and conversions for the two cases are again in good agreement with
actual observations during production (Fig. 5). The computed molecular structural changes along
the reactor tube length were plotted in Fig. 6. The model predicted the associated increase in
density (by short chain branching) with pressure. The model correctly predicts the decrease in
the long chain branching and polydispersity with an increase in pressure.

The computer model can help determine which process parameters should be changed to achieve higher
monomer conversion at equivalent product quality or improve product quality at the same conversion
level. The results give guidance in the process optimization and process control of a commercial
reactor.
2.4
1.2 I I

1 .o

;I:!:
P CONVERSION: 1.7 PERCENT

.2 - I I I
1.28 1.30 1.32 1.34 3.36
lNLET TEMP./REF. TEMP.

Fig. 7 Effect of initiator type on conversion. Fig. 8 Simulation of double injections of

The half-lffe temperature of the initiator in a single reactor zone
peroxides are in the order of ACWC

The reactor temperature profiles directly relate to conversion and resin product properties. The
temperature profile can be controlled using different initiator types, initiator concentrations
and injection modes, and by controlling reactor jacket temperature. Figure 7 shows that proper
selection of initiator can increase conversion at constant product properties with other process
conditions fixed. Multiple injections of initiator to a reactor zone, as shown in Fig. 8, could
also increase monomer conversion. The increase attainable is limited by the heat transfer
capacity in the reactor, however.

The monomer feed split ratio change in a two--zone reactor may offer another avenue for conversion
increase. Figure 9 shows the relative increase in conversion when the split ratio changes from 1
to 3. Curve A assumes no limitation in the pre-warmer, such that constant inlet temperatures to
both zones can be maintained. The model predicts conversion increase with split ratio increase.
J-2 Production of polyethylene 1035

For Curve B, the second zone inlet temperature depends on the exit temperature of the reaction
mass from the first zone. As a result, the inlet temperatures to the second zone are lower at the
low split ratios and higher at the high split ratios, relative to that for Curve A. This affects
the overall conversion and Curve B shows a maximum at about 1.8 split ratio.

A0
,.o 1.4 1.8 2.2 2.8 3.0

SPLIT RATIO

Fig. 9 Effect of comonomer split ratio on the reactor conversion

(in a two--zone reactor). Curve A: Constant inlet temperatures
and peak temperatures in both zones; Curve B: Zone 2 inlet
temperature depends on Zone 1 outlet temperature and the
fresh monomer feed temperature_ C2 - Cdnversion in two-
zone reactor, Cl - Conversion in single zone reactor.

CONCLUSIONS

The present model can be used with good confidence for the simulation of free radical
polymerization at high pressure in tubular LDPE reactors.

As we have seen from these examples, the model can be a powerful tool for testing process
development concepts before the initiation of pilot plant or plant scale-up.

REFERENCES

Agrawal, S. and C.D. Han (1975). AIChE J., -21 (3), 449.

Chen, C-H., J.G. Vermeychuck, and P. Ehrlich (1976). AIChE J., -22 (3). 463.

Donati, G., L. Marini, G. Marziano, C. Mazzaferri, M. Spempinato, and E.Langianni (1982). Proc.
7th Int. Symp. CHem. Reaction Eng. <Boston), 579.

Ehrlich, P. and G.A. Mortimer (1970). Adv. Polym. Sci., 1, 386.

Goto, S. K. Yamamoto. S. Furui, and M. Sugiomoto (1981). J. Appl. Polym. Sci., Appl. Polym.
symp., 36, 21.

Gupta, S. K., A. Kumar and M.V.G. Krishnamurthy (1985). Polym. Engr. Sci., -25 (1). 37.

Lee, K.H. and J.P. Marano (1979). Am. Chem. Sot. Symp.. 104, 221.

Luft, G. and H. Seidl (1981). J. Macromol. Sci-Chem., 415 (11, l-33.

Luft, G. and R. Steiner (1971). Chem. zeitung, 95 (11, 11.

Nigam, K.M. and K.D.P. Nigam (1983). J. Appl. Polym. Sci., (281, 887.

Ray, W.H. (1967). Can. S. Chem. Eng., 41, 346.

Takahaski, T. and P. Ehrlich (1982). Macromolecules, 15, 714.

Thies, J. and K. Schoenemann (1970). 1st Int. Symp. Chem. Reaction Eng. <Washington, D-C_)_

Yoon, B.J. and H.K. Rhee (1985). Chem. Eng. Commum.. (34), 253.
1036 P. P. SHIRODKAR and G. 0. TSIEN J-2

APPENDIX

1. Reaction Mechanism
Rate Constant

Initiation =n+2R 1 %
Propagation Rl + M + R2 K
p
Ri + M+ Ri+1

Monomer Transfer RifM+P

i
+R
1 Kfm
Solvent Transfer Ri + Sn -+ Pi + Rl
Kfsn
Long Chain Branching RffP +R +Pi Kf
j j P
Termination:
Combination Ri + R Kt
j * pi+j
Disproportionation RifR
j
+Pi+P
j
KtC
d
Short Chain Branching R-(CH2)3 + R-CH-C4HV
TCB

where initiator n
I* -
s = solvent n
R" = radical of chain length i or j
M = monomer
P - polymer of chain length i or j
K - reaction rate constant of the step

For each of the reactions discussed earlier, three parameters are used to determine their
kinetic constant value at any temperature and pressure according to the modified Arrhenius
equation:

k = ko exp[-(Ea/1.987 + VaP )/TI

82.06

where ko = frequency factor

Ea = activation energy, cc/mole
Va = activation volume, cc/mole
P = pressure, atm.
T = temperature, OK

The values of these kinetic parameters vary significantly in published literature (Ehrlich
and Mortimer, 1970; Goto and co-workers, 1981; Lee and Marano, 1979; Luft and Steiner, 1971;
Takahashl and Ehrlich, 1982; Thies and Schoenemann. 1970). The finding of appropriate values
for our model were largely through trial and error matching of plant data. The principal
rate constants are shown in Table 1.

TABLE 1 Polymerization Rate Constants

Frequency Activation Activation

Factor ~
Enernv_I
Volume
(mole, 1, sec.) (Cal/mole) (cm3/mol)
--

Propagation 5.8 ~7 7769 -21.3

Termination by Combination 2.8 E8 298 1.0

Termination by Disproportionation 1.3 E8 0 0

Chain Transfer to Monomer -_ -- __

Chain Transfer to Polymer 7.5 E6 8942 1.6

Short Chain Branching 1.3 EV 9935 0

J-2 Production of polyethylene 1037

2. Non-Linear Differential Equations

The following set of equations ere based on the transformed mese and heat balance equations.

dY1 = - Kp . Yl . Ga
dt

F2 dY2 = Kp . !3 . Yl . Gs - y (YP-TJ)
dt

dY3 - t Ki.1 + Kp _ C . Yl . Gs . - l/2 . Ktc . Ga

dt

F4 dY4 = P Kf.1 + Kp . Yl . Gs . (C+l)

dt

F5 dY5 = 2 . Kp . Yl . Y6 + Ktc . Yg
dt

F6 dY6 = EKi . I + KP _ ~1 _ GE + Kp . c . ~1 (GE-~6)

dt
Kt . Gs . Y6 - Kfp [Y4 (Y6<s) - Gs . Y51

F7 dY7 - -Ki.I
dt

F8 dY8 - Kfsn . S, . Gs
dt

where GS G(l,t) = TRi

1

C Cfm + <: Cfsn &)

1 M

where Cfm - Kfm

Kp

Cfsn - Kfsn
Kp

Kt Ktc + Ktd

Yl M = monomer co*c_ (mole/liter)

Y2 T = temperature

Y3 H<l,t) <mole/liter) =: (RI + Pi)

1

Y4 H'(l,t) (mole/liter) = L i(Ri + PI)

1

Y5 H"<l,t) = E i<i-l)(IRi + Pi>

1

Y6 G'(l,t) = "L iRi

1

Y7 I = vector of initiator cow. <mole/liter)

Y8 s = vector of solvent cont. <mole/liter)

LCB Long Chain Branching (# Branch/lOOOc)

SCB Short Chain Branching (# Branch/lOOOc)

a (-El, r = 2, TJ = Jacket Temp.

PCP DQCp
1038 P.P. SHIRODKAR and G. O.TSIEN J-2

(-AH) - heat of polymerization

density of rkctant mixture
P -
C heat capacity of reactant mixture
P
D tube diameter
IJ overall heat-transfer coefficient

3. Molecular Properties

The measurable quantities of the polymerization producte are the number and weight average
molecular weight, and the number of short and long chain branchings. These can be expressed
in terms of the moments of the total polymer concentration as follows:

4-l - X, M’ - M’H’ (1,t)

H (1,t)

M, - x, M' - M' H"(1.t) +1

H' <l,t) >

t
LCB - J 14000 kq, G(l,t)H(l,t)dt
o M'k' Cx,t>

t
SCB - $14000 ksGR G<l,t) dt
0 M'H' (1,t)

where M' is molecular weight of a monomeric unit