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Abstract
A comprehensive mathematical model is developed for the simulation of high-pressure
Low Density Polyethylene (LDPE) plants. Correlations describing the thermodynamic,
physical and transport properties of the ethylene-polyethylene mixture are presented and
compared with experimental data. Energy balances around the compression units are
derived to calculate the energy requirements. A detailed kinetic mechanism is proposed
to describe the molecular and structural developments of the free-radical polymerization
of ethylene. Based on the postulated kinetic mechanism, a system of differential mass
balance equations are derived for the various molecular species, total mass, energy and
momentum in the polymerization system. Simulation results show that the proposed
mathematical model can be successfully applied to the real-time prediction of reactor
temperature profile and polymer melt index. Moreover, model predictions are compared
with industrial measurements on reactor and coolant temperature profiles, reactor
pressure, conversion, and final molecular properties for different polyethylene grades.
Finally, various equations of state (e.g., Sako-Wu-Prausnitz, SAFT, PC-SAFT) are
employed to simulate the operation and phase equilibrium in the flash separation units.
1. Introduction
Low Density Polyethylene (LDPE) is used in a large number of applications (e.g.,
packaging, adhesives, coatings, and films), as a result of the wide range of molecular
and structural properties. LDPE has been commercially produced in high-pressure
reactors for more than 4 decades. Two reactor technologies (i.e., tubular and autoclaves)
are employed in the high-pressure polymerization of ethylene. The polymerization of
ethylene is typically carried out at high temperatures (120-320°C) and pressures (1500-
3000 bar). Thus, in the presence of a mixture of initiators (e.g., peroxides, azo
compounds), ethylene can be polymerized via a free-radical mechanism. A large variety
of LDPE grades is usually produced from a single reactor line, (e.g., with different
polydispersity, long chain branching and density, 0.915-0.935 g/cm3).
A generic flow diagram (Figure 1) of the high-pressure ethylene copolymerization
process can be described as follows: Fresh ethylene, after the primary compression, is
mixed with the recycled ethylene and comonomer (e.g., vinyl acetate, methyl acrylate,
ethyl acrylate, methacrylic acid, etc.), that is then pressurized to the desired reactor
pressure in the second compression stage. Polymerization of the monomers is
596 P. Pladis et al.
---I~~ ~ Cooler
Primary I SecondaryI I1~=1 I1=~= I ! ~ Valve I
Compressor I CompressorI_ ~.. I T I I 1
I °°°'' Ic°°'"' I _ Ic°°''n'
I Sid, F, = =~ ~ ~ / HP Separator
• e eedI SideFeed2 SideFeedN-1 ~ ;
Dryer
Extruder
Initiator(s) decomposition
ii k~ > 2 R* ; i = 1, 2,...,N i
Chain initiation reaction
R* +M k, > R1
Thermal initiation
3M kthj > R 1
Propagation
Rx + M kp > R x+l
Transfer to Monomer
Rx + M k~ ) Dx + R1
Transfer to CTAs
R x + Dy kvij ) Dx + Ry
Intramolecular Chain Transfer (SCB)
R x kbi ) Rx
13scission of secondary and tertiary radicals
Rx k~,k~, ) Dx_l + R1
scission of intemal radicals
R x +Dy k. ) D x + R z + D y - z
Termination by combination
R x + Ry ktcij ) Dx+y
Termination by disproportionation
R x + Ry ktdi) > D x + D y
represent model predictions (obtained through the on-line parameter estimator modulus
of the software) while the discrete points represent the experimental temperature
measurements. It is apparent that the model predictions are in a very good agreement
with measured temperatures. In Figure 3-5, ethylene conversion, number average
molecular weight, and long chain branching per 1000 carbon atoms are plotted with
respect to the reactor length for Grades A, C, E. In all cases, the predicted final
properties are in a good with the experimental measurements.
Separator Units. To accurately predict the performance of the flash separators, a study
of the thermodynamic phase equilibrium behavior of an ethylene/polyethylene mixture
was undertaken. The phase equilibrium in the separator units is of major importance
because it determines the residual amounts of monomer and other gases in the polymer
leaving the high- and low-pressure separators and, on the same time, determines the
flows and compositions of streams in the LDPE plant.
A Comprehensive Investigation on High-Pressure LDPE Manufacturing 599
1.10
1.00 ~ ., I
I ~*_~-- ",
~~ 0.90. .°L'"~.
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.
n
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i
.... GradeE l
I0 ~ ~A~I
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-- [] Grade A exp.
~ o ~E~.I
5
0.50 , ~ Grade C exp.
* Grade E exp.
0.40 , , , , , , , , , , , , 0 , i , i , i , i , I , f , i , i , | , i ,
0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
3. Conclusions
It is well known that the dynamic behaviour of the complete plant can be completely
different from the behaviour of the reactor due to the various recycling streams and
different time-scaled process units (Cervantes, 2000). Grade transition operation is
essential in continuous polymer plants because many grades of polymers are produced
from the same process. The reduction of the amount of off-specification polymer during
the grade transition operation is important for the economical operation of continuous
polymer plants. The development of a comprehensive mathematical model for the high-
pressure LDPE process should include detailed modeling of the following process units:
a) the monomer(s) compression unit, b) the polymerization reactor, and c) the product
separation system as well as accurate predictions of the thermodynamic and transport
properties of the fluid at the various stages of the process. In the present study a
comprehensive mathematical model for the design, simulation of industrial high-
pressure LDPE plants was developed. Various equations of state and correlations for the
predictions of physical, thermodynamic and transport properties of the reaction mixture
were calculated and each of the basic process units were successfully modelled.
600 P. Pladis et al.
• o~¢ l
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6"
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zx Grade C c x p i l
.....................
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z~ ..... , .. .................. .<........ "g 3"
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r,j
..... ":'...
LOxl041
g2
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0.0|, , , , , , , , , , , , , , , , , , , , ,
o ' ! , ! , i , i , u , u ,
0.0 0.1 0.2 03 0.4 0.5 0.6 0.7 0.8 0.9 L0 L1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1
R d a ~ l~actor I a C h Relative Reactor Length
L4xl0 ~ 11111)
1.2x30s
m~m - O- ]i[qtlid~
tOxB ~
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v~ I ...... ~ ............................ __'2_.._
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am
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References
A. Buchelli, M.L. Call, A.I. Brown, C.P. Bokis, S. Ramanathan, and J. Franjione, 2004,
Nonequilibrium Behavior in Ethylene/Polyethylene Flash Separators, Ind. Eng. Chem. Res.,
43, 1768.
A. Cervantes A, S. Tonelli, A. Brandolin, A. Bandoni, L. Biegler, 2000, Large-scale dynamic
optimization of a low density polyethylene plant, Comp. Chem. Eng., 24, 983
C. Kiparissides, A. Baltsas, S. Papadopoulos, J. Congalidis, J. Richards, M. Kelly, and Y. Ye,
2005, Mathematical Modeling of Free-Radical Ethylene Copolymerization in High-Pressure
Tubular Reactors, Ind. Eng. Chem. Res., 44, 2592.
P. Pladis and C. Kiparissides, 1998, A comprehensive Model for the Calculation of Molecular
Weight and Long Chain Branching Distribution in Free-Radical Polymerizations, Chemical
Engineering Science, 53, 18, 3315.