16th European Symposium on Computer Aided Process Engineering and 9th International Symposium on Process Systems Engineering W.

Marquardt, C. Pantelides (Editors) 2006 Published by Elsevier B.V.

595

A comprehensive investigation on high-pressure LDPE manufacturing: Dynamic modelling of compressor, reactor and separation units
Prokopis Pladis, Apostolos Baltsas and Costas Kiparissides
Chemical Engineering Department and Chemical Process Engineering Research Institute Aristotle University of Thessaloniki, P.O.Box 472, 54006 Thessaloniki, Greece

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. Keywords: Modeling, LDPE, Compressor, Reactor, Separation, Phase Equilibrium.

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 (120-320C) and pressures (15003000 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
Ethylene Peroxides Coolant Peroxides Coolant Peroxides Coolant

P. Pladis et al.

Reactor Zone 1

Reactor Zone 2

Reactor Zone N

Feed

. ..
Coolant Side Feed 1 Side Feed 2

Products

Cooler

Primary Compressor

Secondary Compressor Coolant

Valve

..

Coolant

HP Separator

Side Feed N-1

Wax Separator

Cooler

HP recycle Valve

Wax Wax Separator Cooler LP recycle

LP Separator

Wax Dryer Extruder

Silo Polyethylene

Figure 1. Schematic representation of a high-pressure LDPE tubular reactor process.

initiated by adding a mixture of chemical initiators (e.g., organic peroxides). The monomer conversion per reactor pass can vary from 15 to 35 %. The separation is performed in two successive stages. In the first stage, the let down valve drops the pressure of the outlet reactor stream to 150-300 bar. The ethylenepolyethylene mixture entering the high-pressure separator is split into a polymer rich liquid phase (containing 70-80% per weight) and an ethylene rich gas phase (containing ethylene and small amounts of wax). The polymer rich liquid phase from the bottom of the high-pressure separator is directed to the low-pressure separator. In the second stage, the pressure of ethylene-polyethylene mixture entering the low-pressure separator is further reduced to about 1.5 bar. The ethylene gas leaving the low-pressure separator is directed to the primary compressor and is mixed with fresh ethylene feed. The liquid bottom stream leaving the low-pressure separator (containing very low concentration of ethylene) is sent to the extruder where the polymer is pelletized. Over the past 30 years a great number of papers have been published on the modeling of LDPE tubular reactors (Kiparissides et al., 2005). However, most of the published studies are limited to the modeling of the polymerization reactor. As a result, there are only a few publications that deal with the description of the modeling of the high- and low-pressure separation units. The development of a comprehensive mathematical model for the highpressure 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. In this study, the thermodynamic, physical and transport properties of the reaction mixture at the various stages of the process are calculated by using a number of equation of states. In addition the energy requirements of compressor units is calculated. A comprehensive mathematical model for the design and simulation of high-pressure

A Comprehensive Investigation on High-Pressure LDPE Manufacturing

597

LDPE reactors is presented. The predictive capabilities of the proposed mathematical model are demonstrated by direct comparison of the model predictions with literature experimental measurements and industrial data covering a wide range of operating conditions. Finally, the calculation of phase equilibrium and the dynamic operation of high and low-pressure separator units is discussed. The ethylene-polyethylene phase equilibrium is calculated using various equations of state (e.g., Sako-Wu-Prausnitz, SAFT, PC-SAFT). The dynamic model of the separator is able to predict deviations from the theoretical phase equilibrium state as it has been observed in real plant data.

2. Modeling of LDPE Plant Units

Compressor Units. The accurate modeling of primary and secondary compressor units are essential in LDPE production plants. In the primary compressor system, the pressure is raised from about 1.5 bar to about 260 bar. In the secondary compressor system, the pressure of the compressed monomer(s) and solvent(s) is raised to the reactor feed operating conditions (2400 - 2700 bar).The compression of gases is accomplished in high-pressure reciprocating compressors. To account for the temperature increase after a compression stage the energy balance calculations around the compressor unit should be derived. From the steady-state energy balance around the compressor unit, we obtain for the initial (1) and final conditions (2), respectively: H = H 2 H 1 = Ws Normally, the inlet conditions (T1,P1) and the discharge pressure P2. are known. Thus we know only H1 and H2 and Ws are left as unknowns. In a compression process the isentropic work is the minimum shaft work required for compression of a gas from a given initial state to a given discharge pressure: (H )s = Ws (isentropic) In a non-ideal operation the compression efficiency is defined as follows:
= Ws (isentropic ) (H )s = Ws H

Compression efficiencies are usually in the range 70 to 80 percent. The compressor efficiency is used to determine the actual enthalpy change and therefore the actual temperature at the compressor outlet. For the thermodynamic calculations SAFT equation of state was employed. Tubular Reactor Units. Polymers made by free-radical polymerization are typically mixtures of macromolecules with different molecular structural characteristics (e.g., copolymer composition, chain length, and short and long chain branching frequencies). Since the molecular features of the produced polymers are directly related to their enduse properties, control of the polymer chain microstructure during polymerization is of profound importance. This presupposes a thorough understanding of the polymerization kinetics. In the present study, a comprehensive kinetic mechanism is postulated to describe the free-radical polymerization of ethylene. The elementary reactions considered are summarized in Table 1 (Kiparissides et al, 2005; Pladis and Kiparissides, 1998). The kinetic constants are taken by Kiparissides et al. (2005). The predictive capabilities of the mathematical model were examined by simulating the operation of an industrial high-pressure LDPE tubular reactor. Figures 2 - 5 illustrate some representative simulation and experimental results of the industrial LDPE tubular polymerization reactor. In Figure 2, scaled reactor temperature profiles are plotted for three homopolymer polyethylene grades (A, C, E). The number of temperature peaks (three) corresponds to the respective initiator injection points. The continuous lines

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Table 1 : Kinetic Mechanism of Ethylene Polymerization Initiator(s) decomposition
k I i 2R
di

P. Pladis et al.

;
I

i = 1, 2, ..., N i

Chain initiation reaction

+ M
k

k R1

Thermal initiation
thj 3M R1

Propagation

Rx + M

p R x +1

Transfer to Monomer
tm R x + M k Dx + R1

Transfer to CTAs
tsij R x + S k D x + R 1 , k = 1, 2 , Ns

Transfer to Polymer (LCB)

R x + D y D x + R y
Intramolecular Chain Transfer (SCB)

k tpij

Rx

k
bi

Rx

scission of secondary and tertiary radicals

R x D = x 1 + R 1
scission of internal radicals
k R x + Dy Dx + R z + D= yz
B

k ,k '

Termination by combination

R x + R y D x + y
Termination by disproportionation

k tcij

R x + R y D = x + Dy

k tdij

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

1.10

599

Relative Reactor Temperature

1.00 0.90
Ethylene Conversion

30 25 20 15 10 5 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
Grade A Grade C Grade E Grade Aexp. Grade Cexp. Grade E exp.

0.80 0.70 0.60 0.50

Grade A Grade C Grade E Grade A exp. Grade C exp. Grade E exp.

0.40 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0

Relative Reactor Length

Relative Reactor Length

Figure 2. Predicted vs measured temperature profiles (Grades A, C, E).

Figure 3. Predicted vs experimental ethylene conversion profiles (Grades A, C, E).

The separation of LDPE from the unreacted monomer and solvents is carried out in a two-stage process downstream the tubular reactor (Buchelli, 2004). In the first stage, the pressure of the reactor outlet stream is reduced to 260 bar and then is directed at the inlet of the high-pressure separator. The polymer rich liquid phase from the bottom of the high-pressure separator is directed to the low-pressure separator. In the second stage, the pressure of ethylene-polyethylene mixture entering the low-pressure separator is further reduced to about 1.5 bar. In Figure 6 the Molecular weight distributions (MWD) of the vapor and liquid phases as well as the NAMW calculated at 1500 bar using the Sako-Wu-Prausnitz equation of state. As it can be seen the polyethylene of the vapor phase consist of polymer with lower molecular weights compared with the polymer in the other phase. Figure 7 depicts the effect of separator pressure on the number average molecular weight of the polymer that is distributed in the two phases.

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 highpressure 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
3.0x10 2.5x10 2.0x10
4

P. Pladis et al.
7
Grade A Grade C Grade E Grade Aexp. Grade C exp. Grade E exp.

Long Chain Branching

5 4 3 2 1

Grade A Grade C Grade E Grade A exp. Grade C exp. Grade E exp.

NAMW

1.5x10 1.0x10

5.0x10

0.0 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1.0 1.1

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

Relative Reactor Length

Relative Reactor Length

Figure 4. Predicted vs experimental NAMW profiles (Grades A, C, E).

1.4x10 1.2x10 1.0x10
-5

Figure 5. Predicted vs experimental long chain branching profiles (Grades A, C, E).

10000

-5

-5

Total Liquid Vapor

Number Average Molecular Weight

8000 6000
Liquid Vapor

Weight Fraction

8.0x10 6.0x10 4.0x10 2.0x10

-6

-6

4000 2000 0

-6

-6

0.0

100

1000

10000

100000

1000000

Molecular W eight

200

400

600

800

1000 1200 1400 1600 1800

Pressure (bar)

Figure 6. Molecular weight distributions of the vapor and liquid phases calculated using the Sako-Wu-Prausnitz equation of state

Figure 7. Effect of pressure on the number average molecular weight of the polymer in the two phases.

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.