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16th European Symposium on Computer Aided Process Engineering

and 9th International Symposium on Process Systems Engineering


W. Marquardt, C. Pantelides (Editors) 595
© 2006 Published by Elsevier B.V.

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 (120-320°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.

Ethylene Coolant Coolant Coolant


Peroxides Peroxides Peroxides

---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 ~ ;

Wax ~arator (~ Cooler HP recycle


Va,ve
Wax ~ LP Separator

Dryer
Extruder

Polyethylene '"'"'~.. ~ ]11111111


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 ethylene-
polyethylene 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 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.
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: AH - H2 - - H1 : - W s
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: (AH)s - - W S(isentropic)
In a non-ideal operation the compression efficiency is defined as follows:
W s (isentropic) (AH)s
Ws 6H
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 end-
use 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
598 P. Pladis et al.

Table 1 • Kinetic Mechanism of Ethylene Polymerization

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 + Sk kt~iJ ) Dx + R1, k = 1, 2 .... Ns


Transfer to Polymer (LCB)

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'"~.
~
!
.
n
i . . . . . . 1,

! . . . . . . . . . . . . . . . . . .

~ ! , .'7
=~ ls :;
~ 0.70 - ; , .
i. ' .: / I--~• .. ~ C
i
.... GradeE l
I0 ~ ~A~I
.~ 0.60 .... Grade E c I~,de Cexp. |

-- [] 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

Relative Reactor Length

Figure2. Predicted vs measured temperature Figure3. Predicted vs experimental ethylene


profiles (Grades A, C, E). 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 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
I--~A / t . . . . . . . . "*
6"
.. .- . .. ~trade
c E I ;
' ~, o GmdoA~. o CJrad~AcxD. i

~!~,. ~ ~1 .~ 5"
zx Grade C c x p i l

.....................
i
y
"~t1{- ,.... l
4"
• .i .................
z~ ..... , .. .................. .<........ "g 3"
: ;
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..................... ........ : . . . . . ~. : ;
r,j
..... ":'...
LOxl041
g2
o

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

Figure 4. Predicted vs experimental NAMW Figure 5. Predicted vs experimental long chain


profiles (Grades A, C, E). branching profiles (Grades A, C, E).

L4xl0 ~ 11111)

1.2x30s
m~m - O- ]i[qtlid~

tOxB ~
• ..A..
v~ I ...... ~ ............................ __'2_.._

s.mao'
,,... aOxlO~
am

~: 4.mao" i '~ .... ' s


s
s s
2.0x10~ s

...... i

100
, -- ......

1000
i ,

10000
• ..............
.....

100000
k
1 ..............

1000000 Z: o ,
..........

i , i , i ,
-

i , i , I i I , I |

o
Pr~e~)

Figure 6. Molecular weight distributions of Figure 7. Effect of pressure on the number


the vapor and liquid phases calculated using average molecular weight of the polymer in the
the Sako-Wu-Prausnitz equation of state 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.