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Decompositions in the production of

low density polyethylene: Reasons,
consequences and prevention
Dragoslav Stoiljkovic

Hemijska industrija

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PHYSICO-CHEMICAL STAT E OF COMPRESSED ET HYLENE GAS

Dragoslav St oiljkovic

Mat hemat ical Modeling, Opt imizat ion, and Qualit y Cont rol of High-Pressure Et hylene Polymerizat ion R…
Cost as Kiparissides

A T HEORET ICAL ST UDY OF T HE KINET ICS OF POLYET HYLENE REACT OR DECOMPOSIT IONS
y. yan
 English version of article „Dekompozicije pri proizvodnji polietilena niske gustine - uzroci, posledice i
sprečavanje“, Hem. ind., 61(6) 357-363(2007); https://www.researchgate.net/publication/345060491

DECOMPOSITIONS IN THE PRODUCTION OF LOW DENSITY POLYETHYLENE

- CAUSES, CONSEQUENCES AND PREVENTION*

(Professional paper)
678.742+66.095.26:022.362

Dragoslav M. Stoiljković1, Slobodan M. Jovanović2, Jovica B. Đorđević3, Budimir Lj. Damjanović3

1
Faculty of Technology, University of Novi Sad, Serbia, 2Faculty of Technology and Metallurgy,
University of Belgrade, Serbia, 3HIP-Petrohemija, Pančevo, Serbia

In the production of low density polyethylene by free radical polymerization of ethylene at high pressure, ethylene
and polyethylene occasionally decompose to carbon, hydrogen and methane resulting in an enormous increase of
pressure and temperature. Huge explosions occur in a polymerization reactor and in the other parts of the
installation. In addition to the well-known reasons for the decompositions, it is pointed out in this work that the
polymerization in the critical entropy conditions is an additional reason for the explosions which has not been
recognized and elaborated in the scientific literature and industrial practice.

Dedicated to Branislav Kenić, the first manager of the PELD factory in HIP-Petrohemija.

Key words: Low density polyethylene • Polymerization stability • Decompositions

In the production of low density polyethylene (PELD), molecules of ethylene gas are connected to
radicals formed by the decomposition of organic peroxides. The peculiarity of this reaction is that it is
possible only at high pressure (several hundred to several thousand bars) and high temperature (150-290
˚C). However, if a temperature above 300 ˚C is reached in some part of the reactor, even for a short
time, instead of polymerization, the decomposition of ethylene and polyethylene molecules into
methane, carbon and hydrogen prevails. At the same time, there is a sudden local rise in temperature,
which spreads to the entire reactor and strong explosions occur, the so-called decompositions, which in
any case lead to financial losses due to production downtime, and can cause significant damage to
equipment. Decompositions occur in almost every plant in the world, even several times a year. They
represent a key problem in PELD production plants in our country and in the world, a problem that has
been solved for more than seventy years and has not yet been solved.
Numerous causes for the initial local increase in temperature are known. However, our theoretical
research and industrial experience point to another cause, which has not been recognized in professional
practice so far and explained in the scientific literature. The local temperature increase is preceded by a
temperature drop below a certain value when conditions for decomposition occur. The paper gives some
original theoretical explanations of this phenomenon, its consequences and possibilities for its
prevention.
* Part of this paper was presented at the 12th Conference "Risk Management, Prevention and Insurance
in Energetics", Dunav-Preving, Belgrade, November 11-12th, 2004
Author address: Dragoslav Stoiljković, Faculty of Technology, 21000 Novi Sad, Bul. Cara Lazara 1,
Serbia, E-mail: dragos@uns.ac.rs
Received: September 10, 2007; Accepted: October 20, 2007.
CLASSICAL INTERPRETATION OF RADICAL POLYMERIZATION OF ETHYLENE

It is a common comprehension that the polymerization of compressed ethylene gas can be

interpreted by the classical free-radical mechanism [1]:

Initiation: RO-OR  2 RO• (formation of initial radicals) (1a)

RO• + CH2=CH2  RO-CH2-CH2•  R1• (the beginning of chain growth) (1b)
Polymer chain growth (propagation): Rn• + CH2=CH2  Rn+1• + heat (94 kJ/mol) (2)
Chain growth termination: Rm• + Rn•  Pm+n or Pm + Pn (3)

In equations (2) and (3), the subscripts m and n represent the number of ethylene molecules linked in
the polymer chain.
Initiation begins with the disintegration of the initiator (1a). These are most often organic peroxides
(RO-OR) or oxygen. The growth of the polymer chain (1b) begins on the initial radicals thus created.
Further chain growth is achieved by binding one ethylene molecule at a time to the growing radical (Rn•)
(2). Growth termination (3) occurs by the connection or disproportion of growing radicals to form one
(Pm+n) or two (Pm + Pn) polymer chains, respectively. The decomposition of the initiator is achieved at an
elevated temperature (150-300 °C), and in order to initiate the polymerization, it is necessary to initially
heat the reaction mixture. However, since heat is released during the growth of the chain (2), further
heating of the reaction mixture is not necessary.
Assuming that all growing radicals have the same reactivity and that there is a quasi-stationary con-
centration of radicals, expression (4) for the polymerization rate (Rpol) is obtained, which is generally
known in the kinetics of radical polymerization.

Rpol = kp (f ki/kt)1/2 M I1/2 (4)

where: ki, kp and kt are the constants of the rate of initiation, propagation and termination, respectively; f
represents the efficiency of initiation, i.e. the fraction of RO• radicals formed by the decomposition of
initiators (1a) that managed to bind to ethylene molecules (1b); M and I represent the concentrations of
monomers (ethylene) and initiators, respectively.
The activation energy is higher for initiation than for the chain propagation and the termination
reactions. Therefore, according to this common interpretation, and based on expression (4), the
polymerization rate is expected to increase exponentially with increasing temperature (Figure 1).

Figure 1.

Shape of the dependence of polymerization rate

Rpol on temperature expected by the classical
theory of ethylene polymerization (equation 4)

2
 Although the described reactions are very simple, their main feature is that they are possible only if
ethylene gas is under very high pressure of several hundred bar, and in industrial conditions in the range
of 1200 to 3000 bars.

TECHNOLOGICAL PROCEDURE FOR THE PRODUCTION

OF LOW DENSITY POLYETHYLENE (PELD)

The technological procedure consists of several basic sections which are described in more detail in
the paper [2]. Here, only a brief overview of the basic sections will be given (Figure 2) and a brief
description of the procedure applied in HIP-Petrohemija (Pancevo).

Figure 2. Scheme of low density polyethylene production process

Ethylene gas is compressed by reciprocating compressors from atmospheric pressure up to 1200-

3000 bar. Thus compressed ethylene is introduced at a temperature of 20-65 °C into a continuous flow
polymerization reactor, of the autoclave or tubular type. (In HIP-Petrohemija it is an autoclave reactor.)
The cold feed stream of ethylene coming from the compression section is mixed by a stirrer with a hot
reaction mixture in the reactor, whose temperature at the inlet to the reactor is 150° C and at the outlet
up to 290° C. By special lines, initiators are introduced continuously into the reactor, which decompose
into radicals and initiate the polymerization of ethylene. The heat released by polymerization serves to
heat the cold feed stream of ethylene. The temperature in the reactor is automatically regulated by the
amount of initiators introduced into the reactor. The conversion of ethylene is 12-20 % so that the
reaction mixture at the exit of the reactor consists of polyethylene and unreacted ethylene. At the outlet
of the reactor, the pressure is reduced and the content is sent to separators for separating polyethylene
from unreacted ethylene. Polyethylene is cooled, granulated and stored in silos, and unreacted ethylene
after purification is sent for re-compression.

DECOMPOSITIONS OF ETHYLENE AND POLYETHYLENE

Working at such high pressures alone creates mechanical and technological difficulties and is a
source of danger, especially when one considers that ethylene gas is flammable in air. (Flammability
range is 2.8-29% by volume of ethylene).
However, an additional danger is the tendency of ethylene and polyethylene to decompose followed
by an explosion. Namely, in addition to the tendency towards polymerization, ethylene has an even
greater thermodynamic tendency (due to a greater reduction in free energy) towards decomposition into
methane, carbon (soot) and hydrogen. (See reactions in Table 1). Polyethylene also has this
thermodynamic tendency to decompose. Due to the formation of gaseous products (methane and
hydrogen), the pressure could increase from 2000 bar to 4690 bar, and the temperature from 227 C to
1593 C [4]. The favorable circumstance is that at temperatures below 300 C the decomposition of
ethylene and polyethylene is very slow, and the polymerization of ethylene is a fast reaction. Therefore,
in industrial plants, care is taken that the temperature never exceeds 300 C in any part of the facility.
But this still happens sometimes for reasons that will be listed later. To prevent the development of very
high pressure and high temperature, industrial plants are equipped with safety membranes that crack and
emit decomposition products into the atmosphere before complete decomposition of ethylene and
polyethylene into gaseous products and before extremely high pressure and high temperature are
developed.

Table 1. Heats of reaction and free energy changes of polymerization

and degradation of ethylene at 227 C [3]
Reaction Heat of reaction Free energy change
(kJ/mol ethylene) (kJ/mol ethylene)
CH2=CH2  polyethylene 94 - 23
CH2=CH2  2C + 2H2 47 - 80
CH2=CH2  C + CH4 127 -113
Polyethylene  2C + 2H2 - 46 - 58
Polyethylene  C + CH4 35 - 90

TYPES AND CONSEQUENCES OF DECOMPOSITIONS

Many types of decompositions are known, which are only briefly presented here, and are described
in detail in [4]. There are several ways to classify them according to: a) the place of the occurrence, b)
the initial pressure, c) the time of occurrence and d) the way of manifestation.
a) By the place of the occurrence, decompositions can be in the compression section, reactor, separators,
unreacted ethylene recycling system, pipelines, and other parts of the plant.
b) By the initial pressure, they can be: at low (below 1000 bar) and high pressure (above 1000 bar).
4
c) By the time of occurrence, they can be: during the addition of the initiator to start the reaction at the
beginning of production, in the first hour after starting, during steady operation, when changing
production conditions, during production shutdown, and in the first hour after production shutdown.
d) According to the manifestation, there are different decompositions: normal (very noisy with a large
amount of smoke, and a flame from the exhaust pipe is possible after the burst of the reactor safety
membrane); flames (same as normal, except that a large flame is created); aerial explosion (after the
bursting of the safety membrane, the contents of the reactor ignite in the air, which causes great noise
and detonation) and pressure release (caused by the bursting of the safety membrane, the noise is
significantly lower and the temperature in the reactor is lower than normal decomposition).
The consequences of decomposition depend primarily on the place of occurrence. If it is a normal
decomposition in the reactor, the consequences are minimal, since the equipment is designed to
withstand the detonation and temperature increase. Then, the most common consequences are damage to
the internal equipment in the reactor (mixer, its blades, bearings, and motor), but the damage to other
surrounding equipment of the plant is minimized because the reactor is surrounded by a concrete wall
that prevents the expanding of detonation. However, in the case of aerial decomposition, significantly
more severe consequences for the surrounding equipment are possible. In all cases, there is significant
damage due to several hours of production shutdown, and sometimes several days of downtime.

KNOWN CAUSES OF DECOMPOSITIONS AND METHODS OF THEIR PREVENTION

Decomposition is considered to be preceded by a local increase in temperature above 300 °C,

resulting in self-acceleration of polymerization as a result of the rapid formation of large amounts of free
radicals by peroxide decomposition and thermal decomposition of ethylene and polyethylene. Self-
acceleration of polymerization leads to the release of a large amount of heat, and this in turn causes even
greater radical formation, faster polymerization, further temperature rise, etc. This development of
decomposition is very fast - everything happens in a split second - so that the instruments and control
devices, as well as the plant operators, have very little time (and sometimes not at all) to react and to
prevent decomposition. Therefore, plant operators have full authority to decide independently on the
immediate shutdown of a plant if they notice any irregularity in its operation.
Numerous causes of local temperature increase preceding decomposition are known [4]: excessive
initiator injection, accidental presence of oxygen, sudden decrease in cold ethylene feed flow, the
occurrence of "dead" zones in which there is no good mixing of cold ethylene feed stream with hot
reactor content, residual soot from the previous decomposition, adhesion of polyethylene to the reactor
wall and the mixer, electrical power supply disruption, mechanical damage to equipment (valves,
mixers, systems for measuring and controlling pressure and temperature, mixer motors, initiator dosing
pumps, etc.), ethylene pulsations on compressor discharge and many others.
In accordance with these known causes, measures are taken to prevent them during the design of the
plant and the technological process, as well as during the process operation. These are, first of all, good
control of temperature and pressure, removal of oxygen by blowing the plant with ethylene before
starting the reaction, prevention of the formation of dead zones with a properly designed mixer, careful
cleaning of equipment. and others. But, despite all the precautions, the average frequency of
decompositions in almost every plant in the world is 2-3 per year, sometimes even higher.

5
INFLUENCE OF PHASE STATE OF COMPRESSED ETHYLENE
ON POLYMERIZATION RATE AND THERMAL STABILITY OF PROCESS

In our theoretical works [5-7], we have shown that during the compression of ethylene, different
supramolecular ethylene particles are formed and that phase changes of the second- and third-order
occur (Figure 3), which crucially affects the mechanism and kinetics of polymerization. Consequently,
the classical theory of radical polymerization is not applicable in this case.

Figure 3.

Supramolecular particles and

phase state of compressed
ethylene [5-7]

It is an experimental fact that the influence of temperature on the polymerization rate is not as it is
expected according to the classical theory (Figure 1 and Equation 4), but that it has a clearly expressed
sharp maximum at a certain temperature that depends on the pressure at which the polymerization is
performed. Four examples are given in Figure 4, and other examples are given in [5-7]. Regardless of
the differences in terms of pressure, reactor type and initiator type, it was observed that the sharp
maxima of polymerization rate always occur when the entropy (S) of compressed ethylene is close to the
entropy at the critical point (Sc), i.e. S/Sc = 1. The entropy of ethylene is equal to the critical one under
different pressure and temperature conditions [9], which correspond to the Sc curve in Figure 3.
According to these experimental facts and theoretical interpretation, the general curve "polymerization
rate (Rpol) - ethylene entropy" looks like in Figure 5.
6
 Figure 4.

Effect of temperature on the polymerization

rate initiated by four different peroxides [8].
Critical entropy of ethylene is at 410 K (137
C) at 100 MPa.

Having the empirical fact that the polymerization rate has a sharp maximum at such pressure and
temperature conditions where the entropy is equal to the critical (critical isentropic curve S/Sc=1 in
Figure 3), three areas can be distinguished in terms of thermal stability of the process (in the absence of
automatic temperature control ) (Figure 5).

Figure 5.

Effect of ethylene entropy (S/Sc)

on polymerization rate (Rpol) and
process stability

The low entropy region, S/Sc<1, is characterized by a low rate of reaction initiation and a reduced
rate of chain growth termination. In these conditions there is an induction period, i.e. polymerization
does not start immediately upon addition of the initiator but after a certain time which can be from a few
minutes to a few hours (Figure 6). The process is unstable, i.e. accidental decrease in temperature for
any reason (e.g. too cold ethylene feed stream, reduced initiator injection, etc.) can lead to quenching of
the reaction. Spontaneous increase in temperature will lead to a sharp rise in Rpol to a very large value
and possible decomposition of ethylene.

7
 Figure 6.

Effect of ethylene entropy (S/Sc)

on induction period tind [6]

The region of moderate entropy, S/Sc>1, is characterized by the normal rates of initiation and
termination reactions. There is no induction period. The process is stable. A spontaneous increase in
temperature, however, will lead to a decrease in Rpol, less heat will be released and the temperature will
decrease. Conversely, a spontaneous decrease in temperature will increase Rpol, more heat will be
released and the temperature will increase. However, the effect of temperature is completely contrary to
expectations based on the classical theory of radical polymerization (Figure 1 and Equation 4).
The region of high entropy, S/Sc>>1, is characterized by fast decomposition of the initiator, but
slow Rpol, because ethylene is less capable of polymerization. Ethylene is more prone to decomposition
into methane, carbon and hydrogen. The process is unstable and prone to decomposition.

LOCAL REACTOR OVERHEATING INITIATED AT LOW TEMPERATURES AS A

POSSIBLE CAUSE OF DECOMPOSITION - EXPERIENCES AND RECOMMENDATIONS

In order to prevent decomposition, the reactor operation in the range of large entropy should be
avoided, i.e. above 300 ° C, which is generally known. Therefore, the usual conditions in the reactor
correspond to the region of moderate entropy, S/Sc>1, where the reactor is stable.
However, our theoretical considerations and practical experience show that a local increase in
temperature can occur in the region of low entropy, especially at S/Sc=1, which corresponds to
relatively low temperatures, approximately 150-160 ˚C at pressures of 1000-3000 bar (Figure3). Then
the rate of polymerization is highest, which can cause a large increase in temperature, at least in a small
space of the reactor - and then there is a possibility of local decomposition, which can then spread to the
entire reactor.
For example, a large number of decompositions in some plants in the world occurred in the
production of one type of polyethylene under the following conditions in an autoclave reactor: pressure
2000 bar, and a temperature of 150 ˚C at the beginning and 290 ˚C at the end of the reactor. According
to our interpretation, the cause of these decompositions was that in the upper part of the reactor, where
the temperature is 150 ˚C, the entropy of ethylene was close to the critical entropy (Figure 7). Therefore,
there is a sharp maximum of polymerization rate as well as local overheating in that part of the reactor,
which is then transferred to the entire reactor and causes decomposition. The stated experiences and
theoretical interpretation indicate that conditions in the reactor in which the entropy of ethylene is equal
to the critical one should be avoided.
8
 Figure 7.

Ethylene phase state in different

steps of PELD production process

However, this cannot always be avoided completely. Namely, the temperature of ethylene that feeds
the reactor is 20-65 ˚C, and the pressure is 1200-3000 bar. Then the entropy of ethylene is very small,
i.e. S/Sc<<1 [9]. Entering the reactor, cold ethylene is mixed with the hot content of the reactor (170-
250 ˚C). Each particle of the cold feed ethylene stream is heated and passes through the region of critical
entropy (S/Sc=1) (Figure 7) and simultaneously mixed with the initiator. Thus, at least for a short time
and locally, the conditions are created for extremely fast polymerization and local overheating of the
reaction mixture - which is a prerequisite for decomposition.
Local overheating and decomposition can also occur during the polymerization start-up. Namely,
before the start-up, firstly the flow of cold ethylene at a certain pressure through the reactor is
established. Then, ethylene is gradually heated, and when a certain temperature is reached at which the
decomposition of peroxide (reaction 1a) is fast enough to form the initial radicals RO•, the gradual
addition of a small amount of initiator is started. However, in order for these initial radicals to
successfully bind ethylene molecules and start the growth of the polymer chain (reaction 1b), as well as
to continue further polymerization of ethylene (reaction 2), the reactivity of ethylene is crucial, too, and
it depends on the entropy of ethylene. Ethylene is highly reactive if the entropy of ethylene is slightly
higher than critical (S/Sc>1). If the temperature at the moment of adding the initiator at the reaction
start-up is high enough that the entropy of ethylene is slightly higher than the critical one, the efficiency
initiation f will be very high (equations 1b and 4). At these conditions, the polymerization will be fast,
and without an induction period. In this way, a successful start-up of the process is achieved.

9
 However, if the temperature at the moment of the initiator injection at polymerization the start-up is
only a few degrees lower than prescribed by the operating instruction, then the entropy of ethylene will
be less than critical, i.e. S<Sc. Here, ethylene is less reactive, and polymerization will not begin
immediately after the addition of the initiator, but after a certain induction time (Figure 6). Afterward,
the temperature of ethylene begins to rise gradually due to the onset of polymerization and the heat
released. During this heating, the entropy of ethylene reaches a critical value, S=Sc, and ethylene
becomes very reactive. If an excessive amount of initiators is accumulated by that time during the start-
up of the polymerization, an excessive amount of initial radicals will be produced, too: the conditions
are created for very fast polymerization to occur, which can turn into decomposition and explosion. This
is one of the possible causes of decomposition during the start-up of the polymerization.
Decompositions during the quenching of the polymerization reaction can be explained in a similar
way. Namely, before quenching, the temperature in the reactor is high enough that the entropy of
ethylene is higher than the critical one, and the reactor is in a thermally stable state. When quenching the
reaction, whether intentional or spontaneous, the addition of the initiator is interrupted, as a result of
which the temperature in the reactor decreases and ethylene entropy reaches the value corresponding to
the critical one, S=Sc. If a sufficient amount of residual unreacted initiator is still present in the reactor,
conditions are created for very fast polymerization and decomposition. Some of our experiences, as well
as the experiences of some plants in the world, confirm such occurrence development.
Also, it should be noted that in some parts of the plant in the ethylene recycling system and its re-
compression the values of pressure and temperature of ethylene are such that the entropy of ethylene is
equal to the critical one (Figure 7). If there is a sufficient amount of initiator or oxygen in the recycling
ethylene, conditions are created for rapid polymerization, which can lead to decomposition or to the
formation of polymers where it is undesirable. It is not possible to completely avoid critical entropy
conditions in these parts of the plant, but in order to avoid these undesirable phenomena, it is necessary
for the ethylene retention time to be very short in that part of the plant where the ethylene entropy is
equal to the critical one.

CONCLUSION

The local temperature increase is one of the basic preconditions for the appearance of ethylene and
polyethylene decompositions. In addition to numerous generally known causes of local temperature
increase, the paper points to another cause which is a consequence of the formation of supramolecular
ethylene particles and the change of phase state during ethylene compression. This finding is certainly
one of the contributions that the frequency of decompositions in the PELD plant in HIP-Petrohemija
(Pancevo) is lower than the frequency in other plants in the world [4].

LITERATURE

[1] J. Đorđević i V. Unković, Primena novih inicijatora u procesu proizvodnje PENG-a, Svet polimera 3
(2000) 51-56
[2] Đ. Nadeždić, Kratak opis tehnološkog postupka za dobijanje polietilena niske gustine po tehnologiji
"NDCC", Svet polimera 3 (2000) 1-3
[3] A. Renfrew and P. Morgan, Polythene, Illife and Sons, London, 1957.
10
[4] D. Špehar i Đ. Nadeždić, Istorijat dekompozicija u procesu proizvodnje polietilena u fabrici
"PENG", Svet polimera 3 (2000) 57-62
[5] D. Stoiljkovic and S. Jovanovic, Supramolecular organization and polymerization of compressed
ethylene, Acta Polymerica 39 (1988) 670-676
[6] D. Stoiljkovic und S. Jovanovic, Einfluss der Aenderung des Ordnungsgrades des Ethylens mit der
Druckerhoechung auf den Verlauf der radikalischen Polymerisation, Angew. Makromol. Chem. 106
(1982) 195-205
[7] D. Stoiljković, Mehanizam i kinetika polimerizacije etilena pri visokom pritisku, doktorska
disertacija, Tehnološko-metalurški fakultet, Beograd, 1981.
[8] A. P. Golosov, R. A. Terteryan i V. N. Monastirskii: Primenenie initsiatorov pri nizkotemperaturnoii
polimerizatsii etilena, Nefteper. i neftekhim., No. 7 (1973) 23
[9] H. Benzler und A. v. Koch., Ein Zustandsdiagramm fuer Aethylen bis zu 10 000 ata Druck, Chemie-
Ing.-Techn. 27 (1955) 71-75

DEKOMPOZICIJE PRI PROIZVODNJI POLIETILENA NISKE GUSTINE - UZROCI,

POSLEDICE I SPREČAVANJE

Pri proizvodnji polietilena niske gustine radikalnom polimerizacijom etilena pri visokom pritisku
ponekad dolazi do razgradnje (dekompozicije) etilena i polietilena na ugljenik, vodonik i metan uz
izuzetno veliko povećanje pritiska i temperature. Javljaju se burne eksplozije u reaktoru za
polimerizacije i drugim delovima postrojenja. Poznati su mnogi uzroci dekompozicije i razrađene su
mnoge mere za njihovo sprečavanje i ublažavanje.U ovom radu je ukazan na još jedan uzrok, koji do
sada nije prepoznat industrijskoj praksi i obrađen u naučnoj literaturi, a to je polimerizacija u uslovima
pritiska i temperature pri kojima je entropija etilena jednaka kritičnoj.

Ključne reči: Polietilen niske gustine • Stabilnost polimerizacije • Dekompozicije