Materials Today: Proceedings xxx (xxxx) xxx

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Materials Today: Proceedings

journal homepage: www.elsevier.com/locate/matpr

Low-density polyethylene simulated production in high pressure tubular

reactor
Nurzafirah Mohd Supion a, Iylia Idris a, Ayub Md Som a, Fakhrony Sholahudin Rahman b,
Rushdan Ahmad Ilyas c,d, Ashraf Azmi a,⇑
a
School of Chemical Engineering, College of Engineering, Universiti Teknologi MARA, 40450 Shah Alam, Selangor, Malaysia
b
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia, 14300 Nibong Tebal, Pulau Pinang, Malaysia
c
Centre for Advanced Composite Materials (CACM), School of Mechanical Engineering, Faculty of Engineering, Universiti Teknologi Malaysia, 81310 Johor Bahru, Johor, Malaysia
d
School of Chemical and Energy Engineering, Faculty of Engineering, Universiti Teknologi Malaysia (UTM), Johor Bahru, Johor 81310, Malaysia

a r t i c l e i n f o a b s t r a c t

Article history: The importance of the LDPE polymerization process has spawned a slew of LDPE tubular reactor mod-
Available online xxxx elling and simulation projects. Through adjusting input parameters, the sensitivity study of input param-
eters in an industrial low density polyethylene tube reactor was addressed in this paper. This work’s
Keywords: innovation was highlighted with the incorporation of the LDPE melt flow index in the reactor output.
Low-density polyethylene The highest temperature peak and monomer conversion were obtained when initiator concentration
Polymerization were increased by 1.06 factor, whereas the highest melt flow index was obtained when the inlet temper-
Tubular reactor
ature was increased by 1.07 factor. The monomer flow rate, initiator flow rate, and solvent flow rate all
Modeling
Simulation
had a substantial impact on the LDPE process performance in a tubular reactor.
Copyright Ó 2023 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the Composite Sciences and
Technology International Conference.

1. Introduction of LDPE tubular reactor would be in the range of 500–1500 m

Low-density polyethylene (LDPE) is the most frequently used
commercial thermoplastic. It is primarily manufactured from ethy-
lene monomer and is utilized in many important applications,
including coatings and food packaging. Because of its outstanding
flexibility, LDPE is known to have a larger demand for manufacture
on a global scale. Therefore, it is anticipated that from 2019 to
2029, the market for LDPE would increase at a compound annual
growth rate (CAGR) of 5 %.
In order to promote polymerization at high pressure, which
includes joining monomers to polymer chains, ethylene gas is com-
pressed to produce LDPE. The production of LDPE involves a num-
ber of processes, including compression, polymerization, gas
separation, extrusion, and storage, which includes packaging. This
free radical polymerization occurs in a tubular reactor under harsh
working conditions with a variety of initiators present. Further-
more, this reaction operates typically at temperatures of 373.15
– 598.15 K and pressures of 1013.25 – 3039.75 Bar. Typical length
⇑ Corresponding author.
E-mail address: ashraf.azmi@uitm.edu.my (A. Azmi).
which is characterized by immense ratios of length to diameter
(L/D) from 1 to 6
10-4 [2]. A common industrial LDPE tubular
reactor diagram is shown in Fig. 1 [1].
The ethylene monomer, chain-transfer agents (CTA) and initia-
tors (organic peroxides) are present and being used at the feed
inlet of the reactor. Therefore, polymerization process in the LDPE
tubular reactor requires heat prerequisite as the main factor for
this reaction to occur spontaneously. This shows that the initial
section of the tubular reactor acts as the preheater where the ethy-
lene is heated in the presence of steam up to an optimum temper-
ature. The specified temperature is dependent on the type of
initiators being used where it ranges from 190 °C for oxygen to
140 °C for peroxydicarbonate [10].
Polymerization process of ethylene is classified as highly
exothermic and occur in small reaction zones which results due
to peroxide injections. Heat of reaction is partially transferred
through the wall of the tubular reactor by heat-transfer fluid [3].
About half of the heat being generated through the polymerization
reaction process by cooling fluid flowing into the reactor jacket. If
there’s no removal or transfer of heat in reactor, a runaway condi-
tion will occur and it is crucial to monitor the pressure in order to

https://doi.org/10.1016/j.matpr.2022.12.155
2214-7853/Copyright Ó 2023 Elsevier Ltd. All rights reserved.
Selection and peer-review under responsibility of the scientific committee of the Composite Sciences and Technology International Conference.

Please cite this article as: N. Mohd Supion, I. Idris, A. Md Som et al., Low-density polyethylene simulated production in high pressure tubular reactor, Mate-
rials Today: Proceedings, https://doi.org/10.1016/j.matpr.2022.12.155
N. Mohd Supion, I. Idris, A. Md Som et al. Materials Today: Proceedings xxx (xxxx) xxx

Nomenclature

A area v velocity
cp heat capacity x modifier, conversion
Dh heat of reaction z axial coordinate
C concentration
f efficiency of original initiation Greek letters
I initiators D difference
J jacket k i-th moment of live polymer radical
j total number of reaction l i-th moment of dead polymer
k reaction rate constant q density
LCB long chain branching
ṁ mass flow
subscripts
M monomer 0,in initial condition
p polymer b b-scission
R radicals i index of chain length, index of initiator
S solvent
p propagation
SCB short chain branching RX modifier radical
T temperature sec secondary living polymer
U overall heat transfer coefficient

combat the problem on fouling effects due to precipitated poly-
ethylene [1,11].
Sensitivity analysis’ main goal is to increase the monomer con-
version rate, XM (%). The sensitivity study conducted in this study
is to ascertain the impact of the initial initiator (CI), monomer
(CM), and solvent (CS) to the reactor temperature, monomer con-
version, and melt-flow index (MFI) properties, respectively. This
is because melt-flow index (MFI) properties have not been
included in any published literature studies.
2. Materials and methods
2.1. Material preparation
The specified ordinary differential equations listed in Table 2
were resolved using MATLAB R2020. The tubular reactor’s axial
length (z) was separated into two parts for stability where it
enables efficient computational execution. The only consideration
for the current investigation was reaction zone. Since the ode45

Fig. 1. Schematic diagram of LDPE production plant.

2
N. Mohd Supion, I. Idris, A. Md Som et al. Materials Today: Proceedings xxx (xxxx) xxx

solver has the ability to create stabilised non-stiff differential equa- Table 2
tions (NDFs) and stimulate on the numerical differential formulae, Reaction Kinetic Mechanism.

it was chosen to solve these ODEs. Reaction Kinetic Mechanism

Peroxide initiation Kd
I ! 2Rin
2.2. Model formulation Monomer thermal initiation K th
3M ! 2R1
Propagation Kp
Several assumptions were made for this specific reactor model R1 þ M ! Rlþ1
Termination by combination K tc
as stated below: Rl þ Rk ! P lþk
Thermal degradation K thd
Rlþ1 ! P l þ R1
 No axial mixing and ideal plug flow [7]. Chain transfer to monomer K trm
Rl þ M ! P l þ R1
 Pressure drop less than 10 % where pressure inside reactor Chain transfer to polymer kK trp
Rl þ P k ! P l þ Rk
remained constant [2]. Chain transfer to transfer agent K trs
Rl þ S ! P l þ R1
 Reaction mixture was assumed as homogeneous [6]. b-Scission of secondary radical Kb
 Total heat capacities of pure components was assumed as heat Rlþ1 ! P l þ R1
b-Scission of tertiary radical K b1
capacity of reaction mixture [5]. Rlþ1 ! P l þ R1
 Utilization of model where axial length of reactor independent
variable and ODEs being integrated along tubular length [8].

Table 3
2.3. Reaction kinetic mechanism Model Equations.

Initiator Monomer Solvent Mass Energy Balance

Ten reaction kinetic mechanisms are considered in this study as
Mass Mass Balance Balance (CTA)
tabulated in Table 2 [1–2]. Balance
dC lm
v = -2 v dCdzM = - K p v dCdzM = - K ts dT
=
2.4. Model equations dz dt
h i
f di K di C I i C M k0 C S k0 4UðTT j Þ
qC P v DHK p C M k0 
1
Di

The model equations for the LDPE Tubular Reactor were consid-
ered where mass balances were given in Table 3[1–2].
Table 4
2.5. Rate constants and parameters Rate constants for the LDPE Tubular Reactor.

Description on rate constant Rate of reaction constant (1/s)

List of parameters and rate constants for the LDPE Tubular Reac-
Monomer thermal initiation, Kth 4.04E11 exp [1.982E4
tor were taken from Azmi and Aziz [1], and shown in Tables 1 and
(T + 273.15)1]
4, respectively. Propagation, Kp 9.9E5 exp [2.1185E3
(T + 273.15)1]
Termination by combination, Ktc 4.4E4 exp [2.06E3(T + 273.15)1]
3. Results and discussion Chain transfer to monomer, Ktrm 1.2E5 exp [7.2461E3
(T + 273.15)1]
The model simulation was done in MATLAB R2020, and the out- Chain transfer to polymer, Ktrp 1.8E8 exp [4.7303E3
comes were shown in Figs. 2 - 11. The reference conditions for this (T + 273.15)1]
b-scission to sec. radical, Kb 1.4E9 exp [9.6114E3
simulation were the initial concentration (CI) of 3.02
10-9 mol/
(T + 273.15)1]
cm3, the concentration of ethylene (CM) at 9.15
10-5 mol/cm3, b-scission to tertiary radical, Kb1 4.4E9 exp [9.6114E3
the velocity of reaction mixture at 1.40 m/s, the tube length of (T + 273.15)1]
110 m, and the reactor diameter of 0.07 m. The feed temperature Termination by thermal degradation, 7.7E4 exp [9.618E3(T + 273.15)1]
was set to 169.00 °C, and the constant pressure reactor was Kthd

2546 atm. Axial length of the tubular reactor (L) was the indepen-
dent variable, whereas temperature profiles (°C) and monomer
conversion (%) reflect the dependent factors.
flow index (MFI) was 6.60 g/10 min, while the ethylene (monomer)
Fig. 2 shows the region where the reactor temperature rises sig-
conversion was 9.62 %.
nificantly to a peak value between 0 and 11000 cm axial length.
Referring to Figs. 4 and 5, where the CM was increased with the
The highest point where the peak value of the reactor temperature,
factor of 1.04, they clearly depicted that both the reactor tempera-
T, climbed to 250 °C at z = 11000 cm was based on the reference
ture and ethylene conversion were proportional to one another. In
conditions for CI, CM, CS, and inlet temperature that were stated.
addition, greater concentration of initiator, solvent, monomer and
Fig. 30 s result reveals that after running the simulation, the melt-
inlet temperature would lead to higher ethylene conversion that
results in a higher peak temperature since the polymerization of
Table 1 ethylene acts as a highly exothermic reaction. The reaction mixture
List of Parameters for the LDPE Tubular Reactor. was heated to the ideal initiator injection temperature when a
Parameters Value monomer was injected into the tubular reactor under high pres-
sure. It was well known that initiator decomposition was temper-
Length of tubular reactor, L (m) 110
Diameter of reactor, D (m) 0.07
ature sensitive and that it may be hampered if the reaction mixture
Pressure, P (atm) 2546 was larger than the half-life of the applied initiator [1,2].
Initial concentration of monomer, C M0 (mol/L) 0.092 The results that were observed after the increment in the value
Initial concentration of initiator, C I0 (mol/L) 3.02e-06 in CS by 1.05 was shown in Figs. 6 and 7, respectively. It can be
Reaction mixture’s initial velocity, v 0 (m/s) 1.40
observed that the reactor temperature increases from 170 °C to
Inlet temperature, T I (°C) 169.00
Jacket temperature, T j (°C) 160.01 250 °C along the tubular length. As for Fig. 7, ethylene conversion
seemed to decrease slightly from the obtained reference condition

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N. Mohd Supion, I. Idris, A. Md Som et al. Materials Today: Proceedings xxx (xxxx) xxx

Fig. 2. Reactor temperature profile (base case). Fig. 5. Monomer conversion increased by 1.04 along length.

Fig. 3. Monomer conversion (base case). Fig. 6. Reactor temperature profiles increased by 1.05 along length.

Fig. 4. Reactor temperature profile increased by 1.04 along length. Fig. 7. Monomer conversion increased by 1.05 along length.

4
N. Mohd Supion, I. Idris, A. Md Som et al.
Fig. 8. Reactor temperature profiles increased by 1.06 along length.
Fig. 9. Monomer conversion increased by 1.06 along length.
Fig. 10. Reactor temperature profiles increased by 1.07 along length.
(XMref), which was from 9.62 % to 9.61 %. A slightly increment of
the MFI was also observed where it increased from 6.60 g/10 min
to 7.21 g/10 min. It was reported that there would a difference of
10 °C in the reactor feed temperature parameters which may lead
5
Materials Today: Proceedings xxx (xxxx) xxx
Fig. 11. Monomer conversion increased by 1.07 along length.
to reaction peak temperatures to differ more than 10 °C [9]. In
Fig. 7, it was reported that there was a difference of 10 °C in reac-
tion temperature peak was not caused by the 10 °C difference in
reactor feed temperature parameters. Furthermore, the difference
in the reaction peak temperature for this solvent concentration
was quite high since it was above 10 °C. As in comparison, it was
proven that these parameters which involves the reactor tempera-
ture and ethylene conversion were synchronous to one another
when compared with Figs. 2 and 3.
Figs. 8 and 9 showed the results after the increment of the value
in CI by 1.06. It can be observed that the reactor temperature
increases drastically from 170 °C to 300 °C and then decreased
slightly to 298 °C as shown in Fig. 8. Referring to Fig. 9, the result
showed that the ethylene conversion increases to 14.39 % from
9.62 % based on the reference condition whereas the MFI changed
to 19.49 g/10 min. Addition of more initiator would only decrease
the ethylene conversion and zone temperature as it reaches the
optimum peak. Fig. 9 was further studied for this phenomenon.
As seen in Figs. 8 and 9, it was clearly stated that the first initiator
behaves normally in increasing the conversion and peak tempera-
ture. Nonetheless, a difference of 10 °C in the reactor feed temper-
ature parameters may not cause reaction temperature peaks to
differ above than 10 °C [9]. This was due to the fact where higher
initiator concentration promotes greater ethylene conversion
which leads to higher peak temperature since the ethylene poly-
merization was an exothermic reaction [1–3]. Based on the results
obtained in this study, the initiator concentration shows the poten-
tial to be used in controlling the LDPE polymer conversion and
maintaining the reactor temperature.
The results obtained in Figs. 10 and 11 illustrate the increment
effect of value in inlet temperature by 1.07. Based on Fig. 10, the
reactor temperature raised from 180 °C to 300 °C then a sudden
drastic decrease seemed to occur at the final value of 238 °C along
the axial length of tubular reactor. In Fig. 11, the ethylene conver-
sion increased from 0 % to 12.73 %, which depicted a significant
increment between the obtained XM based on reference condition
of 9.62 % to 12.73 %. Changes in the MFI also occured where the
value of 55.57 g/10 min was obtained. It was also believed that
the inlet temperature becomes significant in order to ensure max-
imum utilization of the initiator [2]. It can be seen that after the
injection of initiators, the reaction temperature increases rapidly
to the maximum peak temperature which indicates that the deple-
tion of largest portion of all the initiators as illustrated in Figs. 10
and 11. The cooling of the reaction mixture was carried out by
the coolant which flows through the reactor jacket that occurs in
the cooling zone. The conversion of ethylene becomes static, when
N. Mohd Supion, I. Idris, A. Md Som et al.
the reaction temperature achieves its highest peak. Due to the
depletion of the initiator, the concentration of monomer becoming
constant from this point till the reactor end, this suggests that no
additional reaction would occur from this point. [4].
4. Conclusions
The chosen reaction kinetic mechanism and kinetic constants
from available literatures were successfully used in this LDPE pro-
duction simulation. The results of the current investigation demon-
strated that initiator concentration was the primary factor
affecting the rate of ethylene conversion. At 298 °C and 14.39 %,
respectively, the highest temperature peak and monomer conver-
sion were obtained when initiator concentration were increased
by 1.06 factor. In conclusion, higher quantities of the initiator,
monomer, solvent, and inlet temperature would result in higher
concentrations of free radicals, increasing the rate at which ethy-
lene was converted. As the simulation proceeds, it can be observed
that the reference conditions for the peak temperature of
250.00 °C, the monomer conversion of 9.61 %, and the melt-flow
index (MFI) of 6.60 g/10 min changed with the increment and
decrement of input parameters.
CRediT authorship contribution statement
Nurzafirah Mohd Supion: Writing – original draft, Formal anal-
ysis, Validation, Software, Methodology, Conceptualization. Iylia
Idris: Software, Writing – review & editing, Supervision. Ayub
Md Som: Writing – review & editing, Supervision. Fakhrony Sho-
lahudin Rahman: Methodology, Conceptualization, Writing –
review & editing, Supervision. Rushdan Ahmad Ilyas: Writing –
review & editing, Supervision. Ashraf Azmi: Conceptualization,
Methodology, Software, Validation, Formal analysis, Writing –
review & editing, Supervision, Project administration, Funding
acquisition.
Data availability
No data was used for the research described in the article.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Materials Today: Proceedings xxx (xxxx) xxx
Acknowledgements
The authors gratefully acknowledge the financial support given
by College of Engineering, Universiti Teknologi MARA, Shah Alam
through Synergy 2021 Grant No. 600-TNCPI 5/3/DDF (FKK)
(009/2021) and MyRA Grant No. 600-RMC/GPM LPHD 5/3
(088/2022).
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