Finite Elements in Analysis and Design 229 (2024) 104073

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Finite Elements in Analysis & Design

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

Modeling and simulation of microwave assisted catalytic pyrolysis

system of waste plastics polymer for fuel production
Fares Bandi a, Saad Sulttan a, b, *, Sohrab Rohani a
a
The University of Western Ontario, Department of Chemical and Biochemical Engineering, London, Ontario, N6A 5B9, Canada
b
Department of Chemical Engineering, University of Technology-Iraq, 52 Alsinaa St., PO Box 35010, Baghdad, Iraq

A R T I C L E I N F O A B S T R A C T

Keywords: Pyrolysis is a promising method of chemically recycling plastic waste, as it allows for the recovery
Waste plastics of both energy and materials. In this work, a comprehensive mathematical model has been
Pyrolysis developed to predict the pyrolysis of plastic wastes over ZSM-5 catalyst in microwave-assisted
Microwave
pyrolysis (MAP) system for fuel production. To conduct a transient numerical analysis of the
ZSM-5 catalyst
COMSOL model
underlying processes, a lumped kinetic model that takes into account three lumped pyrolysis
Fuel products (olefins, paraffins, and aromatics) is coupled with the equations that govern the mi­
crowave field, heat transfer, mass transfer, and fluid flow (Darcy’s law). The distributions of
electric field, temperature, and pyrolysis products within MAP are presented. The study inves­
tigated the effects of several factors on the rate of production and consumption in the pyrolysis
reactions of a waste plastic mixture when using MAP. These factors include the microwave power
input, the inlet velocity of the fluidizing gas, as well as the mass and particle size of the catalyst
used. Increasing the input power leads to a higher intensity of the electric field, which causes a
greater increase in temperature within the same time frame. The mass and particle size of the
catalyst used also have a significant impact on the yield of olefins, paraffins, and aromatics.
Reducing the particle size of the catalyst generally increases the reaction rate, but particle sizes
smaller than 50 μm are not ideal for fluidization due to increased intermolecular forces.
Increasing the inlet velocity of the fluidizing gas may result in an incomplete consumption of
intermediates and a low yield of products. All in all, The MAP system is a highly efficient and
effective design for using plastic waste as a source of energy, due to its superior energy efficiency
and lower processing temperature compared to traditional fluidized-bed reactors.

1. Introduction

Plastics are incredibly useful and inexpensive, which is why they are so commonly used in today’s economy. However, by 2050, it is
projected that plastic production will have risen significantly and is expected to reach 500 million tons per year. This will require a
large amount of crude oil, and we have already seen a twentyfold increase in plastic production over the past 50 years [1–3]. However,
the significant increase in plastic production has led to numerous problems, including pollution, harmful production practices, and
poor recycling efforts. Plastic makes up the majority of the 7 billion tons of solid waste produced to date [4], with most of it ending up

* Corresponding author. The University of Western Ontario, Department of Chemical and Biochemical Engineering, London, Ontario, N6A 5B9,
Canada.
E-mail address: [email protected] (S. Sulttan).

https://doi.org/10.1016/j.finel.2023.104073
Received 21 June 2023; Received in revised form 18 October 2023; Accepted 23 October 2023
Available online 31 October 2023
0168-874X/© 2023 Elsevier B.V. All rights reserved.
F. Bandi et al. Finite Elements in Analysis & Design 229 (2024) 104073

Fig. 1. Schematic diagram of the MAP system.

in landfills or the ocean. Most new plastics are not made from renewable resources. Additionally, only small fractions of the 78 million
tons of plastic packaging produced annually is recycled, and even less of it is turned into products of comparable quality [2].
Recycling plastics typically involves collecting, sorting and cleaning them before they are turned into new products. But, this
process has several limitations, including the plastic breaking down during heating and mechanical processes, difficulty handling
mixed plastics and the presence of impurities in the recycled plastics, This can lead to low-quality products with limited recycling
potential, which is known as down cycling, [5]. Therefore, it is important to explore alternative recycling methods to convert plastic
wastes into more valuable products.
Pyrolysis, a chemical recycling process, has been proven to be an effective way to recycle plastic waste. This process converts plastic
into fuels and raw materials for the petrochemical industry to be used for energy generation or material production [6]. Environ­
mentally, pyrolysis is more friendly than incineration from a pollution control standpoint, because it does not release harmful sub­
stances like dioxins. It is a more effective method of material recovery because it can handle contaminated and mixed plastic types that
cannot be processed through mechanical recycling [5]. The effectiveness of plastic pyrolysis technology is subject to diverse factors,
including the type of catalyst employed, the design of the reactor, and the process parameters. In-situ utilization of acid catalyst within
the pyrolysis reactor is an intriguing approach to enhance the selectivity of desired products. Mark et al. have reviewed a compre­
hensive analysis of various catalytic techniques employed in plastic cracking, highlighting the significance of the composition and
porous architecture of catalyst particles in determining the yields and distribution of resulting products [7]. ZSM-5 zeolite is deemed a
fitting acid catalyst for polyolefin pyrolysis, with the aim of achieving a product stream predominantly consisting of light olefins or
gasoline possessing low levels of aromatics [8]. The catalytic pyrolysis or catalytic cracking process is initiated through the formation
of intermediate carbocations, operating under low temperature conditions, and yielding a more constrained distribution of products
[9,10]. Moreover, the pyrolysis process, also known as thermal cracking, proceeds through the involvement of free radicals as tran­
sitional species, leading to indiscriminate cleavage and cleavage of chain termini during the degradation of polyolefin compounds. In a
related study conducted by Elordi and colleagues [11], the efficacy of catalysts based on ZSM-5, HY, and H-Beta zeolites in facilitating
the pyrolysis of HDPE was examined. The results revealed that ZSM-5 zeolite was effective in promoting the production of light olefins,
with a yield of approximately 58 wt %. Conversely, HY and H-Beta zeolite-based catalysts yielded high proportions of nonaromatic
C5–C12 hydrocarbons, with yields of approximately 45 wt %. Furthermore, an investigation into the impact of the acidity level of
ZSM-5 zeolite catalysts revealed that mildly acidic catalysts with weak acid sites facilitated high yields of both light olefins (59.8 wt %)
and nonaromatic compounds, which were comparable to those found in gasoline fractions (32.1 wt %) [12–14].
Catalysts can help lower the temperature and duration required to transform the wax volatiles into liquid and gas, and also improve
the ability to select products with the desired functional groups. But often the use of a higher reaction temperature, longer reaction
time, and higher amount of catalyst is required for plastic pyrolysis reaction [15,16]. The majority of thermoplastics have melting
points lower than 200 ◦ C, meaning they turn into a sticky liquid when heated to that temperature, before beginning to break down at
300 ◦ C. This can lead to operational challenges during pyrolysis, such as difficulties with mixing and fluidization [17,18].
Microwave assisted pyrolysis (MAP) shows potential as a substitute for conventional pyrolysis due to the various benefits provided
by microwave heating compared to conventional heating [19]. One of the main benefits of using microwave heating is that it allows for
precise temperature control, which can be used to process mixed plastics that may cause issues in traditional pyrolysis methods. For
example, polyvinyl chloride (PVC) can be challenging to work with in mixed plastic waste because it releases hydrogen chloride gases
when thermally broken down and produces chlorinated hydrocarbons when pyrolyzed with polyolefins [19]. However, microwave

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F. Bandi et al. Finite Elements in Analysis & Design 229 (2024) 104073

heating allows for selective heat of PVC before other plastics because it has higher dielectric loss factors [20]. The ability to selectively
heat could enable the differentiation of the dehydrochlorination reactions of PVC from the thermal decomposition of other plastics,
potentially leading to advantages [20–22]. Another advantage of using microwave heating is the ability to reach higher heating rates
due to the use of microwave-absorbing materials. When these materials are directly exposed to microwave radiation, they act as a
localized heat source, increasing the uniformity and speed of heat transfer. This is particularly useful as plastics that are melted often
have poor thermal conductivity and can be difficult to heat using conventional methods. Due to the potential benefits of this tech­
nology, different studies on microwave-assisted pyrolysis have been conducted using small lab-scale reactors [23–25]. Therefore,
additional testing is required to assess the practicality of MAP technology.
This investigation introduces a mathematical framework that assesses the feasibility of utilizing a ZSM-5 catalytic cracking
fluidized-bed reactor in conjunction with microwave-assisted pyrolysis (MAP) to transform plastic waste into fuel. The model com­
bines the waste plastic pyrolysis reaction kinetic equations with those for microwave energy, heat and mass transfer, and fluid flow to
conduct a time-based numerical analysis of the underlying fluidized-bed reactor processes. The study aims to optimize the process by
considering various factors such as microwave power, gas flow rate, catalyst mass, and particle size and their effect on the rate of
production and consumption in the pyrolysis of mixed plastic waste.

2. MAP model

2.1. Paradigm

The study designs Microwave-assisted pyrolysis (MAP) system, as illustrated in Fig. 1. The reactor has a 500 mL volume and it is a
fluidized bed reactor. The height to diameter ratio is set to 2 in order to promote proper mixing. The plastic waste is fed from a hopper
at the top of the reactor and it is evacuated by nitrogen. The mixture of waste polymers employed in this simulation was acquired from
the healthcare and hospital waste aggregation hub located in Northern Taiwan. This amalgamation comprises of polyethylene (62 wt
percent; 37 wt percent of which is high-density polyethylene (HDPE) and 25 wt percent of which is low-density polyethylene (LDPE)),
polypropylene (33 wt percent), and roughly 5 wt percent of polystyrene (PS) amalgams [26]. The waste plastic particles are purged
under nitrogen at the top of the reactor and allowed to drop freely into the fluidized bed. The reactor is placed in the center of a
microwave oven (cavity dimensions 33 × 23 × 29.5 cm) that operates at the fixed frequency value of 2.45 GHz and filled with air to
conduct microwave irradiation.
The propagation of energy from the magnetron to the cavity is effected by means of a 5× 10 cm rectangular waveguide, which
functions in the TE10 mode. It is assumed that both the oven and waveguide are made of copper, while silicon carbide is employed for
the absorption of microwave energy and its subsequent transfer to the waste plastics. The height of the silicon carbide is identical to
that of the TE waveguide, standing at 10 cm. Four faces of the waveguide are set as Perfect Electric Conductors, The left and right sides
of the waveguide are the energy sources. The catalysts are ZSM-5 and they move freely as they are not wet with plastic at sufficient
plastic/catalyst ratios. A microwave-heated auger shaft is utilized to enhance the heat and mass transfer in the pyrolysis process. This is
achieved by rapidly and uniformly heating the material, resulting in increased process efficiency and enabling continuous processing
of the plastic feedstock. Moreover, it effectively prevents localized overheating or under heating by evenly distributing microwave
energy throughout the processed material. Once the pyrolysis vapor leaves the reactor, it traverses a glass-fiber filter, which efficiently
captures catalyst fines. To recover these fines, a mechanism involving backwashing or regeneration is employed, dislodging and
collecting the fine catalyst particles. However, these recovery processes may lead to some attrition or degradation, potentially resulting
in a minor loss of valuable catalyst material over time. After this filtration and recovery process, the condensed liquid products are
collected in a separator, and the liquid fraction at the separator’s bottom is analyzed using GC–MS.

2.2. Governing equations

The mathematical model for the microwave-assisted pyrolysis (MAP) links together three main components: the electromagnetic
field, the energy balance, and the flow of free and porous media. The electromagnetic field is calculated using Maxwell’s equations:
̅→
→ → ∂D
∇× H = J + (1)
∂t
̅→
→ ∂H
∇× E = − μ + (2)
∂t
→
∇× B =0 (3)

→
∇ × D = ρe (4)

→ → → →
where, E and H refer to the electric and magnetic field intensities, respectively. D denotes the electric field flux intensity, while B
represents the magnetic field flux intensity. J corresponds to the conduction current, μ signifies the permeability, and ρe pertains to the
free charge density.

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F. Bandi et al. Finite Elements in Analysis & Design 229 (2024) 104073

Fig. 2. A mechanistic and kinetic scheme representing polymer degradation over cracking catalysts. Adapted from the work by Huang et al. [26].

The temperature distribution of the porous media can be determined in this model by utilizing the equation that describes heat
transfer in solids. The energy balance equation can also be applied to compute the temperature of the porous media.
∂y
ρCp − k∇2 T = Q = Qe (5)
∂x

where ρ, which represents fluid density; CP, the fluid’s heat capacity at constant pressure; T, the temperature; t, time; Q, the heat
source; and k, the thermal conductivity. The Navier-Stokes equations describe the flow in the free channel for the fluid modules.
[ ( → →]
∇. μ ∇→ u . I + (∇→
u )T − P. I = ρ(→
u .∇)→
u (6)

ρ∇.→
u =0 (7)

→
where →u refers to the velocity in the open channel (m/s), I is identity matrix, and P is the pressure (Pa). The free flow and porous
media flow are simply combined using the Brinkman equations:
( ) [ ]
ρ → → u μ → μ( → ) 2 →
( u .∇) + →u = ∇. − p. I + ∇ u + (∇→u )T − μ(∇.→ u)I (8)
εp εp κ εp 3

where μ signifies the dynamic viscosity of the fluid (Pa s), while k represents the permeability of the porous medium (m2). ρ represents
the density of the fluid (kg/m3), and εp stands for the porosity, a dimensionless quantity. The Darcy’s Law is utilized by the model to
compute slow fluid flow through a porous medium, taking into account the negligible effects of shear stress that is perpendicular to the
flow direction. The Brinkman equations, based on Darcy’s Law, incorporate the effects of viscous shear forces that lead to the loss of
mechanical energy. The equations describe the flow of fluid through specific types of porous media, which is modeled as a composite of
two materials, where one is represented as a rigid solid and the other as an incompressible fluid. The Navier-Stokes equations, along
with the Brinkman equations, are employed to compute high-velocity porous flow, and to account for the different forces that are
acting on the fluid, including pressure, viscous, inertial, and external forces.

2.3. Catalytic pyrolysis kinetic/mechanistic model

The study puts forward a comprehensive reaction mechanism that explains the role of the carbenium ion in the ZSM-5 catalytic
cracking chemistry for breaking down hydrocarbons. It simplifies the representation of carbenium ion formation to focus on reaction
paths rather than surface species. Theoretical research suggests that the conversion of hydrocarbons on active zeolites occurs through
the use of carbenium ions as transition states, rather than intermediates. Additionally, the product distribution is consistent with
carbenium ion formation, though some debate remains about the exact mechanism of scission. Huang et al. [26] investigated a
kinetic/mechanistic model including the main mechanistic features and kinetic reaction schemes for polymer degradation over

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F. Bandi et al. Finite Elements in Analysis & Design 229 (2024) 104073

Table 1
Summary of materials properties and reaction rate constant applied in the model, [26].
Property Polymer mixture ZSM-5 Catalyst Silicon carbide Quartz Air

Density (kg/m3) 970 720 3200 2600 1.205

Heat capacity (J/kg.K) 1300 1369 1600 260 1005
Thermal conductivity (W/m.K) 0.44 0.12 250 10 2.524
14
Electrical conductivity (S/m) 3.49 0.03 0.16 1 × 10− 0
Relative permittivity 2.5 2.3 9.66 4.2 1

Reactions rate constant value at 360 ◦ C

Rate Constant Value (1/min) Corresponding Reaction

kic 2.286 A→I

krc 0.015 A→C
kpc 0.0012 A→P
kac 0.00006 A→BTX
koi 0.252 I→O
kri 0.007 I→C
kpi 0.092 I→P

cracking catalysts as shown in Fig. 2. The model uses the following assumptions.

I. The process of plastic degradation in the liquid phase starts by dropping solid polymer into the reactor, which immediately
melts and disperses around the catalysts. The molten plastic then forms a complex with the catalyst particles, and the reaction
begins at the surface. The time for the plastic to melt and spread is minimal and does not affect the reaction.
II. The formation of intermediates during scission reactions generates long-chain olefins and precursor molecules for carbenium
ions. The concentration of carbenium ions quickly reaches a steady state. Hydrogen transfer reactions may also produce alkanes,
which are primarily long-chain products at the beginning. The number of active sites typically controls the number of precursor
molecules for carbenium ions.
III. After the intermediates are formed, additional reactions occur to produce shorter chain olefins in balance with surface car­
benium ions, along with alkanes, BTX (benzene, toluene, and xylene) and coke. The equilibrium mixture of olefins and car­
benium ions then undergoes further reactions to create the final products.

Based on the reaction pathway, the rate of formation, ri,j of the product i from reactant r, through reaction j can be written as:
ri,j = ki,j × Wrnj × ηj (9)

where ki,j represents the rate constant associated with the product i originating from the jth reaction, while Wr denotes the weight
fraction of the reactant r that is present on the acid sites. Additionally, ηj accounts for the catalyst activity decay for the jth reaction, and
nj signifies the reaction order of the jth reaction. To incorporate the impact of coke on the catalyst, an exponential decay function was
adopted, which tracks the activity decay of the catalyst as a function of the coke deposited on it.
[ ]
η = exp − α × C(c) (10)

where C(c) represents the coke content deposited on the catalyst. In this context, it is assumed that the deactivation process, represented
by parameter α, remains constant for both polymers. Additionally, it is presumed that the active sites of the acid catalysts considered in
the study deactivate at the same rate [27]. It is assumed that the decay of activity, represented by ηj, remains constant for all reaction
steps, and that the activity level is directly proportional to the number of remaining sites.
ηj = η = exp(− α × Wr ) (11)

equations 12–17 were derived under the assumption that reaction rates can be modeled using basic first-order processes (where nj
= 1), and catalyst deactivation can be represented by six simultaneous equations. In this context, Wr refers to the amount of coke
buildup on the catalyst. Initially, the reaction occurs on the surface, forming a molten polymer/catalyst complex. Therefore, the rate at
which the combined liquid-phase polymer species (Wc*) is consumed can be expressed as:
− dWc∗ ( )
= η × ki,c∗ + kp,c∗ + ka,c∗ + kr,c∗ × Wc∗ (12)
dt
Therefore, the formation of intermediate olefins and carbenium ions (n > 12) can be expressed as:
dWi [( ) ( ) ]
= η × ki,c∗ × Wc∗ − ko,i + kp,i + ka,i + kr,i × (Wi ) (13)
dt

in a similar manner, the changes over time in the olefinic group (Wo), the paraffinic group (Wp), the BTX group (Wa), and the amount of
coke buildup (Wr) are characterized as follows:

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F. Bandi et al. Finite Elements in Analysis & Design 229 (2024) 104073

Fig. 3. 2D axisymmetric of the geometry model mesh which is a representative of the MAP system.

dWo
= η × ko,i × Wi (14)
dt

dWp [ ( )]
= η × kp,i × (Wi ) + kp,c∗ × Wc∗ (15)
dt

dWa [ ( )]
= η × ka,i × (Wi ) + ka,c∗ × Wc∗ (16)
dt

dWr [ ( )]
= η × kr,i × (Wi ) + kr,c∗ × Wc∗ (17)
dt
The mass balance can be written as:
− dWc∗ dWi dWo dWp dWa dWr
= + + + + (18)
dt dt dt dt dt dt
Equations 12–18 were numerically integrated by a fourth-order Runge– Kutta algorithm with MATLAB R2022b software using an
ODE45 solver. Table 1 shows the details of the reaction rate values, material properties, and conditions used in the simulation [26].

2.4. Geometry meshing and numerical procedure

A 3D geometry of the MAP of the above system was built in commercial finite element software, COMSOL Multiphysics® 6.0. Fig. 3
illustrates a 2D axisymmetric of the geometry with different domains generated and various numerical grids. To solve the electro­
magnetic problem accurately, the grid elements used should be smaller than half the wavelength of the microwave radiation, which is
referred to as the Nyquist criterion. More specifically, the maximum size of each grid element (Smax) should not exceed half the
wavelength.
λ c
Smax < = √̅̅̅̅̅ (20)
2
2f ε´μ́

where λ represents the wavelength in meters, and is calculated based on the frequency (f) of the electromagnetic wave, the speed of
́ and the relative permeability (μ ).
light in vacuum (c), the relative dielectric constant (ε ), ́ In the study, a triangular fine mesh was
employed with a conservative maximum element size of 0.00614 m in the waveguide and 0.00116 m in the reactor domain. The high-
frequency electromagnetism module was coupled with the heat transfer in porous media and flow-through porous media using
COMSOL Multiphysics 6.0. The heat source term was extracted from the electromagnetics module. The model made several as­
sumptions, including that the porous media has a uniform porosity throughout the catalyst bed, the thermal properties of the catalyst
bed remain constant despite changes in temperature, no chemical reactions or phase changes occur, the quartz tube that holds the
catalyst bed and is inside the microwave is completely transparent to microwaves, and that the walls of the waveguide are perfect
conductors that do not absorb microwave energy.

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F. Bandi et al. Finite Elements in Analysis & Design 229 (2024) 104073

Fig. 4. Temperature distribution along the centerline in x-axis for microwave heating.

Fig. 5. Validating the developed COMSOL model with MAP products over ZSM-5 catalyst at 360 ◦ C. Huang’s experimental data (Symbols) and
COMSOL model (Solid line). (catalyst particle size = 50 μm, and catalyst to polymer ratio = 40 wt/wt.%).

3. Results and discussion

3.1. Model validation

To validate the accuracy of the MAP model established in this study, the numerically simulated temperature results obtained from
the COMSOL model are compared against the experimental data acquired during microwave-induced bio-oil vapor upgrading runs
utilizing pine sawdust as the biomass source, as detailed by Muley et al. [28]. The temperature was evaluated in three distinct locations
along the X-axis of the quartz tube, utilizing an IR thermocouple and thermal camera. The comparison of the experimental temperature
outcomes with numerical predictions from the COMSOL model showed a close correlation, with a difference of less than 5 %, as
demonstrated in Fig. 4. If there were any differences between the predicted temperature of the catalyst bed through numerical
modeling and the measured temperature, it is mainly because the model assumed an average flow rate, while in reality, the flow rate
fluctuates due to the generation of gas during the reaction. Additionally, the numerical model did not account for external factors like
local superheating in the microwave, the impact of coke deposition, and the poisoning of the catalyst bed, which could have affected
the accuracy of the model.
Moreover, to make sure the COMSOL model is accurate enough and the calculation efficiency is high, the model simulation was
validated with the experimental work reported by Huang et al. [26]. The experimental process used a plastic mixture of 62 % PE (37 %
HDPE, 25 % LDPE), 33 % PP, and 5 % PS undergoing catalytic cracking over ZSM-5 catalyst at 360 ◦ C. The plastic waste was ground to
small particles before being fed into the reactor to facilitate fluidization throughout each reaction. To ensure a smooth and efficient
process, the feed system was intentionally designed to avoid blockages in the inlet tube caused by melted plastic and to eliminate any
air in the feeder. The feed system was linked to a nitrogen supply to remove plastic waste into the fluidized catalyst bed. The output
from the reactor underwent filtration through a glass-fiber filter to capture any catalyst fines and then condensation to collect any
liquid condensable products. A COMSOL model was utilized to represent the distribution of products produced from the degradation of

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F. Bandi et al. Finite Elements in Analysis & Design 229 (2024) 104073

Fig. 6. The normal electric field and temperature distribution of the MAP reactor at microwave power input (P = 2.0 kW), (a) Normal surface
electric field distribution without pyrolysis reactor, (b) Normal surface electric field distribution with pyrolysis reactor, (c) Temperature distribution
of the MAP reactor (d) Temperature distribution at different microwave power input.

the waste polymer mixture using ZSM-5 cracking catalyst in a fluidized-bed setting. The catalytic pyrolysis products were classified in
the model into three groups: volatile hydrocarbons of olefinic fraction (a sum of alkenes from volatile products), volatile hydrocarbons
of paraffinic fraction (a sum of alkanes from volatile products), and BTX fraction (a sum of aromatic products of benzene, styrene,
toluene, and xylene). Fig. 5 displays a close correlation between the model outcomes and Huang’s experimental data on product
distributions resulting from the degradation of the waste polymer mixture using ZSM-5 catalyst at 360 ◦ C. This suggests that the kinetic
model has been accurately implemented and coupled with the transport and electromagnetic governing equations, making it suitable
for studying the microwave-assisted pyrolysis of waste plastic polymer.

3.2. Electric field and temperature profiles

The integration of electric field and temperature profiles plays a pivotal role in achieving a sustainable and efficient fuel production
process. The innovative system harnesses microwave energy to break down waste plastic polymers, and the application of an electric
field augments the process by enhancing the dispersion and interaction of catalytic particles within the reactor. Simultaneously, the
temperature profiles offer valuable insights into the thermal behavior of plastic polymers, guiding the precise control of reaction
conditions to maximize the yield of hydrocarbon-based fuels while minimizing unwanted byproducts. This synergistic combination of
microwave energy, electric field, and temperature profiling presents a promising approach that addresses plastic waste management
and contributes to the development of cleaner and renewable energy sources.
Microwave heating operates through the utilization of an electric field to generate thermal energy, which interacts with molecules
in two distinct manners: by inducing dipolar rotation, causing them to oscillate back and forth, and by facilitating the conduction of
ions. This rotational motion creates friction and subsequently produces heat. Unlike conventional heating methods, microwaves

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F. Bandi et al. Finite Elements in Analysis & Design 229 (2024) 104073

Fig. 7. Concentration profile of product distributions for the degradation of the waste plastic mixture over ZSM-5 catalyst and microwave power
input 2 kW at 360 ◦ C. (catalyst particle size = 50 μm, and catalyst to polymer ratio = 40 wt/wt.%).

exhibit greater energy transfer efficiency since they directly engage with the constituents of the substance being processed. The
introduction of a pyrolysis reactor, as depicted in Fig. 6 (a & b), can impact the distribution of the electric field within the microwave
cavity, leading to a reduction in field intensity. The position of a sample in the cavity can also affect the amount of energy it is exposed
to because the field intensity is not uniform throughout the cavity. Fig. 6 (a & b) illustrates the distribution of the electric field within
the microwave cavity when a pyrolysis reactor is or is not present, when the applied input power is 2.0 kW. As the figure depicts, the
cavity has regions of varying microwave energy. The introduction of a pyrolysis reactor changes the electric field distribution within
the cavity, leading to a decrease in the normal electric field from a maximum of around 27.4 kV/m to 19.6 kV/m. The distribution of
the electromagnetic field is affected by the absorption of microwave energy by the reaction mixture and the reflections from the cavity
walls. This emphasizes the importance of the positioning of a sample within the cavity, as the field strength is not uniform throughout
all regions of the cavity.
Fig. 6 (c) displays the distribution of temperature within the microwave cavity when the pyrolysis reactor is present. As expected,
the temperature distribution within the reaction mixture mirrors the distribution of the electric field. The simulation results also show
the key characteristic of microwave heating, known as volumetric heating, where the temperature is evenly distributed, ranging from
300 to 360 ◦ C in the MAP reactor. Additionally, both the electric field and temperature distribution in the MAP reactor are influenced
by the applied input power. To evaluate the relationship between input power and its impact on temperature distribution, three
different input power values were studied: Po = 2.0 kW, Po = 1.0 kW, and Po = 0.5 kW after 20 min, as shown in Fig. 6 (d). It can be
observed that a higher input power leads to a higher electric field intensity and a faster temperature increase within the same time
frame. The overall temperature in the sample increases over time and also expands the heating zone. This finding is consistent with
previous research results obtained through experimentation and simulation [29,30].

3.3. Conversion profiles

The kinetic mechanism describes the process by which a waste polymer mixture breaks down over ZSM-5 cracking catalysts in a
fluidized-bed reaction, resulting in various product distributions. Fig. 7 illustrates the predicted changes in the concentrations of the
plastic mixture and intermediates with the production rate of olefins, paraffins, BTX, and coke. The data shows that the plastic mixture
is consumed over time, and intermediates are produced and then converted into olefins, paraffins, BTX, and coke. Olefins are the major
product, and paraffins are the next major product, while the contents of BTX and coke in the products are relatively small. The for­
mation of intermediates from the polymer occurs at a much faster rate than other reaction rates. This suggests that ZSM-5 zeolites form
a complex with the polymer, leading to a scission reaction that produces volatile products, indicating that zeolite catalysts are efficient
at converting polymers into intermediates of volatile precursors. The kinetic model predicts a higher formation of intermediate species,
indicating that plastic waste can be cracked at or near the external surface of the catalysts. Therefore, the catalytic factors that in­
fluence the process are related to the number of active acid sites that are accessible and the amount of coke content deposited on the
catalyst.
The objective of this study is not to enhance the effectiveness of a standard microwave reactor utilized in waste plastic pyrolysis but

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F. Bandi et al. Finite Elements in Analysis & Design 229 (2024) 104073

Fig. 8. 3D concentration profile (mol/m3) along MAP reactor of the consumption rate of the waste plastic mixture (A) and Intermediates (I) and the
production rate of olefins (O), paraffins (P), BTX and coke (C) at 360 ◦ C for 20 min and catalyst particle size = 50 μm.

rather to create and present a 3D mathematical model that encompasses all the critical physics of the process. This 3D model enables us
to observe the concentration profiles, electric field, and temperature in all dimensions, giving a better comprehension of the chemical
and physical phenomena that occur during pyrolysis. Fig. 8 provides a 3D more accurate visualization of the spatial predicted con­
centration profiles of the consumption rate of the plastic mixture and intermediates along with the production rate of olefins (O),
paraffins (P), BTX, and coke (C) in the MAP reactor for a microwave input power of 2 kW and 2-min reaction time. The plastic mixture
is quickly converted to intermediates, then paraffins, aromatics and coke. It is important to note that the pyrolysis of waste plastic using
microwaves is a complicated process influenced by various parameters, such as the material properties and operating conditions. The
use of a simplified kinetic model, along with certain assumptions regarding material properties, limits the scope of the results obtained
from this study. However, by presenting a detailed representation of the electric field, temperature, and concentration profiles of waste
plastic degradation, the model helps to overcome the limitations of 2D approaches or experimental results and provides a more

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F. Bandi et al. Finite Elements in Analysis & Design 229 (2024) 104073

Fig. 9. The effect of HZSM-5 catalyst mass on the consumption rate of the plastic mixture (A) and the production rate of olefins (O), paraffins (P),
and BTX in pyrolysis reaction at 360 ◦ C, catalyst particle size = 50 μm and fluidizing gas velocity = 0.001 m/s.

accurate visualization of the decomposition process. The model allows for a detailed examination of the effects of various process
parameters, such as the mass of catalyst, size of catalyst particle, and fluidizing gas velocity.

3.4. The effect of catalyst properties and fluidizing gas velocity

The properties of the catalyst and the fluidizing gas velocity play crucial roles in the outcome of a pyrolysis reaction. Catalyst
properties, such as acidity, surface area, and composition, influence the reaction kinetics and selectivity. A catalyst with strong acidity
can enhance cracking reactions, favoring the production of light hydrocarbons like olefins, while catalysts with different properties
may promote paraffin or BTX production. Additionally, the surface area of the catalyst can impact the catalytic activity and overall
efficiency. The fluidizing gas velocity affects the heat and mass transfer within the reactor, influencing the residence time of reactants,
temperature distribution, and the overall performance of the pyrolysis process. A higher gas velocity can enhance heat and mass
transfer, potentially improving conversion rates, but it needs to be carefully balanced with the catalyst properties to achieve the
desired product distribution and overall process efficiency. The interplay between these factors requires careful consideration for
optimizing a pyrolysis process for specific product goals and economic viability.
Fig. 9 illustrates the impact of HZSM-5 catalyst mass on the consumption rate of the plastic mixture (A) and the production rate of
olefins (O), paraffins (P), and BTX in a pyrolysis reaction conducted at 360 ◦ C, with a catalyst particle size of 50 μm and a fluidizing gas
velocity of 0.001 m/s. It is clearly noticed that varying the catalyst mass has little effect on the rate of plastic mixture consumption. The
plastic readily participates in the reaction, undergoing conversion into intermediates, paraffins, aromatics, and coke, with in­
termediates being the predominant products. This observation is particularly noteworthy as it challenges the conventional under­
standing that polymeric materials often exhibit limited reactivity in inert environments or in the absence of any acidic catalysts.
However, the mere presence of a catalyst triggers a swift transformation of plastics into carbonium ions, acting as intermediates in the
process. Intriguingly, with a small catalyst quantity, the plastic blend undergoes complete conversion along the reactor’s length.
Employing larger amounts of catalyst causes full conversion of the plastic mixture at an earlier stage in the reactor. On the other hand,
increasing the mass of catalyst from 0.1 to 5 g increases the rate of production of olefins and paraffins. Increasing the mass of the
catalyst to 15 g has no significant impact on the rate of production of olefins and paraffins. When the lowest amount of catalyst, 0.1 g, is
used, the rate of production of olefins reaches a peak at around 8 cm length of the reactor. whereas, the peak reaches the 4.2 cm length
of the reactor with the highest amount of catalyst, 15 g, which is in correspondence with the rate of consumption of the intermediates.

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Fig. 10. The effect of HZSM-5 catalyst particle size on the consumption rate of the plastic mixture (A) and the production rate of olefins (O),
paraffins (P), and BTX in pyrolysis reaction at 360 ◦ C and fluidizing gas velocity = 0.001 m/s.

Additionally, the production of aromatics (BTX) and coke over ZSM-5 in pyrolysis reaction has the same trend as the production of
olefins and paraffins. It’s worth pointing out that while increasing the mass of catalyst increases the rate of production of desirable
products such as olefins, paraffins, and aromatics, it also increases the rate of production of coke, which is an undesired product. As the
coke causes the deactivation of the catalysts, regeneration process is required. It can be inferred that an increase in coke makes the
regeneration process more time-consuming and energy-intensive, which is a disadvantage. This finding aligns with prior research
outcomes derived from both experimental investigations and simulations, [29,30].
The effect of catalyst particle size on the rate of consumption of the plastic mixture (A) and the rate of production of olefins (O),
paraffins (P), and BTX aromatics is illustrated in Fig. 10. The data shows that the particle size of the catalyst also has little effect on the
rate of consumption of the plastic mixture. The plastic mixture is quickly converted to intermediates, mostly paraffins, aromatics, and
coke, indicating that conversion of plastics occurs in the presence of a catalyst even with a large particle size. The plastic mixture is
completely processed at approximately 1.7 cm along the reactor when the largest particle diameter of 500 μm is employed, whereas
with the smallest particle diameter of 50 μm, full conversion is achieved at around 1.3 cm into the reactor. In other words, the plastic
mixture undergoing a chemical transformation in a reactor reaches full conversion into its component products at a distinct location,
roughly 1.7 cm from the reactor’s inlet. This data highlights the effectiveness of the reaction process in these conditions, demonstrating
that a small catalyst quantity is enough to accomplish complete conversion of plastic waste into the desired products within the
designated reactor space. Nonetheless, particles with diameter smaller than 50 μm are not suitable for fluidization since small particles
have strong intermolecular forces which cause them to be inadequately fluidized. The consumption of the intermediates is linked to the
production of products, such as olefins and paraffins. It can be predicted that the rate of production of all products increases by
decreasing the particle diameter of the catalyst in the same manner that the rate of consumption of the intermediates increases by
decreasing the particle diameter of the catalyst.
The fluidizing gas velocity serves as a pivotal factor in shaping the dynamics of heat and mass transfer processes within the reactor,
exerting a substantial influence on key aspects such as reactant residence times, temperature distribution, and the overall efficiency of
the pyrolysis process. Higher gas velocities have the potential to enhance heat and mass transfer rates, which in turn can lead to
improved conversion rates. However, the challenge lies in finding the right balance between gas velocity and catalyst properties to

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F. Bandi et al. Finite Elements in Analysis & Design 229 (2024) 104073

Fig. 11. The effect of fluidizing gas velocity on the consumption rate of the plastic mixture (A) and the production rate of olefins (O), paraffins (P),
and BTX in pyrolysis reaction at 360 ◦ C and catalyst particle size = 50 μm.

achieve the desired product distribution and overall process efficiency. Fig. 11 illustrates the impact of fluidizing gas velocity on
various aspects of the pyrolysis process. It demonstrates that as the gas velocity increases, there is a noticeable reduction in the
concentration of reacted plastics (A) within the reactor. This trend is mirrored in the production and consumption of intermediates and
the yields of olefins (O), paraffins (P), and BTX aromatics. Interestingly, when the inlet velocity of the fluidizing gas is raised to 0.001
m/s, the simulation reveals that olefins, paraffins, and aromatics do not reach their anticipated peaks within the initial 14 cm of the
tubular reactor. This particular behavior is beneficial as it curtails the production of these compounds, as well as that of unconverted
intermediates in the reactor, contributing to a more efficient process overall.

4. Conclusions

This study utilizes a mathematical model and the COMSOL Multiphysics program to examine the process of pyrolysis of plastic
waste using a microwave-assisted method for the production of fuel. The microwave-assisted pyrolysis (MAP) system is evaluated as a
potential alternative to traditional heating methods for pyrolysis. The work looks into how various parameters, such as microwave
power input, fluidizing gas inlet velocity, catalyst mass and particle size, impact the rate of production and consumption in the plastic
waste pyrolysis reaction. The results show that the mass and particle diameter of the catalyst has little impact on the consumption of
the plastic mixture or the production of intermediates, but does affect the consumption of intermediates and the production of olefins,
paraffins, aromatics and coke. Additionally, an increase in the mass of catalyst over 5 g has no significant impact on the reaction rate,
however a decrease in particle diameter of catalyst leads to an increase in reaction rate, but particle diameters smaller than 50 μm are
not suitable due to increased intermolecular forces of the particles. Lastly, increasing the inlet velocity of fluidizing gas can lead to
incomplete intermediate consumption and low yields of products.

Declaration of competing interest

We are pleased to submit the manuscript entitled “Modeling and Simulation of Microwave Assisted Catalytic Pyrolysis System
of Waste Plastics Polymer for Fuel Production” on behalf of the authors, I declare that this article is original it has been written by
the stated authors and approved for its submission. This article has not been published previously and is not under consideration for
publication elsewhere. Also state that there is no conflict of interest, if accepted, the article will not be published elsewhere in the same

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F. Bandi et al. Finite Elements in Analysis & Design 229 (2024) 104073

form, in English, or in any other language, without the written consent of the publisher.
I would like to submit this scientific work on the behalf of all co-authors for review and possible publication in the journal.

Data availability

Data will be made available on request.

References

[1] IEA, World Energy Outlook: IEA, 2021. Paris.

[2] Smet M. De, The New Plastics Economy Rethinking the Future of Plastics & Catalysing Action, Ellen MacArthur Found. Cowes, Isle Wight, UK, 2016.
[3] H. Sardon, A.P. Dove, Plastics recycling with a difference: a novel plastic with useful properties can easily be recycled again and again, Science 360 (2018)
380–381, https://doi.org/10.1126/science.aat4997, 80-.
[4] N. Zhou, L. Dai, Y. Lv, H. Li, W. Deng, F. Guo, P. Chen, H. Lei, R. Ruan, Catalytic pyrolysis of plastic wastes in a continuous microwave assisted pyrolysis system
for fuel production, Chem. Eng. J. 418 (2021), 129412, https://doi.org/10.1016/j.cej.2021.129412.
[5] K. Ragaert, L. Delva, K. Van Geem, Mechanical and chemical recycling of solid plastic waste, Waste Manag. 69 (2017) 24–58, https://doi.org/10.1016/J.
WASMAN.2017.07.044.
[6] S.D. Anuar Sharuddin, F. Abnisa, W.M.A. Wan Daud, M.K. Aroua, A review on pyrolysis of plastic wastes, Energy Convers. Manag. 115 (2016) 308–326, https://
doi.org/10.1016/J.ENCONMAN.2016.02.037.
[7] L.O. Mark, M.C. Cendejas, I. Hermans, The use of heterogeneous catalysis in the chemical valorization of plastic waste, ChemSusChem 13 (2020) 5808–5836,
https://doi.org/10.1002/cssc.202001905.
[8] M. Artetxe, G. Lopez, M. Amutio, J. Bilbao, M. Olazar, Kinetic modelling of the cracking of HDPE pyrolysis volatiles on a HZSM-5 zeolite based catalyst, Chem.
Eng. Sci. 116 (2014) 635–644, https://doi.org/10.1016/j.ces.2014.05.044.
[9] R. Palos, A. Gutiérrez, F.J. Vela, M. Olazar, J.M. Arandes, J. Bilbao, Waste refinery: the valorization of waste plastics and end-of-life tires in refinery units,
A Review, Energy and Fuels 35 (2021) 3529–3557, https://doi.org/10.1021/acs.energyfuels.0c03918.
[10] S.R. Sultan, W.J.N. Fernando, S.A. Sata, Combined single particle growth and population balance modeling in stereoregular polymerization of styrene, Iran,
Polym. J. 21 (2012) 423–433, https://doi.org/10.1007/s13726-012-0045-y.
[11] G. Elordi, M. Olazar, G. Lopez, M. Amutio, M. Artetxe, R. Aguado, J. Bilbao, Catalytic pyrolysis of HDPE in continuous mode over zeolite catalysts in a conical
spouted bed reactor, J. Anal. Appl. Pyrolysis 85 (2009) 345–351, https://doi.org/10.1016/j.jaap.2008.10.015.
[12] G. Elordi, M. Olazar, M. Artetxe, P. Castaño, J. Bilbao, Effect of the acidity of the HZSM-5 zeolite catalyst on the cracking of high density polyethylene in a
conical spouted bed reactor, Appl. Catal. Gen. 415 (2012) 89–95, https://doi.org/10.1016/j.apcata.2011.12.011. –416.
[13] M.A. Zahraa, A. Hussein Zaidoon, M. Shakor, F. Al-Sheikh, The yield of gasoline range hydrocarbons from plastic waste pyrolysis, Energy Sources, Part A
Recover, Util. Environ. Eff. 44 (2022) 718–731, https://doi.org/10.1080/15567036.2022.2050851.
[14] M.A. Zahraa, A. Hussein Zaidoon, M. Shakor, F. Al-Sheikh, Thermal and catalytic cracking of plastic waste: a review, Int. J. Environ. Anal. Chem. (2021) 1–18,
https://doi.org/10.1080/03067319.2021.1946527.
[15] R. Miandad, M.A. Barakat, A.S. Aburiazaiza, M. Rehan, A.S. Nizami, Catalytic pyrolysis of plastic waste: a review, Process Saf. Environ. Protect. 102 (2016)
822–838, https://doi.org/10.1016/J.PSEP.2016.06.022.
[16] G. Lopez, M. Artetxe, M. Amutio, J. Bilbao, M. Olazar, Thermochemical routes for the valorization of waste polyolefinic plastics to produce fuels and chemicals.
A review, Renew. Sustain. Energy Rev. 73 (2017) 346–368, https://doi.org/10.1016/J.RSER.2017.01.142.
[17] X. Jing, G. Yan, Y. Zhao, Z. Xu, Study on mild cracking of polyolefins to liquid hydrocarbons in a closed batch reactor for subsequent olefin recovery, Polym.
Degrad. Stabil. 109 (2014) 79–91, https://doi.org/10.1016/j.polymdegradstab.2014.07.003.
[18] U. Arena, M. Mastellone, Defluidization phenomena during the pyrolysis of two plastic wastes, Chem. Eng. Sci. - CHEM ENG SCI. 55 (2000) 2849–2860, https://
doi.org/10.1016/S0009-2509(99)00533-3.
[19] F. Mushtaq, R. Mat, F.N. Ani, A review on microwave assisted pyrolysis of coal and biomass for fuel production, Renew. Sustain. Energy Rev. 39 (2014)
555–574, https://doi.org/10.1016/J.RSER.2014.07.073.
[20] S. Moriwaki, M. Machida, H. Tatsumoto, Y. Otsubo, M. Aikawa, T. Ogura, Dehydrochlorination of poly(vinyl chloride) by microwave irradiation, Appl. Therm.
Eng. 26 (2006) 745–750, https://doi.org/10.1016/j.applthermaleng.2005.09.001.
[21] S.R. Sultan, W.J.N. Fernando, S.A. Sata, Coupled single-particle growth and kinetics modeling for styrene polymerization over silica-supported metallocene
catalyst, J. Math. Chem. 50 (2012) 1060–1078, https://doi.org/10.1007/s10910-011-9949-6.
[22] S.R. Sultan, W.J.N. Fernando, S.A. Sata, Multiscale modeling of syndiospecific styrene polymerization, J. Polym. Res. 19 (2012) 9778, https://doi.org/10.1007/
s10965-011-9778-0.
[23] K. Ding, S. Liu, Y. Huang, S. Liu, N. Zhou, P. Peng, Y. Wang, P. Chen, R. Ruan, Catalytic microwave-assisted pyrolysis of plastic waste over NiO and HY for
gasoline-range hydrocarbons production, Energy Convers. Manag. 196 (2019) 1316–1325, https://doi.org/10.1016/J.ENCONMAN.2019.07.001.
[24] X. Jing, H. Wen, X. Gong, Z. Xu, Heating strategies for the system of PP and Spherical Activated Carbon during microwave cracking for obtaining value-added
products, Fuel Process, Technol. 199 (2020), 106265, https://doi.org/10.1016/J.FUPROC.2019.106265.
[25] X. Zhang, H. Lei, G. Yadavalli, L. Zhu, Y. Wei, Y. Liu, Gasoline-range hydrocarbons produced from microwave-induced pyrolysis of low-density polyethylene
over ZSM-5, Fuel 144 (2015) 33–42, https://doi.org/10.1016/J.FUEL.2014.12.013.
[26] W.C. Huang, M.S. Huang, C.F. Huang, C.C. Chen, K.L. Ou, Thermochemical conversion of polymer wastes into hydrocarbon fuels over various fluidizing
cracking catalysts, Fuel 89 (2010) 2305–2316, https://doi.org/10.1016/J.FUEL.2010.04.013.
[27] Y.-H. Lin, M.-H. Yang, Chemical catalysed recycling of polypropylene over a spent FCC catalyst and various commercial cracking catalysts using TGA,
Thermochim. Acta - THERMOCHIM ACTA 470 (2008) 52–59, https://doi.org/10.1016/j.tca.2008.01.015.
[28] P.D. Muley, C.E. Henkel, G. Aguilar, K.T. Klasson, D. Boldor, Ex situ thermo-catalytic upgrading of biomass pyrolysis vapors using a traveling wave microwave
reactor, Appl. Energy 183 (2016) 995–1004, https://doi.org/10.1016/J.APENERGY.2016.09.047.
[29] M. Miura, H. Kaga, A. Sakurai, T. Kakuchi, K. Takahashi, Rapid pyrolysis of wood block by microwave heating, J. Anal. Appl. Pyrolysis 71 (2004) 187–199,
https://doi.org/10.1016/S0165-2370(03)00087-1.
[30] R. Santaniello, A. Galgano, C. Di Blasi, Coupling transport phenomena and tar cracking in the modeling of microwave-induced pyrolysis of wood, Fuel 96 (2012)
355–373, https://doi.org/10.1016/J.FUEL.2012.01.040.

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