Journal of Analytical and Applied Pyrolysis 170 (2023) 105907

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Journal of Analytical and Applied Pyrolysis

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

A critical review of the correlative effect of process parameters on pyrolysis

of plastic wastes
Mahadevan Vaishnavi a, Prasad Mohan Vasanth b, Sundararajan Rajkumar b, *,
Kannappan Panchamoorthy Gopinath c, Yuvarajan Devarajan d, *
a
Department of Chemical Engineering, Sri Sivasubramaniya Nadar College of Engineering, Kalavakkam, Chennai 603110, India
b
Department of Mechanical Engineering, Sri Sivasubramaniya Nadar College of Engineering, Kalavakkam, Chennai 603110, India
c
Department of Chemical Engineering, Mohamed Sathak Engineering College, Sathak Nagar, SH 49, Keelakarai, Tamil Nadu 62380, India
d
Department of Thermal Engineering, Saveetha School of Engineering, SIMATS, Chennai, Tamilnadu, India

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

Keywords: Plastics contribute significantly to the plight of an ideal solid waste management system, and the dilemma of its
Pyrolysis safe disposal upon harnessing its untapped potential still looms large. An appropriate answer to such a predic­
Pearson correlation coefficient ament is an energy conversion technology that deems both economically and environmentally profitable. Py­
Parameters
rolysis of plastic wastes has been attempted for commercialisation unsuccessfully throughout the last decade,
The study of pressure
Optimisation technique
owing to the substandard economisation of the process and non-compliance of its products to emission standards.
Though the pyrolysis technology and the parameters involved have been extensively studied, a gap exists in the
practical implementation due to its complex mechanism involving many variables that play a significant role in
products’ yield, distribution and the system’s overall performance. The present work strives to statistically
analyse the effect of feedstock and other operational parameters on pyrolysis oil yield and quantify their impacts
utilising Pearson Correlation Coefficient (PCC). The intensity and significance of the impact of the operational
parameters are studied, and a ranking system is attempted to help in the technology’s successful priority-
optimisation technique and implementation. The results suggested that the reaction temperature is the most
critical parameter, with positive PCCs of 0.857 and 0.855 for pyrolysis and co-pyrolysis, respectively. The per­
centages of Carbon and Hydrogen (H %), residence time, heating rate (HR) and amount of catalyst exhibited
positive correlations with oil yield. Among the negatively correlated parameters, the moisture content in feed­
stock presented a high PCC of − 0.830, followed by particle size. This work presents a collective statistical
quantification that aids us in the priority-based optimisation of the pyrolysis process.

particles in the air cause grave danger to human, environmental and

climatic health [26].
1. Introduction Several treaties and agreements have been signed among nations and
continents to restrict the overuse of plastics, ban its entry into ecosys­
Plastics have become undisputable commodities because of their tems and confront the crisis of plastic pollution from different angles
durability, strength, mouldability and versatility in every field. How­ over the last decade [48]. In 2022, United Nations Environmental Pro­
ever, post-application, improper plastic waste management (PWM) gram (UNEP) adopted a global treaty involving 175 countries, with the
causes several critical environmental concerns [11]. The harmful primary goal of developing circular economies, targeting to tackle the
chemicals in plastic waste leach into the soil from inadequately managed entire life cycle of plastics and thus infringing the sovereignty of
landfills, polluting the surface and groundwater [46]. These artificially single-use plastics [34]. This deal, considered one of the most ambitious
designed materials break down into microplastics, causing disturbances and most significantly multilateral by the policy creators, has compelled
in the equilibrium of air, land and aquatic ecosystems [83]. Further, most of the countries to shift their focus towards the implementation of
these microplastics enter the aquatic ecosystem causing irreparable various industrial norms, such as to reduce the dependence on fossil
damage to living organisms and the marine environment. Also, recent fuels by maintaining materials inflow by recycling and reuse and thus
studies on atmospheric microplastic pollution suggest that these

* Corresponding authors.
E-mail addresses: [email protected] (S. Rajkumar), [email protected] (Y. Devarajan).

https://doi.org/10.1016/j.jaap.2023.105907
Received 24 November 2022; Received in revised form 26 January 2023; Accepted 3 February 2023
Available online 5 February 2023
0165-2370/© 2023 Elsevier B.V. All rights reserved.
M. Vaishnavi et al. Journal of Analytical and Applied Pyrolysis 170 (2023) 105907

Nomenclature

HDPE High-Density Poly Ethylene

HTL Hydrothermal Liquefaction
LDPE Low-Density Poly Ethylene
PC Poly Carbonate
PCC Pearson Correlation Coefficient
PP Poly Propylene
PS Poly Styrene
PVC Poly Vinyl Chloride
PWM Plastic Waste Management

putting an end to the delineated pollutions [35]. The conversion of a

linear system to a circular one cuts off the waste products stream by its
conversion into energy or modifies it into valuable products or compo­
nents that can be used to manufacture the top products, as depicted in
Fig. 2. Doughnut charts for Plastic Waste Management methods in
Fig. 1.
Asian countries.
The current PWM system in most Asian countries is severely linear
and comprises discarding or landfilling about 72 per cent of the total
plastic waste collected [33]. In contrast, only a meagre 14 per cent of 2. Background
each is taken up to recycling and incineration [30]. Fig. 2 represents the
doughnut chart depicting plastic waste management methods in sig­ 2.1. Various types of plastic wastes
nificant plastic waste-producing countries (China, India and Singapore)
in the Asian region. Although the distinction between discarding and All plastic considered waste has thousands of monomers with con­
landfilling plastic waste is not very explicit, it is to be noted that these nected covalent bonds. It comes under any one of the following types:
are the two most widely used disposal methods for plastic waste [57]. Polyethylene- High-Density Poly Ethylene (HDPE), Low-Density Poly
Most of the plastic wastes handled by these methods enter the air, Ethylene (LDPE), Poly Propylene (PP), Poly Ethylene Tetra phthalate
aquatic, and land ecosystems in various ways, causing harmful effects on (PET), Poly Vinyl Chloride (PVC), Poly Styrene (PS), Poly Urethane
living organisms. The energy recovery and transformation processes, (PU), and Poly Carbonate (PC) [5,87]. Though these polymers are ob­
recycling of used plastics and incineration are not implemented to the tained from petrochemical products or conventional fossil fuels, like
desired level for various reasons (Tripathi et al. [99]). The process coal and oil, the physical properties of these materials are highly engi­
economics, low value for recycled products, limitations posed by mixed neered to make them suitable for different applications, which in turn is
and multi-layered plastics, their heterogeneous chemical structures and responsible for different effects of plastics on humans and the environ­
make-up, and the physiochemical properties and behaviour of the pro­ ment [83,109].
cess restricts the application of plastic recovery and transformation Table 1 presents the different types of plastics, their chemical for­
processes [13]. However, it is indispensable to analyse the different mula, recycling code, sources of specific polymer types and their effects
types of plastic wastes, their sources, effects and properties before on humans and the environment. Further, based on the recyclable na­
examining the process and methods of disposal, which is discussed in the ture of the polymer types, the intensity of their effect on the ecosystems
next section [70]. varies. According to the data obtained, PC and PP seem to emit less
toxicity on the environment and have less effect on human systems. PVC
and PS are considered dangerous plastics as they harm the land, air,
water systems, and human beings [2]. PET polymers are observed to
cause damage to specific organs of humans. The stumbling block in

Fig. 1. Circular economy requirement for industries.

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M. Vaishnavi et al. Journal of Analytical and Applied Pyrolysis 170 (2023) 105907

Table 1
Various types of plastic polymers, their sources and effects on humans and the environment.

eradicating these plastics from the various ecosystems is that plastic decarbonylation reactions and aid in enhancing the bio-oil quality [19].
wastes are available in various forms. It would require an inclusive
mechanism to process them as a whole rather than segregating them
2.3. Process commercialisation
based on their structural and chemical properties.
Though researchers have been extensively working on various as­
2.2. Thermal conversion method pects of the pyrolysis process and its upgradation methods, the com­
mercialisation of the pyrolysis mechanism is plagued by many imprecise
An ideal plastic waste disposal method reduces waste volume reasons. In India, the development of pyrolysis plants began in 2011 and
considerably in less time without disturbing the environment or eco­ therefore showed tremendous growth till 2018 [76]. With the modifi­
systems and yields supplementary energy and platform products cations in the environmental policies, the Indian government executed
through sustainable energy transformation mechanisms and thus con­ the shutdown of various pyrolysis plants (dealing with waste rubbers,
tributes positively to a circular economy. In this regard, thermal tyres and plastics) because of non-compliance to emission standards
decomposition processes, viz. incineration, paved the way for intro­ regarding the discharge of gaseous pollutants and carbon residues
ducing non-traditional methods with inter-chemical conversions [44]. (Supramono et al. [92]). This flouting of environmental norms by the
Unlike traditional ones, thermochemical conversion processes such as pyrolysis plants led to a high level of pollution, which affected the
pyrolysis and gasification show a promising mode of extracting the surrounding areas and the environment drastically. Fig. 3 depicts India’s
essential multi-functional oil from plastic wastes due to their versatility location and operational status of various pyrolysis plants. From Fig. 3, it
and controlled combustion techniques, which avoid oxidation with el­ can be seen that among the listed 19 states, an overall 672 pyrolysis
ements such as nitrogen [110,17]. plants were in operation for the extraction of oils. In 2019, 260 units
Devolatization or pyrolysis breaks down the polymers into liquid were deemed non-compliant and were announced to shut down their
form under elevated pressure, temperature, and an inert atmosphere operations. In the remaining plants, 175 remained closed, and 4 were
[39]. With different catalysts, feedstock proportions, residence times, non-operating units. Thus, the remaining 233 pyrolysis plants are
temperatures and pressures, the quantitative and qualitative variations operating to produce waste liquid products [109].
in yield and distributions of products were observed with a minor effect
on the environment [113,34,93]. Persuasive conditions for undergoing 3. Requirements for the study
flash, fast and slow pyrolysis differ with temperature, residence time,
and particle size of feedstock, which invariably affect the product for­ Aiming to conclude the gap that exists between the literature works
mation and distribution quantitatively and qualitatively [11,51,58]. and the commercialisation of pyrolysis as a reliable route for liquid fuel
These parameters and their effect are elaborated on later in this section. production, a detailed analysis of the operational parameters is required
Also, recently, co-pyrolysis of biomass with hydrogen-rich feedstock, to obtain clarity on the process points such as the versatility, efficiency,
like plastics, has exhibited undeniable potential as an effective solution and scalability of the pyrolysis process (Tripathi et al. [99]). Thermo­
to help cope with the lower effective carbon-to-hydrogen ratio respon­ chemical conversion technologies involve multiple complex reactions
sible for the formation of oxygenated compounds (Alam et al. [4]). with various parameters influencing the outcome, rendering the ’one-­
These compounds are eliminated by dehydration, decarboxylation and factor-at-a-time’ approach extraordinarily strenuous and

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M. Vaishnavi et al. Journal of Analytical and Applied Pyrolysis 170 (2023) 105907

Fig. 3. Location and operational status of pyrolysis plants in India.

time-consuming. To overcome this and other significant limitations of 95] are being implemented.
this conventional approach, such as the non-inclusion of interactive ef­ Among the multivariate statistical-based approaches, Response
fects between process parameters leading to minimal assurance of Surface Methodology (RSM) is being extensively used from the initial
determination of optimal conditions, several empirical strategies – the stage in designing experiments (DoE) by analysing the operational pa­
statistical-based approach or artificial intelligence-based approach [23, rameters (factors) that are obtained as inputs to arriving at optimal

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M. Vaishnavi et al. Journal of Analytical and Applied Pyrolysis 170 (2023) 105907

conditions for the process-based results (responses) from the in­ %), Sulphur (S%), Moisture (M%), and particle size (PS in mm). Simi­
vestigations. Here, the experimental data fit a polynomial equation and larly, the process parameters, such as the temperature (T in ◦ C), resi­
based on a set of statistical techniques, the best system performance is dence time (t in second), heating rate (HR in ◦ C/min), and amount of
obtained to simultaneously optimise the level of these variables [8]. catalyst (Cat%), were thoroughly covered. For the same, various scien­
However, the application of this method is limited due to its inability to tific and research papers from different resources were obtained. Key
include a wide range of feedstocks and decreased efficiency to search links included, but were not limited to, ’plastic waste’, ’pyroly­
three-level factorial designs ([35](a)). sis’, ’effect of temperature etc [104]. The statistical trends and PCC
Optimised operating conditions for complicated systems can be calculations between the input (feed & process) factors and oil yield
realised by analysing the correlation between the operational parame­ were obtained by XLSTAT, an Excel data analysis add-on software. This
ters and their combinative influence on the yield and quality of the not only helps in gaining a better understanding of the influence of each
desired product. Pearson Correlation Coefficient (PCC) has been exten­ of these parameters on the oil yield but also provides a comparison of the
sively used in applications related to data analysis and classification, PCC for each of these parameters concerning oil yield, which helps
clustering, decision-making, recommended systems and biological determine their intensity of impact on the process [11].
research [6,84,77]. Motivated by the merit of PPC, an attempt is made to
establish a relationship between the various variables of the process, 5.2. Assumptions
such as the elemental feed composition, temperature, time, the bio-oil
yield etc., by employing the Pearson Correlations computation method. Pearson Correlation Coefficient (PCC) is a statistical measure of the
strength and direction of a linear relationship between two random
4. Review focus, scope and novelty variables [119]. This metric usually ranges from − 1 to + 1, wherein + 1
denotes a perfectly linear relationship in the positive direction, and − 1,
This review is based on the existing literature for pyrolysis and co- on the other hand, denotes an ultimate linear correlation in the negative
pyrolysis of plastic waste, which focuses on establishing a correlation direction [28]. The more extensive the absolute value of the correlation
between the operational parameters and oil yield. Particular emphasis coefficient, the stronger the relationship between variables. A compar­
has been given to critical factors like feedstock characteristics, reaction ison of the degree of positive or negative impact between two or more
temperature, reaction time etc., which are studied in depth. The po­ selected parameters with each other and each of the parameters on oil
tential usage of plastic waste as feedstock in pyrolysis for profitable and yield is made possible by employing PCC (Zaker et al. [113]).
sustainable bio-oil production can be achieved by evolving tactics, as Though the pyrolysis process is not limited to those of the parameters
described in detail in this review. Process optimisation, efficiency up­ stated above, the factors used in this review cover a significant range of
grades and enhancements regarding operational parameters have been critical parameters that substantially affect the overall performance and
expounded upon. yield of the system [55]. The 12 parameters reported in this review were
This review aims to comprehensively analyse the vitality of param­ used in the analysis and calculation of PCC. During the analysis, the
eters and their interactive effects on the pyrolysis process. This review ranks were assigned to various parameters based on their PCC. Higher
offers extensive literature potential concerning the various factors, their the absolute value of the coefficient, the higher the rank. The parame­
influence on the efficiency of the process and their optimum range to ter’s direction or trend of influence was decided based on the sign of the
attain the maximum achievable yield. Further, the quantitative analysis PCC. As mentioned earlier, the correlation method used in this study is
method of the effect of parameters presented in this review offers sig­ not limited to the current study alone and is applicable in innumerable
nificant scope in prioritising strategic initiatives against economically fields (Supramono et al. [92]).
beneficial and efficiently productive categories. The whole study relies on the existing literature and all results ob­
In previous works, researchers have discussed, in length and depth, tained and discusses the dataset taken for analysis. Having said that,
the various parameters affecting the yield of the process for a single type though the likelihood of variation in the effect of these parameters with
of feedstock, its trends and mechanisms. However, to the best of the different processes is substantial, the congregation of factors chosen for
author’s knowledge, this study is the first to consolidate information this study guarantees a specific strength of steadiness and stability.
from different types of plastic wastes collectively, establish the corre­
lation that exists among the various parameters statistically, quantita­ 6. Factors/parameters considered
tively signify each parameter, and explicitly express its impact on the oil
yield with the help of Pearson’s matrix coefficient. This review also at­ Though this waste-to-energy technology (WtE) is existentially
tempts to assign a weighted rank to each of the inputs based on its in­ implemented, it is essential to consider the monetary obligation and
tensity of impact on the efficiency of the process, which is ultimately unfavourable impact of the process on the environment due to its sci­
unique to this work. This review also deliberates to derive a comparison entific and technical requisites [76]. Also, to holistically recognise any
between two categories of processes - pyrolysis of plastic waste when process concerning its economic, environmental and energy efficiency,
used in singular and co-pyrolysis of plastic waste when used in it is imperative to thoroughly study, analyse and understand the pa­
conjunction with biomass and other types of waste. Unequivocally, this rameters that drive the whole system. Thus, the pyrolysis process de­
review suggests some reasons that confine the process from being pends on a series of factors and can be divided into two categories –
commercially successful as challenges and opportunities to detail the feedstock and operational/process parameters. These include the
effect of the parameters in the reaction. composition of the feed, its moisture content, process temperature,
residence time, heating rate, and the presence of a catalyst and toxic
5. Methodology elements [62].
Further, co-pyrolysis of plastic with other types of wastes or biomass
5.1. Data procurement possesses vast potential in broadening the range of waste management
alternatives and reducing environmental impacts. The process also
To provide an introspect on the effects of various critical parameters permits the modification of quantity and quality of the formation of
on the pyrolysis technique, an extensive dataset from previously pub­ various products, thus positively affecting the economics of the process
lished research works consisting of characteristics of plastic waste, py­ [114,115,116]. In recent times, the synergetic effect, i.e. the interaction
rolysis process parameters, and liquid product yield was formed [34]. between plastic waste and biomass, is of keen interest to researchers and
The plastic waste characteristics considered in this study are the per­ forms an imperative branch of study. Increased yields of oils for
centages of Carbon (C%), Hydrogen (H%), Nitrogen (N%), Oxygen (O co-pyrolysis with PS, PP, HDPE and PVC were recorded by several

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M. Vaishnavi et al. Journal of Analytical and Applied Pyrolysis 170 (2023) 105907

researchers [14,15,20,27,66]. two or more types of plastic wastes are used in conjunction with each
other in the co-pyrolysis process, the product yields and the composition
obtained are incomparable to the ones during single waste pyrolysis
6.1. Feedstock parameters (Ates et al., 2013). Hence, Table 3 lists the major components of oil
formed from the co-pyrolysis of different plastic waste. [62].
Pyrolysis of plastics involves cracking long-chain hydrocarbons into
small chain molecules through elevated temperatures. This process 6.1.2. Particle size
follows the four main steps: initiation, transfer, decomposition, and Particle size is one of the crucial factors that have vital interlinks
termination [31,63]. During pyrolysis, transient heating of feedstock with other process parameters like reaction temperature, heating rate,
particles takes place, leading to the release of moisture from the feed­ and residence time and thus implicitly affects the product distribution
stock, followed by the release of pyrolytic volatiles and non-volatiles and yield [100]. During the process, as the reaction temperature in­
(pyrolytic products) due to thermal cleavage of chemicals and bonds creases, the core temperature of the feedstock particle is lesser than the
in its only constituents. Essentially, plastic wastes vary in their elemental surrounding temperature, thus creating a temperature gradient within
composition; thus, it is required to understand the reaction chemistry to the particle [83]. This temperature gradient increases with the particle
know the extent of thermal fragmentation and decomposition [64]. size and results in the non-completion of the process within the pre­
Generally, plastic wastes can be categorised as follows – High- scribed time (Erdogan, 2020). Also, regarding heating rate, smaller
Density Polyethylene (HDPE), Low-Density Polyethylene (LDPE), Poly­ particles attribute to larger surface areas, enabling faster heating and
propylene (PP), Polystyrene (PS), Polyvinyl chloride (PVC), Poly­ leading to a high yield of liquid products. In contrast, feedstock with
ethylene terephthalate (PET) and Others (Polyurethane (PU) and larger particle sizes corresponds to lower heating rates and, conse­
Polycarbonate (PC) [12,67]. Thus, each type of plastic has its unique quently, longer residence times ([12], DiBlasi et al., 1996). Nonetheless,
cracking mechanism depending on its chemical structure and composi­ the effect of particle size on product distribution is minimal at high re­
tion [89]. action temperatures because, at higher temperatures, the radiative heat
transfer nullifies the temperature gradient within the particle to a
6.1.1. C, H, N and O content certain extent [12,24].
The elemental composition of each plastic type and the major con­
stituents of the liquid product obtained from pyrolysis are listed in 6.1.3. Catalysts
Table 2. The elemental composition and chemical structure affect the Catalysts play a crucial role in enhancing the overall efficiency of the
yield, product distribution, and the oil quality obtained. Sharuddin et al. process and improving the process conditions by target; thus, many
stated the pyrolysis of PVC resulted in a meagre liquid product yield catalysts have been used and tested for the same in pyrolysis and co-
along with chief compositions of hydrochloric acid and chlorinated pyrolysis operations. The solid catalysts’ properties, such as acidity
compounds that are harmful to the equipment system and environment and specific surface area, play an essential role in the selectivity of liquid
[89]. Also, many researchers have reported the oil obtained from PP had products and can be categorised into – clay catalysts, zeolite catalysts,
a concocted mixture of mono and polyaromatic compounds, with and bimetallic catalysts (Fadillah et al., 2021). Among these, zeolite-
single-ringed structures in a majority [50,62,72]. based catalysts have been extensively explored for their effectiveness
Table 2 gives the range of operational conditions and composition of in the pyrolysis and co-pyrolysis of plastic wastes. Apart from providing
oils when individual plastic wastes are subjected singularly to the py­ efficient mass transport for feedstock particles and beneficially altering
rolysis process [88,89]. the reaction mechanism, other crucial characteristics of the catalyst
In addition to pyrolysis, several researchers adopted the co-pyrolysis include its thermal and chemical stability to perform in high-
technique to process the various types of plastic waste. However, when temperature and chemically complex environments (Kumar et al.,
2014, Pienko et al., 2018, Krol 2020).
Table 2 The most widely used catalysts for plastic-to-fuel conversion
Process conditions and oil composition obtained from pyrolysis of a single type
of plastic wastes.
Table 3
Plastic- Treatment conditions Components in pyrolysis oil Process conditions and oil composition obtained from co-pyrolysis of plastic
type
wastes.
PET 500 ◦ C, 6–10 ◦ C/min, 1 – Proponone, Benzoic acid, Biphenyl
Co-pyrolysis Co-pyrolysis Components in co-pyrolysis oil
Fixed Bed Diphenylmethane, Fluorene, Biphenyl
feedstock Treatment conditions
carboxylic acid, Benzophenone,
Anthracene, Butanone PS + PP Batch, Semi Batch, Benzene, Phenylnaphthalene, Malonic
HDPE 350 – 750 ◦ C, 7–25 ◦ C/ Benzene, Toluene, Xylene, Octene, 425 – 450 ◦ C, 10 ◦ C/ acid, Diphenylcyclopropane, Pthalic acid,
min, Fluidised bed, Batch Heptene, Hexene, Nonene, Decene, C4- min Pentadecane, Tetradecanolacetate
and Semi batch C13 Hydrocarbons, C14 Hydrocarbon, PS + PE Batch, Semi Batch, Phenanthrene, Nonadecene,
Cyclohexane, Methylcyclopentene 425 – 450 ◦ C, 10 ◦ C/ Phenylnaphthalene, Pentadecane,
PVC 500 ◦ C, 10 ◦ C/min, Fixed Naphthalene, Azulene, Biphenyl min Benzene, Cyclononasiloxane, Heneicosane
Bed, Vacuum batch naphthalene, Dimethyl naphthalene, PP + PE Batch, Semi Batch, Pentadecane, Cyclononasiloxane,
Ethyl naphthalene Fluorene, 425 – 450 ◦ C, 10 ◦ C/ Benzene, Nonadecene, Hexadecene,
Phenenthrene, Indene min Heptadecene, Anthracene,
LDPE 450 ◦ C, 5–20 ◦ C/min, Benzene, Toluene, Xylene, Dimethyl Phenylnaphthalene
Fluidised bed, Batch benzene, Trimethyl benzene, Indane, PS + PP + PE Batch, Semi Batch, Tetradecene, Nonadecene, Phenanthrene,
Indene, Naphthalene, Ethylnaphthalene, 425 – 450 ◦ C, 10 ◦ C/ Fumaric acid, Pentadecanol,
Fluorene min Phenylnaphthalene, Hexadecanol,
PP 300 – 750 ◦ C, 3–20 ◦ C/ Benzene, Toluene, Xylene, Ethylbenzene, Benzene, Pthalic acid
min, Semi batch, Batch Indene, Biphenyl, C4-C13 Hydrocarbons, PS + PP + PE Batch, Semi Batch, Pentadecene, Benzene,
C14 Hydrocarbon, Heptene, Octene, + PET 425 – 450 ◦ C, 10 ◦ C/ Phenylnaphthalene, Nonadecene,
Dodecen min Heneicosane, Benzenedicarboxylic acid,
PS Batch, Semi Batch, 425 – Benzene, Toluene, Xylene, Ethyl Phenanthrene, Heptacosanol
450 ◦ C, 10 ◦ C/min benzene, Styrene, Cumene, MPW (pdt Batch, 500 – 600 ◦ C, Hexadecane, Heptadecene, Octadecene,
Propylbenzene, Naphthalene, dis) 10 ◦ C/min Nonadecene, Pentadecane, Tetradecane,
Diphenylmethane, Diphenyl benzene, Dimethyl heptane, Octacosane,
Triphenylbenzene, Bibenzyl, Anthracene Tetratriacontane, Pentatriacontane

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M. Vaishnavi et al. Journal of Analytical and Applied Pyrolysis 170 (2023) 105907

reactions are zeolites due to their umpteen advantages like excellent 53,94,118,120]. Further, the plasma-assisted systems work at heating
thermal stability (Lok et al., 2019), selectivity (Gayubo et al., 2004, rates of range 1–50 ◦ C/s through DC plasma torches providing
Kang et al., 2019), effective enhancement of deoxygenation and high-frequency heating, thus maintaining uniform heat distribution
cracking reaction to produce oil with improved properties [107,41]. throughout the process and excellent heat transfer within the feedstock
Studies on metal-embedded zeolites are in the front run due to their [96,97,98].
amplified effect on the surface area and pore size of the zeolite structure,
which explicitly controls the thermal degradation mechanism of the 6.3. Percentage of plastic waste
feedstock materials [32,3,65]. Therefore, the structural properties,
composition, and type of catalysts are influential and crucial in deter­ Available literature suggests a positive synergetic effect when
mining the product quantification and distribution of the pyrolysis biomass and plastic waste are co-pyrolysed, and the oil derived from the
process (Ghorbannezhad et al., 2020, Lin et al., 2019, [49,38]). process contains less oxygenated compounds due to the deoxidation
effect and thus improving its stability and decreasing the corrosion effect
6.2. Process parameters [15,16,40,52,71,92,112]. Further, it is reported that using biomass with
LDPE waste improved the overall selectivity of the process and increased
6.2.1. Reaction Temperature the production of aromatics such as benzene, toluene and xylene (Wang,
In the pyrolysis of plastics, the temperature is one of the most 2021).
influential parameters since it governs the cracking reaction mechanism Most researchers claim that the usage of catalysts in the co-pyrolysis
of the polymer chain [106]. Thus, the reaction temperature is vital in of plastic waste and biomass helps in the reduction of oxygenated
forming various production phases. Evidence from previous literature compounds in the liquid product and thus increasing its calorific value
work suggests that, for maximising the liquid product, the optimum [111,36,4,66]. Also, the usage of catalysts influences the yield of volatile
reaction temperature is in the range of 300 – 500 ◦ C, and any temper­ compounds, and in most cases, the amount of volatiles formed increases
ature range higher than 500 ◦ C results in a higher yield of gaseous [42,73,75]. Plastic waste has been used with various types of biomass,
products and reduced yield of pyrolysis oil ([88,89], Cen et al., 2014, [7, along with metal-embedded catalysts and metal oxide catalysts, and
37]). Among the different varieties of plastics, PS exhibited the enor­ higher oil yields with high aromatic content were obtained [43,85].
mous potential to be used as a feedstock for plastic pyrolysis by pro­ Also, the catalytic co-pyrolysis of mixed plastic waste with biomass is
ducing a high liquid product yield within the optimum temperature being investigated by many researchers and is found to have a positive
range ([89], Miandad, 2018, Abuiazaiza et al., 2017). As in the case of effect on the yield of liquid products (Chen et al. [13,14]). In this regard,
mixed plastic waste, which consists of more than two types of plastics, Sebestyen et al. [86] reported a case of catalytic poisoning in the
the optimum range of reaction temperature to maximise yield may not co-pyrolysis of the plastic waste mixture and different biomasses, where
be the same as of individual plastics [21,63,67]. This variation in the the oil yield decreased substantially in each case [68].
optimum temperature range is observed due to different plastic com­ In general, it can be summarised that using plastic waste combined
ponents with varying polymer chain lengths that degrade thermally at with biomass proves an overall constructive mechanism for co-pyrolysis
different temperatures facilitating depolymerisation into their mono­ [80,81,29,82]. As stated above, an enhancement in oil yield and positive
mers and re-polymerisation to aromatic compounds [63,65]. effects on its quality has been observed [9]. Nonetheless, the amount or
As aforesaid, in the co-pyrolysis of plastic waste with biomass, the ratio in which the plastic wastes can be utilised to create a positive
optimum temperature range is altered from that of individual plastics synergetic effect both quantitatively and qualitatively, and to what
[22]. Also, the biomass feedstock particles promote depolymerisation by extent the used catalyst affects the whole process, need more study.
aiding in the cracking of plastic polymer chains to lower molecular
weight monomers [106]. Hence, the ratio of biomass incorporated for 7. Statistical trend analysis
co-pyrolysis with plastic waste plays a significant role because biomass
feedstock is usually composed of more oxygen compounds, and the The correlative trend between the input variables and the output
tendency of these compounds to alter the product distribution and affect response is significant in understanding their interaction [117]. The
its quality is substantial ([25], Qian et al., 2014). significant implication of this study is to study the input factors, such as
the feed characteristics and process operative parameters, concerning
6.2.2. Residence time and Heating Rate the quantitative yield of bio-oil in the previous experiments [91]. Figs. 4
Literature investigations on the combined effect of residence time and 5 show the overall statistical trend of various feed and process pa­
and heating rate on plastic pyrolysis are very scarce [69]. This may be rameters analysed for pyrolysis and co-pyrolysis of plastic waste,
because both of these factors are temperature reliant. However, reaction respectively. In the case of both pyrolysis and co-pyrolysis, it can be seen
time affects the properties and quantity of pyrolysis oil to a certain as the main observation that the feed characteristic parameters such as
extent, especially in the presence of a catalyst [99,34]. With the evo­ the carbon content (C %) and hydrogen content (H %) show a positive
lution of varied types of reactors and the usage of catalysts, a continuous trend and parameters such as oxygen (O %), moisture (M%) and particle
mode of operation is preferred, where the quantity and quality of desired size (PS) follow a negative trend. An almost neutral influence is seen in
liquid products are simulated to be stable with time [101]. the case of nitrogen content (N%) for both processes [59]. An overall
Also, with the paradigm shift from conventional heating systems to positive trend is prevalent among all the operating variables, such as the
microwave and plasma-assisted ones, the process of pyrolysis and the temperature, residence time, heating rate and amount of catalyst. The
heating rate of the system experienced a predominant transformation percentage of plastic waste (Plastic %) in co-pyrolysis also exhibited a
from conventional methods to fast and flash pyrolysis [78]. Generally, positive trend regarding oil yield [46].
the conventional pyrolysis systems operate at a heating rate of Pyrolysis oil is a concocted mixture consisting mainly of hydrocar­
8–30 ◦ C/min, where the heat is transferred from the wall of the reactor bons [104]. Thus, a higher fraction of elemental carbon and hydrogen in
to feed particles through conductive and convective heating principles. the feedstock favours the liquid product yield [105]. Similarly, the high
This non-uniform heating leads to a significant energy loss and a rela­ internal oxygen content is barely beneficial in obtaining higher yields of
tively low liquid product yield [45]. Whereas the microwave-supported liquid products, as most of the carbon present in the feedstock undergoes
system operates at the heating rates of 10–50 ◦ C/min, providing initial complete combustion instead of thermal decomposition into combus­
uniform heating and enhanced product yields with upgraded quality. tible products [35]. Though nitrogen is an inert constituent having
Here, the heat transfer across the feedstock occurs using charged ions in nearly zero influence on the process and its conditions, the same is not
the material created by the interaction between varying field forces [54, true regarding the quality of the product obtained. The presence of

7
M. Vaishnavi et al. Journal of Analytical and Applied Pyrolysis 170 (2023) 105907

Fig. 4. Overall statistical trends of feed and process parameters for pyrolysis of plastic wastes.

nitrogenous compounds like amines, amides, nitriles and N-heterocycles co-pyrolysis processes, with a correlation coefficient of 0.891 and 0.870,
renders the obtained liquid product unsuitable for combustion due to the respectively. Among the feed characteristics, carbon content displayed a
evolution of NOx [56]. Also, the initial moisture content of the feedstock strong positive correlation with coefficient values of 0.857 and 0.855 for
not only decreases the energy efficiency of the process but also in­ the pyrolysis and co-pyrolysis processes, respectively [60]. Among the
fluences the amount of water content present in the liquid product [47]. negatively correlated variables, feedstock characteristic parameters
The effect of various process parameters has been discussed in detail in such as moisture (M%) and particle size (PS) have the most destructive
the previous section, and the trends obtained employing statistical influence on oil yield, with coefficient values of − 0.818 and − 0.779 for
analysis are in unity with it [103]. pyrolysis and − 0.830 and − 0.793, respectively.
Table 4 and Table 5 give the different ranges in which the variables Baring the above, both pyrolysis and co-pyrolysis processes have the
were analysed. It is important to note that the trends presented are same influential parameters in ranks 1 – 4. Further, process parameters
pertinent to the data analysed and the range of each variable considered. such as heating rate, residence time and catalyst amount exhibited
For example, the positive trend exhibited by temperature is true to the positive correlations [1]. The oxygen content (O%) presented an
range of 350 – 640 ◦ C, where most of the data studied were present, and above-average negative correlation in both cases. The nitrogen content
it may or may not be so outside this range [90]. (N%), though presented with moderate correlations in pyrolysis and
co-pyrolysis processes [79], and its near-zero value of the coefficient of
8. Correlation between variables determination (0.1 in both cases) invalidates any possible correlations
with oil yield [18]. It is also important to note that the amount of
It is essential to understand the correlation between variables and catalyst used in co-pyrolysis exhibited a higher correlation coefficient
their effect on the overall yield of the process [10]. A total of 10 and 11 value than pyrolysis (0.715 in the case of co-pyrolysis and 0.563 in the
parameters for pyrolysis and co-pyrolysis processes were analysed and case of pyrolysis), thus iterating the significance of the usage of catalysts
ranked based on their statistical influence on the desired yield [79]. in case of co-pyrolysis and the reasons to which have been discussed in
Fig. 6 and Fig. 7 show the Pearson correlation matrix between various Section 6.1.3.
variables for pyrolysis and co-pyrolysis processes, respectively. At the
same time, Table 4 and Table 5 provided the values of the Pearson 9. Conclusion
correlation coefficient and coefficient of determination between the
various parameters and oil yield [61]. The temperature exhibited the The Pearson Correlation Coefficient (PCC) methodology helps
strongest positive correlation with oil yield for both pyrolysis and develop the correlative trend between the input variables (feed and

8
M. Vaishnavi et al. Journal of Analytical and Applied Pyrolysis 170 (2023) 105907

Fig. 5. Overall statistical trends of feed and process parameters for co-pyrolysis of plastic wastes.

Table 4 Table 5
Values of PCC and Coefficient of determination between process parameters and Values of PCC and Coefficient of determination between process parameters and
oil yield for pyrolysis of plastic wastes. oil yield for co-pyrolysis of plastic wastes.
Variable Pearson Coefficient of Rank Range Variable Pearson Coefficient of Rank Range
coefficient determination coefficient determination

T (◦ C) 0.891 0.794 1 350–640 T (◦ C) 0.870 0.758 1 300–800

C (%) 0.855 0.731 2 60–85 C (%) 0.857 0.735 2 12–80
M (%) - 0.818 0.670 3 0–4 M (%) - 0.830 0.689 3 0.3–10
PS (mm) -0.779 0.606 4 2–20 PS (mm) -0.793 0.628 4 2–25
H (%) 0.735 0.540 5 2–15 Cat (%) 0.715 0.511 5 0–12
HR (◦ C/min) 0.683 0.467 6 10–20 H (%) 0.707 0.499 6 5–20
O (%) -0.649 0.421 7 0.1–14 O (%) -0.691 0.493 7 10–83
t (s) 0.616 0.379 8 30–800 HR (◦ C/min) 0.632 0.4 8 10–40
Cat (%) 0.563 0.317 9 0–2.5 Plastic (%) 0.601 0.361 9 2–25
N (%) 0.318 0.101 10 0.1–2.5 t (s) 0.578 0.335 10 30–800
N (%) - 0.332 0.104 11 0.03–5

process) and their respective output response (oil yield %) and classify
them as positive or negative. Analysing and understanding the correla­ • In co-pyrolysis, the percentage of plastic waste strongly influenced
tion between the variables statistically helps in comprehending its the process.
contribution and significance to the overall pyrolysis process and • The reaction temperature was the most influential parameter be­
developing a ranking system using its quantification that aids us in a tween feed and operational characteristics, with PCCs of 0.857 and
priority-based optimisation of the technology. The significant conclu­ 0.855 for pyrolysis and co-pyrolysis processes, respectively.
sions arrived from this review are as follows: • Moisture (M %) and particle size (PS) negatively influenced oil yield,
with PCCs ranging from − 0.830 to − 0.779 for both processes.
• In both pyrolysis and co-pyrolysis processes, feed characteristics – • The PCC of Cat% for the co-pyrolysis process was 27% higher than
Carbon and Hydrogen content and, amongst process parameters – for pyrolysis, indicating the effect of catalyst usage for unconven­
temperature, residence time, heating rate and amount of catalyst tional and mixed feedstock.
exhibit positive correlations.
• The Nitrogen content showcased a neutral trend and, thus, a minor Declaration of Competing Interest
influence on both processes [102].
The authors declare that they have no known competing financial

9
M. Vaishnavi et al. Journal of Analytical and Applied Pyrolysis 170 (2023) 105907

Fig. 6. Pearson matrix between process parameters and oil yield for co-pyrolysis of plastic wastes.

Fig. 7. Pearson matrix between process parameters and oil yield for pyrolysis of plastic wastes.

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