Environmental Chemistry Letters (2021) 19:3609–3629

https://doi.org/10.1007/s10311-021-01245-4

REVIEW

Microwave pyrolysis of coal, biomass and plastic waste: a review

Aravind Suresh1 · Alaguabirami Alagusundaram1 · Ponnusamy Senthil Kumar1   · Dai‑Viet Nguyen Vo2 ·
Femina Carolin Christopher1 · Bharkavi Balaji1 · Vinatha Viswanathan1 · Sibi Sankar1

Received: 25 March 2021 / Accepted: 17 April 2021 / Published online: 17 May 2021
© The Author(s), under exclusive licence to Springer Nature Switzerland AG 2021

Abstract
Growing concerns over climate change have prompted the quest for renewable energies to mitigate adverse impacts caused
by the excessive use of fossil fuels. In particular, using waste and biomass as fuel precursors is currently under active
research. Pyrolysis is a thermal conversion in an inert atmosphere, involving the rapid heating of feedstocks to produce oil,
gas and intermediate chemicals. Here, we review pyrolysis of cellulose, lignin, algae, plastic wastes and coal, with focus on
microwave-assisted processes. We describe the types of char, bio-oils and gas products. We detail various apparatuses used
in microwave-assisted pyrolysis to show that industrial upscaling is possible. Advantages of microwave-assisted pyrolysis
include uniform heating of large particulate size of feed, fast switching on and off controls, and no requirement of fluidiza-
tion. Higher yield of oil should be obtained by microwave-assisted pyrolysis of organic feedstocks.

Keywords  Environment · Biomass · Pyrolysis process · Bio-oil

Abbreviations With possibilities foreseeing that non-renewable energy gets

ASEAN Association of South East Asian Nations completely consumed, and hence alternative sources need to
PHA Polyhydroxyalkanoates be considered. There are rising concerns worldwide about
PLA Polylactic acid depleting non-renewable sources including their negative
DAEM Distributed activated energy model impacts on the environment. As a developing nation with
FCC Federal Communications Commission fast-growing population, India currently has 1.366 billion
LDPE Low-density polythene people and its population is growing at a rate of 1.58% per
NiO Nickel oxide annum. This necessitates an urgent need for increasing fossil
HY High yield fuels import in India because of the excessive demand for
PP Polypropylene coal of about 1300 million tonnes per year (Finkelman and
HDPE High-density polythene Tian 2018).
MTL Microwave-torrefied lignin The preference of these non-renewable sources is also
due to their high availability, accessibility and usability in
comparison with other renewable energy sources. However,
Introduction a potential pitfall currently arises due to the excessive com-
bustion of non-renewable resources inducing greenhouse
The requirement of energy is basically due to the ever-grow- gases emissions. Usual suspects include methane (­ CH4),
ing population in the decades. Two major classifications of nitrous oxides ­(NxOy) and carbon dioxide ­(CO2). Carbon
energy sources are non-renewable and renewable sources. dioxide emission is mainly contributed by ocean release,
respiration, decomposition (biological) and anthropogenic
activities. This gas is released by deforestation, which is
* Ponnusamy Senthil Kumar done to meet increasing wood products demand. Cement
senthilchem8582@gmail.com; senthilkumarp@ssn.edu.in manufacture is also a causative agent in ­CO2 increase due
1
Department of Chemical Engineering, Sri Sivasubramaniya
to the extensive growth of civil society and infrastructure
Nadar College of Engineering, Chennai 603 110, India requirements. Thus, excessive petroleum, natural gas and
2
Center of Excellence for Green Energy and Environmental
coal combustion are needed for meeting the energy require-
Nanomaterials (CE@GrEEN), Nguyen Tat Thanh University, ments (Cassia et al. 2018).
Ho Chi Minh City, Vietnam

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The extensive utilization of these naturally produced
resources over the past decades currently causes the rapid
fossil fuels depletion because of their superior extraction
rate to formation rate. This has consequently resulted in the
spiking of energy prices and thus led to energy insecurity.
Hence, it is crucial to replace these non-permanent and
environmentally detrimental resources by switching to the
renewable energy economy.
The growth in clean energy production has been a tre-
mendous rise. About 35% of total energy requirement for the
period within 2020–2024 is renewable energy, driven mainly
by the emerging economies of Brazil, Russia, India, China
and South Africa (BRICS), Association of South East Asian
Nations (ASEAN), Africa and Middle East (Global Data
2020). Hence, renewable energy sources play a convincing
role to establish themselves as the only alternate available to
reduce environmental impacts caused by deleterious effects
of fossil fuels combustion. Renewable energy sources,
namely wind and solar energy, have proved themselves to
be energy efficient in this decade. This is due to increasing
technological advancements. The challenge of the times is
to provide sustainable renewable energy.
Renewable energy sources like solar, wind, hydro-power
have been utilized by many countries. However, there are
also significant side effects that result from the upkeep and
maintenance of the equipment required for these energy
sources (Aravind et al. 2020). Promising candidates include
biomass and plastic wastes that can be converted to energy
by thermochemical and biochemical methods. Pyrolysis is
a thermochemical method which is useful in the conversion
of raw materials to energy. This review aims to illustrate the
differing raw feedstocks available for pyrolysis, on how they
pyrolyze and product composition with a special emphasis
on microwave pyrolysis. The review attempts to demon-
strate the differences between pyrolyzing plastics, biomass
and coal.
Thermochemical feedstock conversion
In general, the conversion of raw materials to produce
energy can be carried out by biological or thermochemical
methods. The raw materials usually considered for renew-
able energy production can be categorized into two classes.
They are of biological origin and non-biological origin. The
feed of biological origin is commonly called biomass. The
non-biological feed includes plastics and other waste prod-
ucts which can be used for energy production. A particu-
lar interest is also in utilizing coal for energy production
using techniques that yield lesser pollution when compared
to the standard combustion of coal. Thus, this paper will
discuss about the feedstocks like biomass, plastics and coal
and their conversion to energy by thermochemical methods
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Environmental Chemistry Letters (2021) 19:3609–3629
(Nanda and Berruti 2021). Generally, most of the feedstocks
mentioned above are usually products that are left behind as
wastes. The utilization of so-called wastes to produce energy
is an environmentally favorable process. The particular point
of interest is to compare and contrast the product yield from
various feedstocks. This helps in optimizing the feed con-
tent and assists to understand the yield from various types
of feedstocks.
These feedstocks depict diversity in the molecular dimen-
sions and thus making them difficult to use the conventional
treatment methods (i.e., anaerobic digestion, combustion,
etc.). The abovementioned feedstocks are all characterized
by extreme morphological differences, physical and chemi-
cal characters. Despite the common origin of carbon-based
feedstocks, the biological and non-biological origin feeds
are completely dissimilar in molecular structure, chemical
composition and properties. Biological feedstocks can be
classified into two differing classes like terrestrial biomass
and algal biomass, while non-biological feedstock like coal
and plastics are completely dissimilar. These feedstocks
have many different molecules in their structures. These
compositional differences also show that no single prod-
uct is formed on treating the feedstocks, but a series of by-
products are also found to occur along with fuels such as
char, gaseous products, aqueous and organic liquid products.
Further, unlike the conventional and non-renewable fossil
fuels, biomass-based fuels are slightly disadvantageous
due to their high moisture content, differences in composi-
tion from source to source, low heating values and limited
grinding capacity (White et al. 2011). These disadvantages
can easily be nullified by the proper pretreatment of feed-
stocks and adopting modern technologies to achieve high
conversion into fuels. There are two main methods for the
pretreatment of feedstocks. These are called physical and
chemical methods. Physical methods generally involve ther-
mal pretreatment, while chemical methods involve treating
feedstocks with chemicals to alter the chemical composition
of feedstocks (Liu et al. 2012).
In physical methods, the feedstock is converted into large
blocks of mass called briquettes which are produced after
a thermal treatment to remove all moisture. This technique,
however, poses a threat to the environment due to increasing
carbon emissions on burning. To address the issue of high
carbon emissions due to the direct burning of fossils and
biomass feedstocks, researchers started shifting their atten-
tions towards chemical methods. Chemical processes use
enzymes to break down the complex structures of feedstocks
and thus acting as catalysts. This is primarily observed in
biomass, hence this process can also be called as the bio-
chemical treatment. Though biochemical treatment can be
conducted under mild conditions without causing any harm
to the environment, one major disadvantage of this approach
is that the products formed during the biochemical process
Environmental Chemistry Letters (2021) 19:3609–3629 3611
may be harmful to the enzymes. Hence, it requires some
pretreatment of feedstocks in such a way that the microbes
and enzymes can readily adapt to the conditions and aid in
accelerating the progress of the reaction (Behera et al. 2014).
Transesterification is another technique used for the pro-
duction of fuels. In this process, animal fats, cooking wastes
or oils react with methanol or ethanol to produce a mixture
of fatty acids and glycerol. This eco-friendly process occurs
under mild conditions with the presence of a catalyst. The
technology is increasingly gaining attraction because the
final product from this method has a viscosity comparable
to that of conventional fossil fuels (Moazeni et al. 2019).
Torrefaction is a technique that produces coal-like materi-
als by the thermal treatment of biomasses. Unlike the other
techniques used in fuel production, torrefaction results in
solid fuel that can be burnt to produce energy. Solid fuels
obtained from biomass also include the utilization of biochar
produced from various processes like slow pyrolysis (Ghy-
sels et al. 2019; Toloue Farrokh et al. 2018), fast pyrolysis
(Trinh et al. 2013) and hydrothermal carbonization (Atta-
Obeng et al. 2017). However, solid fuels do not find large-
scale industrial fuel applications, though their high heating
values surpass that of coal (Bach and Skreiberg 2016).
A wide variety of thermochemical techniques and cata-
lytic systems are deployed for the effective destruction of
raw materials into useful fuel-based chemicals and the pro-
cesses are optimized under controlled temperature and pres-
sure conditions. A brief classification arises where feedstock
is either treated directly by a single-step process (i.e., one-
pot process) or subjected to several stepwise techniques for
the required fuel grade product formation. Stepwise methods
mainly involve the coupling of depolymerization methods
producing oxygen-rich oils which are further processed with
selective deoxygenation strategies to yield oxygen-free prod-
ucts (Azadi et al. 2013).
Hence, this oil serves as a key raw material that gives rise
to substitute chemicals for blending with conventional fuels.
The techniques mainly involve pyrolysis, liquefaction, gasifi-
cation and several hydrotreating steps (hydrodeoxygenation)
where pyrolysis is the thermal treatment method of degra-
dation, and liquefaction refers to the generation of liquid
fuel-based products from solid feeds (Speight 2016), while
hydrotreating is a reaction taking place under the aid of
hydrogen atmosphere. Pyrolysis takes place with the decom-
position of organic substances under high temperature, viz.,
673–773 K for slow pyrolysis (Li et al. 2016a,2016b,2016c)
and 773–873 K for fast pyrolysis (Zhao et al. 2018). Ele-
vated pressures greater than 1 atm and oxygen absence are
the hallmark of the process. It is an inexpensive and simple
technique which could be implemented easily for different
feedstocks. Additionally, maintaining the pyrolysis equip-
ment is relatively simple compared to other thermochemical
techniques.
Gasification is the next step of pyrolysis in the sense
that, any solid char formation during the pyrolysis process
is broken down to produce syngas. Additionally, the supply
of steam during this process accelerates the conversion of
residual low molecular weight carbon substances to syngas.
This technology is performed under a limited supply of air
and at a temperature of 1200–3300 K (Kang et al. 2015;
Speight 2016). This current objective of this study is to com-
pare and contrast the differences between the by-products
formed when different feedstocks undergo pyrolysis. Due to
the increase in various waste feedstocks, the thermochemical
conversion strategy gives a best way towards the economic
flexible and environmental friendly method and also creates
valuable materials. The studies from this section demon-
strated that the thermochemical conversion technique has
gained more attention than the biological process.
Pyrolysis and products
Conversion of feedstock to energy is the primary objective
of pyrolysis. There are three major constituents obtained
from pyrolysis process. They are pyro-oils (or bio-oils if
the feed is organic in nature), char and pyro-gas (biogas if
the feed is organic). In pyrolysis process, the adjustment of
different operating parameters, namely temperature, reaction
time and heating rate can yield different fractions of oil, char
and gas products. Hence, these factors can be exploited for
specific needs.
Char is a black powdery solid formed by the pyrolysis
of biomass. Char has been widely used as an adsorbent for
the treatment of wastewater, especially the secondary stage
treatment (Ravenni et al. 2020; Yaashikaa et al. 2020). Other
uses include activated carbon production to improve soil
fertility (Doumer et al. 2015) and a reducing agent in the
metal-working industry (Suopajärvi et al. 2013). The past 20
years has necessitated the process of pyro-oil production by
pyrolysis as a suitable alternative to petroleum for transport
fuel. The main utility of pyro-oils is for fuel production.
Additionally, oils have greater energy densities than their
corresponding petroleum equivalents (Grierson et al. 2011).
The third product formed is pyro-gas. It is also called as
biogas, if the feed is biological in nature. The main utility
of biogas is for domestic applications. Recently, biogas has
also been considered as a potential fuel for transport appli-
cations (Dahlgren 2020). In the development of pyrolysis
method, the product plays a huge challenge. The challenges
tend to tends to limits the usage of pyrolysis method in the
commercial scale and hence numerous studies have been
invested for the improvement of this technology.
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Types of pyrolysis
Slow pyrolysis
Slow pyrolysis refers to the process of having a higher
reaction time when compared to fast pyrolysis. The time
for pyrolysis may differ for each feedstock from 10 to 60
min for wood, grasses and dry algae (Ronsse et al. 2013)
to about 5–10 h for straw and poplar (Kloss et al. 2012).
Slow pyrolysis usually has heating rates in the range of 5
to 10 K/min (Dhahak et al. 2020). The average temperature
used for pyrolysis processes is from 500 to 900 K depending
on employed feedstocks. Char is the predominant product
obtained from slow pyrolysis since longer the reaction time,
greater chances of carbonization occur (Cárdenas-Aguiar
et al. 2019). Plastics generally pyrolyze at the temperature
range of 600 to 800 K (Das and Tiwari 2018). Biomass
pyrolysis temperature differs significantly for terrestrial
biomass, tertiary wastes and algal contents, but in general,
fits into 550 to 900 K range. Coal pyrolysis requires a signifi-
cantly higher temperature from 750 to 1000 K than plastics
or biomass (Lievens et al. 2013).
Fast pyrolysis
In contrast, fast pyrolysis has a much lesser reaction time
when compared to slow pyrolysis with the average time
within 10 to 20 min. Temperatures may vary as per feed-
stock requirement, but general ranges are from 700 to 900
K. The heating rates are generally in the range of 50–100
K/min (Xiu et al. 2012). Feedstocks like coal may require
higher temperatures of 850–1200 K for fast pyrolysis, while
plastics and biomass have similar ranges (Venderbosch and
Prins 2010).
Flash pyrolysis
Flash pyrolysis is an intensely short process of lesser than
10 min, with the time period usually being in seconds, to
effect the rapid heating at a heating rate of greater than 100
K/min, which produces bio-oil. The main difference between
fast and flash pyrolysis processes is the reaction time. Flash
pyrolysis produces a greater amount of oil content than fast
pyrolysis (Patel et al. 2020). The average temperature of fast
pyrolysis is from 1000 to 1300 K, differing for each feed-
stock. The flash pyrolysis mechanism is usually performed
in a vacuum, whereas the other two pyrolysis processes are
usually accompanied by an inert gaseous atmosphere (Ge
et al. 2020). Catalysts are used in flash vacuum pyrolysis to
either increase the oil yield from the feedstock or to prevent
noxious gases formation (Imran et al. 2014; Abou Rjeily
et al. 2021).
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Environmental Chemistry Letters (2021) 19:3609–3629
Other forms of pyrolysis
These pyrolysis mechanisms are usually feedstock specific.
Dry distillation in thermochemical terms refers to the action
of heat to bring the lysis of solid materials to form gaseous
products. It may either be a thermal process, in the presence
of oxygen, or a traditional pyrolytic setup can be ensured.
Dry distillation is usually taken not to involve any chemical
reactions and hence resembling classical distillation at very
high temperatures, resulting in only phase changes (Fer-
hat et al. 2007). Destructive distillation on the other hand
involves necessary chemical reactions to take place. Gener-
ally, distillation process is performed for organic feedstocks,
which helps to increase the usage of various compounds for
dry distillation process.
Catalytic pyrolysis has emerged to be a promising
approach as product quality can also be improved by intro-
ducing catalysts so that the thermal energy required can be
reduced than what is required without catalyst (Chen et al.
2019; Fan et al. 2020; Hassan et al. 2020; Luo et al. 2019;
Yang et al. 2019). The above process is feasible, and eco-
nomical enough in the production of biofuels from lignin.
Unlike the direct pyrolysis of feedstock, which generates a
massive portion of char, catalytic fast pyrolysis stands out
due to its catalytic action coupled with thermal treatment
which could improve the conversion of reactants to desired
products. The major advantage of this technique is the regen-
eration of catalyst which can be used multiple runs for eco-
nomic feasibility. However, to overcome this situation, the
synthesis of such stable catalysts with increased activity and
low cost is required for the catalytic fast pyrolysis.
Figure 1 depicts the classification of the types of pyrolysis
processes mentioned in this study. The fast, slow and flash
pyrolysis processes are the methods classified on the basis
of reaction time and temperature. Feedstock-specific pro-
cesses include cracking and catalytic pyrolysis. Flash vac-
uum pyrolysis, the production of polymer-derived ceramics
using pyrolysis, destructive distillation and dry distillation
are all examples of pyrolysis. The choice of equipment is
also important for pyrolysis. Microwave-assisted and con-
ventional pyrolysis are the two types of pyrolysis catego-
rized based on equipment.
These types of pyrolysis are highly used by the research-
ers for the production biofuel. The slow pyrolysis process is
used for the modification of solid material and minimizes the
oil yield. At the same time, slow pyrolysis process provides
greater environmental advantages when compared with the
other types of pyrolysis. But other pyrolysis process pro-
duces maximum bio-oil and biogas by a rapid heating rate
and short residence time.
Environmental Chemistry Letters (2021) 19:3609–3629 3613
Fig. 1  Classification of
pyrolysis processes involved
in the conversion of different
feedstocks into bioenergy
Types of feedstocks
Coal
Coal is a sedimentary rock, with a blackish-brown hue. Its
combustible nature has made it ideal for using as a source
of fuel. Since the ancient days, coal has been primarily used
as a source of heat. It is mostly made of carbon with varying
amounts of hydrogen, sulfur, nitrogen and oxygen. Primary
product given by coal reacting with oxygen is carbon diox-
ide, along with releasing heat energy (Mushtaq et al. 2014).
In terms of classification, coals are divided into two broad
categories, i.e., low- and high-grade coals. Low-grade coals
refer to those which have high moisture content. Ash content
is also observed as a second parameter in judging whether
a coal can be called low grade or not. The reason for high
moisture content in coal is due to lesser carbon content and
more of moisture.
This leads to higher emissions of toxic volatile sub-
stances, lower efficiency of the energy released per ton of
coal and more resources spent in upgrading the coal qual-
ity to meet industry standards. Examples of these coals
include lignite, sub-bituminous and peat. Techniques like
coal blending, involving mixing with several coals, coal bri-
quetting where coals are compressed with other combustible
biomasses, dewatering and drying are used to increase the
quality of coal. This results in higher energy output when
combusted in the presence of oxygen (Katalambula and
Gupta 2009).
Peat coal is generally in the first stage of transformation
of decaying plant material under high compression and heat.
It contains about 40–50% carbon, and burns like wood,
leaving behind large quantities of ash and moisture. Lignite
is another example of a low-grade coal, which has simi-
lar carbon content like peat. It is dark brownish black, and
is highly combustible. The third on type of coal is known
as bituminous coal, containing 40 to 80% carbon content.
This coal has very less trace of the original plant matter and
comparatively lesser moisture content, making a very high
yield of energy when combusted. Anthracite coal is the most
potent coal grade observed, with 80 to 95% carbon. With a
slower ignition time, a superior heating value, it is the most
preferred coal for energy generation. High-grade coal like
Anthracite and Bituminous coals are much preferred and
mixing them together, or co-combusting them gives a lesser
NOx emission when compared to them being burnt individu-
ally (Lee et al. 2011).
Peak coal is the term which refers to maximum produc-
tion of coal that a country can extract from its territory.
Among coal ubiquity, lower-grade coals are found more in
nature when compared to higher-grade coals and thus there
is a need to invest in technologies that are useful in increas-
ing the heating value and energy yield from low-grade coals.
Low-grade coals can also function as a potential pyrolysis
feedstock to increase its value. Often, the pyrolyzed end
product is shown to have superior properties to that of the
parent feed and is less harmful. The idea of using coal as a
potential feedstock for pyrolysis has been borne out of the
fact that pyrolysis of coal leads to the formation of high-
quality tar and syngas. Emission from the by-products of
coal pyrolysis is significantly lesser than coal combustion
(Xu et al. 2017). Another significant product from the pyrol-
ysis of coal is the production of coke. Coke is one of the key
requirements for iron and steel industry (Liu et al. 2020).
Coal as a fuel, though still widely used, is also considered
to be harmful for nature, due to the emission of gases like
SOx, NOx, COx and fly ash (Munawer 2018). Thus, there
needs to be concentrated effort on finding renewable energy
sources and developing them, along with finding cleaner
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technology that helps in eliminating excess pollution from
coal-based fuels.
The coal-based pyrolysis process faces so many chal-
lenges based on the production and consumption and also
the limited resources, low efficiency and higher emissions.
Biological origin
There has been a lot of studies on the feedstocks of bio-
logical origin used in microwave pyrolysis. Biological origin
here refers to the feedstock having a plant-based origin, or
in some cases animal-related origin. Energy from biomass
contributes to about 14% of final energy output. Evaluations
show that varying feedstocks like wood, corn stover, coconut
husk, bamboo, plastics, coal and microalgae can be used as
pyrolysis feedstock. This makes pyrolysis a valuable and
a very versatile technique for feedstock conversion (Reddy
and Vinu 2016).
There are three classes of biomass feedstocks (Aravind
et al. 2020). Primary feedstock refers to the primary products
that are collected from nature. The most obvious category
of primary feedstock is age old used fuelwood that is often
used by rural communities as a feedstock. Secondary feed-
stock is defined for products that are deemed as agricul-
tural wastes. Cash crops like sugarcane and maize are also
used as potential biomass agents available. Biomass in this
categories can also be extended to wastes gotten for com-
mercially viable trees that are cultivated like, olive husks
(Demirbas et al. 2010). Secondary wastes include animal
wastes and produces obtained, like animal dung, fats from
animals like lamb, poultry and swine. Seedcakes, products
that are obtained by crushing seeds to extract the oil, and the
retentate being pressed together in the form of a collective
entity also form an important feedstock source. Research is
actively performed on castor, radish, neem, mustard, Jat-
ropha, cumin and rubber seedcakes (Reshad et al. 2017, Sen
and Kar 2011).
Tertiary feedstock refers to products that are derived from
biomass. Examples include sludges and manures obtained.
Municipal wastes are often candidates used for thermochem-
ical conversions. In this section, there is special focus on
wastes of biological origin. Food and kitchen wastes, paper
waste, biomedical wastes are some of municipal wastes that
are being considered for potential fuel sources. Typical dis-
posal means of municipal waste includes incineration; how-
ever, the process in practice is not done properly in devel-
oping countries, leading to deleterious effects. Fortunately,
with greater technological improvements of production of
these wastes, the process has been streamlined to be envi-
ronmentally friendly. More focus is being given upon con-
verting these waste products into energy through pyrolysis,
gasification, landfill and gas capture.
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Environmental Chemistry Letters (2021) 19:3609–3629
Sewage sludges also form a major part of tertiary biomass
generation. These sludges are formed by human biological
waste disposal. The sludges are often treated in wastewater
plants to separate the solid matter from the liquid wastes.
These sludges are sometimes used as manure. In the USA,
sewage sludge is typically categorized into two major dis-
tinctions; Class A which includes dried and pasteurized
sludge and Class B which may contain volatile matter and
all the other sludges which do not fit into Class A. Research
on using sludge for energy production using pyrolysis has
been well documented (Agrafioti et al. 2013).
India is endowed with quality biomass and potentially
can contribute 16,881 MW from plants and agricultural resi-
dues, 5000 MW from bagasse and sugarcane industry and
2700 MW energy revival from waste (Kumar et al. 2010;
Narnaware et al. 2015; Tomar and Gautam 2018). Invest-
ments to the tune of Rs. 600 crores annually have resulted in
the production of 5 billion units of electricity and have also
yielded annual employment for more than 10 million people
in India’s rural areas.
Apart from this, pyrolysis on emerging sources like algae
and bacteria for pyrolysis has reported. Algal sources are
very broadly classified onto red, green and brown algae.
(Goncalves et al. 2013; Choi et al. 2014). On the basis of
algal size and morphology, there are two classifications,
macro- and microalgae. Microalgae are potential in fuel
production especially in biodiesel while macroalgae do
no contribute much to biodiesel production (Aravind et al.
2020; Peng et al. 2020). Both have been utilized for methane
and biogas production by thermochemical and biochemical
methods.
Chemically, biomass can be classified onto lignocellu-
losic and proteinaceous. Lignocellulosic biomass is rich in
celluloid and lignin derivatives while proteinaceous biomass
is predominantly nitrogen rich, with varying compositions
of different amino acids. Lignocellulosic biomass mainly
consists of lignin and celluloid products like hemicellu-
lose and cellulose. There are limited amounts of inorganic
components and organic extracts present in biomass. These
components degrade over different temperature ranges and
following different mechanisms in various mechanisms. The
by-products like bio-oil formed from the pyrolysis process
all have different chemical constituents. This results in find-
ing different methods of purification and upgradation of bio-
oil formed from the feedstocks.
The decomposition of lignin is observed over a broader
range of temperature in comparison with the other two major
components and thus appears more thermally stable during
pyrolysis. Cellulose and hemicellulose are quick to break-
down in a smaller range of temperature. Cellulose can form
inter and intra-molecular H bonds that give rise to a microfi-
bril structure. The presence of microfibrils creates an impact
on pyrolysis process.
Environmental Chemistry Letters (2021) 19:3609–3629 3615
Hemicellulose accounts for 10–30% of biomass by
weight. Hemicelluloses are represented by formula
­(C5H8O4)m containing about 50–200 monomer units and a
few monosaccharide residues. It is an amorphous structural
polymer. Mannose, xylose, arabinose, galactose and uronic
acids are also present as residues.
Lignin accounts for 20–30% of the biomass by weight.
Lignins are complex polymers that are associated with struc-
tural elements of plants. The percentage of lignin decides
on the hardness of the plant wood. Chemically, lignins are
cross-linked phenol derivative polymers (Pasangulapati et al.
2012). Among the three components, lignin is observed to
be the most heat resistant. The production of char is pre-
ferred for higher temperatures, and thus, lignin pyrolysis
yields more char than cellulose pyrolysis.
Proteinaceous biomass refers to those which have high
amounts of nitrogen content, in the form of amino acids
and proteins. Example would be algal biomass. Though in
general, nitrogen is reported to be of significantly less com-
position than cellulose, there is still the possibility of NOx
release during thermochemical conversion. Common amino
acids found in biomass as a whole include proline, glu-
tamine, asparagine, histidine and tryptophan (Darvell et al.
2012). The usage of biological origin feedstocks pyrolysis
method exhibits the multi-functionality features which con-
vert them into a promising feedstock to fulfill an increasing
demand in the field such as agricultural sustainability and
environmental protection in order to accomplish the circular
bioeconomy.
Plastic waste
Plastic waste has indubitably become one of the most press-
ing concerns regarding man-made disposal. Plastic waste
has been disposed using many techniques like recycling,
landfill, incineration and chemical recycling (Senthil Kumar
et al. 2017; Jahnavi et al. 2020). The plastic pyrolysis has
been managed to exhibit the high yield of liquid fuels, with
properties of pyrolysis oil being very close to conventional
diesel (Anuar Sharuddin et al. 2016; Abnisa et al. 2019).
There are two major categories of plastics: thermosetting
and thermoplastic plastics.
Other resins which do not come under these two catego-
ries are exclusively treated as separate plastics. Biodegrad-
able and non-biodegradable plastics are two classifications
based on their ability to get broken down by the action of
enzymes or bacteria. Biodegradable plastics can have a bio-
logical origin, like polyhydroxyalkanoates (PHAs) which
are produced by various microorganisms, viz., Cupriavi-
dus necator and include poly-3-hydroxybutanoate, polyhy-
droxy valerate and polyhydroxyhexanoate. Other bioplastics
include polylactic acid (PLA), synthesized by fermented
plant starch and starch blends of starch and plasticizers
through gelatinization (Noivoil and Yoksan 2021).
Biodegradable plastics of petroleum origin include com-
pounds like polyglycolic acids, polybutylene succinate and
polycaprolactone. All these are capable of being degraded
by microorganisms. While biodegradable plastics are aided
by microbial digestion, potential concerns arise with oxo-
biodegradation, methane release and biodegradation in the
ocean (Nwankwo et al. 2021). In order to produce high-
efficiency biofuels, the plastic waste can be developed in the
field of pyrolysis-based biorefinery method.
Mechanism of pyrolysis for feedstock types
Pyrolysis of the three major feedstocks like coal, biomass
and plastics are elucidated in detail. There are significant
differences in the compositions of coal, biomass and plastics.
This results in differing temperatures of pyrolysis. The end
products formed from pyrolysis differ significantly in chemi-
cal compositions. Feedstocks like coal can be neatly classi-
fied as having two major steps in pyrolysis, while biomass
and plastics can be much more complex.
Coal
Two predominant stages in coal pyrolysis can be observed.
The first step involves the lysis of the bonds between the
aliphatic moieties. The second step involves the reactions of
hydrogenation, agglomeration or thermal lysis of products
formed by the primary cleavage. This results in all the three
major products of pyrolysis (Apicella et al. 2020).
Before the actual pyrolysis, thermal lysis ensures that the
hydrogen bonds lose their strength. However, the complete
breakdown does not occur in this stage. This is observed
at the temperature range of 523–573 K. The non-covalent
bonds are the ones which will be broken down in this stage.
This process is achieved by the vaporization of volatiles. The
final process in the lower stage temperature of 523–573 K is
where cross-linking occurs in coal. This stage is character-
ized by the release of carbon dioxide and water molecules.
This concludes the pre pyrolysis steps (Xu et al. 2017).
The next steps occur in parallel, and many models have
been proposed to explain the breakdown. One of the mod-
els includes Distributed Activated Energy model (DAEM)
(Yan et al. 2020). This model accounts for the variation of
reactivity among individual coal moieties and accounts for
the activation energy in explaining the reactivity of coal.
The primary pyrolysis occurs at temperature of 623–773
K. Depolymerization is the predominant process where
aromatic molecules breakdown. These molecules attract
hydrogen from the aliphatic molecules which are not bro-
ken down yet. These hydrogen molecules migrate to the
13

3616
broken down aromatic moieties, and hence increasing the
aromatic hydrogen content. The release of moieties is in
the form of tar and oil. This occurs if the moieties are tiny.
This is the standard occurrence in the temperature range
of 623–773 K (Polesek-Karczewska et al. 2020). Cross-
linking is not observed at this temperature.
The next step is at 823 K. Cross-linking starts occur-
ring, and is observed with methane evolution. Functional
groups degrade and produce gases like methane, carbon
dioxide and water. This evolution of gases may produce
cross-linking. Methane is evolved in a substitution reac-
tion in which the attachment of a larger molecule releases
the methyl group (Wang et al. 2012). ­CO2 is released by
condensation after a radical is formed on the ring when a
carboxyl is removed, and ­H2O is formed by the condensa-
tion of two OH groups or an OH group and a COOH group
to produce an ether link.
An important part after the increase in the aromatic con-
tent and the end of cross-linking is the release of hydro-
gen. This is observed in the ranges of 923–1023 K. The
production of hydrogen at higher temperatures suppresses
char yield, and increases the tar yield. The coexistence of
hydrogen and carbon dioxide increases water yield, due to
equilibrium shifts in the water gas reaction. This effect is
observed when the inert gas atmosphere for pyrolysis is
replaced by coal gas formed in the prior pyrolysis process
(Jin et al. 2019).
The completion of primary pyrolysis of coal is marked
by the depletion of donatable hydrogen atoms from the
aliphatic or aromatic regions. The above mechanisms are
supported by the carbon, hydrogen and oxygen balances for
both pyrolysis products and functional groups of the coal
molecule (Hu et al. 2017).
Biomass
The following processes are observed in biomass pyrolysis:
isomerization, depolymerization, repolymerization and the
formation of low molecular materials. The formation of liq-
uid oil by pyrolysis is comparatively less by thermochemical
methods than by biochemical methods. As discussed before,
biomass conversion can result in biofuel production, along
with other valuable chemicals by two different pathways—
the biochemical conversion and thermochemical conversion
techniques. The least heat stable polymer is hemicellulose.
It undergoes fast decomposition on heating to temperatures
between 473 and 573 K. The middle ground in heat stabil-
ity is occupied by cellulose, which decomposes rapidly in
temperature ranges of 573–673 K. Lignin gradually breaks
down in the temperature ranges from 473 to 773 K (Wild
et al. 2009).
13
Environmental Chemistry Letters (2021) 19:3609–3629
Cellulose pyrolysis
Broido–Shafizadeh reaction model is observed to offer
reliable explanation as to how cellulose degrades in a
pyrolytic pathway (Richter and Rein 2020). The mecha-
nism is divided into 3 main steps.
1. Activation of cellulose
2. Conversion of a fraction to volatiles
3. Remaining fractions get converted to char and gas.
This depolymerization reaction starts at temperature as
low as or lower than 323 K. In general, although there have
been differing temperatures noted for the degradation due
to differing reaction conditions, lower temperature favors
slower degradation predominantly favoring charring and
decomposition. A higher pyrolysis temperature induces the
rapid volatilization with the formation of levoglucosan.
Cellulose is cleaved, from which glucosan is formed. The
loss of water molecule is also observed in this process.
Glucosans consist of starch, cellulose and dextrins. Milder
conditions, widely categorized as slow pyrolysis (low tem-
peratures and heating rates), favor char production over tar.
The char consists of mainly water-soluble compounds and
undecomposed cellulose. The oil fraction was observed to
be aqueous with minute traces of lower aliphatic aldehydes
from ethanol to pentanal. Smaller molecules like furan
and methanol were also observed. The tar fraction was
observed to contain levoglucosan.
This predominance of char products based on heating
rates can be interpreted in terms of occurrence of dehydra-
tion reactions. The change around 573 K reflects the exist-
ence of two reaction pathways (Richter and Rein 2017).
Slower heating rates and temperatures below 573 K make
it suitable for the dominance of dehydration reaction of
cellulose. Anhydrocellulose is formed with the evolution
of ­CO2 and CO. Anhydrocellulose is stable than hemicel-
lulose and cellulose and thus leads to higher char produc-
tion. At higher heating rates and elevated temperatures
(above 573 K), levoglucosan mechanism takes over, as
higher heating rates (104 K/s) do not permit enough time
for dehydration to occur. As a result, the stable anhydro-
cellulose is not formed and the material left depolymerizes
as volatiles resulting in lesser char production. The first
pathway occurs when the cellulose moiety has gained suf-
ficient activation energy (Usino et al. 2020). This results
in transglycosylation and results in the production of levo-
glucosan, its furanose isomer and oligosaccharides. The
increase in temperature induces the preferred tar formation
to char and gas generation.
Environmental Chemistry Letters (2021) 19:3609–3629 3617
Hemicellulose pyrolysis
Hemicellulose’s branched amorphous structure with less
strength results in degradation at lower temperatures 473 to
573 K. The degradation at lower temperatures can be attrib-
uted a softening point of hemicellulose that is small, when
contrasted with lignin. Xylans are present in hemicelluloses
and its degradation yields methanol, methanoic acid etha-
noic acid, butanone, 2-furfuraldehyde, water, uronic acid
and hydroxy-1-propanone. Xylan degradation results in char
yield that is higher than the char yield obtained from cellu-
lose. The degradation of constituents in biomass is specifi-
cally governed by temperature gradients, and there is a rela-
tive absence of interaction between the differing components
(Yu et al. 2017).
Lignin pyrolysis
The cross-linking lignols are all derived from phenyl pro-
pane. These lignols bind themselves to cellulose to form
lignocellulosic complexes. The complex is resistant to deg-
radation but treating it with strong sulfuric acid can cleave
and separate the lignin fraction. The reason is because lignin
does not dissolve in mineral acids like sulfuric acid. The
formation of phenolics is from lignin. This is achieved by
the destructive thermal lysis of the phenyl propane units
from the parent feed. The main product obtained from the
pyrolysis of coniferous (Softwood) wood is guaiacol. Guai-
acol is formed by the oxidation of lignin. Guaiacol, pyro-
gallol dimethyl ether exhibit lignin’s aromatic nature from
deciduous woods both ether and C–C linkages exist between
monomeric guaiacylpropane units in lignin (Richter and
Rein 2020).
Among the three fractions of lignin, cellulose and hemi-
cellulose, lignin is the most thermally stable. The decom-
position temperature is observed for lignin from 523 to 823
K. This is observed to produce greater char quantity during
lignin pyrolysis, when compared to cellulose and hemicel-
lulose pyrolysis.
Algae
Algae inhabit aquatic environments and thus there is no need
for them to have lignocellulosic structural components like
how terrestrial plants require. The composition of algae is
mostly nitrogen-rich compounds, and the active metabolites
are highly influenced by environmental and nutritional con-
straints (Brindhadevi et al. 2021; Srivastava et al. 2020).
Terrestrial biomass thermal lysis primarily follows the
decomposition of simple sugars and carbohydrates, while
algal pyrolysis results in release of nitriles, amines, linear
chain alcohols, pyrroles, indoles and amides (Ojha et al.
2017). There are similarities between lignin pyrolysis and
algal pyrolysis, due to absence of methoxy phenols (Anand
et al. 2016; Lorenzetti et al. 2016). Algal decomposition is
observed to occur at lower temperatures than lignin or cel-
lulose pyrolysis at 523 K, and is thermally unstable. The
pyrolysis process is similar to biomass pyrolysis as men-
tioned (Shuping et al. 2010).
The by-product release involves CO, C ­ O2, ­H2O and ­NH3
with volatile organics. The first step involves the release of
ammonia in trace amounts and carbon dioxide by decarboxy-
lation. Once this is done, dehydration occurs to yield HCN,
tars, methane and carbon monoxide. Proteins yield greater
amounts of char and HCN when compared to their corre-
sponding amino acid counterparts (Ren et al. 2020). This
is attributed to cyclization reaction pathways. The mecha-
nism of decomposition of carbohydrates and lipids is similar
to that in terrestrial biomass and is already discussed. The
sugars in algae resemble hemicellulose structures and thus
a mechanism similar to hemicellulose degradation can be
observed.
Plastic waste
Plastic pyrolysis is not as simple, when compared to coal and
biomass pyrolysis. Catalyst addition is a unified mechanism
even more difficult, due to various pathways. Pyrolysis rate
depends on the plastic’s chemical composition. The presence
of tertiary carbon atoms in many plastics ensures that it is
less thermally stable than those with only primary carbon
atoms (Almeida and De Fatima Marques 2016).
Catalytic pyrolysis favors lower decomposition tempera-
tures and better product selectivity. The method involves
the isomerization, scission of random chains, cleavage of
β bonds, intermolecular hydrogen transfer, oligomerization
and aromatization (Almeida and De Fátima Marques 2016).
Table 1 summarizes the chemical differences between the
products of pyrolysis obtained from various feedstocks dis-
cussed in the previous section. The discussion of the util-
ity of pyro-oils obtained from different feedstocks is also
present. The complicated mechanism of the reaction was
explored in each feedstocks in order to get effective biofuel
and energy.
Microwave pyrolysis of feedstocks
The products produced are influenced by several parameters
like reaction time, temperature and catalyst used. These fac-
tors influence product purity (Almeida and Marques 2015).
Temperature variation like very high-temperature results
in gaseous products while very low temperature causes the
formation of undesirable char and thus resulting in poor
product quality and crippling of process feasibility (Joffres
et al. 2013). Hence, it is important to choose the optimum
13

3618 Environmental Chemistry Letters (2021) 19:3609–3629

reaction conditions to get the desired liquid products. There

Kawale and Kishore (2019)

are several methods by which end products are achieved.

Mangesh et al. (2020)

Slow and fast pyrolysis methods give different end prod-

Ansari et al. (2019)

Chen et al. (2020)

Zhou et al. (2017)

ucts as observed by the oil and char percentage indications

Qu et al. (2019)
(Jahirul et al. 2012).
References

The consistency of heating of particles uniformly is a

mandate required to get a significant yield of products.
Hence, this can be a challenging task to achieve in conven-
tional pyrolysis techniques due to the large size of feed mate-
Need the catalytic treatment to reduce sugars to obtain pure

Pyridines, furans, phenols, oximes, styrene and caprolactam Nitrogenous content in bio-oils makes it difficult to be used
Oil from coal-assisted shale pyrolysis can be utilized as an

high isothermal stability. Useful for carbon fiber produc-

The polymerization of bio-oils with additives can result in

Oil can be used for potential applications in diesel engine

rial and improper mixing. A promising technique is micro-
wave-assisted pyrolysis which shall enable due to the high
impact purity, yield, quality and stability of bio-oils
Increased amounts of acetic acid in bio-oil negatively

heat penetration that could be met by the microwaves into

the materials and arrest energy. The most commonly used

as an alternative for petroleum-based fuel

microwave frequency that has shown expected in pyrolysis
reactions are 915 and 2450 MHz (Motasemi and Afzal 2013)
due to the perfect penetration depth offered. This charac-
teristic property of microwave stands out as a differentiator
which results in uniform heat generation throughout the vol-
alternative to crude oil

ume of the material thus slashing the need for external heat-
Comments on Pyro-oil

ing sources as required by other pyrolysis techniques. The

uniform heat distribution achieved by this method rightfully
enables the use of new chemistry thus resulting in enhancing
product quality and quantity.
bio-oils

The other significant advantages it offers as compared

tion

fuel

to other conventional pyrolysis techniques are uniform

heating of large particulate size of feed, fast switching on
can be used for selectively increasing product requirement
Light aromatics like benzene, toluene, xylene and naphtha-

Xylan pyrolysis yields water, formic acid, acetic acid, alde-

Absence of biomolecules in pyrolytic products. Catalysts

Phenol derivatives predominate like guaiacol and syringol
lene predominate over phenol and derivatives of phenol

and off controls, no requirement of fluidization. Further

Pyrans, furans, acetic acid, hydroxyacetaldehyde, cyclic

Alkanes, naphthalene and derivatives, benzene alkenes.

study suggests that this technology can be scaled suitably

as required by biomass. Carbon makes up a major portion
hydes, ketones and minor quantities of phenol

biomass feedstock, and it was observed the carbon materials

ketones and anhydrous monosaccharides

are effectively heated by microwaves as they are extremely

good absorbents of microwaves (Borges et al. 2014; Bu et al.
2016; Fan et al. 2017). Hence, microwave-assisted pyrolysis
is a promising approach that can be used for valorizing waste
feedstocks. Microwave-assisted heating can be better than
conventional heating due to its various benefits.
Pyro-oil constituents

Fundamentals of microwave pyrolysis

Microwave technology is used for point-to-point telecommu-

nications, microwave ovens and in radar technology. How-
ever, they are extensively used for point to point commu-
Table 1  Pyrolysis of various feedstocks

ture range

523–1023
No. Feedstock component Tempera-

323–573

473–573

523–823

443–643

723–873

nication. Federal Communications Commission (FCC) has

reserved 0.915 GHz and 2.45 GHz frequencies in industrial,
(K)

scientific and medical purposes (Anas et al. 2021). Micro-

wave heating is a phenomenon where a material exposed to
electromagnetic radiation gets heated. Microwave irradiation
Hemicellulose

may pass through the material showing zero emissive loss

Cellulose

(Teflon) or reflected back due to its inability to penetrate

Plastics
Lignin

Algae

the material (e.g., metals) or be absorbed by the material,

Coal

e.g., water and oil (Motasemi and Afzal 2013). Efficiency of

microwave heating is limited by material properties.
1

13
Environmental Chemistry Letters (2021) 19:3609–3629 3619

The difference between conventional and microwave heat-
ing needs to be highlighted. Conventional heating is through
conduction and convection, while microwave is by radiation.
Passing of heat into material by conventional heating results
in increase in process time and non-uniformity. Thus, con-
ventional heating is not suitable for uniform distribution of
heat. Microwave heating is significantly better than conven-
tional heating techniques due to its ability to deliver heat to
the material uniformly and directly. Microwaves penetrate
the feedstock particle and heat is produced by the conver-
sion of microwave energy (Ravikumar et al. 2017). On the
account of heat loss effect from the particle surface, heat
is continuously generated and directed towards the outside
from the inside.
Thus, microwave heating enhances the uniformity of
heat distribution while heating. Electromagnetic energy is
converted to molecular kinetic energy in microwave heat-
ing. Dielectric loss is the phenomenon in which a dielectric
material dissipates its electromagnetic energy in form of heat
or other forms. Dielectric loss is inherent to all materials and
occurs naturally. The microwave pyrolysis is the selective
heating of feedstocks in which no waste can be obtained in
heating bulk of feedstocks.
Effect of parameters on microwave pyrolysis
Figure 2 represents the parameters which are crucial for
understanding microwave pyrolysis. These include tempera-
ture at which the reaction takes place, the reaction time, the
supply of microwave power, the origin of the microwave
feedstock, particle size of the feedstock, ratios at which the
feedstocks are mixed, dielectric constants of feedstock, pre-
treatment of feedstock, catalysts involved in the reaction and
microwave absorbers used in the reaction. All these param-
eters are discussed in brief in this section.
Temperature
Table 2 shows the relation between the process temperatures
at which microwave pyrolysis was done and the amounts of
char, oil and gas being produced. Lignocellulosic feedstock

Fig. 2  A list of main operat-

ing parameters required for
microwave-assisted pyrolysis
process for the production of
biofuel

Table 2  Temperatures used for the pyrolysis of various feedstocks

Feed Temperature (K) Pyro-char (%) Pyro-oil (%) Pyro-gas (%) References

Palm kernel shell 623–723 40 40 20 Jamaluddin et al. (2013)

Oil palm shell 1073 – 32.34 – Mushtaq et al. (2015)
Corn stover 773 20 15.6–22.6 47 Zhang et al. (2015)
Chlorella sp. strain 823 27 57 18 Borges et al. (2014)
Nannochloropsis strain 773 25 59 17.50 Borges et al. (2014)
Low-density polyethylene (LDPE) 723 1.89 32.59 65.15 Zhang et al. (2015)
Low-density polyethylene (LDPE) 773 7.10 24.2–38.5 56.60 Fan et al. (2017)
Polypropylene (PP) 766 9.10 56.50 34.40 Undri et al. (2014)
High-density polythene (HDPE) 851 0.60 80.20 19.20 Undri et al. (2014)
High ash Indian coal 1053 71 14 15 Reddy et al. (2020)
Medium ash Indian coal 1073 70 10 20 Reddy et al. (2020)

13

3620 Environmental Chemistry Letters (2021) 19:3609–3629

pyrolyzes at lesser temperatures, due to the weaker bond
strength between the molecules. In contrast, coal-based
feedstock requires higher temperatures. Plastics appear to
be like a transition-based point, between lower tempera-
ture-based lignocellulosic materials and high-temperature
coal feedstock. When compared to conventional pyrolysis,
microwave-based pyrolysis shows remarkable efficiency.
Experiment by Shuttleworth et al. (2012) reported that the
microwave pyrolysis of wheat straw, pelletized softwood and
microalgae occur at temperatures of 423–443 K. This could
be attributed to the uniform heating of feedstocks. Micro-
wave absorbers or catalysts help to lower the temperature
of pyrolysis further. The advantage of microwave pyrolysis
is that fine-tuned regulation of temperature is possible. This
allows for temperature control to yield products with specific
chemical compositions or allows for maximal pyro-oil yield.
Particle size and reaction time
Reaction time specifically refers to the time that the feed-
stock spends inside the reactor. Bartoli et al. (2015) offer
an excellent example of the effect of reaction time and
how it impacts the feed formation. In their experiment,
the microwave-assisted pyrolysis of polystyrene at differ-
ent time intervals gave differing amounts of pyro-oils being
produced. The peak bio-oil production was observed at 28
min and 94.3%. At 22 min, the oil production was about
84.3%, which increased to the peak. After the peak, the yield
started decreasing and at 49 min reached 75%. Generally,
the pyro-oil yield is reported to increase marginally with
increase in time (Shang et al. 2015). Short retention times
result in the pyrolysis process not proceeding to completion.
Cheng et al. (2013) in their experiments with pyrolyz-
ing rice straw with bromide-1 ethyl 3-methyl-imidazole
ionic liquid observed that the reaction time must be kept
as short as possible with an optimum time period of being
10 min and yield of 28% bio-oil formed. This could be
explained with the reasoning that longer holding times of
the feedstock might also result in the thermal lysis of the
catalyst. The selection of a catalyst also suitably changes
the holding time. Kinetics play a huge role in pyrolysis
mechanisms. Feedstocks are generally heterogeneous, so
each component has a different rate constant and a dif-
ferent activation energy, thus differing time of reaction.
(Dai et al. 2017; Gautam et al. 2019) showed that time
period can be restricted to 15–20 min at 700 W to obtain
maximum pyro-oil. Table 3 shows the particle size of the
feedstocks. It also shows the reaction time for the feed-
stocks to get completely pyrolyzed. These two parameters
are crucial in determining the kinetics of the reaction.
The particle size of feedstocks is generally in microme-
ters (Wang et al. 2014). Some feedstocks have their dimen-
sions in millimeters, as observed. Smaller the particle size,
more easily it gets pyrolyzed. This can be attributed to
greater heat transfer due to smaller volume and greater
surface area (Shang et al. 2015). (Huang et al. 2008) dem-
onstrated that for particles of rice straw lesser than 0.25
mm inhibits effective heat transfer. Experiment conducted
by Wang et al. (2014), compared the size of particles for
pyrolysis. It was observed that the smaller-sized particle
(63–125 μm) gave lesser pyro-oils but greater pyro-gas.
As the size increased (283–500 μm), pyro-oil yield was
observed to rise, with gas yield reduction. (Shang et al.
2015) demonstrated that for particles greater than 0.8 mm,
the pyro-oil yield decreases with corresponding pyro-gas
increase. Generally, depending on the nature of feeds and
reaction conditions, particle size plays a crucial role in
determining which two quantities vary. The study men-
tioned above had char production to be constant, while oil
and gas amounts varied.

Table 3  Reaction times and particle sizes used for the pyrolysis of various feedstocks
Feed Particle size Time (min) Pyro-char yield (%) Pyro-oils yield (%) Pyro-gas yield (%) References

Polystyrene 2 × 2 cm 28 1 92.30 6.70 Bartoli et al. (2015)

Polystyrene 2 × 2 cm 22 7.20 84.30 6.70 Bartoli et al. (2015)
Polystyrene 2 × 2 cm 32 5.50 90.70 3.80 Bartoli et al. (2015)
Polystyrene 2 × 2 cm 49 10.10 75 14.90 Bartoli et al. (2015)
Polystyrene 2 × 2 cm 30 4.40 87.50 16.10 Bartoli et al. (2015)
Polystyrene 2 × 2 cm 42 8 82.20 9.80 Bartoli et al. (2015)
Kappaphycus alvarezii 1–2 mm 15 22.10 32.40 45.60 Gautam et al. (2019)
Sargassum wightii 1–2 mm 15 33.30 25.90 40.90 Gautam et al. (2019)
Turbinaria ornate 1–2 mm 15 30.90 27 42.10 Gautam et al. (2019)
Indonesian coal 63–125 μm 10 30.89–32.36 14.8–15.2 52.83–54.11 Wang et al. (2014)
Indonesian coal 280–500 μm 10 27.80–29.86 16.62–17.24 53.97–55.49 Wang et al. (2014)

13
Environmental Chemistry Letters (2021) 19:3609–3629 3621
Catalyst and absorber addition
Feedstock with high moisture content takes time to pyro-
lyze. To hasten the pyrolysis process, materials known as
microwave absorbers are added to increase the efficiency
of the process and to reduce the reaction time (Dai et al.
2017). Absorbers are usually associated with the pyro-char
that is formed from the feedstock after pyrolysis or any
thermochemical conversions. Absorbers are expected to
have good storing and conversion of microwaves (Boldor
et al. 2017). A portion of the char formed previously from
the feed is reused into the next batch. Mixing of the char
and the feedstock must be done properly to ensure that
there is a proper distribution of radiation and uniform
heating occurrence.
Utilization of char is also economical in nature. Plastics
were observed to have low dielectric constants, so the addi-
tion of a microwave absorber proved to be invaluable. Com-
mon absorbers are SiC, zeolites and graphite (Shang et al.
2015). (Martín et al. 2017) in their experiment of pyrolyzing
scrub wood biomass under microwave conditions demon-
strate that the yield of bio-oil obtained when using a mixture
of activated carbon and biomass char was greater than only
using the biomass char obtained from previous runs. The
yield was 50.8% bio-oil in case of the char and activated
carbon absorber, and 44.8% when only used biochar. This
suggests that a synergistic effect is seen when two absorbers
are used together.
The term absorber and catalyst refer to the chemicals that
increase the rate of reaction with smaller activation energy
requirement than what is required. However, there are two
crucial differences. When the microwave absorber is mixed
with the raw feed and then pyrolyzed, the final product con-
tains a mixture of the newly pyrolyzed substance and the
absorber. They cannot be separated chemically. On the other
hand, the catalysts are not mixed with the raw feed directly,
and recovery of catalysts is possible.
The second difference is that the absorber is usually char
that is obtained from previous pyrolysis of feedstock. The
nature of the feed may be organic like biomass, or inor-
ganic like plastics. Hence the nature of the absorber may
be organic or inorganic. The commonly used catalysts are
inorganic in nature. Some commonly used catalysts include
metal oxides, chlorides and nitrates. Some examples
include titanium oxide, potassium phosphate and benton-
ite (Mohamed et al. 2019). Some catalysts can also show
simultaneous microwave absorption and catalytic property.
(Mohamed et al. 2019) in their study of pyrolyzing biomass
with a mixture of potassium phosphate (KP), bentonite and
clinoptilolite observed that the mixture of 10% KP and ben-
tonite by weight was responsible for increased mass loss
by 85% at 100 K/min when compared to no catalyst aided
reaction.
Ding et  al. (2019) pyrolyzed low-density polythene
(LDPE) using nickel oxide (NiO) and high yield zeolite
(HY) as in situ and ex situ catalysts, respectively. 56.8%
wt oil was produced along with 93.8% gasoline fraction
achieved. Octane number was seen to have risen when used
NiO. HY: LDPE ratio increase from 0 to 5 improved the
percentage of aromatics and isomeric aliphatics from 23.4
to 80%. The above studies demonstrated that the addition of
catalysts can significantly improve mass loss, increase the
production of pyro-oil and regioselective chemicals can be
achieved.
The last factor which can significantly affect the process
of pyrolysis is the pretreatment of feed by chemicals. Pre-
treated feed reacting with catalysts in a microwave environ-
ment can significantly improve product yield. Most micro-
wave pyrolysis experiments include adding the catalyst on
a suitable ratio to maximize the yield of bio-oils (Rex et al.
2020; Rosi et al. 2018; Salema and Ani 2012). Depending on
the ratio of used char and feedstock, oil production or char
production can be maximized as per need. Table 4 gives the
list of catalysts and absorbers used for feedstocks.
Microwave power output
Table 5 shows the power supplied by the microwave device
for the pyrolysis of feedstocks. Microwave pyrolysis and
yield are directly proportional to the power consumption
(Xie et al. 2015; Zhao et al. 2018). The power supplied to the
feedstock is directly dependant on the pyro-oil formed. Mar-
tín et al. (2017) demonstrated that increasing the power from
300 to 400 W resulted in the yield of bio-oil produced from
saw dust increase from 45 to 58%. Further increase resulted
in the decrease in oil yield. This could be attributed as since
the power output increased, the temperature of the system
increased, leading to formation of non-condensable gases.
Feedstock generally requires certain temperatures and
certain powers to pyrolyze. Biomass begins to pyrolyze
around 300 W (Bu et al. 2018), plastics take around 300 to
500 W (Ding et al. 2019) and coal pyrolyzes around 500 to
700 W of power (Reddy and Vinu 2016). This suggests a
relation between the nature of the feedstock and the power
required for pyrolysis. There is also a relation between tem-
perature of pyrolysis and the power supplied by the micro-
wave. Each feedstock has a temperature below which the
process of pyrolysis does not begin. Thus, there is a mini-
mum power demand associated with the process of pyrolysis
to begin. This minimum temperature and minimum power
are related by various mathematical models.
According to (Reddy and Vinu 2016), as the power input
of microwave (480 to 640 W) was increased for the pyrol-
ysis of coal, the char yield increased, while the gas yield
decreased marginally. Oil yield remains more or less simi-
lar. This trend is also observed in other feedstock types like
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3622 Environmental Chemistry Letters (2021) 19:3609–3629

Table 4  Catalysts and absorbers used for microwave pyrolysis

Feed Catalyst/microwave Nature of compound Pyro-char (%) Pyro-oil (%) Pyro-gas (%) References
absorber

Corn stover ZSM-5 Catalyst 26.40 41.60 35.20 Zhou et al. (2018)
Oil palm shell Activated carbon Absorber 43 15 42 Salema and Ani (2012)
Sawdust Additives of SiC, Catalysts – – 81.55% Shang et al. (2015)
activated carbon,
­K2CO3, NaOH and
produced coke
Formic acid pretreated SiC Absorber 16.66–23.23 26.45–32.14 44.63–63.89 Dai et al. (2017)
bamboo sawdust
Sewage sludges Graphite Absorber 22–50 4–20 – Domínguez et al.
(2003)
Microalgae and scum HZSM-5 Catalyst 43 22 30 Xie et al. (2015)
Algae in Taihu Lake 10% of activated Absorber 15–20 49.1-N2, 19–28 Li et al. (2014)
carbon 51.7-H2/Ar,
54.3-CO2
Chlorella sp. Char produced from Absorber – 28.6 49.8 (syngas) Du et al. (2011)
pyrolysis of biomass
feedstock
Electronic equipment Carbon Absorber 14.20 76.60 10.20 Rosi et al. (2018)
plastic wastes
Electronic equipment Iron (purity 99.9%) Catalyst 21.20 76.60 2.20 Rosi et al. (2018)
plastic wastes
Mix of polystyrene Rice husk activated Absorber 1.22 69.55 29.23 Rex et al. (2020)
and polypropylene carbon
waste
Mix of polystyrene Coconut husk acti- Absorber – 77.40 22.60 Rex et al. (2020)
and polypropylene vated carbon
waste
Mix of polystyrene Activated carbon Absorber 1.98 59.05 38.97 Rex et al. (2020)
and polypropylene
waste

biomass and plastic. The power output also depends on the
size of reactor, quantity of feedstock and catalyst. Microwave
ovens for domestic purposes are used in the laboratory scale
and their power levels are used with the maximum output
of about 800 W (Borges et al. 2014; Li et al. 2014). For
commercial incineration purposes of plastic waste, or coal
pyrolysis to produce bio-oils, higher power is required in
the range of 1-3 kW (Bu et al. 2018; Ding et al. 2019; Rus-
sell et al. 2012). The power outputs mentioned for various
feeds in Table 5 refer to the maximum yield of biochar, oil
and gas formed.
Apparatuses for microwave pyrolysis
A standard laboratory setup for microwave pyrolysis
includes microwave generator, reactor vessel, thermal sen-
sor, agitation system and inert gas flow meter (Dominguez
et al. 2003). The first component to be discussed about is
the microwave generator. Microwave generators are usually
microwave ovens used for domestic purposes. The standard
frequency at which the ovens operate is 0.5 to 2.45 GHz
(Borges et al. 2014). There are two modes of operation,
called as single-mode and multimode operations. Single
mode results in the same frequency being used throughout
the experiment, while multimode uses differing frequencies
for specific time intervals.
The second component is reaction vessel. Generally,
round-bottom flasks made out of microwave transparent
materials are preferred, so that they can withstand high tem-
peratures during reaction. Quartz is generally preferred for
its low dielectric constant. However, quartz is expensive than
normal glass and hence it is used only for a process which
requires limited feed and high temperatures for pyrolysis
(Mushtaq et al. 2016). Teflon is also used as a cost-effective
material for the reaction container. Metals and plastics are
strictly avoided because of absorbing the radiation before
going to the feedstocks.
The third component is thermal sensor. These thermal
sensors are required for getting the thermal profiles occur-
ring during the degradation of feedstocks. Thermocouples
are made from stainless steel, and optical pyrometers are all

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Environmental Chemistry Letters (2021) 19:3609–3629 3623

Table 5  Microwave power used for the pyrolysis of various feedstocks

Feed Power (kW) Pyro-char (%) Pyro-oil (%) Pyro-gas (%) References

Low-density polyethene + cellulose 0.7 10.87 45.49 42.41 Zhang et al. (2015)

Bamboo and polypropylene (PP) 1 3.74 52.05 – Zhao et al. (2018)
Corn stover 0.75 – 31.20 – Zhang et al. (2015)
Wood sawdust 0.75 – 65 – Borges et al. (2014)
Corn stover 0.75 – 64 Borges et al. (2014)
Microalgae-spirulina 3 3 13.00 75 Hong et al. (2017)
Chlorella 3–6 Hong et al. (2017)
Macroalgae porphyra 4–11 2–4 87.1 (73.7 syngas) Hong et al. (2017)
Low-rank coal 0.8 60 5 35 Zhang et al. (2020)
Low-density polyethylene 1 – 20 38.90 Bu et al. (2018)
(LDPE) + microwave-torrefied lignin
(MTL)
Torrefied biomass (rice straw) and low- 1 – 24.24 39.71 (syngas) and 64.17 (volatiles) Bu et al. (2018)
density polyethylene (LDPE)
High-density polyethylene (HDPE) 3 Minimal 69 – Russell et al. (2012)
Feed Power (kW) Pyro-char (%) Pyro-oil (%) Pyro-gas (%) Reference
Low-density polyethene + cellulose 0.7 10.87 45.49 42.41 Zhang et al. (2015)
Bamboo and polypropylene (PP) 1 3.74 52.05 – Zhao et al. (2018)
Corn stover 0.75 – 31.20 – Zhang et al. (2015)
Wood sawdust 0.75 – 65 – Borges et al. (2014)
Corn stover 0.75 – 64 Borges et al. (2014)
Microalgae-spirulina 3 3 13.00 75 Hong et al. (2017)
Chlorella 3–6 Hong et al. (2017)
Macroalgae porphyra 4–11 2–4 87.1 (73.7 syngas) Hong et al. (2017)
Low-rank coal 0.8 60 5 35 Zhang et al. (2020)
Low-density polyethylene 1 – 20 38.90 Bu et al. (2018)
(LDPE) + microwave-torrefied lignin
(MTL)
Torrefied biomass (rice straw) and low- 1 – 24.24 39.71 (syngas) and 64.17 (volatiles) Bu et al. (2018)
density polyethylene (LDPE)
High-density polyethylene (HDPE) 3 Minimal 69 – Russell et al. (2012)

good choices, because they can withstand high temperatures
in small spaces. Normally, covering of aluminum foil is put
on the sensors uniformly, so as not to expose parts of the
sensor to non-uniform heating (Du et al. 2011). The fourth
component in most microwave systems is to involve agita-
tion. Agitation systems are required to make sure that the
microwave absorbers and feed are mixed properly. Improper
mixing results in the non-uniform heating and improper
decomposition of feed. Manual mixing is done in small
amounts of feed. For larger quantities of feed, agitators are
used. The agitation system incorporates an impeller with
two 450 pitched blades, and a motor with a max speed of 6
RPM. The shaft is made of 11-mm stainless steel pipe. This
is a standard for laboratory scale (Aishwarya and Sindhu
2016). Figure 3 shows the setup of the microwave pyrolysis
apparatus. The final component in a microwave system is
gas flow meters. Table 6 shows the list of equipment used
by different researchers for their experiments.
Perspective
The current review mainly focussed upon the differences
occurring in pyrolysis of feedstocks like coal, plastics and
biomass. The chemical differences in the feedstocks do not
significantly affect the microwave-assisted pyrolysis process.
Current microwave pyrolysis process is performed only in
batch scale in laboratories. However, there are significant
obstacles that are faced in batch scale processes that include
the inability to generate high power density. Another signifi-
cant factor is the small processing volume. Currently, there
are problems with scaling up of microwave technology due
to electrical and chemical engineering constraints. The next

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3624 Environmental Chemistry Letters (2021) 19:3609–3629

Fig. 3  Laboratory microwave-
assisted pyrolysis setup for
bio-oil production

Table 6  Types of reactor materials and temperature measurement devices

Feed type Reactor Power of Fre- Temperature Inert gas Microwave absorber References
microwave quency measurement
(W) (MHz) device

Sewage sludge Quartz 1000 2450 Optical pyrometer He Graphite Dominguez et al. (2003)
Plastic waste Quartz vessel 5000 2450 Thermocouple N2 Carbon black Aishwarya and Sindhu (2016)
with agitation
system
Coal Quartz vessel 800 2450 Thermocouple N2 Carbon Mushtaq et al. (2016)
Microalgae Quartz 1250 2450 Infrared optical N2 Char Du et al. (2011)
pyrometer and
thermocouple
Biomass Quartz 750 2450 Thermocouple – SiC Borges et al. (2014)

big challenge is to create the uniform heating of feed by
microwave for the industrial scale.
For large-scale systems, assisted microwave power to the
reactors might be feasible. Rotary kilns, fluidized beds might
be useful for a large volumetric feed. A possible solution to
this problem might be the utilization of continuous operation
mode. This is an effective way to have high power density.
However, the utilization of these reactors aided with micro-
wave technology is still scarce (Beneroso et al. 2017).
A major concern is also involved about the purification
of the pyro-oil that is obtained from pyrolysis. The pyro-oil
obtained from biomass usually contains polyunsaturated aro-
matics. (Ge et al. 2021) mentioned that the purification of
these oils could be done with metal oxide catalysts like cal-
cium oxide, copper oxide, magnesium oxide and nickel oxide.
Additionally, the oils need to be tested more in advance to
determine their synergistic effect. A combination of oils from
biomass, coal and plastics need to be observed and tested for
fuel properties. A potential way to gauge the future of fuel
obtained from the pyrolysis of feedstocks is to look at its eco-
nomic value.
Haeldermans et al. (2020) performed a complete techno-
economic assessment and Monte Carlo risk analysis on
large-scale (3 tonne/h) biomass production. The methods of
production were conventional pyrolysis and microwave pyroly-
sis. The conventional pyrolysis production was cheaper with
prices ranging from € 436/tonne to € 863/tonne. In contrast,
the microwave pyrolysis was about € 564/tonne to € 979/tonne.
Economically, the conventional pyrolysis process was cheaper,
but the quality of the char produced from microwave-assisted
pyrolysis was proven to be of higher quality. Therefore, con-
cerns are still present regarding the viability of char versus the
economic cost.

13
Environmental Chemistry Letters (2021) 19:3609–3629 3625
Conclusion
Microwave pyrolysis has been an increasingly viable tech-
nique for the valorization of different feedstocks. It has many
advantages over the conventional pyrolysis such as lesser
power usage, greater bio-oil yield and controlled pyro-gas
yield. The pyrolysis mechanisms of coal, biomass and plastic
differ with respect to the temperature profiles, by-product
chemical constituents and utility of pyro-oils. The differ-
ing parameters that significantly impact microwave pyroly-
sis like temperature, reaction time, particle size, micro-
wave power and catalyst have been critically discussed in
this review article. The equipment required for pilot-scale
microwave processes is also described briefly in this study.
Future studies should ideally concentrate on the differences
in pyro-oils produced from various feedstocks and find a
way to utilize each feedstock appropriately. Scaling up of the
process is another potential concern, along with the purifica-
tion techniques required for pyro-oils blending and usage.
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