Fuel Processing Technology xxx (xxxx) xxx–xxx

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Fuel Processing Technology

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

Review

Municipal solid waste (MSW) pyrolysis for bio-fuel production: A review of

effects of MSW components and catalysts
⁎
Ayesha Tariq Sipra, Ningbo Gao , Haris Sarwar
School of Energy and Power Engineering, Xi'an Jiaotong University, Xi'an 710049, China

A R T I C LE I N FO A B S T R A C T

Keywords: With the realization of fossil fuels depletion, research has been started on the alternate energy sources. Biomass
Review is a renewable energy source, from which bio-fuels can been produced. These bio-fuels are then used for power
Pyrolysis generation. Municipal solid waste (MSW) is a type of biomass which has been widely used in the production of
Municipal solid waste bio-fuels. Since 1900s, studies have shown that a lot of research has been done in determining the optimum
Pyrolysis products yield
processes for producing bio-fuel through MSW. Pyrolysis is one of these processes. This process roots out various
Fuel
drawbacks which are present in other processes. It produces high grade pyrolysis fuel and reduces production
cost. This review paper focuses on pyrolysis of MSW by using its components as a feedstock material with
varying composition. The effects of interaction between different components of MSW and their heating values
has been reviewed. The heating values are then compared with conventional fuels to highlight the significance of
MSW pyrolysis products. The case of catalytic pyrolysis has also been reviewed and the corresponding heating
values are compared to obtain high quality fuel. Moreover, a comparison has been made that how pyrolysis is an
efficient process as compared to other processes.

1. Introduction
In the recent years, the imports of crude oil have been facing
challenges due to rise in crude oil prices, the fluctuating political sce-
nario in the Middle East and the unpredictability of the global oil
market. The fossil fuel burning also has hazardous environmental im-
pacts on land, water and air. The fossil fuel energy has a great potential
of changing world's climate. A small climate change can adversely af-
fect the world's agricultural production [1]. The fossil fuels' combustion
produces energy and chemicals, this results in the emission of various
greenhouse gases (GHGs) like carbon dioxide, nitrogen oxides and other
toxic volatile compounds in the atmosphere [2]. It is concluded that the
combustion of fossil fuel has a net increase of 10.65 billion tons of at-
mospheric carbon dioxide per year [3]. Therefore, the selection of most
environment friendly fuel is the major concern over a past few decades.
Due to these challenges, the use of renewable energy resources (e.g.
wind, geothermal, hydropower, biomass) came into action. Among
these sources, biomass, being a non-fossil fuel, holds importance as a
feedstock. It helps in the mitigation of CO2 emissions [4]. There are
numerous sources of biomass including agricultural residues, woody
biomass, dedicated energy crops and municipal solid waste (MSW) [5].
Because of accelerated urbanization and development of global
economy, a bulk quantity of MSW has been collected and disposed of by
the municipalities. Due to this drastic increase in the disposal of MSW,
the need for its management is quite necessary to preserve environ-
ment. According to the census in 2011, the growth rate of MSW in
China has reached 179.36 million tons and is continually rising at a rate
of 8–10% each year [6]. Similarly, in 2013, about 254 million tons of
trash was generated in the USA Figs. 1 and 2 show the total MSW
generation rates of America before recycling.
Municipal solid waste (MSW), commonly known as trash or gar-
bage, consists of everyday items which are used and then thrown away,
such as product packaging, grass clippings, furniture, clothing, bottles,
food scraps, newspapers, appliances, paint, and batteries. These mate-
rials come from houses, schools, hospitals, and industries. [7] MSW is a
type of biomass which mainly consists of food waste, paper, plastics,
wood, textiles, metals, and glass [8]. It is most commonly managed by
an open dumping system. In this system, MSW is open to the atmo-
sphere [9], causing severe health and environmental issues. The open
landfills results in pollution in the air, land and water, due to bacteria
and insects inside the tons of dumped garbage [10]. Moreover, landfill
dumping has maintenance and labor issues, the transportation cost and
increase in population also hinders the efficient execution of dumping
in landfills. MSW, however, due to its versatile composition, stores
energy in the form of chemical bonds between carbon, hydrogen and
oxygen molecules [11]. These chemical bonds release vast amount of

⁎
Corresponding author.
E-mail address: nbogao@xjtu.edu.cn (N. Gao).

https://doi.org/10.1016/j.fuproc.2018.02.012
Received 24 October 2017; Received in revised form 22 November 2017; Accepted 11 February 2018
0378-3820/ © 2018 Elsevier B.V. All rights reserved.

Please cite this article as: Sipra, A.T., Fuel Processing Technology (2018), https://doi.org/10.1016/j.fuproc.2018.02.012
A.T. Sipra et al.
Fig. 1. MSW generation rates, 1960–2013, [7].
Fig. 2. Total MSW Generation (by Material), 2013 254 million tons (before
recycling) [7].
energy when broken down, in order to produce gases, liquids or solids
that are known as bio-fuel [12]. MSW produces heating value of around
20.57 MJ/kg [13], which can be utilized in power generation, trans-
portation and various petrochemical industries. Therefore, MSW has a
great potential to produce bio-energy.
The global MSW scenario has been reviewed in this paper to identify
why the pyrolysis of MSW is necessary for the world environment.
Every year, approximately 1.9 billion tons of MSW is produced
worldwide. This means an annual production of 218 kg/person. The
literature highlights that 19% of MSW gathered is reprocessed, 11% in
used for energy regaining processes and the remainder is dumped on
landfills. [14] Due to the abundance in the use of plastics, the World
Bank statistics show that 8–12% of overall MSW produced in various
parts of the world is plastic waste. Moreover, the estimated plastic
waste production will rise to 9–13% in 2025. This will be different
according to the geographical locations. [15] In Europe, measures have
been taken to recover 50% of the plastic waste, however, the remainder
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has still been dumped causing environmental effects [16]. Similarly,
according to the data collected in 2013, Sweden generated 4.5 M tons
(460 kg/person) of MSW annually. In this MSW, 32% was reprocessed,
15% was applied in biological treatment and 52% was used for energy
recycling [14,17]. Moreover, continuing exploring the MSW scenario in
Europe, Finland has some contribution as well. The polyvinyl chloride
(PVC) plastic is abundant in dry fraction of the household waste, with
90% of chlorine in it [18]. Chlorine is disastrous for health and en-
vironment, therefore, MSW needs to be processed to overcome the
adverse effects. Moreover, towards the Middle Eastern side of the
world, the Kingdom of Saudi Arabia (KSA) is the second biggest waste
disposal country, producing approximately 6 M metric tons of plastic
every year [19,20]. For Asian region, China has 81.64% of average
physical combustibles and 18.36% of non-combustibles. Fig. 3 shows
the percentage breakdown of the composition of MSW in Chinese cities.
[21] MSW in China is not efficiently classified by the residents, it is also
mixed with various food wastes. This food waste is a source of chlorine
and the salt content is quite high. Due to this non-classification, the
MSW characteristics in China has low calorific values and high moisture
content [22]. Generally, in America and Europe the moisture in MSW
(10–30% only) is less as compared to China [23]. This is due to the
varying climatic conditions and life patterns. However, in Taiwan,
MSW is comprised of paper (28.95%), cellulosic cloth (8.11%), yard
waste (3.10%), food (23.18%), plastic (19.59%), leather and rubber
(0.43%), metals (7.89%), glass (6.98%), and ceramic, earthen materials
and miscellaneous (1.77%) [24]. The literature shows that newspaper is
the major ingredient of waste papers of MSW [25]. The waste paper has
high heating value of about 17 MJ/kg and thus has the potential to be
converted to commercial fuel. So, it can be seen that recovery of MSW
components is a major concern throughout the globe and the research is
directed towards devising improved and cost effective technologies to
solve the issue.
Thermochemical conversion processes have been adopted to pro-
duce fuel from MSW. The amount of MSW for thermal treatment has
touched 921 kton/yr in 2010–2015 [26]. This review focuses on pyr-
olysis of MSW in order to produce fuel. Pyrolysis is the conversion of
biomass (specifically MSW in this case) into liquid (bio-fuel), solid, and
gaseous fractions by heating the MSW in the absence of air [27]. The
main products of pyrolysis are gases, bio-oil and char. The reason for
adopting pyrolysis, instead of gasification, combustion or incineration,
is the production of bio-oil as well as synthesis gas and char as by-
products. Another reason is the higher energy recovery efficiency as
A.T. Sipra et al.
Fig. 3. The mean physical composition of MSW in China [21].
compared to other thermochemical reactions. This process has also
gained evident attention due to production of high liquid yield under
very high heating rates, reaction temperature within the range of
425–600 °C and short residence time (< 3 s) of vapor in the reactor
[28]. Hence, due to these reasons pyrolysis has been favored as an ef-
ficient process for liquid bio-fuel production, which is the new source
for power generation. The other by-products, produced by pyrolysis,
can also be re-used, therefore increasing the efficiency of the process,
reducing the overall cost and lowering the NOx and SO2 emissions
[29,30]. The pyrolysis process and its comparison with other thermal
treatment processes has been explained in detail in Section 2.
Various comprehensive reviews have been published about the
pyrolysis of individual components of MSW. Numerous reviews have
focused on providing the effect of pyrolysis on plastic wastes from MSW
[31,32]. However, review papers on the co-pyrolysis of various com-
ponents of MSW have not been found. This paper aims to review and
compare how different compositions of the components of MSW can
affect the produced pyrolysis fuel. Since calorific values determine the
quality or grade of produced fuel, therefore, the paper also focuses on
the synergistic effect of the components on the heating values of the
product formed. Since most of the literature has already focused on the
effect of operating conditions like temperature, residence time etc.,
therefore, these factors have not been discussed in detail in this review
[33–40]. The synergy of MSW with biomass is also beyond the scope of
this paper. Moreover, a comprehensive description of world's MSW
disposal scenario has been discussed in this literature. Therefore, this
review paper gives a comprehensive update of the pyrolysis of MSW to
obtain fuel.
2. MSW to energy conversion processes
Energy recovery from waste is the conversion of non-recyclable
waste materials into usable heat, electricity, or fuel through a variety of
processes, including combustion, gasification, pyrolysis, anaerobic di-
gestion and landfill gas recovery. This process is often called waste to
energy. [41].
The waste management system, as depicted in Fig. 4, is divided into
three treatment techniques. It is important that recyclable material is
removed first, and the energy is recovered from the residual waste. The
energy recovery processes involve biological and thermal treatment of
the waste. The waste which can neither be recycled, nor can be treated
to recover energy, is disposed of as landfill.
2.1. Biological treatment
Biological treatment includes composting process, which is the
anaerobic digestion of organic waste into methane-rich biogas. It uses
microorganisms like bacteria to carry out the process. This process is
very efficient for wet organic wastes like food waste, sewage sludge,
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agricultural residues or energy crops. Another product produced from
composting is bio-fertilizer also known as digestate. It can be used as a
good alternative for chemical fertilizers on agricultural land. [42].
2.2. Thermal treatment
Thermal treatment includes: combustion (incineration), gasification
and pyrolysis processes. Incineration is a waste treatment process that
involves the combustion of organic substances contained in waste ma-
terials [43]. This process occurs at very high temperatures. It produces
bottom ash and fly ash as by-products. Gasification involves partial
oxidation of organic waste at relatively less temperatures as compared
to incineration. This process produces bio-gas as a valuable product.
The pyrolysis involves decomposition of organic materials in the ab-
sence of oxygen/air at considerable temperature ranges.
2.2.1. Pyrolysis process
Pyrolysis is the thermal degradation of organic material in the ab-
sence of oxygen producing gas, liquid and solid products. Thermal
degradation involves cracking of large chain hydrocarbons into small
chain hydrocarbons at high temperatures (300–600 °C) [44]. The pyr-
olysis process is completed in three major steps: initiation, propagation
and termination. A general radical chain mechanism of thermal de-
gradation of polymers is described in the Fig. 5.
The products produced from pyrolysis differ in yield and composi-
tion due to various parameters which includes type of feedstock, reactor
system, residence time of gas, heating rate, contact time, temperature,
pressure ranges, effect of catalysts (if any present) and presence of
hydrogen gas or hydrogen giving compounds [45–48]. The pyrolysis
process is further divided on the basis of these parameters into slow and
fast pyrolysis. Table 1 shows the difference between slow and fast
pyrolysis in terms of the above-mentioned parameters.
It can be concluded from the Table 1, that the slow pyrolysis reduces
the processing efficiency of the pyrolysis process, and hence researchers
have mostly carried out their research with fast pyrolysis. Another type
of pyrolysis technique is microwave assisted pyrolysis. In microwave
assisted pyrolysis, unlike conventional heating, which transfers heat
from the surface to the center of the feedstock, the microwaves reach
the center of the material and the energy is transferred throughout the
volume of the feedstock. [52] Fig. 6 mentions the difference in con-
ventional and microwave heating mechanism on a cylindrical furnace.
Since, the feedstock is heated directly, therefore, this method
overcomes the need for feedstock shredding. It also improves the
quality of heating and hence the value-added products are produced. It
can be used for large scale commercialization due to its low cost pro-
duction, flexibility of the process as well as easy transportation of the
equipment.
2.2.2. Pyrolysis behavior of MSW by thermogravimetric analysis (TGA)
As mentioned previously in Section 1, MSW is a complex mixture of
plastics, paper, wood, food remains, yard trimmings, metals and glass
[21]. Since metals and glass components are incombustibles, therefore,
they are physically separated in order to avoid any adverse effects
during pyrolysis [53–55]. The rest of the components mentioned above
are further divided into groups, based on their elemental composition
and pyrolysis behavior. Polymers constitutes a major portion of MSW.
Polyethylene (PE), which is further divided into high-density poly-
ethylene (HDPE) and low-density polyethylene (LDPE), polypropylene
(PP), polyethylene terephthalate (PET), polystyrene (PS) and poly-
vinylchloride (PVC) are the six main plastics found in MSW [29].
H. Zhou et al. classified MSW based on 26 kinds of MSW component
samples. This study categorized the samples using the proximate and
ultimate analysis, heating values and thermogravimetric analysis
(TGA). The categorized groups included starch food, orange peel, ve-
getables (including banana peel), printing paper, wood waste, cellulose,
PET (including terylene), PVC, PE/PP, PS, and rubber. The cluster
A.T. Sipra et al.
Fig. 4. Waste management system [39].
analysis method was used to classify these 11 groups. [56] Table 2
shows the behavior of various MSW components during thermogravi-
metric (TG) and derivative thermogravimetric (DTG) analysis with re-
spect to their pyrolysis temperature, heating rates, atmospheric condi-
tions etc. It shows a contrast of how MSW components behave in
different thermogravimetric (TG) operating conditions. Since, in in-
dustries the heating rates are generally quite high. Therefore, J. Zheng
et al. [57] implemented a new design of TGA apparatus, in order to
closely achieve high heating rates for the MSW pyrolysis. From his set-
up, 864.8 °C/min was the maximum heating rate recorded. The pyr-
olysis was performed at 850 °C, and the high heating rates showed
different behavior from the data mentioned in Table 2. The peaks were
merged, since some steps of the reaction occurred over the same time
period. Moreover, the pyrolysis of rubber showed four peaks and it was
the most difficult of all the other MSW components. However, PE was
pyrolyzed easily with biomass (wood, fabric, food, paper) because of its
endothermic reaction, it decreased the feedstock heating rate and thus
decomposed easily. Therefore, it can be concluded that very high
heating rates have a significant effect on the thermal behavior of MSW
components. An extensive future work is required in this domain, in
order to commercialize the MSW pyrolysis process. The Table 2 also
Fig. 5. Typical radical chain mechanism of polymers thermal degradation [30].
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Table 1
Difference between slow and fast pyrolysis [49–51].
Slow pyrolysis Fast pyrolysis
Longer residence time (> few minutes) Less residence time (few seconds)
Slow heating rates High heating rates
Enhanced tar cracking and higher gas yields Rapid cooling of vapors to form liquid oil
Primary products: char Primary products: bio-oil and gas
Temperature range: 227–677 °C Temperature range: 577–977 °C
shows a comparison between N2 and CO2 atmosphere. It can be con-
cluded from the results in the table that below 500 °C, CO2 has no de-
finite effect, however, once the temperature rises, an evident mass
decay is observed due to Boudouard reaction, which results in the de-
crease of char. [58].
This review provides a detailed discussion on how different com-
ponents (as mentioned above) in MSW can combine together to yield
high-grade pyrolysis oil. Hence, this discussion is quite helpful for the
future of MSW to obtain fuel. The next sections highlight various stu-
dies regarding slow and fast pyrolysis. Moreover, a separate section has
A.T. Sipra et al. Fuel Processing Technology xxx (xxxx) xxx–xxx

been reserved, in this review paper, regarding the catalytic pyrolysis

and its limitations.

2.2.3. Comparison of thermal treatment techniques

Fig. 6. Conventional vs. microwave heating [52].
All the thermal treatment processes generate heat and electricity
which is used for power generation in various combined Heat and
Power Plants (CHPs). However, each of these treatment processes differ
from one another on the basis of various parameters like temperature
range, reactor system etc. A comparison of these techniques has been
mentioned in Table 3, pyrolysis is concluded as the most environment
friendly process, based on its produced emissions.
Incineration involves the combustion of MSW at high temperatures
(higher than 1000 °C) and results in the formation of NOx. Gasification
has high transportation cost and requires more complex gas clean-up. It
involves partial oxidation of MSW at 700 °C–900 °C. However, pyrolysis
involves decomposition of organic materials in the absence of oxygen/
air at temperature around 500 °C–700 °C. As compared to combustion
and gasification, pyrolysis results in the least production of NOx and
SO2, which are highly dangerous for the atmosphere. Moreover,
along with the harmful emissions of above mentioned acidic gases,
volatile organic compounds like poly-aromatic hydrocarbons (PAH),

Table 2
Behavior of various MSW components during thermogravimetric analysis (TGA) in waste-to-energy research [56,39,58].
Group MSW components Heating rate Atmosphere Flow rate Final temperature Results and discussion
°
C/min ml/min (°C)

Food residue Vegetables, banana peel 10 N2 100 1000 Multiple peaks below 320 °C due to decomposition of hemi-cellulose
etc. and cellulose, and due to the pyrolysis of hemi-cellulose.
Tangerine peel, orange 10 N2 100 1000 < 3% ash content; ~20% fixed carbon content
peel
Starch food 10 N2 100 1000 Single peak at 300 °C
Chinese cabbage, orange 10 N2 100 1000 one peak of cellulose (300–400 °C), two close peaks of hemi-
peel cellulose (210–400 °C) and lignin mass loss between (280–400 °C)
10 CO2 100 1000 A significant peak appears after 700 °C which shows apparent mass
reduction
Wood waste – 10 N2 100 1000 Weak peak of hemi-cellulose
Strong peak of cellulose
Another peak of lignin
Poplar wood 10 N2 100 1000 Four DTG peaks at 161, 345,490 and 701 °C
10 CO2 100 1000 Three DTG peaks at 345, 830 and 936 °C
Paper Blank printing paper, 10 N2 100 1000 Approximate 80% volatile
newspaper 10% ash content
Main DTG peak at 350 °C
Glossy paper, cardboard 10 N2 150 500–600 Single DTG peak at approximately 360 °C due to lower content of
hemi-cellulose and/or catalytic effects. The residues from the sulfate
production process in cardboard, results in cellulose degradation at
lower temperatures.
– 10 N2 100 1000 Single peak at 350 °C
10 CO2 100 1000 Two peaks at 354 and 848 °C
Rubber – 10 N2 100 1000 Main peak at 378.4 °C
Cellulose Tissue paper, cotton, 10 N2 100 1000 Single peak at 333–353 °C
cloth, absorbent cotton
gauze
Plastics PE, PP 10 N2 100 1000 Very strong peak at 455–485 °C
Terylene, PET 10 N2 100 1000 Main peak at 440 °C
PVC 10 N2 100 1000 High chlorine content
Two stages pyrolysis
PS 10 N2 100 1000 Single peak at 413.9 °C; lower temperature than that of HDPE,
LDPE, and PP
PVC 10 N2 150 500–600 Two step degradation
a. 200–380 °C (high amount of chlorine release)
b. 380–550 °C (degradation of hydrocarbons)
PS, PP, LDPE, HDPE 10 N2 150 500–600 Thermal degradation at 350–500 °C.
PE 10 N2 100 1000 DTG peak at 477 °C
10 CO2 100 1000 DTG peak at 473 °C
PS 10 N2 100 1000 DTG peak at 417 °C
10 CO2 100 1000 DTG peak at 413 °C
PVC 10 N2 100 1000 DTG peaks at 287 and 467 °C
10 CO2 100 1000 DTG peaks at 299 and 469 °C
Textile Polyester fabrics 10 N2 100 1000 DTG peak at 438 °C
10 CO2 100 1000 DTG peaks at 432 and 951 °C

DTG means derivative thermogravimetric.

5
A.T. Sipra et al.
Table 3
Comparison between thermochemical conversion processes of MSW [2,62,63,50,55,64].
Process Advantages
Incineration (combustion) • Well established technology
• Inexpensive extraction of heat energy
• Efficient electricity generation
• Large reduction of the amount of MSW by weight and
volume (70–80%)
• Requires less time
Gasification • No greenhouse gas (GHG) emissions
• 50–90% reduction in MSW volume
• Technology can be expanded easily
• Used for all kinds of wastes
Pyrolysis • Up to 80% energy recovery rate
• Less land requirement
• Smaller NO & SO emissions
• Washing
x 2
of syngas before its combustion
• Better quality of solid residues; high calorific value
products(~38 MJ/kg)
• Liquid fuel easy to transport
• waste;
Production of lesser volume of flue gases per kg of
thus reducing the flue gas treatment capital cost
polychlorinated biphenyls (PCBs) and polychlorinated di-benzo-p-di-
oxine/-furans (PCDD/Fs) and other toxic heavy metals are also released
by incineration. Therefore, pyrolysis is adopted, since it minimizes the
corrosion due to heavy metals and completely avoid PCDD/Fs forma-
tion due to strong reduction atmosphere and lower temperature.
Therefore, pyrolysis is the most environment friendly thermochemical
conversion process. Moreover, gasification also requires some moisture
content and air for proper functioning of the process. But, the greater
the moisture content and more air introduce, the lesser is the heating
value (HV) of fuel produced. Since pyrolysis reaction occurs under
oxygen absence, large molecules are easily evolved from MSW, and
after condensation produce the liquid products. Therefore, pyrolysis is
the optimal option for the production of bio-oils. [27] Furthermore,
pyrolysis has a high energy recovery rate with high attenuation ratio,
therefore it is regarded a better thermal recycling method in compar-
ison to other processes [59]. In pyrolysis, due to the reduction atmo-
sphere, H2S is formed and thus sulfur is easy to remove than from SO2
[60]. The other advantages of pyrolysis over other thermochemical
processes include negligible formation of combustion products, less
dumping of produced pyrolyzed product (especially solid) due to re-
utilization of char and the condensate after separation of water is re-
covered [61].
Hence, this paper reviews the pyrolysis of MSW to obtain fuel. The
reason of opting MSW as a feedstock is rapid increase in the globali-
zation and population increase [65]. There is a need to eradicate the
pollution caused by dumping MSW and therefore, various researches
have been conducted to produce useful products from MSW. MSW
contains various components which can be taken in different ratios to
produce high-grade pyrolysis oil. This oil is suitable for heat, power
generation and as a transportation fuel.
3. Influence of MSW components on pyrolysis products yield
The components of MSW play a significant role while obtaining
better quality fuel. In most of the research, particular MSW is in-
vestigated [34]. However, the MSW has different composition based on
geographical location and time period [66]. Therefore, the products
obtained from the pyrolysis of MSW cannot be generalized, because of
varying thermal and chemical compositions. Reaction temperature,
elemental composition and the structure of the input material are key
factors for the distribution of the individual products. Moreover, a lot of
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Disadvantages
• Production of dioxins and other persistent organic pollutants (POPs) resulting in
air pollution and creating hindrance in the extraction of valuable chemicals from
the MSW
• High capital and operating cost
• Needs special care for the safe disposal of produced fly ash
• Highly inefficient upon burning of high moisture content waste
• Minimum energy extraction
• Maximum capital cost
• Production of tar
• More suitable for large scale power plants using Rankine cycle
• Higher operating costs
• Greater capital cost
• Corrosion of metal tubes during reaction
• Higher energy consumption
• Oily liquid products have high water content resulting due to moisture in
feedstock
• Coke formation from liquid products
researches have been conducted about the features of MSW compo-
nents, such as plastics and wood [67]. Along with individual compo-
nents, some of the research has also focused on the interactions be-
tween the components of real MSW. This review highlights how various
synergistic interactions are suitable to obtain high quality fuel.
As previously mentioned in Sections 1 and 2, MSW is composed of
mainly six components. The research has been done to produce high
grade pyrolytic oil with the real MSW as a feedstock. Moreover, since
plastics constitutes a major portion of MSW and their pyrolysis behavior
is quite positive to obtain valuable products. Therefore, the sections
below cover the influence of both real MSW and plastics on the pyr-
olysis products yield. Table 4 shows the pyrolysis behavior of real MSW
and plastics in MSW, the pyrolysis temperature, type of pyrolysis re-
action, type of reactor, classification of feedstock and the end products
yields are mentioned in the table for a comparative analysis.
Table 4 shows different studies on MSW, with varied composition.
The table mentions different products yields, with and without the use
of various catalysts. It is observed from various studies that 400–550 °C
is the optimum temperature range to produce maximum pyrolytic oil
yield. The values of temperature in the table supports the argument. It
can be observed from the table that with varying composition of the
components of MSW, the product yield varies. The heating values ob-
tained from real MSW pyrolysis are quite less as compared to conven-
tional diesel or petroleum. Therefore, the researchers are focused on
providing optimum mixing ratios of various components in order to
produce high quality pyrolytic oil.
3.1. Influence of real MSW on pyrolysis products yield
Many researches have been done in order to check the effect of real
MSW pyrolysis on the products of pyrolysis. This section provides a
review from various studies of real MSW in order to provide a com-
parative analysis of real MSW pyrolysis. A few of these studies are also
mentioned in Table 4.
H. Zhou et al. [21] provided an overview of characteristics of MSW
fuel in China. The paper focused on the proximate and ultimate analysis
of the main components of MSW mentioned in Section 2. The heating
values were predicted after the received results. The Table 5 shows
HHV of individual MSW component, as dry basis, in kJ/kg. It is ob-
served that HHV of chlorine-free plastics (PP, PE, PS, etc.) is highest
followed by rubber, PVC, wood waste and so on. The lowest value of
A.T. Sipra et al. Fuel Processing Technology xxx (xxxx) xxx–xxx

Table 4
Several studies on the use of MSW pyrolysis.
Classification Ref. Feedstock Type of Operating conditions Type of reactor End products yield
pyrolysis
process

Bakung district, [68] Plastics (52%), biomass (34%), Slow Mass of sample: 500 g Fixed bed vacuum Thermal Cracking
Bandarlampung, Indonesia paper (9%), rubber (3%) and w/o catalyst reactor Solids: 34.6 wt%
textile (2%) 750 g with catalyst Bio-oil: 15.2 wt%
Particle size: 5–10 cm Gases: 48.2 wt%
Reaction time: 60 min Water: 2 wt%
Reaction temp: 400 °C Catalytic cracking:
Solids: 28.6 wt%
Bio-oil: 21.4 wt%
Gases: 50 wt%
Water: 0 wt%
disposable plates, grocery bags, [69] PS Fast Mass of sample: 1 kg Batch pyrolyzer Liquid oil: 80.8%
and juices or drinking cups Particle size: 2 cm2 reactor Char: 6.2%
in KSA Reaction time: 75 min Gases: 13.0%
Reaction temp: 450 °C Wax: Nil
PP Heating rate: 10 °C/ Liquid oil: 42.0%
min Char: 3.5%
Gases: 54.5%
Wax: Nil
PE Liquid oil: Nil
Char: 13.0%
Gases: 62.0%
Wax: 25.0%
PS/PP (50/50) Liquid oil: 25.0%
Char: 5.1%
Gases: 69.9%
Wax: Nil
disposable plates, grocery bags, [69] PS/PE (50/50) Fast Mass of sample: 1 kg Batch pyrolyzer Liquid oil: 54.0%
and juices or drinking cups Particle size: 2 cm2 reactor Char: 7.7%
in KSA Reaction time: 75 min Gases: 38.3%
Reaction temp: 450 °C Wax: Nil
PP/PE (50/50) Heating rate: 10 °C/ Liquid oil: 24.0%
min Char: 24.8%
Gases: 51.2%
Wax: Nil
PS/PP/PE (50/25/25) Liquid oil: 49.0%
Char: 3.9%
Gases: 47.1%
Wax: Nil
PS/PP/PE/PET (40/20/20/20) Liquid oil: 40.0%
Char: 18.0%
Gases: 42.0%
Wax: Nil
Samples collected from landfill [70] Kitchen wastes (15.07 wt%), Fast pyrolysis Mass of sample: 100 g Fixed-bed pyrolysis Liquid: decreased from 27.3 to
in Jiangsu Province, China paper (5.86 wt%), cloth and fiber and reforming Particle size: 10 mm reactor completed by a 16.5 wt%
(27.10 wt%), plastics (21.89 wt process Reaction time: 30 min downstream volatile Gases: Increased from 0.25 N m3 kg−1
%), residue (30.07 wt%) Reaction temp: reforming reactor of to 0.37 N m3 kg−1
500–600 °C (with and Char: HHV of char decreases from
w/o char) 6.89 MJ kg−1 (without reforming) to
Heating rate: 10 K/ 4.63 MJ kg−1
min
Samples collected from waste [71] Kitchen garbage (68.96 wt%), Catalytic Feedstock input rate: bench-scale Liquid oil: Decreased from 37.98% to
dumpsites at Huazhong paper(9.95 wt%), textile (2.17 wt pyrolysis 0.3 kg/h downstream fixed-bed 5.13%.
University of Science and %), wood (7.40 wt%), plastic Particle size: 5 mm reactor Gases: Increased 44.07% to 78.87%
Technology (HUST), (11.52 wt%) Reaction time: 60 min Char: Decreased from 15.86% to
Wuhan, China Reaction temp: 900 °C 14.92%
(w/o catalyst)
750–900 °C (with
catalyst)
Heating rate: 10 °C/
min
PS disposable plastic plates [72] – Thermal Catalyst to feedstock Small pilot scale Liquid oil: 80.8%
pyrolysis ratio of 1:10 pyrolysis reactor Gases: 13.0%
Reaction time: 75 min Char: 6.2%
Catalytic Reaction temp: Natural Synthetic zeolite
pyrolysis 450 °C zeolite
Heating rate: 10 °C/ Liquid oil: Liquid oil: 50%
min 54.0% Gases: 22.6%
Gases: 12.8% Char: 27.4%
Char: 32.8%
[73] Fast
(continued on next page)

7
A.T. Sipra et al. Fuel Processing Technology xxx (xxxx) xxx–xxx

Table 4 (continued)

Classification Ref. Feedstock Type of Operating conditions Type of reactor End products yield
pyrolysis
process

Samples collected from Padang Wood waste (37.58%), kitchen Mass of sample: Downstream fixed-bed Catalytic (calcined dolomite)
Siding landfill, Malaysia garbage (16.32%), plastic bag 9–10 g. reactor Liquid oil: 10.88%
(15.27%), solid plastic (14.57%), Particle size: 2 mm Gas: 56.67%
Reaction time: 25 min Char: 32.44%
Reaction temp: Catalytic (zeolite)
200–750 °C Liquid oil: 36.35%
Heating rate: 50 °C/ Gas: 24.98%
min Char: 38.66%
Textile (9.63%), glass (4.20%) Non-catalytic
and ferrous materials (2.42%). Liquid oil: 21.72%
Gas: 39.91%
Char: 38.36%
Sample collected from Bandar [74] Polypropylene (PI080 grade), Catalytic FCC catalyst/PP ratio: Semi-batch reactor Temperature effect (%)
Imam Petrochemical Co., ethylene and propylene (purity 0–60% 420 °C
Mahshahr, Iran and Tehran 99.9%) Reaction temp: Liquids: 88.6
Petrochemical Co, Tehran, (420–510 °C) Heating Gases: 8.3
Iran rate: 25 °C/min Coke: 3.1
450 °C
Liquids: 92.3
Gases: 4.1
Coke: 3.6
480 °C
Liquids: 82.4
Gases: 12.5
Coke: 5.1
510 °C
Liquids: 76.1
Gases: 17.1
Coke: 6.8
Catalyst/PP ratio effect (%)
0
Liquids: 95.2
Gases: 4.4
Coke: 0.4
0.1
Sample collected from Bandar [74] Polypropylene (PI080 grade), Catalytic FCC catalyst/PP ratio: Semi-batch reactor Liquids: 92.3
Imam Petrochemical Co., ethylene and propylene (purity 0–60% Gases: 4.1
Mahshahr, Iran and Tehran 99.9%) Reaction temp: Coke: 3.6
Petrochemical Co, Tehran, (420–510 °C) 0.2
Iran Heating rate: 25 °C/ Liquids: 85.2
min Gases: 9.6
Coke: 5.2
0.4
Liquids: 79.3
Gases: 13.8
Coke: 6.9
0.6
Liquids: 76.7
Gases: 14
Coke: 9.3
Carrier gas effect (%)
H2
Liquids: 96.7
Gases: 3
Coke: 0.3
He
Liquids: 94.7
Gases: 3.2
Coke: 2.1
N2
Liquids: 92.3
Gases: 4.1
Coke: 3.6
(continued on next page)

8
A.T. Sipra et al. Fuel Processing Technology xxx (xxxx) xxx–xxx

Table 4 (continued)

Classification Ref. Feedstock Type of Operating conditions Type of reactor End products yield
pyrolysis
process

Sample collected from Bandar [74] Polypropylene (PI080 grade), Catalytic FCC catalyst/PP ratio: Semi-batch reactor Ethylene
Imam Petrochemical Co., ethylene and propylene (purity 0–60% Liquids: 93.8
Mahshahr, Iran and Tehran 99.9%) Reaction temp: Gases: 5.1
Petrochemical Co, Tehran, (420–510 °C) Coke: 1.1
Iran Heating rate: 25 °C/ Propylene
min Liquids: 87.8
Gases: 9.7
Coke: 2.5
Ar
Liquids: 84.8
Gases: 9.8
Coke: 5.4
No gas
Liquids: 33.8
Gases: 14.9
Coke: not detected
Stirrer rate effect (%)
0(w/o stirrer)
Liquids: 65.3
Gases: 26.5
Coke: 8.2
0
Liquids: 81.6
Gases: 13.5
Coke: 4.9
50
Liquids: 92.3
Gases: 4.1
Coke: 3.6
Sample collected from Bandar [74] Polypropylene (PI080 grade), Catalytic FCC catalyst/PP ratio: Semi-batch reactor 100
Imam Petrochemical Co., ethylene and propylene (purity 0–60% Liquids: 87.4
Mahshahr, Iran and Tehran 99.9%) Reaction temp: Gases: 9.5
Petrochemical Co, Tehran, (420–510 °C) Coke: 3.1
Iran Heating rate: 25 °C/ 300
min Liquids: 82.4
Gases: 14.6
Coke: 3
Non-recyclable, non-dangerous [50] Mixture of carpet disposal, Slow Particle size: 2 mm Home-built semi- Liquids: 51.3 wt%
waste from a waste residues of plastic/metal/ Reaction time: 2 h continuous lab-scale Gases: 37.0 wt%
treatment plant drinking cartons sorting Reaction temp: 550 °C reactor Solids: 11.7 wt%
installation, residues of paper and Heating rate: 4 °C/min Wax: Nil
different fractions of synthetic
materials
Non-recyclable, non-dangerous [50] Mixture of carpet disposal, Fast Mass of sample: 70 g Home-built semi- 480 °C, 12 g material/min
waste from a waste residues of plastic/metal/ Particle size: 2 mm continuous lab-scale Liquids: 48.1 wt%
treatment plant drinking cartons sorting Reaction time: few reactor Gases: 50.1 wt%
installation, residues of paper and seconds Solids: 1.8 wt%
different fractions of synthetic Reaction temp: Wax: 15.1 wt%
materials 480,510,550 °C 510 °C, 12 g material/min
Input transfer rate: Liquids: 51.5 wt%
24 g material/min or Gases: 48.4 wt%
12 g material/min. Solids: 0.1 wt%
Wax: 10.2 wt%
450 °C, 24 g material/min
Liquids: 49.9 wt%
Gases: 50.0 wt%
Solids: 0.1 wt%
Wax: 15.0 wt%
480 °C, 24 g material/min
Liquids: 51.4 wt%
Gases: 47.6 wt%
Solids: 1.0 wt%
Wax: 12.3 wt%
510 °C, 24 g material/min
Liquids: 71.6 wt%
Gases: 28.0 wt%
Solids: 0.4 wt%
Wax: 25.1 wt%
550 °C, 24 g material/min
Liquids: 41.7 wt%
Gases: 57.5 wt%
Solids: 0.8 wt%,Wax: 6.5 wt%

9
A.T. Sipra et al.
Table 5
Average HHV of components of MSW in Chinese cities [21].
MSW component Higher heating value (HHV) in kJ/kg
Food residue 15,386
Wood waste 19,461
Paper 15,894
Chlorine-free plastics 43,448
Chlorinated plastics (PVC) 21,172
Rubber 29,789
food residue among the heating values of MSW components is due to
the high chlorine content, because of salts present in the food content.
Similarly, the HHV of paper is also near to the food residue, this is also
because of the interaction of paper with food residue. The plastics are
differentiated in two groups: chlorine-free plastics and chlorinated
plastics. The Table 5 further shows that the HHV of chlorine-free
plastics is approximately twice of chlorinated plastics, because as the
name suggests, chlorinated plastics have rich chlorine content resulting
in lower HHV.
I.M. Gandidi et al. [68] used real MSW to produce bio-crude oil
(BCO) under thermal and catalytic pyrolysis at 400 °C and 60 min re-
action time. This composition of MSW consisted of 52% plastics (such
as bottles, plastic bags). Natural activated zeolite catalyst was used to
enhance the yield of BCO. Gas chromatography-Mass spectrometry (GC-
MS) was used to analyze the BCO, and the carbon number range could
be determined according to the percentage of peak region. The results
show that the catalytic pyrolysis performance is better than that of
thermal cracking. Table 4 shows, that 15.2% and 21.4% of BCO was
produced by pyrolysis and catalytic pyrolysis, respectively, with mainly
gasoline and diesel fractions. In addition, paraffin and olefin fractions
are the main types of gasoline and diesel. The results show that the
content of waste and its process have certain influence on the fuel
produced. The BCO produced by pyrolysis have a higher concentration
in the gasoline range. This can be described as the result of secondary
cracking, which converts a small amount of gasoline into syngas, diesel
into gasoline and solids into diesel because of the presence of catalysts.
More plastics produce more gasoline in domestic waste, while more
biomass produces more amount in diesel range. In this paper, the
produced BCO is comparable to diesel-48, since it has the carbon range
of diesel. The challenges in the BCO production by MSW pyrolysis and
its possible solutions are mentioned in the Section 3.4.
As shown in Table 4, N. Wang et al. [70] used kitchen wastes, paper,
cloth, fiber and plastics as a feedstock. The volatile products obtained
from the pyrolysis of municipal solid waste (including syngas and
pyrolysis oil) were forced to contact with hot char in the process of
500–600 °C pyrolysis in a fixed-bed reactor. The yield and performance
of syngas, char and pyrolysis oil were studied, and the energy redis-
tribution of char reforming products was calculated. An initial labora-
tory scale investigation indicated that the catalytic reforming of hot
char has resulted in the production of dry syngas from 0.25 to
0.37 Nm3 kg−1 MSW at 550 °C. As a result, the carbon conversion ratio
to syngas increased from 29.6% to 35%, and the chemical energy from
waste to syngas was increased from 41.8% to 47.4%. The Table 4 also
shows that the yield of pyrolysis liquid products, including pyrolysis oil
and water, is reduced from 27.3 to 16.5%, while the molecular weight
of oil becomes light. When the volatile matter passes through the empty
hot bed without the hot char, the higher temperature decides secondary
cracking, namely further thermal degradation, which results in the in-
crease of gas production and the corresponding decrease of liquid
output. About 60% of the vapor contained in the volatile matter is
converted into syngas. After reforming process, the concentration of
SO2 and HCN in syngas decreased and the content of NO and NO2 in-
creased. The char concentrations of N, H, C and alkali metals decreased
and their calorific value was also decreased but energy fraction in-
creases from 6.36–7.26 MJ kg−1. The HHV is 15 MJ Nm−3 which is
10
Fuel Processing Technology xxx (xxxx) xxx–xxx
higher than obtained through gasification process. The volatile char
reformation also resulted in the increase of H2 yield and the complete
disappearance of C3–C4 in Syngas. At the same time, the pyrolysis oil
becomes lightweight and its small compounds such as naphthalene,
caprolactam and biphenyl disappear or decrease, which provides a
potential substitute for Syngas as an energy carrier. Combined with the
prevention of the evaporation, moisture and energy balance of alkali
metals in the three products, the reforming temperature of the 550 °C is
proposed: the energy fraction of char is only 12.3%, so that more
carbon can be obtained to ensure stable heavy metals. This temperature
is also commonly used in pyrolysis operations, which do not require
additional heating of char.
Similarly, M. He et al. [71] obtained syngas with LHV around
13–14 MJ Nm−3, from the waste dumpsites in Wuhan, China. As shown
in Table 4, kitchen garbage, paper, textile, wood and plastic were
pyrolyzed at 750–900 °C in a bench-scale downstream fixed-bed re-
actor. The effects of weight hourly space velocity (WHSV) and tem-
perature of reactor on product yield and gas composition were in-
vestigated. 47–67 mol% of syngas was produced from pyrolysis. The
results show that the existence of calcined dolomite has great influence
on the product yield and gas composition in the pyrolysis process, and
has remarkable catalytic performance to increase gas production rate,
reduce oil production rate and char yield. High temperature resulted in
the conversion of waste into syngas, H2 and CO content increased sig-
nificantly. However, the production of CO2, CH4, C2H4 and C2H6 de-
creased. This is because as the temperature of the reactor increases, the
amount of volatile matter released from the MSW particles is greater.
The degree of secondary reactions is affected by the temperature of the
reactor. At higher temperatures (> 700 °C), the main occurrence of
secondary reactions, such as cyclanes cracking and macromolecular
long chain rupture, the reaction rate increases with the temperature,
resulting in higher gas production rate and the reduction of tar content.
At the same time, produced pyrolysis syngas is a very desirable raw
material for the production of transport fuel (Fischer–tropsch synth-
esis). It can also be used directly as a MHV fuel with a lower heating
value of about 13.87 MJ/n m3. The yield profile of the pyrolysis product
confirms that the catalyst facilitates the degradation process resulting in
strong decomposition (low solid yield) or strong liquid phase splitting
(low liquid yielding), and therefore higher hydrogen formation because
the gas is formed by pyrolysis of the liquid.
The pyrolysis gas of municipal solid waste (MSW) was studied, by O.
Tursunov [73], by using zeolite and calcined dolomite as catalysts, and
the temperature range of 200–750 °C in the downstream fixed bed re-
actor was analyzed. The gas produced by pyrolysis of MSW is in the
range of 49–57 mol%. The results show that the existence of calcined
dolomite has a significant effect on the yield and composition of the
products during the pyrolysis process, and using calcined dolomite as a
catalyst, results in the performance of increasing gas production, de-
creasing oil production rate and char yield as compared to zeolite and
no catalytic pyrolysis process. High temperature 600–750 °C led to the
conversion of MSW into gas production, and the CO content increased
greatly. Therefore, CO is a key factor in the production of renewable
energy and bio-gases like syngas and methane. The heating value of
MSW was obtained to be 2388 kcal/kg based on the bomb calorimeter
test. Table 4 shows increase in gas yield from 24.98 wt% with zeolite to
56.67 wt% with calcined dolomite. It also shows that the oil yield de-
creased significantly from 36.35 wt% with zeolite to 10.88 wt% with
calcined dolomite. This is because the low yield oil rate is caused by the
removal of oxygen to water, CO2 and CO, from the coke-forming on the
catalyst and significantly increased gas production due to catalysis.
With calcined dolomite 32.44 wt% and with zeolite 38.66 wt% of char
is produced. Therefore, the yield profile of the pyrolysis product con-
firms that the catalyst promotes the degradation process to produce
strong decomposition (low solids yield) or strong liquid phase pyrolysis
(Low liquid rate), and therefore higher hydrogen formation because the
gas is formed by cracking the liquid. As the temperature of the reactor
A.T. Sipra et al.
increases, the volatile matter is released from the waste particles. The
degree of secondary reactions is affected by the temperature of the
reactor. At higher temperatures (> 500 °C), there are mainly two re-
actions such as cracking of cyclanes and long chain macromolecules,
whose reaction rate increases with increasing temperature, resulting in
a decrease in gas production and tar production at higher temperatures.
Moreover, F. Ates et al. [75] investigated the pyrolysis of municipal
solid waste (MSW) and municipal plastic waste (MPW) in the absence
and presence of catalysts (Y-zeolite, b-zeolite, equilibrium FCC, MoO3,
Ni–Mo Catalyst, HZSM-5 and Al (OH) 3) at 500, 550 and 600 °C in a
batch reactor. In the presence of the catalyst, the yield of the volatile
increased, while the reaction time was reduced for the need for the total
cracking. Catalysts were found productive and selective in converting
aliphatic hydrocarbons into aromatic and cyclic compounds in oil
products. Gases from municipal waste were composed of hydrogen, CO
and CO2, while in the MPW only hydrogen and hydrocarbons were
detected. The catalytic efficiency of MPW is higher than that of muni-
cipal solid waste. Depending on the feedstock, the pyrolysis oil contains
aliphatic hydrocarbons, aromatic hydrocarbons, cyclic compounds and
fewer ketones, alcohols, acids or esters. The results show that the re-
action time for the total pyrolysis of the MPW is short when the catalyst
exists, but it is not needed in the process of MSW degradation under the
same temperature and catalyst conditions. The next section describes
the influence of pyrolysis of plastics in MSW on the products yield.
3.2. Influence of plastics on pyrolysis products yield
In 2011, the total plastic waste production in the world was about
280 million tons [76]. Plastic waste is one of the main components of
municipal solid waste (MSW). Because of its durability, light weight
and low cost, plastic consumption is growing at an alarming rate
worldwide by 4% annually [32]. Since plastics are quite useful com-
ponent of MSW to obtain fuel. Therefore, most of the research is di-
rected towards the pyrolysis of different kinds of plastics. There are five
major types of plastics. They are polystyrene (PS), polyethylene (PE),
polypropylene (PP), polyvinyl chloride (PVC) and polyethylene ter-
ephthalate (PET). From which PS, PE and PP are the most used plastic
types in pyrolysis studies [32,77,78]. PS is light with high strength and
heat resilience [69], thus providing low temperature as a pyrolysis
feedstock as compared to PP and PE. Based on density and molecular
branching frequency, PE is further divided into two categories. High
density polyethylene (HDPE) and low density polyethylene (LDPE).
HDPE needs high temperature (> 500 °C) because of its highly crys-
talline long chain structure. Moreover, it forms wax instead of liquid oil
in pyrolysis. [32,79,80,31] Therefore, appropriate proportion of HDPE
should be used while pyrolysis.
B.K. Sharma et al. [44] worked on the pyrolysis of HDPE plastic
grocery bags to produce fuel. 74% of the product formed after pyrolysis
was plastic crude oil (PCO) at a temperature range of 420–440 °C. The
PCO has properties comparable to conventional petroleum diesel fuel. It
has higher carbon and hydrogen content and lesser oxygen and nitrogen
content, therefore, the HHV falls around 49–50 MJ/kg. Basically, HDPE
waste plastic grocery bags were pyrolyzed and then distilled to produce
a key liquid hydrocarbon product (PPEH-L). PPEH gives ~64% fraction
of diesel since it contains saturated aliphatic paraffinic hydrogens
(94.0%), aliphatic olefinic hydrogens (5.4%) and aromatic hydrogens
(1.0%). These compounds have boiling range 190–290 °C, which is
comparable to conventional petroleum diesel fuel.
Moreover, M.S. Abbas-Abadi et al. [74] gave a very efficient utili-
zation of plastic waste for the production of liquid fuels. He showed that
how pyrolysis plant construction along with the olefinic petrochemical
plants results in better production of pyrolytic products. The pyrolysis
of polypropylene (PP) with an equilibrium fluid catalytic cracking
(FCC) catalyst in a stirred reactor was studied to obtain hydrocarbon
compounds with similar fuel properties. The results show that the
temperature has an effect on PP cracking. The addition of catalysts
11
Fuel Processing Technology xxx (xxxx) xxx–xxx
increases the economic viability of the production process of light hy-
drocarbons. The results of PP pyrolysis showed that the yield of max-
imum condensation products was 450 °C and 10% catalyst respectively.
Hydrogen as a reaction carrier gas increases the production of con-
densing and paraffin products. The results show that the active carrier
gas has a certain effect on the yield and composition of the product. The
catalyst efficiency of the stirred reactor can be improved by stirring the
proper heat transfer. The molecular weight of the product decreases
with the increase of temperature, as determined from the results. At
higher temperatures the main process involves the direct conversion of
liquid products to aromatic hydrocarbons and some gases, as well as the
stripping of gases to form aromatic hydrocarbons and final chars.
Diels–alder reaction produces aromatics, followed by dehydrogenation
in the pyrolysis process. The carbon distribution of the product transfers
to lower carbon when temperature rises from 420 to 510 °C and Ga-
soline (C5–C9) gives weak peak at the 480 °C. The results showed that
the yield of coke increased with the increase of the amount of catalyst.
The increase of the catalyst often shows the concentrated product, and
the carbon number distribution is narrow, the distribution of hydro-
carbon is from C3 to C13 compounds. C5–C9 in concentrated products
are the main compounds. Compared with the neutral carrier gas with
similar molecular weight, the active carrier gas can improve the pro-
duct formation. This is because the reaction gas can shift the balance,
resulting in greater liquid production. H2, ethylene and propylene can
be involved in the pyrolysis process by producing free radicals at ele-
vated temperatures. Free radicals can participate in the pyrolysis pro-
cess through the formation of free radicals, and their contribution is
supported by carrier gas type, process temperature and catalyst type
and proportion. This is also supported by Briones L. et al. [81] in hy-
drogen environment, the pyrolysis of LDPE produces more paraffin
instead of olefins. This results in better quality of pyrolytic oil which
can be used as a fuel.
R. Miandad et al. [69] performed the individual and combined
pyrolysis of different components in plastic waste types. In this study,
various combinations were made and the effect of different combina-
tions on the pyrolysis of liquid oil was investigated. It was noted that all
the waste components produced liquid oil product at 450 °C with a
retention time of 75 min, however, PE formed wax because of in-
complete breakdown of its long carbon chain structure [50]. PS plastic
waste shows the largest feedstock conversion to liquid oil compared to
other types of plastic wastes (80.8%) and the least gas (13%) and Coke
(6.2%). The synergistic effects of PE and PS reduces the formation of
wax and increases the oil yield. This is mainly due to the free radical
production of PS plastic, which converts PE into liquid oil instead of
wax, after mixing with PS. Moreover, the interaction of PS and PP with
PE, increased the liquid oil yield, along with gases and char, and no wax
is produced through this combination. This has shown the importance
of synergistic effect of various types of plastics, in order to produce the
required yield of bio-oil. Moreover, catalytic pyrolysis has been dis-
cussed in this paper, in order to avoid the formation of wax and thereby
increasing the oil yield. The Table 6 shows the compounds contained in
the produced pyrolytic oils of different types of plastic waste. Based on
the pyrolysis of the plastic types, it was observed that the produced
pyrolytic oils have HHV of 41.4–41.8 MJ/kg, which is quite similar to
conventional diesel. Some other properties like dynamic and kinematic
viscosities, density, pour point, freezing point and flash point were also
comparable to the conventional diesel. The literature further supported
that the pyrolytic yield of PP and PVC is comparable to that of PE [82].
In another research of plastics (polymer) combination high aromatic
hydrocarbons (styrene, toluene and ethylbenzene: 470%) and un-
saturated hydrocarbons (420%) in liquid yield were reported. This was
due to high retention time and temperature along with the contact
between different types of plastics [33].
M. Rehan et al. [72] studied the quality and application of liquid oil
made from the pyrolysis of polystyrene (PS) plastic scrap. Maximum
liquid oil produced by pyrolysis (80.8%) and gas (13%) and char
A.T. Sipra et al.
Table 6
Composition of liquid oil obtained from pyrolysis of different types of plastic waste [69].
Type of plastic waste Mixing ratio Composition of liquid oil
PS – Styrene(48.3%), toluene (25.6%), ethylbenzene (21.2%)
PP – Propylbenzene(23.4%), ethylbenzene (7.3%), benzene(7.8%), alphamethylstyrene(4.9%), xylene(7.8%), naphthalene (5.3%),
methylnaphthalene(8.4%), biphenyl (4.1%); phenantherene (7.6%), 2-phenylnaphthalene (3.3%)
Mixture of PS and PP 50/50% Methylstyrene (52.0%), styrene(24.5%), ethylbenzene(6.6%), benzene(10.6%), propylbenzene (6.3%)
Mixture of PS, PE and PP 50/25/25% Alphamethylstyrene(37.2%), styrene(19.6%), ethylbenzene(9.6%), benzene (6.4%), benzene1-propenyl(5.1%)
(6.2%), while catalytic pyrolysis uses synthetic and natural zeolite to
reduce liquid oil production (52%) with increased gas (17.7%) and char
(30.1%) production. The production of liquid oil produced by catalytic
pyrolysis is low but the quality is improved because of the catalytic
characteristics of zeolite, such as microporous structure and high BET
surface area. Liquid oil, from heat and catalytic pyrolysis, consists of
approximately 99% aromatic hydrocarbons, further confirmed by GC
MS results. FT-IR analysis further showed the chemical bonding and
functional groups of the main aromatic hydrocarbons, which is con-
sistent with the GC-MS results. Table 4 is also consistent with these
results. In this study, the average HHV of PS plastic raw materials, li-
quid oil produced by heat and catalytic pyrolysis with natural and
synthetic zeolite catalysts were found to be 39.3, 41.6, 41.7 and
40.6 MJ/kg respectively.
The challenges faced by plastics pyrolysis on the products yield, and
their possible solutions are described in the sections to follow.
3.3. Influence of co-pyrolysis of other MSW components on pyrolysis
products yield
Along with the plastics, the co-pyrolysis of other waste components
has also been seen in the literature. Co-pyrolysis of non-degradable
waste mixtures (waste rubber and plastics) with and without the ad-
dition of cornstalk have been investigated by H. Li et al. [83]. It is
observed that due to co-pyrolysis and addition of stalk additive the oil
yield and heating value increases. The feedstock-to-oil energy conver-
sion efficiency (FOECE) was observed to be maximum at 80 wt% mass
fraction of rubber. The heating value of the produced pyrolytic oil
reached 39.93 MJ kg−1, which is comparable to conventional diesel
and can be post-treated to use a fuel.
Similarly, R. Zevenhoven et al. [84] co-pyrolyzed PVC and mixtures
of PVC with LDPE and wood (Finnish pine) in nitrogen atmosphere at a
temperature range of 250–400 °C. Dechlorinated fuel was produced
from pyrolysis, and the results gave a net calorific value of 38.2 MJ/kg.
It was concluded that at maximum temperature where approximately
100% PVC is de-hydrochlorinated, due to wood or LDPE, the formation
of combustible gases containing carbon was decreased.
B. Grycová et al. [61] investigated the products of pyrolysis by using
food waste (waste cereal (WaCe) and waste peanut crisps (WaPC)) as
feedstock. Fast pyrolysis was carried out with a final temperature of
800 °C in a tube furnace. Nitrogen was used an inert medium. The mass
balance of the products produced, analysis of the syngas, and evalua-
tion of liquid and solid products was performed. Since fast pyrolysis was
performed, therefore, the liquid yields were higher (62 g for WaPC and
46 g for WaCe). This high amount of liquid was also mainly due to the
presence of greater oxygen content which resulted in the greater pro-
duction of oxygenated products. The gas analysis revealed that the re-
lease of hydrogen increases with the increase in temperature. At
750–800 °C the quantity of hydrogen released was 61 vol% and 66 vol%
by WaCe and WaPC, respectively. The results also showed that the
hydrocarbons and CO are reduced with an increase in temperature.
WaCe showed an evident release of gas during the temperature of
around 540 °C. The solid residue (chars) were also investigated because
of their good adsorption capacities. The surface area of chars was quite
small (< 10 m2/g) as compared to commercial activated carbons (ap-
prox. 1000 m2/g). The chars can be further treated with steam in order
12
Fuel Processing Technology xxx (xxxx) xxx–xxx
to enhance its surface area. The chars produced by WaCe sample can be
used for treating wastewater in order to catch heavy metals ions or
other organic substances). The adsorption capacity for WaPC chars was
affected badly due to the spatial structure of WaPC. However, the
higher heating value (HHV) of the chars samples were 31.44 and
29.60 MJ/kg for WaCe and WaPC, respectively. These HHVs prove this
food waste as a great source for energy recovery. Finally, the con-
densates produced by the feedstock also have higher HHV (27.14 MJ/
kg for WaCe). Hence, it can be seen that food waste has a great potential
for energy recovery due to good calorific values and utilization of chars
produced. Similarly, pyrolysis of newspaper was also conducted, the
products produced included non-hydrocarbons (H2, CO, CO2, and H2O)
and hydrocarbons (C1–3, C4, C5, C6, 1-ring, C10–12, C13–15, and C16–18).
The gases produced like CO, H2 etc. have high calorific value, thus can
be used as a commercial fuel. [85].
H. Zhou et al. [86] used food residue (rice), wood waste (poplar
wood) and plastics (PVC) to observe the interactions of these compo-
nents of real MSW. The thermogravimetric analyzer coupled with
Fourier transform infrared spectrometer (TG-FTIR) was used. It was
observed that interaction of wood and PVC as well as rice and PVC were
very evident. Due to PVC addition, CO and CO2 were generated and
hence the pyrolysis process was slowed down. The second and third
peaks of PVC do not appear in the experiment, which is very different
from the linear superposition result. HCl from 350 to 500 °C can par-
ticipate in the pyrolysis of rice or poplar wood and the formation of
organic chlorides. In addition, in municipal solid waste, the presence of
chlorinated polymers may increase the yield of char during pyrolysis.
Hence, the interactions of PVC with different MSW fractions needs to be
discussed further in order to produce good quality pyrolytic oil.
Therefore, H. Zhou et al. [87] further investigated the interactions of
three MSW components (orange peel, tissue paper and PVC). The
combined effect of tissue and PVC was evident as shown by TGA-FTIR
experiments. The overlap ratio of TG curve is introduced and its in-
teraction is quantitatively evaluated. The interaction between orange
peel and tissue paper was slight. The interaction between orange peel
and PVC inhibited the generation of alkyl and olefins, weakening the
peaks of HCl and benzene. The interaction between tissue paper and
PVC was significant and promoted low temperature pyrolysis
(< 300 °C) and suppresses pyrolysis at elevated temperatures. At the
same time, residue increased. The production of CO2, alkyl, olefin and
carboxyl groups is strongly influenced by the interaction of tissue paper
and PVC. The second and third peaks of the HCl disappeared because
the HCl reacts with other organic compounds.
3.4. Challenges faced by MSW pyrolysis for the pyrolysis products yield
In the previous sections, a detailed analysis of the pyrolysis products
(solids, liquids and chars) is explained. Their yields are also mentioned
and how the operating conditions effect the yield has also been ex-
plained. It is observed from the literature, that the heterogeneity of
MSW plays a vital role in determining the product's yield. In the real
MSW, plastics constitutes a major portion. But the plastics are further
divided into chlorine-free and chlorinated plastics (PVC). Different
types of chlorine-free plastics have similar properties. Although PVC
shows different properties, the average HHV of PVC is about half of the
chlorine-free plastics [21]. It is recommended that these two kinds
A.T. Sipra et al.
should be classified separately. Certain sample methods should be de-
vised and employed for the purpose. Another challenge that MSW faces
as a feedstock material is its high moisture content. Less liquid (bio-oil)
yield is produced because real MSW needs additional drying, hence this
results in higher gas yield and water content also contaminates the
produced bio-oil yield. The high water content, makes the MSW apt to
microbial contaminations. This could also be a potential hazard to-
wards human health as pathogens can also infect MSW. The high
moisture content causes an increase in the volume and weight of MSW,
therefore MSW should be dried well, at suitable high temperatures, in
order to minimize the cost of transportation. However, these processes
require energy and cost, making it an expensive process. Since the
production of MSW is present in every other municipality, a decen-
tralized system, where low-volume facilities locally use MSW, is pro-
posed by the researchers, in order to avoid drying and long-distance
transportation [88]. Also a series of precipitation and filtration pro-
cesses should be employed in order to separate water content from the
produced bio-oil. The reason for higher gas yield can also be because of
the presence of biomass (wood, food residue etc.) in the real MSW [89].
Since real MSW constitutes impurities, these impurities seem to play an
important role in influencing the composition of bio-crude oil (BCO)
[90]. The presence of impurities causes secondary thermal cracking of
waste, and hence the end-product yield is affected greatly. The varied
composition of MSW results in the presence of metals in the produced
BCO. Therefore, sand-made pyrolysis reactor can be employed. Sand
has the capacity to retain metallic species and hence the bio-oil would
be free of metallic pieces. Moreover, hot-gas filters should be used in
order to prevent flow of metals in the liquid fraction of MSW. The chars
produced also acts as a retainer and a lot of metallic species present in
real MSW are trapped by the solid fractions. [50] Moreover, the heating
value is also another challenge for bio-oil production. It is observed that
as the plastics concentration is increased in the MSW, the product after
pyrolysis has more BCO yield in gasoline range, however, greater bio-
mass percentage increases BCO yield in diesel range. Therefore, the
plastics concentration greatly effects the heating value of the bio-oil.
The presence of fine particles also degrades the quality of the produced
bio-oil. Traditional mechanical recovery techniques, such as sorting,
grinding, washing and extruding, can only be recycled for all plastic
scrap types of 15–20%. Beyond this level, plastics become con-
taminated with materials such as soil, dust, aluminum foil, food waste
and paper labels. Therefore, traditional upgrading techniques or using
ceramic membrane might be a plausible solution to ensure high quality
production of bio-oil. The upgrading techniques include refining and
blending the pyrolytic oil with conventional diesel or kerosene oil to
ensure that it is acceptable for the commercial applications. [69]
However, blending techniques has its own limitations. The physical
properties of the fuel lead to an increase in ignition time, thus reducing
the resulting torque [91]. Therefore, research is needed to explore new
methods for upgradation and purification of liquid oil.
However, it can be seen from the literature reviewed above, that
plastics provide values quite closer to conventional diesel as a fuel.
Therefore, the pyrolysis of plastic types is the major consideration to
obtain fuel that can replace commercial fossil fuels. However, since real
MSW is not usually classified, therefore, impurities cling on the surface
of plastics, thereby decreasing the favorable properties of gasoline,
diesel, etc. Therefore, careful collection and cleaning of the plastic
waste is required to yield substantial quantity of gasoline and light oil
by pyrolysis. For commercial use of plastics as a fuel, the capacity of the
already established pilot scale reactors needs to be increased five to six
times the current size of its facility [92]. However, due to dimensional
constraints and feed capacity issues, researchers have worked quite
little on commercial perspective. Moreover, there is a different tem-
perature distribution inside the reactor and hence safety of the plant is a
major concern. Furthermore, even distribution of catalyst is quite ne-
cessary on the catalyst bed to ensure efficient activity, therefore, this is
another geometrical constraint for the commercial use of plastics as
13
Fuel Processing Technology xxx (xxxx) xxx–xxx
fuel. [93] Moreover, some acids are formed during pyrolysis of PVC
plastics which can corrode the currently installed pilot scale systems.
Therefore, before commercializing this technology effort is needed to
ensure the handling and removal of higher thresholds of acids forma-
tion. Another challenge of plastic-to-fuel (PTF) conversion technology is
the variety in the scrap material. The scrap plastic material varies from
non-recycled caps, labels, agricultural plastics, oil bottles, auto-
shredder residue (ASR) plastics, scrap carpet, engineering grade resins,
mixed resin products to thermosets etc. The pilot systems of PTF
technology, which are adopted worldwide, cannot accommodate all the
types of these materials. Due to this, the economics and the quality of
the fuel is affected. All in all, though PTF technologies are quite ben-
eficial, but they are designed only to treat scrap plastics. This could be a
major problem for a locality that has landfill restrictions in the near
future and desires to look for possible alternatives to treat the total of
the MSW stream. According to the U.S. Environmental Protection
Agency (EPA) [94], plastics only represent a total of 12.3% of the waste
stream. PTF technologies are however reasonable option for commu-
nities that are looking at long-term solutions for extending the life of
landfills and finding new means to transform non-recycled plastics into
a resource. [92] Moreover, it is observed, from the pyrolysis and co-
pyrolysis of different MSW components, that polycyclic aromatic hy-
drocarbons (PAHs) are also produced. These PAHs are highly toxic and
dangerous for the human body. Therefore, researchers are investigating
on ideal blending ratios in order to ensure least production of PAHs and
better quality of fuel fraction. It is concluded from H. Zhou et al. that
maximum generation of PAH was found from the co-pyrolysis of PVC
and PS [95]. The plastics are long chain hydrocarbons, therefore on
pyrolysis, plastic fractions in MSW significantly produce PAHs. Hence, a
lot of further research is needed in order to reduce PAH formation while
producing high grade pyrolytic oil from plastics.
The type of pyrolysis process also affects the efficiency of MSW
pyrolysis process. Table 4 various case studies regarding thermal and
catalytic pyrolysis. The oil obtained from thermal pyrolysis is unstable,
acid-corrosive, low-grade, tarry and dis-colored. The catalytic pyrolysis
is better process, the quality of bio-oil is enhanced greatly but the
quantity is decreased. The catalytic pyrolysis and a variety of catalyst
used for MSW pyrolysis have been reviewed in the next section.
4. Effect of catalysts on pyrolysis products yield
The MSW pyrolysis yield pyrolysis liquids as by-products. There is a
dire need to convert these liquids into permanent gases. This is because
of the presence of water and organic compounds like alcohols, alde-
hydes, organic acids, ketones, phenols and ethers. These compounds
make the pyrolysis liquids highly oxygenated and acidic, therefore,
these cannot be used as fuel. [96] The research has been done in in-
corporating catalysts in order to post-treat the pyrolysis liquid, so that
the quality can be improved.
Catalysts overcome the lower efficiency of pyrolysis process, with
respect to endothermic reaction at elevated temperatures, by de-
creasing the activation energy and thus, enhancing the decomposition
of feedstock resulting in an increase in the product yield. The catalyst
are divided into three groups:
1. Primary catalyst – added directly to the feedstock [97]
2. Downstream catalyst - positioned in the secondary reactor, down-
stream from pyrolysis reactor [98]
3. Placed inside the pyrolysis reactor [99], provides direct contact with
yielded products (gas, liquid and tar).
The cost of catalyst is a major concern. Synthetic catalysts are less
favorable due to high cost. Therefore, different researchers have sug-
gested to reuse the catalysts or use catalysts in the form of certain
natural minerals or use the catalysts in less quantities [100]. Moreover,
fluid catalytic cracking (FCC) has also been used by some researchers to
A.T. Sipra et al.
Fig. 7. Mechanism of catalytic pyrolysis of MSW [102,103].
decrease the expense on catalyst during pyrolysis. But, catalyst's reuse is
a concern as coke formation on the catalyst shortens its life span and
function with the passage of time [35]. The catalytic reforming also
results in tar cracking due to extreme temperature. This results in the
evaporation of alkali and alkaline–earth metals (AAEM) into gaseous
phase. This paper reviews the major catalysts used in the recent pyr-
olysis studies, their effect on products yield and the potential to be used
as a fuel. Fig. 7 shows the mechanism of catalytic pyrolysis of MSW. The
primary and secondary reactions described in the figure will lead to
reduced tar vapors and increased gas and water production. Char re-
mains as a residue, when all volatile matter is removed from solids.
4.1. Effect of char as a catalyst on pyrolysis products yield
Char is one of the catalysts being widely used to improve the quality
of pyrolysis products. It is used because it is cheap, since it is available
from the pyrolysis process and hence, no external input of the catalyst is
required. Moreover, when volatiles from MSW are passed over char, the
latent heat of water vaporization is utilized and sensible heats of both
char and volatile are preserved. This is because volatile and char ga-
sification takes place simultaneously and hence, they come in contact
before any temperature drop. The alkali and alkaline-earth metallic
(AAEM) species are preserved in char from MSW pyrolysis as compared
to the one obtained from biomass. [101].
As mentioned in the previous section, in Table 4, N. Wang et al. has
investigated the influence of reforming temperature on the yield of
pyrolysis products (gas and liquid) with and without hot-char, as a
catalyst. The higher gas yield, lower liquid product and a raise in
carbon conversion ratio into syngas were observed, since around 60%
of the moisture in the volatile is expended in the reforming process. The
char reforming of volatile prompts increment of H2 yield from 18.9 to
41.6% in the syngas. Then, the pyrolysis oil turns out to be light and its
minor segments, for example, naphthalene, caprolactam and so on di-
minish, giving a potential other option to the syngas as energy bearer.
The effect of reforming on the characterization of char has also been
observed. The high heating value (HHV) of char decreases by reforming
and hence can be used for construction purposes or to trap heavy me-
tals. It was also noted that char reforming results in the decrease of SO2
and HCN contents while NO and NO2 contents increase in the syngas.
[70] N. Miskolczi et al. investigated that how seven different catalysts
has an effect on char formation using MSW and Municipal Plastic Waste
(MPW) as a feedstock. The char formation was greater by MSW pyr-
olysis. Ni-Mo-catalyst has a significant impact on char morphology. Due
to its extruded structure and greater BET surface area, char was finely
formed over the catalyst. [102].
Char such as activated carbon has great potential for the production
14
Fuel Processing Technology xxx (xxxx) xxx–xxx
of better quality pyrolytic products. Hence, this field needs to be further
studied. The char residue is present on the feedstock, when the feed-
stock is pyrolysed, the behavior of the char produced is determined by
following characteristics: (a) the disorganized and porous structures;
[103,104] (b) the presence of O-containing groups on the char surface;
[105,106] (c) the structure of the carbonaceous matrix; [107,108] (d)
active sites formed by the alkaline (Na, K) and alkaline earth (Mg, Ca)
species distributed in the char matrix [104,109,110]. The literature
suggests that co-pyrolysis of HDPE (MSW plastic waste component)
with other organic species can alter the combustion characteristics of
the char. It is assumed that the blending of natural matter with plastic
char can steadily affect the char morphology and creates hindrance in
its melting during burning. [111] Also, M. Hervy et al. [112] in-
vestigated pyrolysis char made from the waste generated on cruise ships
(used wood pallets (UWP), food waste (FW), coagulation flocculation
sludge (CFS)). Each of these components of MSW have different types of
minerals present. The synergistic effects of these feedstock resulted in
the decrease of chlorine release during pyrolysis. Moreover, due to
hydroxyapatite particles (Ca5(PO4)3(OH)), present in the char matrix,
the catalytic activity of the mixture of FW and CFS has been increased.
This further proves char to be an efficient low-cost and eco-friendly
catalyst for tar cracking. Char made from quick pyrolysis of other types
of plastics can also be studied and compared in future.
4.2. Effect of dolomite as a catalyst on pyrolysis products yield
Dolomite is an inexpensive and abundant material. M.He et al. used
calcined dolomite, as a catalyst, under high temperature to obtain in-
creasing gas yield while decreasing char and tar yield. In the presence
of catalyst, at 900 °C, the gas yield increases from 44.07 wt% to
78.87 wt% while the oil yield decreased from 37.98 wt% to 5.13 wt%.
This is due to the coke formation on the catalyst, oxygen removal from
water or evident increase in gas yield due to catalysis. The char yield
also decreases from 15.86 to 14.92 wt%. Therefore, in the presence of
catalyst, the syngas produced is quite useful and valuable product. It
can be used as a transportation fuel or directly as a MHV fuel. [71]
Calcined dolomite is also used by the researchers in order to eradicate
tar production in the product gas. However, this catalyst has a tem-
perature limitation and it actively functions only above 500 °C. [73].
4.3. Effect of zeolite catalyst on pyrolysis liquid oil
Zeolite has a microporous structure and high BET surface area. As
mentioned previously, M. Rehan et al. [72] mixed powdered zeolite
with PS plastic (feedstock) in the pyrolysis reactor, hence the third kind
of catalyst group was adopted. Both natural and synthetic zeolite was
A.T. Sipra et al.
used. A comparison between thermal and catalytic cracking was made.
It is observed that approximately 99% of liquid oils produced, con-
tained aromatic hydrocarbons. Though the catalytic pyrolysis decreases
the liquid oil yield from 80.8% to 52% but the quality of oil is improved
due to catalysis. The produced oil has chemical composition and HHVs
quite similar to diesel. The HHV of liquid oil after thermal cracking and
catalytic cracking with synthetic and natural zeolite as catalyst is found
to be 41.6, 40.6, 41.7 MJ/kg respectively. This value is quite near to
HHV of conventional diesel (43.1 MJ/kg). This gap of HHV is due to
greater amount of aromatic hydrocarbons in liquid oil. Therefore, re-
fining is necessary to use this produced oil. The catalytic cracking also
increases gas yield from 13% to 17.7% and char yield from 6.2% to
30.1%.
Natural zeolite was adopted by the researchers in order to avoid cost
expenditure on synthetic catalysts. Activated zeolite is stable at high
temperatures and has good crystalline properties. Therefore, it en-
hanced the secondary cracking of hydrocarbons resulting in an in-
creased yield of bio-crude oil (BCO) by 40.79%. [68] The existence of
activated zeolite during pyrolysis significantly improved the secondary
pyrolysis of small hydrocarbon chains, and as compared to the absence
of catalysts, the yield of BCO increased by about 40.79%. This means
that zeolite in the pyrolysis process has excellent productivity behavior
as a catalyst. [72].
4.4. Effect of Ni and Ru catalysts on hydrogen gas production
Since plastics in MSW has various chemical structures and hence
different reactivity, therefore, T. Namioka et al. used Ruthenium (Ru)
catalyst in order to reduce the fluctuation between the steam reforming
reaction rates of PS and PP. Previously Ni-based catalysts were to hy-
drogen gas from waste plastics. Ru proved to be quite effective in
bridging the gap between varying chemical structures, moreover, this
process required temperature lower than 200 K. This lower temperature
enhanced the thermal efficiency and inhibited the decomposition of
catalyst under high temperatures. [113].
4.5. Effect of other catalysts on pyrolysis products yield
Therefore, the catalyst use in pyrolysis optimizes the selection of the
product as well as decreases the energy used initially [114]. Along with
the above-mentioned catalysts, another economical enhancement of
pyrolysis via catalytic cracking is to blend the polymer waste in com-
bination with using a fluid catalytic cracking (FCC) system. These FCC
catalysts elevate the market feasibility of the transformation of plastic
waste into a FCC unit. However, the equilibrium FCC catalysts (zeolite
based) are efficient as compared to natural FCC's in pyrolysis process.
[115–117].
4.6. Limitations of catalytic pyrolysis and its solutions
The Section 4 highlights usage of various natural and synthetic
catalysts in the process of MSW pyrolysis. It also mentions the im-
portance of various catalysts due to their structure and compatibility
with the MSW feedstock. However, though the catalysts are quite
fruitful in the production of good quality pyrolysis product, but they
have certain limitations. Because of heterogeneity in MSW composition,
a lot of impurities and contaminants are present in the MSW. The cat-
alysts deactivate due to the presence of these impurities in the feed-
stock. Synthetic catalyst are deactivated at a much faster rate than the
natural catalyst. Because these catalyst are custom made and hence, are
affected more easily. It is also seen from the literature that the slow
pyrolysis conditions also restrict the catalyst to some selective proper-
ties. The full activation of the catalyst requires a relatively higher
temperature. Along with the reaction temperature, the particle size of
the catalyst is also a key factor in influencing the yield of the pyrolysis
products. The cracking reaction mention in Fig. 7 depends on active
15
Fuel Processing Technology xxx (xxxx) xxx–xxx
sites and acidity of the catalysts. For example, the chars contain
abundance of heavy metals, thus making it more active, as a catalyst,
for volatile reforming and tar cracking. However, heavy metal chars are
quite expensive as a catalyst, and the dumping of these chars is also a
problem due to the presence of heavy metals. Therefore, the structure of
the catalyst and its physical and chemical properties should be thor-
oughly examined before carrying out the pyrolysis process. Moreover,
the char formed as a by-product in the pyrolysis reaction also deposits
on the surface of the catalyst during the reaction. This creates hindrance
in the functioning of the catalyst. Therefore, a continuous supply of
catalyst is required. Moreover, the right placement of catalyst inside the
tub reactor should be done in order to avoid this issue. The surface area
of the catalyst is another factor which can limit the functioning of the
pyrolysis process. The higher the surface area, the better the pyrolysis
process. This results in good quality products even when the catalyst
was taken in low content [118,119].
5. Future work
Since the composition of MSW varies from region to region, there-
fore, pre-treatment methods like drying and shredding are quite ne-
cessary. A proper system needs to be devised with efficient pre-treat-
ment techniques in order to sort out the MSW accurately. The
techniques like vacuum pyrolysis for the retrieval of electronic printed
circuit boards and waste from animals should be further studied and
implemented [120,121]. The microwave assisted pyrolysis can also be
considered to increase the efficiency of the pyrolysis process. Moreover,
the installation of pyrolysis plants with gasification or combustion
systems needs to be operated at the commercial level. Similarly, the
large scale MSW treatment plants need to be set-up in order to bridge
the gap between MSW disposal and utilization rate. Since the 1980s,
Europe has been operating some pilot scale plants in Germany, Sweden
and Italy [122]. More plants on commercial scale need to be established
around the world in order to minimize the MSW disposal rate.
In addition, it can be seen from the literature that municipal solid
waste has different components, therefore, further studies are needed to
examine the synergistic effects of different waste components, and the
mixing ratios of these components in pyrolysis will affect the quality of
the pyrolysis products. HHVs should also be measured. Future scope
should also pay attention to how these co-pyrolytic products are sui-
table for use as fuel. However, it is necessary to strengthen the se-
paration technology to remove the moisture in the condensate, the
activation of chars is also needed with regard to adsorption character-
istics, so that the amount of solid residue in the pyrolysis process can be
reduced.
6. Conclusions
In this paper, co-pyrolysis of different components of MSW to obtain
fuel with high heating values has been reviewed. The aim is to provide
solution of the conventional fossil fuel deficiency and the reduction in
the environmental hazards due to pyrolysis. It is observed that sy-
nergistic interactions of various MSW components (especially plastics)
produce fuels with heating values comparable to conventional fossil
fuels. Therefore, pyrolysis of MSW has a great potential to be im-
plemented in the recycling industry.
This paper provides an extensive literature review on the influence
of pyrolysis products yield by using real MSW, plastics in MSW and
various MSW components as a feedstock. The challenges faced by MSW
pyrolysis are also mentioned in detail. The possible solutions are also
proposed in order to make MSW an efficient feedstock for the pyrolysis
process. However, the review has provided facts based on the small-
scale laboratory set-up. Efforts are needed to be made in order to
commercialize pyrolysis of MSW to obtain high graded fuel. Advanced
post-treatment methods needs to be employed to scale-up this process.
If such challenges are faced, then less expensive replacement of fossil
A.T. Sipra et al.
fuels, along with the reduction of MSW landfills, will be accomplished.
This will be a major breakthrough in the global energy industry.
However, substantial efforts are required to overcome this rising issue.
The catalytic process has also been discussed in this review paper.
The limitations of the catalyst due to its structure, physical properties
and chemical properties has also been mentioned. The use of synthetic
and natural catalysts has been discussed and it can be concluded from
the literature that the use of natural catalysts to avoid excessive cost
needs to be further discussed.
This review is limited to the co-pyrolysis of different components of
MSW. However, there is a need to discuss the effect of interaction of
MSW components (especially plastics) with biomass, to obtain high
quality fuel.
Acknowledgements
The authors would like to appreciate the support of the National
Natural Science Foundation of China (NSFC) (51476023), China
Postdoctoral Science Foundation (2016M600790) and the Fundamental
Research Funds for the Central Universities (No. 1191319722).
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