Renewable and Sustainable Energy Reviews 54 (2016) 421428

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Renewable and Sustainable Energy Reviews

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

Plastics to fuel: a review

Bidhya Kunwar a,n, H.N. Cheng b, Sriram R Chandrashekaran a, Brajendra K Sharma a
a
Illinois Sustainable Technology Center, University of Illinois, 1 Hazelwood Drive, Champaign, IL 61820, United States
b
USDA Agricultural Research Service, Southern Regional Research Center, 1100 Robert E. Lee Blvd., New Orleans, LA 70124, United States

art ic l e i nf o a b s t r a c t

Article history: The thermal and catalytic processes of converting waste plactics into fuels are promising techniques to
Received 1 June 2015 eliminate the refuse which otherwise is harmful to the enivironment, and decrease the dependence on
Received in revised form fossil fuels. Thermal degradation decomposes plastic into three fractions: gas, crude oil, and solid residue.
16 September 2015
Crude oil from non-catalytic pyrolysis is usually composed of higher boiling point hydrocarbons. The
Accepted 6 October 2015
optimization of conversion parameters such as the choice of catalyst, reactor design, pyrolysis tem-
Available online 11 November 2015
perature, and plastic-to-catalyst ratio plays a very important role in the efcient generation of gasoline
Keywords: and diesel grade fuel. The use of a catalyst for thermal conversion lowers the energy required for con-
Plastic waste version, and the catalyst choice is important for efcient fuel production. The suitable selection of cat-
Plastics pyrolysis
alysts can increase the yield of crude oil with lower hydrocarbon content. Co-pyrolysis of plastics with
Catalytic conversion
coal or shale oil improves crude oil quality by decreasing its viscosity. A large number of publications
Gasoline
Diesel have appeared on various processes, and continued improvements and/or innovations are expected in
Co-pyrolysis the future. Further investigations on the catalytic systems are required in order to advance the eld,
particularly to enhance the added value of fuels and to minimize the use of energy. This review aims to
provide both the highlights of the remarkable achievements of this eld and the milestones that need to
be achieved in the future.
& 2015 Elsevier Ltd. All rights reserved.

Contents

1. Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 421
2. Methods and processes available . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 422
3. Process optimization . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
3.1. Factors affecting the conversion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 423
3.2. Energy and mass balance . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
3.3. Kinetic studies . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
4. Examples of plastic-to-fuel processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
4.1. Non-catalytic processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 424
4.2. Catalytic processes. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 425
4.3. Conversion of PVC . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 426
4.4. Co-pyrolysis of plastics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 426
5. Techno-economic evaluation. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 426
6. Conclusions and future prospects . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 426
Acknowledgment . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427
References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 427

1. Introduction

n
Corresponding author. Plastics are produced in large quantities due to the high
E-mail addresses: bkunwar@illinois.edu (B. Kunwar),
demand of their use in agriculture [1], households [2], automobiles
hn.cheng@ars.usda.gov (H.N. Cheng), schandr@illinois.edu (S. Chandrashekaran),
bksharma@illinois.edu (B. Sharma). [3], packing materials [4], toys [5], electronics [6], and a variety of

http://dx.doi.org/10.1016/j.rser.2015.10.015
1364-0321/& 2015 Elsevier Ltd. All rights reserved.
422 B. Kunwar et al. / Renewable and Sustainable Energy Reviews 54 (2016) 421428

other applications [7]. The demand for plastics has increased by 5% Table 1
every year since 1990 [8]. The increase in plastics use corre- Elemental composition and higher heating value (HHV)a of various plastics repor-
ted by different research groups
spondingly increases the amount of plastic wastes being produced.
Plastic waste can be classied into at least two categories: muni- Investigator Plastics C% H% O% HHV (MJ/kg)
cipal and industrial [9]. Industrial plastics are generally more
homogeneous and contamination-free, making them useful for Sharma et. al [40] HDPE 83.9 14.9 0.74 49.4
downcycling into lower-grade plastic products. Municipal plastics Sorum et. al [44] HDPE 86.1 13.0 0.90 46.4
LDPE 85.7 14.2 0.05 46.6
tend to be more heterogeneous and contain extraneous materials. PP 86.1 13.7 0.20 46.4
In general, about 10.6 75.1 wt% of municipal wastes consists of PS 92.7 7.9 0.00 42.1
plastics [10,11]. Municipal plastic waste consists primarily of low- Encinar et. al [45] PS 90.2 8.5 1.30
density polyethylene (LDPE), high-density polyethylene (HDPE), PE 85.4 14.4 0.03
PP 85.5 14.4 0.08
poly(ethylene terephthalate) (PET), polypropylene (PP), poly-
Zhou et. al [46] PE 80.5 15.5 3.90
styrene (PS), and poly(vinyl chloride) (PVC) [8]. Overall, about 50-
70% of the total plastic waste is packaging materials derived from a
The higher heating value (also known gross caloric value) of a fuel is dened
polyethylene, polypropylene, polystyrene, and polyvinyl chloride as the heat released by a specied quantity of fuel (initially at 25 C) when it is
[12]. On average, polyethylene makes up the greatest fraction of all combusted and the products returned to 25 C, and where the latent heat of
vaporization of water is taken into account.
plastic wastes (69%), especially plastic bags [11], and polyethylene
comprises 63% of the total packaging waste [12].
needs [19]. Many countries spend a signicant portion of their
Polyethylene (PE, low density and high density) and poly-
gross national income (GNI) to purchase oil and gas. A number of
propylene (PP) are the most widely used plastics [13]. HDPE is
studies have been conducted to investigate alternative ways of
recyclable and can be found in plastic bottles, storage boxes, pipes
producing energy. Some of the alternatives for fossil fuel energy
and cable insulations, and many other uses. LDPE can be utilized
are biomass energy [30], wind energy [31,32], hydroelectric
for making computer parts, toys, soft bottles, wrappers, back
energy [33], and nuclear energy [34]. Bio-based oils such as palm
sheets for diapers, and numerous additional applications. In the
oil, soybean oil, corn oil, cottonseed oil and their derivatives are
packaging industry, all three polymers, PP, PS and PE, are widely
used as lubricants and fuel additives to replace petrochemicals
used [14,15]. A copolymer of ethylene and propylene is also fre-
[3539]. However, even these additional energy sources may not
quently employed, e.g., as a rubber and in computers [14]. Poly
completely solve the problem of increasing energy demand.
(vinyl chloride) (PVC) is another popular plastic that is associated
The challenges of plastic waste management and increasing
with a variety of applications, e.g., plumbing pipes, electrical cable
insulation, tubings, automobile seat covers, and rubber replace- energy demand can simultaneously be addressed by the produc-
ment in some applications [16]. Poly(ethylene terephthalate) (PET) tion of fuel from plastics, and a number of research groups are
is also a common polymer that has found many applications, e.g., currently developing this capacity. The fuels produced from plas-
lms, bers, and food containers and beverage bottles [17]. tics can be clean and have fuel properties similar to fossil fuels
Plastic disposal is a major concern in many countries, including [40]. HDPE, LDPE, and PP (plastics identication codes 2, 4 and 5,
the United States [12]. After its initial use, over 60% of the total plastic respectively) are polymers containing only carbon and hydrogen.
solid waste (PSW) produced is discarded in landlls throughout the Unlike biofuels, the absence of oxygen and higher carbon and
world [8]. Less than 10% of plastic waste is recycled [18]. This is hydrogen content (Table 1) in plastic fuels avoids the need of
problematic, as plastic waste is a major environmental threat due to further upgrading. The absence of water in plastic fuels makes the
its non-degradability [19,20], its potential health risks to aquatic and caloric value very high, and the absenceof oxygen content makes
terrestrial animals [21], and its impact on environmental pollution the fuel non-acidic and non-corrosive, unlike biofuel [4043].
[22]. The waste plastics ending up in ocean makes a huge plastic Therefore, conversion of these plastic wastes to usable oil is a
soup and garbage patch like the great Pacic garbage patch risking growing and important eld of study that can potentially mitigate
the health of aquatic animals. In the last 40 years the plastic waste in the energy crisis. However, the techno-economic evaluation plays
the North Pacic ocean has increased by 100-fold. The plastic foot- an important role in the commercial success of the plastics-to-fuel
print is consider more dangerous than carbon footprint [2325]. conversion. In this state-of-the-art review,we will examine the
Some of the proposed solutions for PSW management are incinera- relevant lab-scale processes and the literature to date.
tion or mechanical recycling. However, incineration can contribute to
pollution by causing harmful and toxic emissions [26]. Additionally,
both of these processes are costly and may or may not be econom- 2. Methods and processes available
ically viable in different situations [12,27].
Aside from the challenge of plastic waste disposal, another The production of fuel from plastics is one of the most
global issue is the energy crisis. Transportation consumes one demanding research topics throughout the world. Hydrocracking,
third of the worlds energy. The main energy sources for trans- thermochemical, and catalytic conversion are the most widely
portation are fossil fuels, coal, oil, and natural gas, all of which are used methods for fuel production from plastics [27]. Among them,
non-renewable sources of energy. Fossil fuels are also major thermochemical conversion/pyrolysis treatment seems to be the
sources of environmental pollution, greenhouse gases, and ocean dominant mode used.
acidication [19,28]. Today, these fuels are being consumed at an Thermochemical treatment breaks large polymers into smaller
unsustainably high rate throughout the world [29]. Even though hydrocarbons of various carbon numbers and boiling points in an
more than a hundred billion tons of oil and gas have been dis- inert, air-free, or controlled environment at elevated temperature
covered in the last 40 years [28], the rate at which it is consumed [9]. The hydrocarbons between the boiling points of 35 and 185 C
has also increased. The US alone consumes one quarter of the can be used as motor gasoline, between 185 and 290 C as diesel
global oil supply, while only having 1.6% of the total oil reserve. At #1, between 290 and 350 C as diesel #2, between 350 and 538 C
the current rate of consumption, the global supply of fossil fuels as vacuum gas oil, and 4538 C as the residue [40]. These frac-
will be depleted within 4070 years. Among 195 countries in the tions can be obtained in different proportions by the appropriate
world, only 40 can produce fossil fuel, and for some countries, choice of thermal treatment/degradation temperature, type
their independent oil reserves still do not satisfy all of their energy of plastics, degradation time, and catalyst type [43,47,48].
 B. Kunwar et al. / Renewable and Sustainable Energy Reviews 54 (2016) 421428 423

Table 2
Mass balance of crude oil, residue and gas yields on pyrolysis of polyethylene, polypropylene and polystyrene using various temperatures.

Investigation Plastics Reactor Pyrolysis temperature catalyst Crude oil (wt Residue (wt %) Gas (wt %)
(C) %)

William et Al. [18] PE Parr mini bench top 500 None 93 0.0 7.0
PP 95 0.0 5.0
PS 71 27 2.0
PET 15 53.0 32.0
Sarker et al. [19] Mixed Proprietary (Natural State 370420 None 90 5.0 5.0
Research Inc)
Alston et al. [6] Mixed 800 None 73 23.5 30.4
Sharma et al. [40] HDPE 2 L batch reactor 440 None 74 17.0 9
Buekens et al. [10] PP 740 None 48.8 1.6 49.6
PE 760 42.4 1.8 55.8
PS 581 24.6 0.6 9.90
Beltrame et al. [51] PE 400 None 44.0 30.0 20.0
H-Y-Zeolite 91.0 0.0 9.0
SilicaAlumina 93.0 7.0 0.0
600 None 29.0 65.0 6.0
Sarker et al. [52] PETE-1 Distillation unit 405 Ca(OH)2 14.25 (21.7 51.5 12.4
H2O)
Scott et al. [12] PE Activated carbon bed 515-795 None 8896
Miskolczi et al. [41] HDPE Continuous reactor 520 ZSM-5
PP None
Elordi et al. [43] HDPE Conical spouted bed 500 HZSM-5 5870
HY
zeolite
Uemichi et al. [53] LDPE Fixed-bed tubular ow reactor 425 HZSM-5 SiO2Al2O3
Lin et al. [54] Mixed Fluidized bed reactor 330-450 Hybrid uid catalytic crack- 1587
ing series

The product yields of liquid, gas, and residue vary depending on
the type of polymer, degradation temperature, and atmosphere.
Some data on product yields obtained for thermal treatments at
400800 C are presented in Table 2. Although the results vary
somewhat because they come from different studies, thermo-
chemical treatment seems to be a promising method of producing
hydrocarbons from polymers.
A subset of the thermal treatment is the gasication process. In
this case the plastic is decomposed to combustible gaseous pro-
ducts at high temperatures, usually with the help of an oxidizing
or a gasication agent [49,50]. Both of these techniques to convert
plastics to fuel do not have negative impacts on the environment.
Hydrocracking is the cracking of larger hydrocarbons, such as
polymers, into fuel-range hydrocarbons in the presence of
hydrogen at elevated temperatures [9,55]. Scott et al. [12] studied
polyethylene hydrocracking at 600 C in an activated carbon bed.
No char was formed in the process and the major products were
gases that had a hydrocarbon range of C5 ; this process produced
double the gas fractions of C5 that were produced from thermal
cracking in an inert atmosphere [12]. Hydrocracking is also more
effective when performed with a catalyst. The most widely used
hydrocracking catalysts are acidic supporting materials (alumina,
silicaalumina, zeolites) loaded with transition metals (Pt,Fe, Ni,
and Mo) [9]. For example, Ding et al. [55] used a hybrid catalyst
containing a 4:1 weight ratio of SiO2Al2O3: HZSM-5 loaded with
Ni or NiMo. The hydrocracking reaction was carried out at 375 C
and 1000 psig for 1 h. The optimal conditions resulted in conver-
sions up to 99%. The product contained mostly hydrocarbons with
a range of r C13 [55]. In general, catalytic hydrocracking improves
the conversion of polymers into hydrocarbons, compared to non-
catalytic hydrocracking.
In catalytic conversion, catalysts are added to pyrolysis reactions
to improve conversion, improve fuel quality, increase selectivity,
and lower the pyrolysis temperature and residence time [9]. The
acidic nature of most of the catalysts used enhances conversion by
protonating the defective sites of polymers forming on-chain
carbonium ions [10]. Selectivity and fuel quality vary with the
strength of the catalysts acidity. Acid catalysts with meso and
micropores give higher conversion. Primary cracking takes place in
the macroporous surface and, once the polymer is cracked, further
cracking is enhanced by micropores [41]. The use of a strong cat-
alyst results in the production of lower hydrocarbons ranging
between C3 and C5. A polymer-to-catalyst ratio of 10:1 yields 100%
conversion within an hour of contact time [26]. The catalysts used
for plastic upgrading are grouped into a few main categories: uid
cracking catalysts (FCC), reforming catalysts, and activated carbon
[10]. FCC catalysts include zeolite [10,41,43,56], silica-alumina [9],
and clay [9,12]. Reforming catalysts include transition metals
loaded in silicaalumina [10]. Activated carbon is also widely used
and can be loaded with or without transition metals [12,26]. The
life of a catalyst can be increased by using a two-step process that
involves thermal cracking followed by catalytic cracking [26].
3. Process optimization
Numerous studies have been conducted to optimize the dif-
ferent methods and processes involved. Examples are given in the
following sections.
3.1. Factors affecting the conversion
Many factors such as feed composition, catalyst type, particle
size, catalyst loading, and polymer-to-catalyst ratio affect conver-
sion and fuel quality. PE and PP decomposition is faster in the
presence of PS because it catalyzes the radical formation reaction.
Zeolite-based catalysts are more effective. Ultra-stable zeolites sig-
nicantly reduce the temperature of cracking. Acidic sites are also
very important in cracking; as pore size increases, hydrocarbons
further degrade into smaller hydrocarbons such as gas. Fe in char-
coal can catalyze the reaction by a radical formation reaction.
Reforming catalysts such as Pt/SiO2Al2O3 have multiple functions
for increasing the octane number without increasing the carbon
number. The metals in reforming catalysts catalyze hydrogenation
424 B. Kunwar et al. / Renewable and Sustainable Energy Reviews 54 (2016) 421428
and dehydrogenation, whereas acidic sites catalyze isomerization
reactions. Particle size also plays an important role in catalytic
reactions. Catalysts with smaller particle sizes have larger surface
areas for catalytic activities. However, catalysts with larger surface
areas may also have a smaller pore size for cracking. Another
important factor is catalyst loading. The catalyst can be loaded in
two different ways. The rst involves liquid phase contact, in which
the catalyst is mixed with plastic. However, the catalyst recovery is
poor in this method [9]. The second method involves vapor phase
contact, in which the catalyst is loaded into a basket [9,12,57,58].
However, conversion is not very effective due to the lack of direct
contact between the plastic and the catalyst.
3.2. Energy and mass balance
Some of the constraints in plastic pyrolysis are mass and energy
transfer due to the high viscosity and the low thermal conductivity
of plastics. The type of reactor utilized, operating conditions, and
product distributions are some of the factors affecting mass and
energy transfer [26]. Uniform heat distribution is very important for
effective mass and energy transfer, and it is integral to obtaining a
valuable and narrow range of hydrocarbons. Fluidized bed reactors
are among the reactors that facilitate the uniform distribution of
energy [59]. Sharatt et al. [60] performed the catalytic cracking of
HDPE with ZSM-5 in a uidized bed reactor, and were able to
obtain 465% of hydrocarbons with a range of C3C5. The screw kiln
reactor also has advantages over batch reactors for producing a
lower percentage of heavy products [61].
Molten plastics have high viscosity values. Therefore, it is very
important to reduce the viscosity for mass and heat transfer. This
can be done by mixing plastics with solvents or oil such as vacuum
gas oil (VGO) or waste lubricant oil. The use of lubricating oil [61]
and VGO lower the pyrolysis temperature, resulting in a higher
yield. Serrono et al. [61] mixed lubricating oil base and LDPE in a
range of concentration ratios. The reactions were run in a screw
kiln reactor in the presence of either HZSM-5 or Al-MCM-41 as a
catalyst. Complete conversion was obtained at a temperature
between 450 and 500 C. The major products using HZSM-5 were
aromatics, whereas the use of Al-MCM-41 primarily resulted in
olens.
3.3. Kinetic studies
Generally, the kinetics of pyrolysis can be studied by per-
forming plastic degradation via thermogravimetric analysis (TGA)
techniques. Kinetic evaluation involves measuring the amount of
mass degraded versus the temperature at regular time intervals
[62]. Results of kinetic studies performed by various research
groups demonstrate high variability in the rate of the reactions
due to variation in pyrolysis parameters, including the measure-
ment system, heating rate, sample mass, and experimental errors
[63]. Kinetics studies also show that plastic degradation is a rst-
order reaction, consisting of a single-step degradation process,
except with PVC [63]. Sorum et al. [44] used a single reaction
model for kinetic study, using PS, LDPE, HDPE, and PP, and deter-
mined that the activation energy of PS degradation is as low as
311.5 kJ/mole, and HDPE is as high as 445.1 kJ/mole. The difference
in activation energy is due to the difference in the number and
type of bonds, such as CC, CH, and C C. The dissociation energy
of CC is 347 kJ/mole, whereas that of C C is 611 kJ/mole [44].
Dou et al. [64] used refuse plastic fuel for their kinetic study. The
rate limiting steps were surface chemical reactions and gas diffu-
sion through the surface; activation energy was 70.2 and 65.9 kJ/
mol, respectively. Yoon et al. [65] performed statistical analyses
including pentagonal statistical design and F-test to study the
effect of temperature and reaction time on the pyrolysis of waste
plastic with waste motor oil. The maximum oil yield from LDPE
(95%) and HDPE (92%) was obtained at 450 C with a 30-min
residence time, whereas a high PP oil yield (84%) was observed at
426 C with a 12-min residence time. These results showed that PP
has a lower activation energy compared to the activation energies
of LDPE and HDPE. The co-processing of waste oil and plastics falls
within the pentagonal design boundary; the oil yield values were
within 90 to 99% condence limit with runs performed at 460 C
and with a residence time of 30 min.
4. Examples of plastic-to-fuel processes
4.1. Non-catalytic processes
Thermal treatment of plastic wastes usually involves a pyrolysis
process conducted in the absence of oxygen at a temperature
between 350 and 900 C [9,66]. Under these conditions, a wide
distribution of hydrocarbonsis obtained. The weight percent of
gases produced increases with temperatures at 650700 C [26].
Oil containing aromatic hydrocarbons is achieved at  500 C [26].
However, the product distribution depends on the type of the
reactor used as well as on the heat distribution during pyrolysis.
Fluidized-bed reactors are utilized for the uniform distribution of
heat. The addition of a solvent during cracking is also used for
decreasing the viscosity of the products, altering the nal product
distribution [26]. Sarker et al. [19] chose temperatures between
370 and 420 C for the degradation of waste plastics into liquid
slurry in the presence of oxygen. The liquid slurry was then con-
densed and converted into ve liquid fractions. The yield was 5%
gas, 5% char, and 90% liquid. The range of hydrocarbon was
between C4H8 and C28H58 [19].
Waste electrical and electronic equipment (WEEE), which
includes household appliances, communications equipment, elec-
tronic tools, toys, sports equipment, and medical devices, con-
stitutes another major source of waste plastic in landlls. WEEE
comprises a wide range of polymers with only some being reusable
and recyclable. Alston et al. [6] pyrolyzed WEEE at 800 C. The
sample contained a wide range of polymers such as LDPE, PP, PET,
PVC, and PS. The gas was 30.445.5% of the nal product, with
99.9% of those gases being CH4 to styrene. High reaction tempera-
tures and fast pyrolysis result in products with higher gas percen-
tages. Oils and tars were 27.846.7% of the nal product, with 93%
of the oils/tars being benzene and toluene. The remaining 23.5
26.7% of the nal product was composed of PAHs, alcohols, acids,
aldehydes, nitriles, and residues. The total potential fuel was 72
73.4% of all the product mass. Williams et al. [18] pyrolyzed waste
plastic mixtures and individual plastics in the presence of nitrogen
and hydrogen at 500 C. Nitrogen was used for pyrolysis, whereas
hydrogen was used for liquefaction. Hydrogen gas, tetralin, or acidic
catalysts were employed as hydrogen donors in many reactions
[6769]. Intermolecular interactions and catalytic activity are pro-
moted by using mixed plastic feedstocks. The compositions of the
gas products obtained from plastics mixtures and individual plastics
were very similar, whereas higher concentrations of alkanes and
aromatics were observed in oil products from mixed plastics [70].
Sharma et al. [40] pyrolyzed HDPE (grocery bags) in a 2 L batch
reactor and analyzed the properties of hydrocarbons produced from
the reaction using simulated-distillation, gas chromatography-
ame ionization detector (GC-FID), size exclusion chromatography
(SEC), nuclear magnetic resonance spectroscopy (NMR), and Fourier
transform-infrared spectroscopy (FT-IR). Other fuel properties were
studied by wet chemistry techniques. The properties of blends of
pyrolyzed hydrocarbons with ultra low sulfur diesel (ULSD) and
biodiesel were also studied. The oil produced from pyrolysis had
parafnic hydrocarbons as high as 96.8%, a heating value of
 B. Kunwar et al. / Renewable and Sustainable Energy Reviews 54 (2016) 421428
Table 3
Fuel properties and ASTM method for analysis.
Properties [38, 44, 71] Method
Moisture content ASTM E 790-87
Ash content ASTM E 830-87
High heating value ASTM D 3286-73
Volatile matter ASTM E 897-88
Boiling point distribution ASTM 7169-05
Viscosity ASTM D 445-95
Pour and cloud points ASTM D-5949
46.16 MJ/kg, and an absence of any oxygenated products, making it
suitable for diesel fuel and petroleum diesel blends. The simulated
distillation result showed the presence of approximately 20% motor
gasoline, 41% diesel #1, 23% diesel #2, and 16% vacuum gas oil. For
convenience, the ASTM methodsused for evaluating the above fuel
properties are presented in Table 3 [40].
Many patents have been published on the economical and
efcient conversion of plastics to fuel and lubricant oil. As an
example, US patent 6,822,126 B2 [72] discloses a three-step pro-
cess for converting plastics to lube oil. The rst step is melting the
plastic between 150 and 350 C in an inert environment without
depolymerizing. The second step is to pyrolyze the molten plastics
in a ow reactor between 500 and 650 C in an inert condition.
This technique reduces the contact time to 1560 min. The pyr-
olyzed sample is hydrotreated at 190340 C. The nal step is
catalytic dewaxing and recovery of lubricating oil. US patent
7,252,691 B2 [73] discloses a high-value fuel production technique
from municipal waste plastics. This process involves removal of
recyclable waste, anaerobic digestion, de-watering, and pelletizing
of municipal waste (free of recyclable and hazardous material)
with high BTU-value waste such as carpet or rubber. These pellets
were either used alone or mixed with shredded tires for boiler
fuel. The fuel was cleaner than coal or oil. US patent 6,862,568 B1
[74] describes a method in which plastics were decomposed in an
oil medium. This method lowers the need for high temperatures
that are required for decomposition of plastics to fuel. The
mechanism involves free radicals for depolymerization, which
were provided from precursors such as PVC, nylon, or initiator
compounds containing carbonnitrogen, carbonoxygen. The oil
medium avoids the recombination of reactive products at a tem-
perature below 375 C.
4.2. Catalytic processes
Sarker et al. [52] used waste polyethylene terephthalate (PETE-
1) to produce hydrocarbons via thermal degradation at 405 C,
where Ca(OH)2 was used for cracking terephthalic acid. The range
of hydrocarbons obtained was from C3 to C27 with very few major
components containing oxygenated compounds. Scott et al. [12]
pyrolyzed polyethylene in an activated carbon bed at 515 to795 C
in an inert atmosphere. At 600 C, 50% of the hydrocarbons pro-
duced were liquid, with boiling points ranging from 40 to 240 C.
The gas products were at a hydrocarbon range of C5 . At higher
temperatures, mostly char was obtained. When the same reaction
was carried out with an activated carbon bed containing Fe, the
percentage of aromatic hydrocarbons increased, while the C5 gas
percentage decreased. However, when the reaction was carried
out in the presence of hydrogen, char formation was suppressed,
the percentage of gases products increased, and the percentage of
liquid hydrocarbons increased from 52% to 60%.
Product distribution also depends on the type of polymer, the
structure of raw materials, and their sources. Miskolczi et al. [41]
used two sources of polymer, including HDPE and PP from agri-
cultural and industrial sectors. Plastics from the agricultural sector
425
include elements such as Ca, P, S, and N, and the fuel properties
were distorted due to the presence of these contaminants. How-
ever, the use of a catalyst has the additional benet of reducing the
concentration of impurities because they attach to the catalyst and
are thus removed from the hydrocarbons. Pyrolysis was carried
out in the presence and absence of ZSM-5 catalysts at 520 C. The
percentage of gases, lighter hydrocarbons, and gasoline products
were higher with the trials performed in the presence of this
catalyst. Macro- and micropores play an important role in product
formation. The primary cracking takes place in the macroporous
surface. The catalyst also promotes the formation of isobutane.
Higher volatiles were obtained from PP in comparison to HDPE
[41]. Elordi et al. [43] used HZSM-5, HY, and zeolite catalysts at
500 C in a conical spouted bed reactor. The yields were compared
with the uidized bed reactor yields from the literature. The major
differences in pyrolysis yields were based on the properties of the
catalysts. ZSM-5 has a smaller pore size, resulting in a higher yield
of lighter olens, aromatics, and gases. Non-aromatic compounds
and higher hydrocarbons are predominantly produced during
pyrolysis runs that utilized a catalyst with larger pores.
Catalysts used in combination, such as HZSM-5 and SiO2Al2O3,
seem to be more benecial than used individually. The major
product of cracking plastics in the presence of HZSM-5 is a
gasoline-range lower aromatic compound, whereas the presence
of SiO2Al2O3 produced a lower quality fuel. The usage of dual
catalysts results in a high yield of gasoline with a high octane
rating. Uemichi et al. [53] used a dual catalyst comprised of HZSM-
5 and SiO2Al2O3. The octane rating of the resulting product was
improved due to the combination of the two catalystsproperties of
mesoporosity and acidity. Lin et al. [54] investigated the produc-
tion of fuel by pyrolyzing mixed plastic waste with a pre-used
hybrid uid catalytic cracking catalyst in a uidized bed reactor at
temperatures ranging from 330 to 450 C. Lower temperatures
increased the length of plastic degradation time. Hybrid catalysts
varying in meso- and microporosity enhanced the selectivity of
hydrocarbon products. Catalyst deactivation can be prevented by
performing the process in two steps: the rst step is pyrolysis, and
the second step is a catalyst reforming reaction in which gases
from the pyrolysis product are treated at higher temperatures for
selectivity [47]. Syamsiro et al. [47] used this two-step process for
the production of gas from municipal plastic waste. The rst step
was pyrolysis at 450 C, followed by a catalytic reforming reaction
at 450 C. The two catalysts used for this reaction were natural
zeolite and Y-zeolite. The nature of plastics and catalysts strongly
inuenced the quality of liquid, gas, and solid obtained from the
reaction. The natural zeolite has a smaller surface area compared
to Y-zeolite. Therefore, the liquid yield was higher using natural
zeolite, whereas the gas yield was higher using Y-zeolite. The
higher surface area means more contact between the catalyst and
pyrolysis gas, which cracked to produce gaseous products. The
heating value was comparable for pyrolysis using natural zeolite
and Y-zeolite. Solids left after the reaction also have high heating
value and can be used as a blend with coal [47].
Kumar et al. [48] studied the performance of fuel produced
from catalytic pyrolysis of waste HDPE as a blend with diesel.
Kaolin clay was employed as a catalyst for oil production from
HDPE. Performance of the blend was reduced compared to that of
diesel fuel. NOx emission increased with an increase in plastic oil
percentage. The CO2 emission percentage was lower than that of
diesel in all blends.
Among the patent literature, US patent 4,851,601 [75] discloses
a method in which plastics were softened and melted in a thermal
cracking zone between 390 and 500 C followed by catalytic
cracking between 250 and 340 C. The level of molten plastic was
maintained by continuous stirring. The maximum heat transfer
was achieved by using inorganic materials called red mud.
426 B. Kunwar et al. / Renewable and Sustainable Energy Reviews 54 (2016) 421428
The acidity of red mud is lower than the zeolites that are used in
the catalytic cracking step. Zeolites such as ZSM-5, ZSM-11 are
employed for catalytic cracking. The use of zeolites increases the
selectivity, reduces the operation temperature, and enhances
isomerization.
From these studies, we can see that the use of FCC can be very
effective in producing lower hydrocarbons, and the choice of cat-
alysts and pyrolysis temperatures can inuence solid, liquid, and
gas yields. For example, zeolite catalysts produce higher quality
fuel than silicaalumina, and can increase the yield of aromatic
hydrocarbons. Catalysts lower the activation energy of conversion
of plastic to hydrocarbons, and therefore lower energy require-
ments for the conversion.
4.3. Conversion of PVC
The major problem with the conversion of PVC to hydrocarbons is
the production of large quantities of corrosive HCl, which is unde-
sirable in fuel applications. Currently, a signicant amount of
research is being conducted to investigate the removal of chlorine
from PVC before it is pyrolyzed or the use of adsorbent to remove HCl
immediately and minimize its adverse effect [76]. The most widely
used adsorbents are FeOOH, Fe3O4 and Fe2O3. The production of fuel
from PVC commonly involves a two-step reaction, with the rst step
involving dechlorination at lower temperatures and the second step
involving catalytic conversion at higher temperatures [56,77]. Lopez-
Urionabarrenechea et al. [76] used ZSM-5 in conventional pyrolysis,
in catalytic stepwise pyrolysis, and in the non-catalytic dechlorina-
tion step followed by catalytic pyrolysis. Dechlorination is effective at
300 C. Therefore, unlike other methods that require higher reaction
temperatures, dechlorination followed by catalytic pyrolysis effec-
tively reduces the liquid chlorine content by more than 75%. The
utilization of a mechanochemical method in which PVC and CaO
are ground with a planetary ball mill and washed with water is
another method of removing chlorine without any heat application
[78]. The speed of the mill enhances dechlorination [78].
4.4. Co-pyrolysis of plastics
Plastics have also been co-pyrolyzedfor fuel production with
many other materials, including coal [69,79], oil shales [58],
vacuum gas oil (VGO) [27], petroleum waste [77], and waste motor
oil [65]. Co-pyrolyzing with these materials increases conversion
and decreases the viscosity of the product.
Aboulkas et al. [58] co-pyrolyzed HDPE, LDPE, and PP with oil
shales for fuel production. Plastics such as PP were used as cata-
lysts for degradation of oil shales. The effect of temperature on fuel
production was studied between 400 and 600 C at a heating rate
of 10 C/min. The maximum oil yield was achieved between
500 and 525 C. This process was compared to pyrolysis of oil
shales without plastics, and it was determined that oil yield was
higher in the presence of plastics, demonstrating the promoter
property of plastic in producing oil from oil shales. Ali et al. [77]
used PVC with and without petroleum residues and VGO for their
thermal and catalytic pyrolysis studies. Petroleum residue was
engaged in the one-step reactions, while VGO was used for the
two-step reactions. The use of VGO gave better results than runs
utilizing petroleum residue. The dechlorination of PVC occurred
below 350 C in an N2/H2 environment. Pyrolysis runs utilizing
hydrocracking catalysts in the presence of VGO and in a hydrogen
environment resulted in the production of transportation grade
fuel. The conversion of PS with petroleum residue was above 90%,
which is higher than the products from the conversion of PE and
PP. Miranda et al. [80] co-pyrolyzed plastics from household waste
with rubber tire waste. The main aim of that work was to nd a
possible route for efcient conversion into fuel by performing a
kinetic study. The major effect of the product composition and
yield depends on temperature used for the pyrolysis. The best
temperature for pyrolysis is approximately 500 C.
Co-pyrolysis of plastic with other materials such as petroleum
residue can improve the conversion to about 90%. From these
studies, we can see that the optimal process is co-pyrolysis of PS
with petroleum residue. Oil shale conversion to oil is also
improved in the presence of a plastic.
5. Techno-economic evaluation
The cost of fuel production from plastic is affected by various
factors such as capital investment, xed costs, production costs
and variable costs. Some of the variable costs (such as type of
plastics, transportation, separation of plastic from municipal
waste, labor, mainatance cost, laboratory cost, staff, rent, waste
calorie value, electrical and heat generation efciencies of the
pyrolysis units and most importantly energy used for the pro-
duction) must be considered while calculating the return on
investment (ROI) [81,82]. The cost of each step varies from U.S. $65
to $400 per ton [41]. The labor cost makes a huge difference in ROI.
ROI is the prot before taxes per total capital investment [82]. A
techno-economic analysis of a mixed plastics in Netherlands
shows that Bubbling Fluidzed Bed (BFB) reactor which operates at
740 C have ROI of 21.7%, a Rotating Cone Reactor (RCR) which
operates at 625 C have ROI 14.2%, while a Circulating Fluidized
Bed (CFB) which operates at 840 C have ROI of 29.5%. The energy
recovery is not 100%; therefore, a lower pyrolysis temperature is
benecal from economic and environmental prospective [82]. The
estimated capital investment of CFB pyrolysis plant which has a
capacity of 50 kton/year is between 7.84 and 11.2 million USD [82].
Another study by Shelley et al. [83] shows that the 15% ROI can be
achieved by setting the tipping fee between $35 and $45 and
feeding rate on a reactor to 200 t/day [83]. Salem et al. [81] studied
the thermo-chemical coversion of plastics in UK. The study shows
that the hydrocracking has a better ROI when compared to low
temperature pyrolysis (LTP). At the scale of 150 kton per annum,
the ROI is 53% whereas with LTP the ROI is 43%. However, the net
present value and pre-tax prots is higher in hydrocarking than
LTP [81]. Arena et al. [84] studied the techno-economic aspect of
uidized bed gasication unit for conversion of plastic into energy
in Italy. The study shows that with 23.7% energy conversion ef-
ciency the ROI is 8.3% when the plant costs is 4.79 k/kWe and
operating costs is 0.74 (k/y)/kWe. The operating costs include all
the variable cost [84].
6. Conclusions and future prospects
Fuel production from plastics is attractive because it simulta-
neously addresses the issues of waste management and alternative
energy generation. The optimization of conversion parameters
such as the choice of catalysts, reactor design, pyrolysis tempera-
ture, and plastic-to-catalyst ratio plays a very important role in the
efcient processing of gasoline and diesel grade fuel. The use of a
catalyst for thermal conversion lowers the energy required for
conversion, and catalyst choice is important for efcient fuel
production. A catalyst with higher acidic properties and a higher
porosity can enhance conversion; for example, FCC catalysts cat-
alyze the production of aromatic and gaseous hydrocarbons,
whereas dual catalysts like zeolite and metal loaded catalysts can
be used for producing hydrocarbons and isomerized products,
which increase the octane rating of fuels. Uniform distribution of
heat and mass is another important factor in conversion.
 B. Kunwar et al. / Renewable and Sustainable Energy Reviews 54 (2016) 421428
A uidized bed reactor is an excellent choice to ensure uniform
distribution of heat, resulting in better conversion.
Despite the recent advancements in plastic conversion tech-
nology, several issues remain. A major challenge with the pro-
duction of fuel from plastic solid waste is the presence of PVC,
which produces HCl gas during pyrolysis. However, researchers
have been able to remove chlorine to some extent by using HCl
adsorbents to pretreat the plastics.
Catalysts will also need improvement. For example, it will be
useful to use dual catalysts with a combination of high acidic prop-
erties, porosity and hydrogenation properties, identify accessible and
cheaper catalysts to use on large scales, and to prevent deactivation
and increase catalyst reuse. In fact, the use of metal-loaded biochar
may partly mitigate the high cost of catalysts. It is very important to
devise efcient methods to produce fuel from mixed plastics, or to
exclude or remove PET and PVC from mixed plastics before pyrolysis.
The product yield and quality can be improved by nding alternative
heating modes such as IR and microwave heating to reach the nal
temperature quickly. A thorough study of the effect of heating rates
on product yields and distribution will be very important to produce
fuel-range hydrocarbons.
There are many other factors that affect the economics of fuel
production in terms of raw material handling, such as collection,
classication, washing and shredding, transportation, electric energy,
heating gas, and cooling water. The cost of each step varies from U.S.
$65 to $400/ton [41].The landll costs in USA may vary from $25 to
$150/ton depending on the region of the the country [83]. It was
reported that a well-run curbside recycling program can cost, under
general circumstances, between $50 and $150/ton [85]. Therefore,
the cost of recycling plastic is relatively inexpensive compared to the
production of fuel from plastic, and the cost of fossil fuel is currently
cheaper than the production of fuel from plastics [41]. However, the
demand of fossil fuel, the issue of disposing of plastic waste and
environmental effect make the production of fuel from plastic eco-
nomically attractive in the longer term. Certainly continued research
and development is needed in this eld.
Acknowledgment
Mention of trade names or commercial products in this pub-
lication is solely for the purpose of providing specic information
and does not imply recommendation or endorsement by the U.S.
Department of Agriculture. USDA is an equal opportunity provider
and employer.
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