Pyrolysis of plastic waste for liquid fuel production as prospective energy resource

Pyrolysis of Plastic Waste for Liquid Fuel Production as

Prospective Energy Resources
Vrushabh Dharmik, Wallabh Borkar, Zia Ul Haque Khan, Prarthana Langi
Guide: Prof. M. A. Suryawanshi
Chemical Engineering Department, Bharati Vidyapeeth College of Engineering, Navi Mumbai
Maharashtra, Bharat

Abstract: 1. Introduction:
The worldwide plastic generation expanded In order to overcome the challenges faced for
over years because of the variety applications of recycling such as the needs of sorting that is
plastics in numerous sectors that caused the labor intensive, a much more reliable method is
accumulation of plastic waste in the landfill. established. Nowadays, converting the waste
The growing of plastics demand definitely into valuable energy resource has been a
affected the petroleum resources availability as brilliant way to fully utilize the waste in order to
non-renewable fossil fuel since plastics were the meet the increased energy demand. Plastic
petroleum-based material. A few options that wastes can be turned into valuable energy since
have been considered for plastic waste they are derived from petrochemical source
management were recycling and energy which having significant calorific value. The
recovery technique. Nevertheless, several conversion can be made possible through
obstacles of recycling technique such as the several thermal treatments technologies such as
needs of sorting process that was labor intensive gasification, pyrolysis, plasma process and
and water pollution that lessened the process incineration [1]. Among all these methods,
sustainability. As a result, the plastic waste pyrolysis is the most desirable process since the
conversion into energy was developed through initial volume of the waste is significantly
innovation advancement and extensive research. reduced, more energy can be recovered from the
Since plastics were part of petroleum, the oil plastic waste by producing varieties of products,
produced through the pyrolysis process was said requires lower decomposition temperature and
to have high calorific value that could be used low capital cost [1].
as an alternative fuel. This paper reviewed the
Pyrolysis is the process of thermally degrading
thermal and catalytic degradation of plastics
long chain polymer molecules into smaller, less
through pyrolysis process and the key factors
complex molecules through heat. The process
that affected the final end product, for instance,
requires intense heat with shorter duration and
oil, gaseous and char. Additionally, the liquid
in absence of oxygen. The three major products
fuel properties and a discussion on several
that are produced during pyrolysis are oil, gas
perspectives regarding the optimization of the
and char which are valuable for industries
liquid oil yield for every plastic were also
especially production and refineries. Pyrolysis
included in this paper.
was chosen
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 Pyrolysis of plastic waste for liquid fuel production as prospective energy resource

by many researchers since the process able to Municipal plastic waste consists primarily of
produce high amount of liquid oil up to 80 wt. low density polyethylene (LDPE), high-density
% at moderate temperature around 500⁰C. In Polyethylene (HDPE), polyethylene
addition, pyrolysis is also very flexible since the terephthalate) (PET), polypropylene (PP),
process parameters can be manipulated to polystyrene (PS), and polyvinyl chloride (PVC).
optimize the product yield based on preferences. Overall, about 50- 70% of the total plastic waste
The liquid oil produced can be used in multiple is packaging materials derived from
applications such as furnaces, boilers, turbines polyethylene, polypropylene, polystyrene, and
and diesel engines without the needs of polyvinyl chloride [5]. On average,
upgrading or treatment [5]. The oil produced polyethylene makes up the greatest fraction of
from biomass pyrolysis has received positive all plastic wastes (69%), especially plastic bags,
notice as a more environmentally friendly fuel and polyethylene comprises 63% of the total
because it contributes to reducing the amount of packaging waste.
CO2 in the atmosphere. Unlike recycling, the
process handling is also much easier and
flexible than the common recycling method 2. Methods and processes available:
since it does not need an intense sorting process,
The production of fuel from plastics is one of
thus less labor intensive.
the most demanding research topics throughout
Plastics are produced in large quantities due to the world. Hydrocracking, thermochemical, and
the high demand of their use in agriculture, catalytic conversion are the most widely used
households, automobiles, packing materials, methods for fuel production from plastics.
toys, electronics, and a variety of other Among them, thermochemical
applications. The demand for plastics has conversion/pyrolysis treatment seems to be the
increased by 5% every year since 1990 [3]. The dominant mode used. Thermochemical
increase in plastics use correspondingly treatment breaks large polymers into smaller
increases the amount of plastic wastes being hydrocarbons of various carbon numbers and
produced. Plastic waste can be classified into at boiling points in an inert, air-free, or controlled
least two categories: municipal and industrial environment at elevated temperature [4]. The
[4]. Industrial plastics are generally more hydrocarbons between the boiling points of 35
homogeneous and contamination-free, making and 185 °C can be used as motor gasoline,
them useful for down-cycling into lower-grade between 185 and 290 °C as diesel #1, between
plastic products. Municipal plastics tend to be 290 and 350 °C as diesel #2, between 350 and
more heterogeneous and contain extraneous 538 °C as vacuum gas oil, and 4538 °C as the
materials. In general, about 10.675.1 wt. % of residue [6]. These fractions can be obtained in
municipal wastes consists of plastics [5]. different proportions by the appropriate choice
of thermal treatment/degradation temperature,
type of plastics, degradation time and catalyst
type.

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 Pyrolysis of plastic waste for liquid fuel production as prospective energy resource

Table 1 [7]
Mass balance of crude oil, residue and gas yields on pyrolysis of polyethylene, polypropylene and polystyrene using various

temperatures.

had a hydrocarbon range of C5þ; this process

produced double the gas fractions of C5þ that
The product yields of liquid, gas, and residue
vary depending on the type of polymer,
degradation temperature and atmosphere. Some
were produced from thermal cracking in an inert
data on product yields obtained for thermal
atmosphere [8]. Hydrocracking is also more
treatments at 400–800 °C are presented in Table
effective when performed with a catalyst. The
1 hydrocarbons from polymers. A subset of the
most widely used hydrocracking catalysts are
thermal treatment is the gasification process. In
acidic supporting materials (alumina, silica–
this case the plastic is decomposed to
alumina and zeolites) loaded with transition
combustible gaseous products at high
metals (Pt, Fe, Ni, and Mo) [4]. For example,
temperatures, usually with the help of an
Ding et al. [9] used a hybrid catalyst containing
oxidizing or a gasification agent [7]. Both of
a 4:1 weight ratio of SiO2–Al2O3: HZSM-5
these techniques to convert plastics to fuel do
loaded with Ni or NiMo. The hydrocracking
not have negative impacts on the environment.
reaction was carried out at 375 °C and 1000 psig
Hydrocracking is the cracking of larger
for 1 h. The optimal conditions resulted in
hydrocarbons, such as polymers, into fuel-range
conversions up to 99%. The product contained
hydrocarbons in the presence of hydrogen at
mostly hydrocarbons with a range of rC13 [9].
elevated temperatures [4]. Scott et al. [8] studied
In general, catalytic hydrocracking improves the
polyethylene hydrocracking at 600 °C in an
conversion of polymers into hydrocarbons,
activated carbon bed. No char was formed in the
compared to non-catalytic hydrocracking.
process and the major products were gases that
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 Pyrolysis of plastic waste for liquid fuel production as prospective energy resource
Although the results vary somewhat because
they come from different studies,
thermochemical treatment seems to be a
promising method of producing hydrocarbons
from polymers.
hydrocarbon [10]. Overall, PET and PVC had
the lowest calorific value below 30 MJ/kg due
to the presence of benzoic acid in PET and
3. Liquid fuel properties from pyrolysis of
chlorine compound in PVC that deteriorated the
plastics:
fuel quality. Benzoic acid also consisted of
Table 2 summarized the fuel properties of the aromatic ring that explained the low calorific
liquid oil produced in pyrolysis process. The value in PET. Overall, Table 1 clearly depicted
experimental calorific value of HDPE, PP and that the physical properties of plastics pyrolysis
LDPE are all above 40 MJ/kg and were oil were very close to the properties of
considered high for energy utilization. The commercial gasoline and diesel. Therefore,
calorific value of PS was commonly lower than plastic pyrolysis oil has very high potential to be
the polyolefin plastic due to the existence of the used as new energy resources.
aromatic ring in the chemical structure which
had lesser combustion energy than the aliphatic

Table 2 [11]
Fuel properties of plastic pyrolysis oil - Commercial Standard Value (ASTM 1979)
Physical Proprties PET HDPE PVC LDPE PP PS Gasoline Diesel

(1) Sarker et al. [11] used waste

polyethylene terephthalate (PETE1) to
4. Catalytic and Non-Catalytic Processes:
produce hydrocarbons via thermal
Catalytic Processes – degradation at 405 °C, where Ca(OH) 2

4
 Pyrolysis of plastic waste for liquid fuel production as prospective energy resource
was used for cracking terephthalic acid. catalytic chamber used was fluidized
The range of kind of catalytic chamber. The
atmosphere was maintained neutral
using N2 gas at atmospheric pressure. In
this process, space time was taken of
about 20 minutes and the Nitrogen
flowrate was taken of 70mL/min. The
hydrocarbons obtained was from C3 to C27 catalyst to feedstock ratio was varied as
with very few major components containing 0.6, 1.3, 1.5, 2, 2.5 and 2.71 for various
oxygenated compounds. Scott et al. [12] results. The best result was obtained at
pyrolyzed polyethylene in an activated 600 ᵒC and catalyst to feedstock ratio of
carbon bed at 515 to795 °C in an inert 2.5. Without refining or distillation, the
product obtained was under ready jet
fuel category. The catalyst giving best
atmosphere. At 600 °C, 50% of the quality fuel was estimated to
hydrocarbons produced were liquid, with
boiling points ranging from 40 to 240 be NORIT GAS 1240 and followed by
°C. The gas products were at a NORIT C GRAN.
hydrocarbon range of C5þ. At higher
temperatures, mostly char was obtained.
When the same reaction was carried out Non-Catalytic Processes –
with an activated carbon bed containing
(1) Thermal treatment of plastic wastes
Fe, the percentage of aromatic
usually involves a pyrolysis process
hydrocarbons increased, while the C5þ
conducted in the absence of oxygen at a
gas percentage decreased. However,
temperature between 350 and 900 °C
when the reaction was carried out in the
[4]. Under these conditions, a wide
presence of hydrogen, char formation
distribution of hydrocarbons is obtained.
was suppressed, the percentage of gases
The weight percent of gases produced
products increased, and the percentage
increases with temperatures at 650–700
of liquid hydrocarbons increased from
°C. Oil containing aromatic
52% to 60%.
hydrocarbons is achieved at 500 °C.
(2) Yayun Zhang, Dengle Duan [13] used 6
However, the product distribution
different grades of activated carbons, at
depends on the type of the reactor used
temperature range from 400-650 °C. The
as well as on the heat distribution during
plastic used contained polystyrene (PS),
pyrolysis. Fluidized-bed reactors are
polyethylene (PE), polypropylene (PP),
utilized for the uniform distribution of
polyethylene terephthalate (PET) and out
heat. The addition of a solvent during
of which the degraded gases were
cracking is also used for decreasing the
condensed and collected which had
viscosity of the products, altering the
composition as C4-C23 carbon chains, out
final product distribution. Sarker et al.
of which 71.8% chains were aliphatic
[12] chose temperatures between 370
and 28.2% chains were aromatic. The
and 420 °C for the degradation of waste
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 Pyrolysis of plastic waste for liquid fuel production as prospective energy resource
plastics into liquid slurry in the presence higher gas percentages. Oils and tars
of oxygen. The liquid slurry was then were 27.8–46.7% of the final product,
condensed and converted into five liquid with 93% of the oils/tars being benzene
fractions. The yield was 5% gas, 5% and toluene. The remaining 23.5– 26.7%
char, and 90% liquid. The range of of the final product was composed of
hydrocarbon was between C4H8 and PAHs, alcohols, acids, aldehydes,
C28H58 [12]. nitriles, and residues. The total potential
(2) Waste electrical and electronic fuel was 72– 73.4% of all the product
equipment (WEEE), which includes mass. Williams et al. [7] pyrolyzed
household appliances, communications waste plastic mixtures and individual
equipment, electronic tools, toys, sports plastics in the presence of nitrogen and
equipment, and medical devices, hydrogen at 500 °C. Nitrogen was used
constitutes another major source of for pyrolysis, whereas hydrogen was
waste plastic in landfills. WEEE used for liquefaction. Hydrogen gas,
comprises a wide range of Pyrolysis of tetralin, or acidic catalysts were
plastic waste for liquid fuel production employed as hydrogen donors in many
as prospective energy resource 8 reactions. Intermolecular interactions
polymers with only some being reusable and catalytic activity are promoted by
and recyclable. Alston et al. [14] using mixed plastic feedstock. The
pyrolyzed WEEE at 800 °C. The sample compositions of the gas products
contained a wide range of polymers such obtained from plastics mixtures and
as LDPE, PP, PET, PVC, and PS. The individual plastics were very similar,
gas was 30.4–45.5% of the final product, whereas higher concentrations of alkanes
with 99.9% of those gases being CH4 to and aromatics were observed in oil
styrene. High reaction temperatures and products from mixed plastics.
fast pyrolysis result in products with

5. Conclusion: selection. The sustainability of the process is

unquestionable since the amount of plastic
Pyrolysis process was chosen by most
wastes available in every country is reaching
researchers among other thermal treatment
millions of tons. With the pyrolysis method, the
technologies mainly because of its potential to
waste management becomes more efficient, less
convert the most energy from plastic waste to
capacity of landfill needed, less pollution and
valuable liquid oil, gaseous and char. The
also cost effective. Moreover, with the existenc
flexibility that it provides in terms of product
preference could be achieved by adjusting the
parameters accordingly. The pyrolysis could be
done in both thermal and catalytic process.
However, the catalytic process provided lower of pyrolysis method to decompose plastic into
operating temperature with greater yield of valuable energy fuel, the dependence on fossil
liquid oil for most plastics with the right catalyst fuel as the non-renewable energy can be

6
 Pyrolysis of plastic waste for liquid fuel production as prospective energy resource
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