1. Seminar report 2019-20 Plastic waste into fuel using pyrolysis process
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1.1 INRODUCTION
The usage of plastic has exploded worldwide leading to increase in researches to search for
an alternate application of used plastics. Plastics are non-biodegradable polymers mostly
containing carbon, hydrogen, and few other elements. Economic growth and changing
consumption and production patterns are resulting into rapid increase in generation of waste
plastics in the world Due to its non-biodegradable nature, the plastic waste contributes significant
problem for waste management. Waste plastics like polyethylene used for domestic and industry
purpose are not recycled for about 43% of its volume.
Due to lack of integrated solid waste management, most of the plastic waste is neither
collected properly nor disposed of in appropriate manner to avoid its negative impacts on
environment and public health. On the other hand, plastic waste recycling can provide an
opportunity to collect and dispose of plastic waste in the most environmental friendly way and it
can be converted into a resource. . In general, the conversion of waste plastic into fuel requires
feed stocks which are non-hazardous and combustible. The composition of the plastics used as
feedstock may be very different and some plastic articles might contain undesirable Substances
nitrogen, halogens, sulphur or any other hazardous substances which pose potential risks to
humans and to the environment. The broad classification of plastic includes high density
polyethylene, low density polyethylene, polypropylene and polystyrene. Also, plastics are
classified by their chemical structure of the polymer's backbone and side chains. Most of the
plastics are recycled and sometimes they are not done so due to lack of sufficient market value
and energy consumption. Ever increasing diesel consumption, large outflow of foreign exchange
and concern for environment have prompted developing countries like India to search for a
suitable environmental friendly alternative to diesel fuel. The countries have to simultaneous
address the issues of energy insecurity, increasing oil prices and large-scale of unemployment.
This seminar deals with an objective to convert plastic waste in to fuel.
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1.1.1 Fuel Demand
The present rate of economic growth is unsustainable without saving of fossil energy like crude
oil, natural gas or coal. International Energy Outlook 2010 reports the world consumption of
liquid and petroleum products grows from186.1 million barrels per day in 2007 to 92.1 million
barrels per day in 2020 and1110.6 million barrels per day in 2035 and natural gas consumption
increases from1108 trillion cubic feet in 2007 to 156 trillion cubic feet in 2035. This way, the oil
and gas reserve available can meet only 43 and 167years further. Thus mankind has to rely on
the alternate/renewable energy sources like biomass, hydropower, geothermal energy, wind
energy, solar energy, nuclear energy, etc. Waste plastic to liquid fuel is also an alternate energy
source path, which can contribute to depletion of fossil fuel as in this process liquid. Fuel with
similar properties as that of petrol fuels is obtained.
Fig: 1 Gasoline consumption per capita (kg/oil)
(Source: https://www.economicshelp.org)
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2.1 PYROLYSIS
Pyrolysis is generally defined as the controlled heating of a material in the absence1of oxygen. It
involves a change of chemical composition and is irreversible. The word is coined from
the Greek-derived elements pyro "fire" and lysis “separating".Pyrolysis is most commonly used
in the treatment of organic materials. It is one of the processes involved in charring wood. In
general, pyrolysis of organic substances produces volatile products and leaves a solid residue
enriched in carbon, char. Extreme pyrolysis, which leaves mostly carbon as the residue, is
called carbonization. The process is used heavily in the chemical industry, for example, to
produce ethylene, many forms of carbon, and other chemicals from petroleum, coal, and even
wood, to produce coke from coal.Aspirational applications of pyrolysis would
convert biomass into syngas and biochar, waste plastics back into usable oil, or waste into safely
disposable substances. There are mainly 3 types of pyrolysis. Mainly thermal Pyrolysis, Catalytic
Pyrolysis, Catalytic Hydrogenation Pyrolysis.
2.1.1 Thermal Pyrolysis
It is the process of heating of plastic material in an inert atmosphere, a process that decomposes
the organic part of the plastic polymer material and generates liquids and gases that are used as
fuels and/or raw materials. This method is suitable for complex polymer waste that contains a
number of highly mixed materials and prior separation step is not needed. Thermal pyrolysis is
done at temperatures ranging between 400 to 800deg C.It shows that fuel oil yield is highest at
reaction temperatures between 400 to 450degC.
2.1.2 Catalytic Pyrolysis
It is the process of heating of the material in an inert atmosphere in the presence of catalysts, a
process that decomposes organic part of the plastic polymer material and generates liquids and
gases that are used as fuels and /or raw materials. This method is done at temperatures ranging
between 350 to 550 °C.It has following advantages over thermal pyrolysis,
1. Reduction of time and temperature of the reaction, with the consequent decrease in
energy consumption,
2. Better selectivity to desired compounds depending on the characteristics of the catalyst,
3. Avoiding the formation of undesired compounds, for example, inhibiting the formation of
halogenated compounds from samples containing PVC.
Disadvantages of using catalysts as follows
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1. cost of the catalysts
2. recoverability of the catalysts
3. Reusability of the catalysts.
2.1.3 Catalytic Hydrogenation Pyrolysis
In this pyrolysis. By using hydrogen atmosphere along with catalytic conversion to increase
saturated compounds in resulting fuel oil.
Fig: 2 Simplified
depiction of pyrolysis
chemistry
(Source:www.ggogle.com/pyrolysischemisty)
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3.1 METHODOLOGY
Fig: 3 Schematic diagram of Experimental setup
(Source: IRJET, Plastic waste into fuel using pyrolysis process)
3.1.1 Condenser
It cools the entire heated vapour coming out of the reactor. It has an inlet and an outlet for cold
water to run through its outer area. This is used for cooling of the vapour. The gaseous
hydrocarbons at a temperature of about 350°C are condensed to about 30 – 35°C.
3.1.2 Reactor
It is a stainless steel cylindrical container of length 1000mm, internal diameter 300m, outer
diameter 320mm sealed at one end and an outlet tube at the other end. The whole cylindrical
container is placed inside the reactor. The external heating is carried out using the raw material
viz., cole, wood, coke, etc., below the container and inside the reactor. The reactor is made with
the following: stainless steel, mild steel and clay for lagging. The reactor is heated to a
temperature of about 450°C and more.
Fig: 4 Waste-Plastic-Pyrolysis-Plant-3D-Models.jpg
(Source: https://bestonpyrolysisplant.com)
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4.1 PROCESSOF PLASTIC PYROLYSIS
Thermal cracking process without catalyst was used in converting waste plastic into liquid fuel.
Only one type of waste plastic is selected for this particular experiment i.e., Low density
polyethylene. Waste plastic are solid soft form. Collected waste plastic was cleaned using liquid
soap and water. Washed waste plastics are cut into 3-5 cm size to fit into the reactor
conservatively. For experimental purpose we used 6.5 Kg of LDPE. The experiment is carried
out under a closed air system with no vacuum process applied during this thermal cracking
process. We used low density polyethylene plastics in a batch process system because conversion
temperatures for these plastics are relatively low. Heat is applied from 100°C at start to begin
melting the waste plastics, the melted waste plastic turn into liquid slurry form when temperature
is increased gradually. When temperature is increased to 270° C liquid slurry turns into vapour
and the vapour then passes through a condenser unit. At the end we collect liquid fuel. Between
100º C and 250º C around 20 -30% of the fuel is collected and then when raised to 325º C the
next 40% is collected and finally when held at 400º C the yield is fully completed. During the
thermal cracking process plastic portions are not and finally when held at 400º C the yield is
fully completed. During the thermal cracking process plastic portions are not broken down
immediately because plastics have short chain hydrocarbon to long chain hydrocarbon. 1st stage
of heat applied breaks down only the short chain hydrocarbon. When temperature profile is
increased the plastic carbon-carbon bond breakdown slowly. As the temperature is increased the
long chains are breakdown step by step. During in this thermal cracking process some light gas
such as methane, ethane, propane and butane are produced. These compounds are not able to
condense because they have negative boiling point. These light gases could be alkane or alkene
group and it can also contain CO or CO2 emissions. Light gas production percentage is about
6%. This gas portion analysis is under consideration. The method which is considered for
treating the light gas is an alkali wash system. After experiment is concluded some solid black
residue is collected from the reactor. This solid black residue percentage is about 4%. Liquid fuel
yield percentage is 90%. To purify the liquid fuel a purification system to remove water portion
and ash or fuel sediment is used and it is also filtered with filter paper to remove some solid
waste mixed in fuel while collecting in bottle. Liquid fuel density is 775kg/m3. Finally we
obtained 4 liters of plasto-fuel.
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Fig.5. An illustration of Conversion of a Mixture of Plastic Wastes to Fuel.
(Source:www.google.com/pyrolysis)
4.1.1 Characteristics of plastic pyrolysis oil
4.1.1.1 Physical properties
The experimental calorific value of HDPE, PP and LDPE are all above 40MJ/kg and were
considered high for energy utilization. The calculated calorific value for both HDPE and PP were
above 45 MJ/kg, and thus very closer to the commercial fuel grade criteria of gasoline and diesel.
The calorific value of PS was commonly lower than the polyolefin plastic due to the existence of
the aromatic ring in the chemical structure which had lesser combustion energy than the aliphatic
hydrocarbon. Overall, PET and PVC had the lowest calorific value below 30 MJ/kg due to the
presence of benzoic acid in PET and chlorine compound in PVC that deteriorated the fuel
quality. Benzoic acid also consisted of aromatic ring that explained the low calorific value in
PET. API gravity was the method used for measuring the density of the petroleum relative to
water which was established by the American Petroleum Institute (API) and was also known as
specific gravity. The API gravity of HDPE and PP were 27.48 and 33.03 respectively while the
densities were 0.89 and 0.86g/cm3 accordingly. The API gravity of PVC was very close to the
diesel API gravity value which was 38.98. On the other hand, the API gravity of LDPE was
approaching the gasoline standard value which was 47.75. Therefore, all of these values were
comparable to the commercial diesel fuel except LDPE which was comparable to the standard
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gasoline. In terms of density, all values seem comparable with the commercial standard value of
both gasoline and diesel.
Table 1 The effect of carrier gas on the product yield and composition
(Source: S.D. Anuar Sharuddin et al./Energy Conversion and Management)
Table 2 Fuel properties of plastic pyrolysis oil.
(Source: S.D. Anuar Sharuddin et al./Energy Conversion and Management)
The viscosity on the other hand was defined as a measurement of the fluid resistance to flow.
Viscosity is very crucial in petroleum industry since it determines how easy the oil can flow from
the reservoir to the well during extraction process and also plays a crucial role in fuel injection
process. The value of kinematic viscosity of all plastics were very close with the viscosity of
diesel except for PS which the viscosity value was closer to the gasoline viscosity. In terms of
ash content, HDPE and PP had negligible ash content and these indicated that the HDPE and PP
pyrolysis oil was free from any metal contamination. The ash content in PS was also lower than
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the standard diesel which was less than 0.01 wt%. LDPE had slightly higher ash content of 0.02
wt% but the value was still tolerable since the difference was very minimal.
Besides that, the research octane number (RON) and motor octane number (MON) which was
important to characterize the anti-knock quality for the gasoline range (C6–C10) was also
determined. The high octane number indicates the better anti-knock quality that the fuel
possesses. Knock is usually caused by the rapid combustion of gasoline in an engine that
produces an explosive noise and degrades the engine performance over time. Therefore, the anti-
knock quality is very important to avoid engine damage. The MON and RON value for HDPE
pyrolysis oil was 85.3 and 95.3 respectively. PP pyrolysis oil had higher MON and RON value
which were 87.6 and 97.8 accordingly. The RON value for PS also matched the range of
standard gasoline value which was in the range of 90–98. This suggests that the octane number
of HDPE, PP and PS were comparable with commercial gasoline (MON= 81–85, RON =91–95).
Pour point is known as the temperature at which the fluid stops to flow .Generally, the
increase in viscosity may cause the fluid losses its flow characteristic. Liquid fuel that has lower
pour point has lesser paraffin content but greater aromatic content HDPE, PP and PS pyrolysis
oil had lower pour point around -5,-90C and -67 0C respectively than the commercial diesel
which having the pour point of 6C. This indicates that the pyrolysis oil obtained from plastic
pyrolysis were rich with aromatic content. This relates to the lower calorific value of HDPE, PP
and PS pyrolysis oil in comparison with the commercial gasoline and diesel.
One of the important properties in fuel handling to prevent fire hazard during storage was the
flash point. Flash point of the liquid is defined as the lowest temperature at which the liquid may
vaporize and form a mixture in the air that ignites when an external flame is applied. The flash
point of HDPE, PVC and LDPE pyrolysis oil were very close to the commercial gasoline. This
indicates that the flash point of those three plastics was comparable to the light petroleum
distillate fuel. The flash point of PP and PS were lower than both commercial gasoline and
diesel. This shows that PP and PS pyrolysis oil easier vaporized and thus need an extra
precaution when handling.
Aniline point is a temperature at which the aniline compound (C6H5NH2) forms a single phase
with the liquid oil .Lower aniline point indicates the higher existence of aromatic compound.
Oppositely, the higher aniline point indicates the higher amount of paraffin compound in the oil.
Olefin has the aniline point in between those aromatic and paraffin value. The aniline point of
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HDPE and PP pyrolysis oil were 450C and 400C respectively which were much lower than the
commercial gasoline and diesel. Gasoline and diesel were both having aniline point of 71oC and
77.50C. This once again proves that the pyrolysis oil obtained from HDPE and PP was rich with
aromatic compounds.
Diesel index evaluates the ignition quality of the diesel fuel in which the higher diesel index of
the fuel indicates the higher quality of the fuel. The diesel index of the HDPE pyrolysis oil was
31.05 while PP was 34.35. Even though the diesel index was not meeting the ASTM 1979
standard, the mixing of additives to fuel oil can improve the ignition quality of the diesel fuel and
has shown growing acceptance nowadays. Therefore, the liquid product produced by HDPE and
PP met the commercial fuel grade and suggested to be a blend of gasoline and diesel
hydrocarbon range.
4.1.1.2 Chemical properties
In PET pyrolysis, Cepeliogullar and Putun reported that almost half of the liquid oil around
49.93% contained benzoic acid compound. The corrosiveness of the acid made it unfavorable to
be used in thermo chemical conversion system. As the reaction proceeded during pyrolysis, PET
tended to lose more aliphatic compound than the aromatic compound and this resulted in higher
liquid yield than PVC. According to Cepeliogullar and Putun, PET pyrolysis yielded 23.1 wt%
liquid oil while PVC only produced 12.3 wt% liquid oil. This shows that the liquid yield of PET
almost doubled the PVC. The low liquid yield in PVC indicated the high production of gaseous
product during the pyrolysis. High temperature during the pyrolysis would cause the dehydro
chlorination process to occur, consequently increased the gaseous product and reduced the liquid
oil yield. The release of hydrochloric acid and chlorine compound during the PVC pyrolysis
indicated that the liquid oil was not suitable to be used as fuel since it depreciated the fuel
quality. It was clearly seen that most of the PVC compound was decomposed to naphthalene and
its derivative around 33.55%.In PP and HDPE pyrolysis oil, Jung et al observed that the liquid
oil contained primarily aliphatic, monoaromatic and polyaromatic compounds. As for the PP
fraction, the increase in the temperature reduced the aliphatic concentration in the oil to 2.9 wt%
at 7460C. In contrast, high aliphatic concentration was found in HDPE pyrolysisoil around 20
wt% at 728 0C. This indicates the complexity of the HDPE structure to degrade during thermal
degradation process. Besides that, the BTX aromatics in PP pyrolysis oil (53wt %) were found
higher than in the HDPE fraction (32wt %) at the same temperature as mentioned previously.
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The most abundant compound comprised in the BTX aromatics was the benzene. The
concentration of benzene and toluene increased with the temperature except xylene compound
which did not have a significant difference with the temperature. In terms of hydrocarbon
product distribution, paraffin’s were the main product observed (66.55%) for PP derived liquid
compared than HDPE (59.70%). Hence, PP pyrolytic oil was more value added than the HDPE
derived liquid since paraffin’s released extra energy for combustion than other hydrocarbon
groups such as olefins and naphthenes. As for the LDPE derived liquid oil, Williams and
Williams reported that the aliphatic compound which consisted of alkenes, alkenes and
alkadienes was the main composition found. As the temperature increased, the aliphatic
concentration was in decreasing trend. However, the aromatic compound showed an opposite
trend in which the aromatic concentration increased with the temperature. Among the aromatic
compound, benzene and toluene concentration showed a dramatic increase as the temperature
increased except xylene and this observation matched the trend observed in PP and HDPE
pyrolysis as reported by Jung et al.However, it should be noted that the chemical concentration
depends strongly on the pyrolysis operating temperature. According to Williams and Williams
the oil contained no aromatic and polyaromatic hydrocarbon at temperature of 500–550 0C.
Nevertheless, a significant increase in the single ring aromatic compound and polycyclic
aromatic compound (PAH) happened when the temperature increased to 7000C that comprised
around 25% of the liquid oil composition. For PS pyrolysis oil, Onwudili et al. reported that the
benzene, toluene and ethyl benzene were three main components in the PS oil product that
increased with the temperature. On the other hand, styrene monomer kept decreasing with the
temperature and this suggest that the styrene radical formed during the degradation process of PS
was very reactive. The styrene and monoaromatics were among the major components in the
liquid oil product that they covered around 80 wt% in the liquid fraction. These components
were categorized in the low boiling point fraction of less or equal to 2000C.
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(a) (b)
(c)
Fig: 6 Comparison of obtained Plasto-Fuel with various properties (a) Comparison of
Kinematic Viscosity & Dynamic Viscosity (b) Comparison of gross calorific valve (c)
Comparison of Sulfur content and Carbon Residue
(Source: IRJET, Plastic waste into fuel using pyrolysis process)
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Sl no Properties Regular Petrol Regular Diesel Plasto– Fuel
1. Specific Gravity 0.742 0.85 0.775
2. Density (Kg/m3) 742 850 775
3. Kinematic
Viscosity(centistokes)
2.42 3.05 2.525
4. Dynamic Viscosity
(centipoises)
1.796 2.592 1.957
5. Gross Calorific Value
(KJ/Kg)
46858 42000 42686
6. Flash Point ( 0C) 23 50 29
7. Fire Point ( 0C) 29 56 36
8. Sulphur (% w/w) 0.0015 < 0.002 0.002
9. Carbon residue (% w/w) < 0.01 0.01 Nil
Table -3: Comparison of obtained Plasto-Fuel with Regular Petrol and Diesel
(Source: IRJET, Plastic waste into fuel using pyrolysis process)
4.1.2 Pyrolysis products and their possible applications
Usually the pyrolysis of waste is aimed at energy recovery, because the products often have good
properties as fuels. Moreover, energy (especially electricity) is always a desirable product, which
is easy to sell. Additionally, parts of the products can be combusted in order to meet the
pyrolysis energy demand. Pyrolysis also makes it possible to convert waste into an energy source
for the home and on a larger scale pyrolysis plants may use the pyrolysis products for other
purposes, which increases the profitability of the process. The complex composition of pyrolytic
oil and some properties of char could make them favorable as a raw material for some industry
sectors and a few propositions are mentioned below.
4.1.2.1 Pyrolytic gas
In general, it is possible to say that the composition of the pyrolytic gas is strongly dependent on
the pyrolysis temperature and feedstock. Slow pyrolysis of biomass waste such as wood, garden
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waste and food residue at low temperatures (below 4000C) produces small amounts of gas, which
is high in CO2, CO and light hydrocarbons. The yields of gas at these conditions usually do not
exceed 30 wt% of products. Increasing the temperature causes an increase in gas yields, because
of the secondary reactions and partial char decomposition. The gas heating value from slow
pyrolysis is around 10 – 15 MJ/Nm3 and varies in dependence on temperature and heating rate.
Fast pyrolysis of biomass produces gas with a heating value around14 MJ/Nm3. On the other
hand, higher temperatures (above 7000C), especially when pyrolysis is combined with
gasification, produces syngas, which contains more hydrogen and carbon monoxide. In this case
gas is the main product of the process. The pyrolysis of plastics produces pyrolytic gas, of which
the major components are hydrogen light hydrocarbons: methane, ethane, ethene, propane,
propene, butane and butane. This gas has a significant calorific value, e.g.a heating value of gas
from PP and PE varied between 42 and 50MJ/kg.
4.1.2.2 Pyrolytic oil
Pyrolytic oil offers more opportunities for use than gas, but, depending on the composition of the
feedstock and the process parameters, the composition of the liquid product from pyrolysis may
differ radically. Pyrolytic oils originating from biomass consist largely of the following
compounds: acids, sugars, alcohols, ketones, aldehydes, phenols and their derivatives, furans and
other mixed oxygenates. Phenolic compounds are often present in high concentrations (up to 50
wt %), consisting of relatively small amounts of phenol, eugenol, cresols, xylenols, and much
larger quantities of alkylated (poly-) phenols. They can be used for the production of heat,
electricity, synthetic gas or chemicals. Temperatures between 500 and 600 0C provide the highest
yields of oil, when biomass is processed with heating values of around 15–20 MJ/kg. On the
other hand, pyrolytic oil from plastics has a higher heating value, about 30 – 45 MJ/kg,
depending on the polymer and it contains a smaller aqueous fraction. The oil from the pyrolysis
of PP and HDPE with Gasoline and Diesel. Physical properties such as viscosity, the research
octane number and the motor octane number, pour point, flash point or Diesel index could be a
good indication of pyrolytic oil quality as a fuel. The heating value of oils from mixed plastic
waste could be estimated at 40 MJ/kg.
4.1.2.3 Pyrolytic char
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Pyrolysis conditions are usually optimizedin order to maximize the liquid and gas products;
however, a solid fraction named as pyrolytic char is also produced. This char mainly consists of a
carbon-rich matrix that contains almost all the inorganic compounds present in the raw wastes
and a significant amount of condensed by-products formed during the pyrolysis process and
dispersed throughout the solid porous structure. The heating value of char obtained from co-
pyrolysis of waste (mixture of biodegradable and non–biodegradable) is approximately 34
MJ/kg, which is comparable with typical coal. However, as expected some heavy metals and
other hazardous elements, like S, Cl and N, may also be retained in the solid products. Therefore,
it is important to fully characterize chars to assess their impact on the environment and humans.
In general, this product can be combusted to provide energy for the pyrolysis process or other
purposes.
Char obtained in pyrolysis is not only a good fuel, but it can also be processed into activated
carbon. This possible application was investigated by Zeng et al.Char reactivity was measured in
order to find a correlation between the evolution of the char surface area and pore volume and
the temperature and heating rate. Experiments were performed at four heating rates of 5, 50, 150
and 45C/s to the final temperatures of 800, 1200 and 200C; and then two other temperatures of
600C and 160 0C with the heating rate of 5 C/s were used. The chars obtained mainly consisted
of carbon with mass content higher than 75%. At a temperature of 2000C the char was
completely carbonized with almost 100% carbon content. Additionally, the BET surface area
increased from 70 m2/g to 110 m2/g and adsorption volume increased also from0.0028cm3/g to
0.047cm3/g when the temperature increased from 800 0C to 1200 0C with a heating rate of 50
0C/s. Southern yellow pine wood pyrolyzed at 474 0C in a pilot scale pyrolysis plant produced
bio-char with 70.27% of fixed carbon and 186 m2/g measured surface area.
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4.1 CONCLUSION
The continual increase in the amount of waste produced by society makes clear the urgent need
for developing new and better methods of disposal. Traditional waste management methods like
composting, landfilling and incineration are outdated and should be replaced by modern,
effective and easy-to-operate solutions, such as pyrolysis.
Pyrolysis allows the utilization of all carbon-containing materials both organic and inorganic as
opposed to commonly used biological methods of waste disposal. In general, slow pyrolysis of
organic waste (wood, food and garden waste, paper, natural textiles etc.) is usually carried out at
temperatures about 400– 5000C and heating rates of 5–200C/min under nitrogen flow. Fast
pyrolysis is more complicated, but it is also used. Addition of inorganic waste (plastics, artificial
textiles, tyres) results in improved product quality: gas contains more light hydrocarbons and less
CO2; liquid contains a lower aqueous fraction and a greater oil fraction, and has a better heating
value. The combination of organic and inorganic waste occurs in MSW, thus pyrolysis is a
favorable method for waste treatment. Over 14 million tons of plastics are dumped into the
oceans annually, killing about 1,000,000 species of oceanic life. The transformation about these
waste plastic under fuel serves us will spare the sea marine an aggregation. The oil that has been
generated by the LDPE plastic by prescribed experimental process shows that the properties are
very much comparable to the petrol. Ultimately, pyrolysis of LDPE does not only recover the
energy contained in the plastic, but also manage the environment by alternate disposal technique
of the waste plastic. This double beneficiary, if will exist just Concerning illustration long
Likewise the waste plastics last, in any case will definitely gatherings give a solid stage to us
with expand on a sustainable, clean and green future.
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