Conversion of waste plastic to fuel oil using different catalysts.

1. EFFECT OF CATALYSTS ON
CONVERSION OF PLASTIC WASTE
TO FUEL OIL
Under the guidance of
Dr. G .T Mohanraj , Assistant professor,
Department of Chemical Engineering ,
BIT Mesra
Rakhi Sharma
ME/CHE/10002/15

2. INTRODUCTION
 Economic growth and changing in consumption, resulting into the
rapid increase in generation of waste plastics.
 The change in consumption is from 5 to 100 million tonnes in 5
decades.
 Decomposition time of plastic is longer, so it challenging to dispose
it for solid waste management team.
 So to dispose plastic conversion is performed by various methods
like ; Slow, fast, flash, Microwave, Catalytic, Non-catalytic and
Thermal pyrolysis.
 Definition of pyrolysis:
Pyrolysis is a thermo-chemical decomposition of organic material at
elevated temperatures in the absence of oxygen.

3. SOURCES OF PLASTIC WASTE
 Plastic waste comes from plastic industry, automotive industry and
other sources of waste plastic include domestic items such as ; food
container, packaging disposal cups, drainage pipe etc.
 Industrial sources of waste plastic is very high as it give 40% of total
plastic waste.
Waste to energy:
 various technology available like catalytic cracking, non catalytic
cracking, pyrolysis process and thermal cracking.

4. Pyrolysis:
 Pyrolysis doesn't involve reaction with oxygen, water or any other
reagent.
 In practice it is not possible to achieve oxygen free atmosphere.
 So because of presence of oxygen, small amount oxidation takes place.
 In pyrolysis process the temperature must be above 450°C,
Below this temperature cracking doesn't takes place.
Production method;
 The production method for the conversion of plastics to liquid fuel is
based on the pyrolysis of the plastics and the condensation of the
resulting hydrocarbons.

5.  The production process of liquid fuel, the plastics that are suitable
for the conversion are introduced into a reactor where they will
decompose at 450 to 550°C.
 The pyrolysis process is done by batch operation.
 Initial waste plastics sample is melted and it take about 30 minute
for Cracking to produce vapor to first drop of fuel 0il.
 After some time, drop of fuel oil production rate spontaneously
increases ,so as to bring out the stable state of fuel oil production,
the temperature is maintained.

6.  ADVANTAGES AND DISADVANTAGE:
advantages
 Cheap and economical system.
 Environmental friendly.
 Energy efficient.
Disadvantages
 Require treatment for storage and disposal of hazardous waste.
 Ineffective in destroying and separating inorganics from
contaminated medium.

7. OBJECTIVE
 To investigate effect of catalysts on pyrolysis of plastic wastes
to fuel oil.
 To determine the Characteristic of fuel oil produced by
various technique.

8. LITRATURE REVIEW
1) G.Manoj Kumar, R.Pavan Kumar, catalyst are CaCO3 and Na2CO3 catalytic
pyrolysis of waste plastic has done at anaerobic condition. Catalysts are
commonly used in conversion of waste plastic into fuel, which are very helpful in
thermal cracking of waste plastic. Commonly zeolite and silica alumina are used
as catalysts. But these are very costly. So we are used similar propertied
catalysts which are having low cost compare to zeolite. These will effects on
decreasing the overall production cost. It is analyzed by this that, According to
our research “BaCO3, MgCO3,Na2CO3 & CaCO3” catalysts showed similar effect
on output fuel like zeolite and silica alumina catalysts, but only difference occurs
while in the field of yield. 2016
2) Débora Almeida,Maria de Fátima Marques, Zeolites can be used as catalysts in
catalytic pyrolysis and influence the final product obtained. Zeolites have a
specific molecular pore size and access of such molecules to catalytic reactive
sites, as well as growth of the final products within such pores is limited by its
size. The other experimental parameters such as temperature, reaction time,
reactor type and flow of carrier gas also influence the composition of the products
obtained. Pyrolysis can be carried out either for pure polymers or for polymer
blends. 2016 [4]
3) M.A.hajrat, M.G.Rasul, M.M.K. Khan, thermo-catalytic process resolves the
problem of halogen contents in the PVC type plastics by converting them into
residues with the use of NaHCO3 and AgNO3 which capture chlorine type
products from the gaseous hydrocarbons, It was also found that the mixture of
LDPE, HDPE, PP and PS yield 87.19% fuel with 20 wt% ZnO catalyst at 200 –
400 °C in a steel reactor. thus the fuels produced from this process can be
considered as one of the potential alternative resources of fuel production
resulting

9. 4) Anil Vyas1, Suresh Kumar Singh2, Komal Sharma3, Sukhwant
Singh2, Polypropylene (PP) is rated first as volume leader in the plastic
sector. Its non-biodegradable property poses serious environmental problem
in case of disposal. The catalytic cracking of PP was performed with various
catalysts i.e. ZSM-5, Zeolite, RB and SPS. The effective of feed to catalyst
ratio was found 3:1 at a temperature range of 420˚C - 510˚C and catalyst
ZSM-5 gives maximum liquid conversion of waste PP,2016.
5) Sachin Kumar* and R. K. Singh,.Results of pyrolysis experiments
showed that, at a temperature of 450ºC and below, the major product of the
pyrolysis was oily liquid which became a viscous liquid or waxy solid at
temperatures above 475ºC. The yield of the liquid fraction obtained
increased with the residence time for waste HDPE. The liquid fractions
obtained were analyzed for composition using FTIR and GC-MS. Reaction
time decreases with an increase in temperature. It has been shown that a
simple batch pyrolysis method can convert waste HDPE to liquid
hydrocarbon. 2014
6) Sonawane YB, Shindikar MR and Khaladkar MY, There are different
methods for recovering chemicals and hydrocarbon fuel from plastic waste
like solvent extraction, liquefaction, pyrolysis, catalytic cracking etc. HDPE
milk carry-bags were used as a raw material. Temperature was optimized for
maximum liquid fuel production. The liquid fuel obtained by using silica-
alumina has calorific value in the range of 43.5-43.8 MJ/Kg. The calorific
value of diesel is in the range of 45 MJ/Kg. 2015.

10. 7) Sriraam R. Chandrasekaran, Bidhya Kunwar, Bryan R.
Moser,Nandakishore Rajagopalan, and Brajendra K. Sharma,
Thermo gravimetric analysis (TGA) was used to investigate thermal
and catalytic pyrolysis of waste plastics) into crude plastic oils. It is
inferred from this paper that the fuel properties were better in the
gasoline and diesel obtained from catalytic pyrolysis than that
obtained from non-catalytic pyrolysis at the same temperature. 2015
8) Y.Q. LIU1, J. WANG1, Z. DONG2 AND J.H. TAY, it is inferred that
pyrolysis oil from main MSW components were analyzed. It was
found that the physical property of plastic oil was the best due to
zero water content, near neutral pH and low viscosity.2011
9) Moinuddin Sarker*, Mohammad Mamunor Rashid, Mohammed
Molla , Muhammad Sadikur Rahman, it is inferred that the process
of thermally breaking down the hydrocarbon of chains of plastic has
been studied and implemented to produce a liquid fuel in the
presence of activated carbon. The activated carbon acts as a filter to
absorb dye from the waste plastic during the thermal process to
increase the quality of the final product. Various technique (Gas
Chromatography and Mass Spectrometer, FT-IR and DSC) are used
for produced fuel analysis. GC/MS result is showing hydrocarbon
compound ranges from C3-C28 and light gas are present C1-C4.
2014

11. Experimental
 The catalytic cracking of waste plastic is performed in the pyrolysis
equipment. In the process the waste plastic like (LDPE and HDPE)
is converted into fuel oil.
 The Catalytic pyrolysis is performed for all the four different
catalysts with the same type of plastic waste.
 The properties of the extracted fuel Oil is evaluated to know the
nature and quality by various methods.
 Raw material:
The raw material used for pyrolysis is LDPE and HDPE plastic as waste
and the different catalysts used are; Sodium Carbonate, Calcium
Carbonate, Zinc-Oxide and Zeolite.

12. Optimize Temperature
 To evaluate the optimal temperature of fuel oil the experiment is
performed at three different temperature with LDPE and HDPE
plastic Waste.
 The experiment is performed at these temperature 4500C,4800C and
5000C without catalyst. The yield percentage of oil is very less in
yield percentage at 4500C and slight increase in yield is noticed at
4800C and the maximum amount of yield is obtained at 5000C.
420
430
440
450
460
470
480
490
500
1
2
3
temperature0C
no. of samples
Series1
Temp(0C) Yield (gm) Yield %
450 27.3 5.46
480 36.4 7.28
500 50.05 10.01

13. Catalyst appearance
Na2CO3
A
CaCO3
ZnO Zeolite

14.  The parameter for catalytic prolysis is mainly reactor temperature,
silicon oil, cold water and Asbestos Sheet.
Amount of catalyst= 10 gm (2% of Waste)
Amount of plastic waste=500 gm.
 Mixing of the catalyst and waste plastic is performed by Extruder
where proper mixing is performed
 After Mixing the mixed waste is chopped by chopper and the fed in
the furnaceReactor.
 Then the temperature is maintained at 5000C then the furnace is
completely closed and silicon oil is used for thermo coupling and
Asbestos sheet is used to minimize the leakage in furnace.

15.  For condensation supply cold water to the condenser. In condenser
condensation takes place and vapor converted into liquid fuel.
 Then heat is supplied to the reactor by using electric heater. Then
cracking starts in furnace.
 After 30 min first drop of oil obtained is continuously collected for
next 2:30 hours.
 Amount of oil yield is increases for certain period then, oil amount
is decreases in terms of yield.
 This shows completion of experimental procedure.

16.  The flow sheet for the Pyrolysis procedure;
Catalyst
s
LDPE/HDP
E Waste
Pyrolysis
Reactor
5000C
Extruder
(Mixing)
Fuel
Oil
GC-MS FTIR CV
Characterizatio
n of fuel oil

17.  The catalytic pyrolysis for all the four catalysts are performed;
1) First catalyst taken was calcium carbonate.
2) Second catalyst was Sodium Carbonate.
3) Third catalyst was Zinc-Oxide.
4) Fourth catalyst was zeolite
And rest of the procedure performed for pyrolysis is same as
mentioned in flow sheet.
 For performing the pyrolysis, pyrolysis equipment is used which is
shown in next slide.
Schematic of Pyrolysis of Equipment.
Laboratory Equipment for Pyrolysis.

18. Schematic of Equipment Laboratory Equipment

19. CAPACITY OF THE EQUIPMENT.
-HEIGHT OF THE REACTOR=15 INCH OR 246ML.
-DIAMETER OF THE REACTOR=4 INCH OR 65ML.
-
DIMENSION OF THE EQUIPMENT
volume of reactor=5.0L
area of reactor=1276.74 Cm2

20. RESULT
 By Performing the above mentioned procedure for all the four
catalysts the yield percentage of the fuel oil is obtained by
yield %= [(Amount of fuel oil obtained total amount of waste
used) * 100].
 Amount of Yield % of fuel oil with different catalyst are;
No. Oil
yield
(g)
Waste
left(g)
Losses
as gas
and
waxes(g)
Yield
%
1. Na2CO3 136.5 230 133.5 27.3
2. CaCO3 192.5 180 127.5 38.5
3 ZnO 68.85 250 181.15 13.77
4. Zeolite 76 235 188.5 15.2

21.  The different properties of oil is determined by different apparatus
and Equipment.
 The properties of fuel oil are API and density, ASTM Distillation,
flash and fire point, Cloud and Pour point, Kinematic viscosity,
Viscosity Index, Aniline point, Diesel index and Boiling point
temperature.
 All the properties of fuel oil for the result is mentioned in the next
slide.

22. Properties of oil Name of the all four oil
O-SC O-CC O-ZnO O-ZSM
Pour point 5 -5 1 1
Cloud point 9 -1 5 4
Flash point 45 50 52 51
Fire point 65 80 70 80
Density 0.91 0.77 0.81 0.76
Specific gravity 0.91 0.77 0.81 0.76
API gravity 24 52.27 43.19 54.68
Aniline point 35 62 64 55
Boiling temperature Very high 90 98 80
Watson
characterization
Not determined 12.32 11.04 13.02
Diesel index 22.8 75.05 56.58 80.04
ASTM distillation 64.28 78.57 90 91
Kinematic viscosity 7.65 40.73 53.78 12
Viscosity index 11.02 53.78 75.4 40.74

23. Calorific value of fuel oil
extracted
 The properties of fuel oil is determined by using Calorific Value. This
gives the nature of fuel oil.
Num. Name of fuel oil CV (MJ/Kg) Properties of oil
1. Na2CO3 22.2 1) Calorific value lower then
combustion is lower.
2) Calorific value is higher then,
combustion rate of fuel oil is also
higher.
3) The calorific value of fuel oil is
mentioned so CV of oil shows the
nature of oil or in which group it
comes under.
2. CaCO3 31.2
3. ZnO 29.6
4. Zeolite 38.4
5. Petrol 45.8
6. Diesel 43.5
7. Gasoline 38
8. Kerosene 35

24.  The standard Fuel oil values is shown below in the table and
comparison is done with the help of this data.
Properties Diesel Petrol Kerosene Gas oil
CV(MJ/Kg) 45.5 45.8 35 38
Fire point (0C) 62-106 >65 45-70 49-60
Pour point(0C) -40 -2 -1 -10
Aniline point(0C) 40 45 50 52
Kinematic
Viscosity(centist
okes)
6-29.8 32 35 50-73
API 34.47 89.60 43.20 47

25. Functional group analysis from FTIR
graphFunctional groups Characteristic
absorption(s)
O-CC O-SC
Alkenyl C-H
Stretch
3100 - 3010 3070 3070.68
Alkyl C-H Stretch 2950 - 2850 2927.94 2931.80
Alkyl C-H Stretch 2950 - 2850 2854.65 2858.51
Carboxylic Acid
C=O Stretch
1780 - 1710 1716.65 1712.7
Amide C=O
Stretch
1690 - 1630 1639.49 1639.49
Tertiary N-C 1487-1428 1458.18 1468.18
CH3 Bend 1377 1373.32 1373.32
Trans CH=
Wagging
986-995 991.41 991.41
Vibration from
CH2 and CH3
group
889.1-909.5 906.54 906.54
Aromatic C-H
Bending
860 - 680 726.23 725.23

26. GRAPH OF FTIR ANALYSIS FOR ALL THE
FOUR DIFFERENT OILS

27. Functional
groups
Characteristic
absorption(s)
O-ZnO O-ZSM
Alkenyl C-H
Stretch
3100 - 3010 3070.68 3074.53
Alkyl C-H
Stretch
2950 - 2850 2924.09 2924.09,
2854.65
Alkyl C-H
Stretch
2950 - 2850 2854.65 1820.20
Aromatics 1650-1900 1820.80 1716.65
Amide C=O
Stretch
1690 - 1630 1639.49 1639.49
Tertiary N-C 1487-1428 1454.33 1462.14
CH3 Bend 1377 1373.32 1373.32
Trans CH=
Wagging
986-995 991.41 991.41
Vibration from
CH2 and CH3
group
889.1-909.5 906.54 910.40
Aromatic C-H
Bending
860 - 680 725.23 810.10,725.23

29. GC-MS Analysis of O-ZSM
Number Compound Name
1. BENZENE
2. ETHYLBENZENE
3. PHENYLETHANE
4. ETHYLBENZOL
5. 2-BENZYLOXY-4-PHENYL
6. 1,3,4-OXADIAZOLIN-5-ONE
Chemical components present in Oil

30.  The GC-MS is used to know that which component is present in Fuel
Oil. The Graph of oil is shown Below;

31. Discussion
 The properties of oils like API and Density decide the nature of oil
whether it is aromatic, paraffinic or naphthenic in nature the oils
which is extracted have paraffin nature by this properties except the
o-sc.
 According to kinematic Viscosity and viscosity index it signifies that
the flow resistance of fuel oil in the temperature increase and
decrease.
 From flash and fire point we can say that till what temperature the
fuel oil will not catch fire. And it is very important according to
safety.
 Cloud and Pour point test is performed that at which lowest
temperature the fuel oil is in flow condition otherwise at lowest
temperature it will clog the engine or any other equipment where it
is used.

32.  ASTM distillation decide the that initial boiling point of fuel oil and
ease of start and the final boiling point. If the temperature of IBP is
low then the quality of oil is good. Lesser the IBP better the quality
of fuel oil.
 Aniline point and Diesel index:. It is an approximate method of
testing the ignition quality of a diesel fuel. In the case of petroleum
fuel the higher the paraffin content the higher the ignition quality,
though it is not always true for other fuel such as oil, distillates etc.
Lower the aniline point better the quality of fuel oil. And diesel index
is determined by specific formula.
 Watson Characterization: this characterization of fuel oil decide that
that whether the oil is aromatic, paraffinic or intermediate
compound which is either naphthenic or aromatic. it also have
certain range.

33.  Calorific value of the fuel oil is very important characteristic of oil. It also
considered largely while fuel oil characterization done. If the oil have
higher CV then the fuel oil is paraffinic in nature other wise may be
intermediate or aromatic nature of oil or it shows it is a better quality of
fuel oil.
 FTIR (Fourier Transform Infrared Spectroscopy) : this analysis gives the
functional group present in oil. This also decide the nature of oil in good
or bad.
 GC-MS(Gas Chromatography- Mass Spectroscopy): This gives the
chemical component present in oil. The also decide the nature of oil
whether the component present in oil is Paraffinic or Aromatic or
intermediate compound which is Aromatic and Naphthenic. If the
component present is straight chain carbon hydrogen then it is
paraffinic and better quality of fuel oil. and If more amount of cyclic
compound are present then the oil is of Aromatic nature then the lower
grade of fuel oil.

34. Summary and Conclusion
 The summary of this work is that, the oil extracted by the pyrolysis of waste
plastic oil has approximately similar properties as fuel oil. After determining
the properties of fuel oils like calorific value, pour point, cloud point, fire
point, flash point, API, density, Specific gravity, Aniline point, boiling
temperature, Watson characterization, diesel index, ASTM distillation,
kinematic viscosity, viscosity index. The properties of oil shows that these oil
may also have similar properties like kerosene and gasoline (mainly shown
by Calorific Value). From the result part it is concluded that, the zeolite
catalyst based oil has better quality of oil because the calorific value of oil is
higher among all, O-CC also have similar properties as Zeolite oil. And the
other properties all favor this conclusion and the lowest quality of oil is
Na2CO3 Catalyst based oil have lower quality of oil as its property indicate.
The other characterization of perform for the fuel oil which is FTIR analysis
and GC-MS analysis in which FTIR shows the different functional group
present in oil and GC-MS shows the Components present in oil, it also decide
the carbon range present in fuel.
 It is concluded from above all the analysis, the O-ZSM is best quality of fuel
oil among all four different fuel oil extracted, and O-CC also have similar
properties so it can also considered as fuel oil near to kerosene and gasoline.

35. Future Scope
 Further this work continued, to perform the GC-MS test for other
three oils extracted.
 To performed same type of experiment by using same catalyst and
waste plastic with varying temperature to know to change in Oil
yield.
 To perform the experiment by using same catalyst and same
temperature with different type of plastic.
 Kinetic study can also be done by using TGA and DSC analysis.

36. References
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 .

38.  G.Manoj Kumar, R.Pavan Kumar (Asst.Professor)Department of
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 M.G. Rasal, M.M.K. Khan, A Study on Thermo-catalytic Degradation
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 FUELS AND COMBUSTION Syllabus Introduction to Fuels,
Properties of Fuel oil, Coal and Gas, Storage, handling and
preparation of fuels, Principles of Combustion, Combustion of Oil,
Coal, and Gas. This chapter is a prelude to boilers and furnaces

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