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IMRESM

INTERNATIONAL JOURNAL OF ADVANCED RESEARCH IN


ENGINEERING, SCIENCE & MANAGEMENT
CATALYTIC CONVERSION OF PLASTIC WASTE TO FUEL
Niraj Nair, Rajan Kher, Rashmita Patel
Student, Chemical Engg, Sarvajanik College of Engg & Technology, Surat, Gujarat, India1
Student, Chemical Engg, Sarvajanik College of Engg & Technology, Surat, Gujarat, India2
Asst. Professor, Chemical Engg, Sarvajanik College of Engg & Tech., Surat, Gujarat, India3

Abstract: Economic growth and changing consumption and production patterns are
resulting into rapid increase in generation of waste plastics in the world. 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
most of the situations, plastic waste recycling could also be economically viable, as it
generates resources, which are in high demand. This paper is an effort for the conversion
of plastics into fuel which are in commercial use, under pilot implementation and under
laboratory testing, aimed to raise awareness on available options. The results of pyrolysis
of plastic has compared without catalyst and with catalyst. Catalyst used here were
Calcium Bantonite and Zeolite. Calcium Bantonite has proved better for the conversion of
LDPE to liquid fuel. The kinetic study has also carried out by different models and
reaction follows Mapels first order reaction.

Keywords: Catalytic conversion, Kinetics, Pyrolysis, Waste plastic.

I.INTRODUCTION
Economic growth and changing consumption and production patterns are resulting into
rapid increase in generation of waste plastics in the world. Due to the increase in
generation, waste plastics are becoming a major stream in solid waste. After food waste
and paper waste, plastic waste is the major constitute of municipal and industrial waste
in cities. Even the cities with low economic growth have started producing more plastic
waste due to plastic packaging, plastic shopping bags, PET bottles and other
goods/appliances using plastic as the major component. 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 most of the
situations, plastic waste recycling could also be economically viable, as it generates
resources, which are in high demand [1]. Plastic waste recycling also has a great
potential for resource conservation and harmful emissions reduction, such as producing
Diesel fuel from plastic waste.
This paper is a compilation for the conversion of plastics into fuel which are in
commercial use, under pilot implementation and under laboratory testing, aimed to
raise awareness on available options.

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Pyrolysis is the thermos-chemical decomposition of organic material at elevated
temperatures in the absence of oxygen. It occurs under pressure and at operating
temperatures above 430oC (800oF) [2,3]. Some plastics wastes are suitable for Pyrolysis
such as: HDPE (high density polyethylene), LDPE (low density polyethylene),
polypropylene, polystyrene, polyvinyl alcohol, poly-oxymethylene, polyamide,
polyurethane, poly-phenylene, polyvinyl chloride etc [4]. But for the purpose of this
study low density polyethylene (LDPE) was used since it is commonly found littered
around our environment . Polyethylene is an excellent source of hydrocarbon
products.In the process of conversion of waste plastics into fuels, random de-
polymerisation is carried out in a specially designed reactor in the absence of oxygen
and certain catalytic additives. The maximum reaction temperature is 350C. There is
total conversion of waste plastics into value-added fuel products.

II.MATERIALS AND METHODS


Materials used are recycled low density polyethylene (LDPE), glass round bottom flask,
condenser and catalyst i.e., zeolite and calcium bentonite.
Experimental procedure
The pyrolysis process is an advanced conversion technology that has the ability to produce a
clean, high calorific value hydrocarbon from waste (polyethylene). The detailed procedure is
given below:
1. 100-200 gms of the sample was prepared and stuffed inside the reactor. Silica alumina
/calcium bentonite was used as a catalyst. Also, a sample without catalyst was stuffed
and results were observed.
2. The temperature was set on the controller for the pyrolysis to start. This temperature
was noted.
3. When the first drop of liquid came out the temperature was noted.
4. The weight of the waxy residue left inside the reactor after the process was noted.
5. According to literature review, for both thermal and catalytic pyrolysis, the maximum
liquid yield expected to be recorded is 550C. The liquid product yield increases from
temperature 400C to 500C before it starts to drop.
6. Nitrogen gas was used for Purging inside the reactor batch wise.
7. Different properties of liquid fuel were tested and compared with standard results.

III KINETICS STUDY,


A. Kinetic Study for Pyrolysis process
Kinetic information can be extracted from dynamic experiments by means of various
methods. All kinetic studies assume that the isothermal rate of conversion, d =dt; is a linear
function of a temperature-dependent rate constant, k, and a temperature-independent function
of the conversion, .There are two types of methods integral and differential to determine the
kinetic parameters [5,6].
Analyses of the changes in thermo gravimetric data brought about by variation of heating rate
, , are the basis of the most powerful differential methods for the determination of kinetic
parameters. Kissingers method has been used to determine the activation energy of solid

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state reactions [10]. The activation energy can be determined by Kissingers method without
a precise knowledge of the reaction mechanism.
The integral methods involve an approximate integration. Some of these methods discussed
here are:
1) FlynnWallOzawa
2) CoatsRedfern
3) HorowitzMetzge Van Krevelen [8].
Amongst the above stated methods, we will apply Coats and Redfern method because it
gives better approximation compared to other methods. CoatsRedfern used an asymptotic
approximation.
luST<- ) = In AR.>
E
PE RT
1) Thermo gravimetric Analysis: Thermogravimetric analysis or thermal gravimetric analysis
is a type of testingperformed on samples that determines changes in weight in
relation toa temperature program in a controlled atmosphere [9]. Such analysis relies on a
high degree of precision in three measurements: weight, temperature, and temperature
change.
101

100 00 C 200 00 C 300.00 C


100 395 % 100 412 % 100.327 %
90 -

80 - 400.00 C
90 054 %

70 -

60 - 425 00 C
g 60 633 %
aB
50 -
B
I
40 - 450 00 C
10.103 %

30 -

20 500.00 C
1.331 %
560 00 C
0.939 %
10 -

o
50 100 150 200 250 300 350 400 450 500 560
Temperature ( = C)

0
Fig TGA graph for sample at heating rate 10 C/min

2) Solid state kinetic model:Reaction kinetics in the solid state are often studied by
thermogravimetry, but they can also be studied by other analytical method. Kinetic analysis
can be performed by either model fitting or model free. Different solid state kinetic analysis
methods have been recently reviewed [10].A model is a theoretical , mathematical description
of what occurs experimentally. Many models have been proposed in solid state kinetics , and
these models have been developed based on certain mechanistic assumption. Following
models have been employed in our experiment.
Avea mi- E rof eyev ( A 2) A3
0 0
-2 0.001 ( 007 0 003 0 004
-2
0.001 0.002 0.003 0.004
y = -3672 x - 3.4528
-4 R 2 = 0.4826 y = -1532.3 x - 8.8422
-4
R2 = 0.9386
-6
-6
Aveami -Erofeyev ( A 2 )
M -8
-8 A3
- -10
c c
Linear -10 Linear ( A3 )
- 12
( Aveami -Erofeyev ( A 2 ))
- 12
-14
-16 -14

-18 -16
1/ T
1/T

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A4 POWER LAW ( P4)
-11.6 -12
-11.8 d 0.001 0.002 0.003 -12.2 CL o ooi non? 0003 o oo4
\ ^004 . .

- 12
y = -954.65 x - 10.124 -12.4 V
-12.2 y = -590.77 x - 11.224
R2 = 0.9118 -12.6
-12.4 R2 = 0.7362
N -12.6
A4 c
.
> -12.8 POWER LAW ( P4 )
-12.8 -13
-13 X Linear ( A4)
-13.2 Linear ( POWER LAW
-13.2
-13.4 ( P4 ))
-13.4
-13.6 -13.6
-13.8 -13.8
1/T 1/ T

POWER LAW ( P3 ) POWER LAW ( P 2)


-12 0
0.001 002 0.003 0.004 y = -1966.7 x - 8.4598
y = -1049.4 x - 10.303 0 0.001 0.002 0.003 0.004 R 2 = 0.9001
-12.5 R2 = 0.8425
-5

-13 POWER LAW ( P3 ) POWER LAW


>
c
>
c 10-- (P2)
-13.5 Linear ( POWER LAW Linear ( POWER
( P3 -15 LAW ( P 2 ))
-14

-14.5 -20
1/T 1/ T

Third order Contacting cylinder


0.012 0.012

0.01 0.01

Contacting cylinder
0.008 0.008

0.006 Third order 0.006 Linear ( Contacting


Linear ( Third order ) cylinder )
0.004 0.004
y = -0.0007 x - 0.0058 Linear ( Contacting
y = -0.0002 x + 0.0023 R2 = 0.9443 cylinder )
2 0.002 0.002
R = 0.7491

0 0
- 25 -20 -15 -10 -5 0 5 - 25 -20 -15 -10 -5 0

Second Order One Dimensional Diffusion


0.012 0.012

0.01 0.01

0.008 0.008
One Dimensional
0.006 Second Order 0.006 Diffusion

Linear (Second Order ) Linear ( One


0.004 " 0.004 Dimensional Diffusion )

y = -0.0003 x + 0 $$
R 2 = 0.8031
0
% R 2 = 0.542^ ^
y = -0.00027 0110 T- 0.002

0
- 25 - 20 -15 -10 -5 0 -40 -30 -20 -10 0

Diffusion Control ( Crank ) Diffusion Control (Jander )


0.012 0.01-2

0.01 0.01

0.008 0.008
Diffusion Control Diffusion Control
0.006 (Crank ) 0.006 (Jander )

Linear (Diffusion Linear ( Diffusion


0.004 Control ( Crank )) 0.004
Control ( Jander ))
y = -0.0002 x - rnims3 - 0.002 y = -0 0007 x - OT 0.002
R2 = 0.5368 R 2 = 0.5323
0 0
- 40 -30 -20 -10 0 -40 -30 -20 -10 0

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Mapel First Order


0
a 0.001 0.002 0.003 0.004

-5 Mapel First Order

- 10
Linear ( Mapel First
Order )

Linear ( Mapel First


-1 5 Order )
Linear ( Mapel First
-2 0 y = -6 1 5 3 . 6 x + 1,4 1 1 Order )
R2 = 0.9655

- 25

Fig Various models applied to check which one of the above does system follows.

From the above graphs , Mapel first order fits properly. Thus we can determine Activation
energy(E) and exponential factor (A).Activation energy can be determined by slope of the
equation.
E = 12.227 kcal/kmole
Exponential factor can be determined by intercept.
A = 7.14*10^6 min-1

IV EXPERIMENTS AND RESULTS


TABLE 1: OBSERVATION WITHOUT CATALYST
EXPERIME
EXPERIMENT2 EXPERIMENT3 EXPERIMENT4
NT 1
Weight of
200 100 100 100
LDPE (g)
Temperature
400 600 400 450
(oC)
Pressure (atm) 1 1 1 1
Time (hr) 0.5 2 2 1
Reaction was Vapours started After properly Smooth flow of
incomplete coming out of the evaluating and gas was observed
and pyrolysis non condensable solving the after 35 mins
did not take gas outlet after 45 leakage problem from the outlet of
place. mins and burned by tightening the non condensable
Observations Nitrogen with blue flame. connections, few gas streamline,
purging was Liquid oil was drops of oil were but no
stopped after not observed observed and non condensation of
initial inlet. condensable vapours occurred.
gases evolved
continuously.

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TABLE 2: OBSERVATION WITH CATALYST
Catalyst Zeolite Calcium Bentonite
Weight of LDPE 100 g 100 g
o
Temperature/Pressure 400 C/ 1 atm 400 oC/1atm
Time 45 min 45 min
Liquid yield 60 74
Solid residue 31 19
Gas 9 7

TABLE 3: RESULTS OF PYROLYSIS WITH CATALYST


Diesel(std ) Liquid Liquid fuel Solid Residue
fuel(Zeolite) (Cal. Bentonite)
Aniline Point >50 115 110 -
Cetane 55 50 53 -
Number
Fire Point 62-120 38 44 -
Flash Point 52-96 32 36 -
Soft Point - - 86
Calorific Value >10,000 9456 kcal/kg 9525 Kcal/kg
kcal/kg

VI CONCLUSION
After performing the experiment of pyrolysis of waste plastic (LDPE) to Crude fuel oil,
without catalyst, we found that the cracking of the plastic waste is difficult and at different
temperatures different observations were obtained.
Then we added catalyst and carried out pyrolysis process and we found that yield of product
oil obtained through catalytic conversion was more as compared to that in without catalyst.
Here catalyst employed was Calcium Bentonite and Zeolite.
Also time of experiment reduces significantly in case of catalytic conversion and cracking
temperature of the plastic waste decreases significantly.
From kinetic study of our sample we found that our reaction follows Mapels first order
reaction which is homogeneous reaction. Activation energy and frequency factor of the same
was calculated.
Quality (Cetane number)of fuel obtained by using Calcium Bentonite was found to be better.

ACKNOWLEDGMENT
It invokes in me a great sense of gratitude for each and every person who lent me their kind
co-operation without which the report would have been a mission without aim. I express my
gratefulness to Prof. Rashmita Patel, who encouraged me and whose able guidance and co-
operation has led towards the fulfillment of my efforts into this report. I would also like to
thank Dr. Swati Sharma, Prof. Srujal Rana and Prof. Rakesh Vaiwala who helped me by
providing some valuable information.I am very much thankful to lab assistant, Mrs Shilpa
Modi and Mrs Ekta Desai,for their valuable guidelines regarding operation of instruments
that were employed.
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We are thankful to Sarvajanik college of Engg & Tech for providing facility to carry out
research.

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