PROJECT REPORT ON

PYROLYSIS OF CARBONACEOUS SOLID WASTES AS A

MEANS OF DISPOSAL AND GENERATION OF VALUE ADDED
FUELS AND CHEMICALS

Submitted to

Department of Science, Technology and Environment,

Govt. of Pondicherry

Prepared by

Dr. K.Subbarayudu,
Asst. Professor

Department of Mechanical Engineering

PONDICHERRY ENGINEERING COLLEGE
(Sponsored by Govt. of Pondicherry and affiliated to Pondicherry University)
Pondicherry – 605 014.

Ph. Nos: 0413-2655281-287 Internet : www.pec.edu

Fax No : 0413-2655101
PYROLYSIS OF CARBONACEOUS SOLID WASTES
AS A MEANS OF DISPOSAL AND GENERATION OF
VALUE ADDED FUELS AND CHEMICALS

ii
 ACKNOWLEDGEMENTS

The project titled “Pyrolysis of carbonaceous solid wastes as a means of

disposal and generation of value added fuels and chemicals” is a small step in the
research and development of a promising means of waste disposal. It is my duty to
thank all those who are in one way or other connected with the project.
At the outset, I thank Dr. V.Soundararajan, Head of Department of
Mechanical Engineering, Pondicherry Engineering College, for his support in the
execution of the project and also for allowing me to use the facilities available in the
department.
I am grateful to Dr. T.G.Palanivelu, Principal, Pondicherry Engineering
College, for allowing me to take up the project and for his help in the procurement of
equipments pertaining to the project.
This project was executed with the financial grant from Department of Science,
Technology and Environment (DSTE), Government of Pondicherry. I express my
gratitude to DSTE for selecting the project for funding. I sincerely thank
Dr. P. T. Rudra Goud, Director, DSTE, and Er. S.Sekar, Scientific Officer, DSTE
for their constant support in the successful completion of the project.
I appreciate the assistance rendered by Mr. L.Kumararaja, Sr. Lecturer,
Department of Mechanical Engineering, Pondicherry Engineering College for helping
me in the execution of the project.

Dr. K. SUBBARAYUDU

iii
 CONTENTS
------------------------------------------------------------
Chapter No. Title Page No.
------------------------------------------------------------

Acknowledgements iii

List of Figures v

List of Tables vi

Summary vii

1 Introduction 1

2 Solid Wastes and their Properties 2

3 Literature Review 6

4 Design and Construction 11

5 Experiments 16

6 Results and Discussion 18

7 Conclusions 24

Related Literatures 25

------------------------------------------------------------

iv
 LIST OF FIGURES
------------------------------------------------------------
Fig. No. Title Page No.
------------------------------------------------------------
4.1 Schematic diagram of pyrolysis system 11

4.2 Pyrolysis Reactor 12

4.3 Schematic View of Heaters 13

4.4 Volatiles condenser 14

4.5 Gas liquid separator 14

4.6 Overall experimental set up 15

6.1 Types of solid wastes and final residues after pyrolysis 18

6.2 Plot of temperature Vs time for pyrolyser without charge 19

6.3 Plot of temperature Vs time for scrap tyre pyrolysis 20

6.4 Plot of temperature Vs time for LDPE pyrolysis 20

6.5 Plot of temperature Vs time for PVC pyrolysis 21

6.6 Yield of pyrolysis products 21

------------------------------------------------------------

v
 LIST OF TABLES
------------------------------------------------------------
Table No. Title Page No.
------------------------------------------------------------

2.1 Composition of tyre samples 2

2.2 Elemental composition of scrap tyres 3

2.3 Elemental composition of Polyethylene 3

2.4 Elemental composition of PVC 4

2.5 Average composition of MSW 5

3.1 Pyrolysis reactor details 9

6.1 Average pyrolytic reactivities of different wastes 22

6.2 pH values of water after pyrolysis of different wastes 23

------------------------------------------------------------

vi
 SUMMARY

The ever increasing quantity of solid wastes generated in the modern world has
posed several social and health problems. Among the safer methods of waste disposal,
pyrolysis is a technique in which the feedstock is thermally degraded in the absence of
oxygen. The resulting products of pyrolysis are solid char, liquid pyrolytic oil and
gases. Each of the products formed has potential usage as energy carriers and
chemical feed stocks for further processing. In this work, a lab scale semi batch type
pyrolyser was fabricated along with the downstream components like volatiles
condenser, gas-liquid separator etc. General types of solid wastes like scrap tyres,
LDPE, PVC, screened MSW and dry leaves were pyrolysed. Temperature rise,
specific electrical energy consumption for pyrolysis, yields of residual char, pyrolytic
oil and gases, average pyrolytic reactivity for each type of waste were determined.
The temperature rise for scrap tyre pyrolysis is faster than other types. Specific energy
consumption is lowest for tyre pyrolysis. The yields of different products depend very
much on the process variables. The pyrolytic oil can be blended with the conventional
liquid fuels. The pyrolytic waste disposal will also mitigate the problems of
environmental pollution.

vii
 Chapter 1
INTRODUCTION

The generation of solid wastes like waste tyres, plastics, PVC, bio residues etc., is
steadily rising. The local civic bodies like Corporations, Municipalities and
Panchayats face a difficult task in the safe disposal of wastes. The pile up of these
wastes in the land filling sites cause problems such as:
• Breeding of insects, mosquitoes etc.,
• Emissions of pollutants and obnoxious gases,
• Requirement of more land filling sites,
• Water contamination
There are several scientific disposal methods like materials recovery and recycling,
thermo chemical methods such as incineration, gasification, pyrolysis, and bio
chemical methods such as composting, anaerobic digestion etc. These are the various
safe disposal methods. Among them, a promising method is pyrolysing the
carbonaceous solid wastes. The benefits resulting from pyrolysis are:
• 60-90 % of volume reduction and 70-98 % of weight reduction are possible
which means only lesser land area requirement for filling.
• Certain products can be recovered and recycled.
• There are no health hazards and there is a possibility of clean environment.
• Pyrolysis oil can be used directly as fuel or blended with petroleum products.
• Pyrolysis oil is a source of various chemicals.
• The resulting char can be used as a fuel or it can be activated for a more
valuable purpose.
Pyrolysis is defined as the thermal decomposition of the solid wastes in absence of
oxygen. During pyrolysis, gases, pyrolytic oil and char are produced. The gases are a
mixture of carbon dioxide, methane and hydrocarbons, water vapour etc.; their relative
proportions vary much with the reaction parameters during pyrolysis, and nature of
solid wastes.
The solid wastes selected for testing in this project, were scrap tyres, plastic
wastes like LDPE, PVC, screened municipal solid wastes and bio residues.
 Chapter 2
SOLID WASTES AND THEIR PROPERTIES

The solid wastes are of different types; because they are generated by different
people of various economic statuses, through their various activities involving a
variety of products and commodities. The quantum of solid wastes generated is also
burgeoning as people’s activities have increased very much in this materialistic world.
Among these types of wastes, the properties of some of them are given below.
2.1 Scrap tyres:
The composition of tyre varies with manufacturers. Even in the same tyre, the
composition differs between the tread and side wall portion. Some of the typical
composition of tyres is given in Table 2.1.
Table 2.1 Composition of tyre samples
Sl. Composition Tyre of Tyre of Tyre of
No. company A company B company C
(wt%) (wt%) (wt%)
1 Styrene Butadiene Rubber 39.1 - 20
2 Natural Rubber - 41.3 45
3 Butadiene Rubber - 22.3 25
4 Carbon Black 36.9 23.2 -
5 Oil 19.5 4.1 -
6 Others 4.5 9.1 10
Total 100.0 100.0 100

The heat content of rubber is higher than that of coal; tyre rubber could be a
source of alternate fuel for power generation and other usage. For example, the used
tyres can be burn directly in co-fired boilers to generate power. The elemental analysis
of a typical tyre is shown in Table 2.2.

-2-
 Table 2.2 Elemental composition of scrap tyres
Sl. Element Wt%
No.
1 Carbon 84.39
2 Hydrogen 7.13
3 Nitrogen 0.24
4 Sulphur 1.24
5 Other (by diff.) 7.0
Total 100.0

The disposal of used automotive tyres is becoming an ever more pressing

problem as it causes many environmental and economical problems to most of the
countries. Their continuing accumulation is one of the worst solid waste disposal
problems plaguing the countries. The chemical structure of rubber used in making
tyres makes them difficult to recycle.
2.2 Polyethylene (PE):
Polyethylene of different density ranges are obtained by chain polymerization
of ethylene. Commercial categories are
(a) Low Density Poly Ethylene (LDPE) of density range 915 – 940 kg/m3 and
(b) High Density Poly Ethylene (HDPE) of density range 945 – 960 kg/m3
LDPE is more branched i.e., 25 – 50 branches per 1000 linear carbon atoms. It has
lower melting point of 110 – 117°C. HDPE are linear having only 2 – 5 branches per
1000 linear carbon atoms. It has higher melting point of 125 – 130 °C. HDPE is more
resistant to chemicals than LDPE; LDPE is permeable to gases than HDPE. The
factors contributing to widespread use of polyethylene are low cost, easy
processability, chemical inertness, electrical insulation properties, low temperature
toughness, flexibility, clarity etc. The elemental composition of PE is given in table
2.3.
Table 2.3 Elemental composition of Polyethylene
Sl. Element Wt%
No.
1 Carbon 85.7
2 Hydrogen 14.3
Total 100.0

-3-
2.3 Polyvinyl Chloride (PVC):
Its monomer is CH2 = CHCl. PVC is a hard plastic that is made softer and
more flexible by the addition of plasticizers, the most widely used being phthalates.

H H H H
H H

C == C —C— C— C—C—

Cl H Cl H Cl H

Vinyl Chloride monomer Poly Vinyl Chloride polymer

It has a chlorine content of 53.8%. On heating, HCl is liberated as volatile. PVC is

used in chemical plant equipments, pipes, sheets, window frames, transparent roof
sheeting. In the temperature range of 200 – 400°C, PVC decomposes into HCl and a
coke like residue. This residue can be burnt at higher temperatures without any
chlorine related limitation. The elemental composition of PVC is given in table 2.4.
Table 2.4 Elemental composition of PVC
Sl. Element Wt%
No.
1 Carbon 40.1
2 Hydrogen 5.1
3 Chlorine 53.8
4 Other (by diff.) 1.0
Total 100.0

2.4 Municipal Solid Wastes (MSW):

MSW is the most heterogeneous substance with the quantity of any particular
constituent varying widely with location. However, for a general idea a normal
composition of MSW is given in table 2.5.

-4-
 Table 2.5 Average composition of MSW
Sl. Constituent Wt (%)
No.
1 Paper 37.8
2 Plastics 4.6
3 Rubber and leather 2.2
4 Textiles 3.3
5 Wood 3.0
6 Food wastes 14.2
7 Yard wastes 14.6
8 Glass and ceramics 9.0
9 Metals 8.2
10 Miscellaneous 3.1

-5-
 Chapter 3
LITERATURE REVIEW

An extensive survey of technical journals, internet and books related to

pyrolysis was done before embarking on the project. This was done to keep ourselves
abreast with the latest developments in the field. A brief summary of the technical
articles collected from the technical journals are given below.
1. Soo Hyun Chung, et.al, [1] in their paper “Pyrolysis of Waste Plastics using
Synthesized Catalysts from Fly Ash” proposed that waste plastics can be converted
into fuel oil by pyrolysis using suitable catalysts. These synthesized catalysts were
more effective for PP than for PE which is difficult to pyrolyse. Experimental
results showed that synthesized catalysts from fly ash can be used for the pyrolysis
of most of waste plastics including the olefin series to make fuel oil.
2. Yang Yongrong, et.al, [2] authored a paper titled “Technical Advances on the
Pyrolysis of Used Tyres in China”. The objective of their work is to give an
outline of the research activities on the pyrolysis of tyre rubber. They also describe
the kinetics of pyrolysis, pyrolysis mechanism and design of pyrolysis reactor.
3. M.T.Gonullu, E.Arslankaya, et.al, [3] in their paper titled “An Experimental
Research on Pyrolysis and Gasification of Scrap Tyres” described that pyrolysis is
a method to get valuable new materials and energy. It has been reported that
experimental research was conducted to get optimum operating parameters for
pyrolysis of rubber scrap tyres. In their experiments, heating was done upto
600°C; thermal decomposition of waste tyres began at temperature 150°C and
almost finished by 550-580°C.
4. Masemore, et.al, [4] authored a paper titled “Process for pyrolyzing tyre shreds
and tyre pyrolysis systems”. They have reported that tyre pyrolysis systems and
processes were developed which include feeding tyre shreds to a pyrolysis reactor,
pyrolyzing the shreds in the pyrolysis reactor to produce a hydrocarbon rich gas
and carbon rich solid fuel.
5. Ron Zevenhovena and Ernst Petter Axelsenb, [5] described their work in the paper
“Pyrolysis of waste derived fuel mixtures containing PVC”. This paper describes
the experimental analysis of pyrolysis of PVC and mixtures of PVC with wood
(Finnish pine) and LDPE (Low Density Poly Ethylene) in nitrogen at 250±400oC.

-6-
 Results are presented for various process temperatures for PVC, PVC/wood and
PVC/LDPE mixtures.
6. P. T. Williams [6] described their work in the paper “High Value Products from the
Pyrolysis of Scrap Tyres”. They have reported that pyrolysis of tyres produced
oil, carbon and gaseous products, in addition to the steel cord, all of which have the
potential to be recycled. In this paper, process routes have been described for the
production of high grade activated carbon and high value aromatic chemicals from
the pyrolysis of scrap tyres which may improve the commercial viability of tyre
pyrolysis.
7. F. Pinto et.al, [7] have written a paper titled “Pyrolysis of plastic wastes - Effect of
plastic waste composition on product yield”. They opined that accumulation of
enormous amounts of plastic waste produced all over the world has negative
implications on the environment. Pyrolysis of plastic waste can have an important
role in converting this waste into valuable hydrocarbons.
8. A.A. Zabaniotou et.al, [8] have written a paper titled “Pyrolysis of used automobile
tyres and residual char utilization”. In their study, the rubber portion of used car
tyres was transformed by atmospheric pyrolysis into oil, gas and char. The
experiments were performed in a captive sample reactor at atmospheric pressure
under helium atmosphere. The effect of temperature on the products yield was
investigated by them.
9. A. Chaala et.al, [9] described their work in their paper “Vacuum pyrolysis of
automobile shredder residues: use of the pyrolytic oil as a modifier for road
bitumen”. The physicochemical properties and the rheological behavior of the
pyrolytic oil residue obtained from the vacuum pyrolysis of automobile shredder
residues have been studied. The pyrolysis experiments were performed batch wise
in a large retort.
10. Paul T. Williams et.al, [10] described their work in the paper “Catalytic pyrolysis
of tyres: influence of catalyst temperature”. Two stage thermal decomposition i.e.,
pyrolysis-catalysis of used tyres was done by them. The tyres were first pyrolysed
in a fixed bed reactor and then the evolved pyrolysis gases were passed through a
secondary fixed bed reactor containing Zeolite catalyst. The pyrolysis reactor was
maintained at 500°C and the influence of catalyst temperature between 430°C and
600°C on the yield and composition of the derived oils were examined.

-7-
11. Jian-Bing Zhao et.al, [11] have written a paper titled “Pyrolysis of Waste Tyres
with Copper Nitrate”. They studied the influence of copper nitrate on the pyrolysis
of waste tyres in a 50 cm3 static batch reactor in nitrogen atmosphere. The results
showed that the gaseous mixture contained H2, C2H6, C3H8, CO2, CH4, C3H6, CO
in the sequence of their yields.
12. L.Sorum et.al, [12] in their paper titled “Pyrolysis characteristics and kinetics of
municipal solid wastes”, have observed that the large variety in municipal solid
waste (MSW) composition and difference in thermal degradation behaviour of
MSW component makes modelling, design and operation of thermal conversion
system a challenge.
13. EPA, 1992, [13] Pyrolysis Treatment, Engineering Bulletin. This bulletin
describes that pyrolysis could transform hazardous organic materials into gaseous
components, small quantities of liquid, and a solid residue (coke) containing fixed
carbon and ash. Pyrolysis of organic materials produces combustible gases,
including carbon monoxide, hydrogen and methane, and other hydrocarbons.
14. Fagbemi et.al, [23] have written a paper titled “Pyrolysis products from different
biomass: application to thermal cracking of tar”. Their work involved conducting
experiments in a small capacity pyrolyser provided with external heaters. The
heating is achieved either by dropping the biomass basket into the heated section or
by placing a small quantity of biomass on a wire mesh and passing required current
through it or by feeding at slow rates in to the heated reactor. During the trials,
inert gas was used to sweep the volatiles produced during the pyrolysis.
The pyrolysis reactor details which have been compiled from the different articles
collected from international technical journals are given in Table 3.1.

-8-
 Table 3.1 Pyrolysis reactor details
Thickness
Material
Diameter Height Temperature Type of Sample used Heating rate of the Type of
Title of paper used for
(cm) (cm) (°C) reactor and quantity (°C s-1) reactor wall heating
reactor
(cm)
Pyrolysis of used Electrical
automobile tires and Captive Used tyres heating
Stainless
residual char utilization[8] 7 12 390-800 sample of 70-90 1
steel
reactor 500 g

Experimental studies on
pyrolysis of Dantong coal Electrical
with solid heat carrier in Datong coal heating
Fixed bed Stainless __ __
fixed bed reactor 12 45 350-500 of
reactor steel
[13] 1,3,5,8mm

Characterization potential
application of pyrolytic Continuou
char ablative pyrolysis of s ablative
__ __ Stainless __ __ __
used tires[14] 550 reactor Used tires
steel
(CAR)

Hardware component
waste pyrolysis energy Tubular
recovery and liquid quartz
Hardware __ __ __ Electrical
fraction valorization[15] 4 70 600 reactor
component heating

Vacuum pyrolysis of
Automobile
automobile shredder Vacuum
shredder
residues: Pyrolysis Electrical
60 300 450 residues: __ __ __
use of the pyrolytic oil as in a pilot heating
130 kg
a modifier for road plant
bitumen [9]

-9-
 Table 3.1 : Pyrolysis reactor details (Contd.)

Thickness
Material
Diameter Height Temperature Type of Sample used Heating rate of the Type of
Title of paper used for
(cm) (cm) (°C) reactor and quantity (°C s-1) reactor wall heating
reactor
(cm)
Charecterisation of
pyrolytic light napha
from vacuum Pyrolysis Used tyres
Horizontal __ __ __ __
of used tyres 60 300 500 (SBR)
reactor
comparition with 19 kg
petroleum naphtha [17]
Charecteristion of
product from the
Polyester/gla
recycling of glass fibre Electrical
450 Fixed bed ss fibre , Stainless __ __
reinforced polyester 0.6 202 heating
reactor 30wt%,7wt% steel
waste by pyrolysis[18 ]
1.5 kg
Catalytic pyrolysis of
tyres: influence of Used tyres
catalyst Fixed bed 200 gm of Stainless __ Electrical
10 15 500 10
temperature[10] reactor sample steel heating

Production of biocrudes
from biomass in fixed Fixed bed
bed tabulated reactor: Stainless Electrical
tubular Sunflower 7 Kmin-1 __
product yields and 1.1 80 400-700 Steel 316 heating
reactor
compositions [21 ]
Characteristics of
evolution of tar from
Inconel
wood pyrolysis in a Fixed bed __ __ Electrical
2 30 700 Wood 600
fixed- bed reactor reactor heating
alloy
[13 ]

- 10 -
 Chapter 4
DESIGN AND CONSTRUCTION

4.1 System components:

On the basis of literature survey conducted, it was found that most of the
researchers had developed only lab scale model for their investigation on pyrolysis
This is because, the solid wastes pyrolysis must be analyzed first in the lab scale
reactor, before the establishment of any large scale pyrolyser plant. The essential
components of the pyrolysis system have thus been identified from the literatures
collected. The schematic diagram of solid waste pyrolysis system is shown in fig.4.1.

5
1 6
2 3 4

Water Water Pyrolytic

in out oil
1. Pyrolysis reactor 4. Scrubber
2. Volatiles condenser 5. Sucking blower
3. Gas-liquid separator 6. Gas burner
Fig.4.1 Schematic diagram of pyrolysis system
4.2 Pyrolysis reactor:
The reactor which has been designed for the solid waste pyrolysis is a
cylindrical shell. Refer fig.4.2. It is a semi batch type, fixed bed reactor made up of
mild steel sheet. The net volume of the reactor is about 5.3 l. The thermal degradation
of the waste is caused by electrical resistance heating. There are three heaters arranged
inside the cylindrical shell vertically protruding into the reactor from the bottom closed
side. Refer fig.4.3. They form the three vertices of a virtual equilateral triangle inside
the shell. Each heater is rated 1 kW; all the three heaters are connected in parallel to
the applied external power supply, so that the total rate of heating comes to about 3
kW. The total resistance has been measured as 16 ohms. The heater is made up of 20
SWG nichrome wire wound in the form of a coil. The top side is open through which
solid wastes are fed at the beginning and the solid residue is removed after pyrolysis.
During the reaction, the top side is kept closed by a cover plate tightly secured to the

11
flanged opening. This prevents ingression of atmospheric air into the reactor, thereby
achieving pyrolysis. The reactor weighs approximately 17 kg. The pyrolyser is
provided with ceramic wool insulation on the outer side. An exit pipe at the side
carries away the evolved gases during pyrolysis. The temperature inside the reactor is
measured by a thermocouple.

φ 152

Top lid

Exit pipe

Thermocouple
250
380

Heater
350

All dimensions are in mm

Fig.4.2 Pyrolysis Reactor

12
 Heater

φ 42

φ 152

All dimensions are in mm

Fig.4.3 Schematic View of Heaters

4.3 Volatiles condenser:

The condenser is provided to cool and condense the gases evolved out from the
pyrolyser. As a result of cooling, the condensable gases become liquid which is called
pyrolytic oil. The condenser is a vertical shell and tube type heat exchanger as shown
in fig.4.4. The evolved gases from the pyrolyser pass through the tubes and the cooling
water is circulated on the shell side. It has 1- shell pass and 1- tube pass counter flow
type of arrangement. The cooling water is circulated by a water pump. As the evolved
gases may contain particulate matter and tar, they are passed on the tube side, so that
cleaning would be easier after the experiments. Instead of room temperature water
being circulated from the water pump, chilled water from a water chiller can also be
supplied to increase the pyrolytic oil yield. However, a certain fraction of gases cannot
be condensed and they are termed as non condensable gases.

13
 Fig.4.4 Volatiles condenser

4.4 Gas-Liquid Separator

The pyrolytic oil formed in the volatiles condenser drips down and get collected at
the bottom of the gas liquid separator. Besides, those liquid droplets borne by the
gases can also be separated out due to differential inertia as the velocity is very much
reduced in the separator. Refer fig.4.5. The separator has two chambers separated

Fig.4.5 Gas liquid separator

by a segmented baffle. The oil laden gases enter the separator from the top into the first
chamber; flow downwards and then rise up in the second chamber. During the flow,
the liquid oil gets collected at the bottom and the non condensable gases rising up in
the second chamber leaves through a hole at the top. The non condensable gases are
taken through a pipe and bubbled into water kept in a pan.

14
4.5 Instrumentation:
The instrumentation panel consists of a fuse unit, MCB, on-off switch,
voltmeter, ammeter and single phase energy meter. The temperature of the pyrolyser
is measured by a K- type thermocouple connected to a digital temperature indicator of
1°C accuracy. The time is measured by a digital timer of 0.01 second accuracy. The
weights of input feedstock and residue after pyrolysis are measured by a digital
weighing balance of 1 gm accuracy. The pH is determined in Deluxe pH meter
(Model 101E).
The overall arrangement of the components is shown in fig.4.6.

Fig.4.6 Overall experimental set up

15
 Chapter 5
EXPERIMENTS

The experiments were conducted by maintaining the pyrolyser under non-

isothermal conditions by heating. During the experiments, pyrolysis was carried out
only in the range from slow to moderate rate of heating. The following quantities
were involved in the experimental studies.
5.1 Variables changed:
• Type of raw feedstock (Scrap tyre, LDPE, PVC)
• Rate of heating
For each type of raw feedstock, tests were conducted for three different heating rates.
5.2 Parameters observed:
• Initial weight of raw feedstock
• Initial weight of water in bubbling tank
• Temperature of pyrolyser at regular time intervals
• Voltage at regular time intervals
• Current at regular time intervals
• Heater energy consumption at regular time intervals
• Time period to attain 600°C in every trial
• Final weight of solid residue
• Final weight of liquid oil collected
• Final weight of water in bubbling tank
• pH value of water in bubbling tank
5.3 Parameters calculated:
• Rate of temperature rise
• Reactivity
• Yields of pyrolysis products
5.4 Procedure:
5.4.1 Heating without any charge:
Initially, the rate of temperature rise of the pyrolyser without containing any
charge was observed when heated. The time to reach 600°C was also noted. This was
done to compare the electrical energy consumption for the pyrolysis of feed stocks
with that of the uncharged pyrolyser.

16
5.4.2 Pyrolysing scrap tyre:
Scrap tyre of a two wheeler was obtained and cut into pieces so that they can be
easily fed into the pyrolyser to occupy its full volume. The initial quantity of scrap
tyre pieces was weighed before charging into it. The top lid was tightly secured to the
pyrolyser by bolts and nuts. Cooling water was circulated in the volatiles condenser by
means of a pump. A measured quantity of water was taken in the bubbling tank. In
the first test, only one heater was energized ‘ON’. During the heating process,
temperature, voltage, current, heater energy consumption were observed at regular
time intervals. This was continued till the pyrolyser temperature reached 600°C; the
heating was stopped at this condition.
The system was allowed to cool up to room temperature naturally. Then the
top lid of the pyrolyser was opened; solid residue remaining in the pyrolyser was taken
out and weighed. The stopper at the bottom of the gas-liquid separator was also
opened and pyrolytic oil was drained into a jar. The pyrolyser was cleaned with
acetone and made ready for the subsequent test. The same procedure was followed for
the cases of a) when two heaters ‘ON’ and b) when all the three heaters ‘ON’.
5.4.3 Pyrolysing LDPE:
LDPE roll of virgin grade was procured and cut into pieces and then fed into
the pyrolyser till it covers the entire volume of the reactor. The procedure detailed in
Section 5.4.2 for scrap tyre was followed for LDPE also.
5.4.4. Pyrolysing PVC:
PVC pipes were procured and cut into pieces so that they could be easily
charged into the pyrolyser up to the brim. The procedure detailed in Section 5.4.2 for
scrap tyre was followed for PVC also.

17
 Chapter 6
RESULTS AND DISCUSSION
6.1 Physical observation:
The photographs of raw feed stocks and the solid residues obtained after
pyrolysis are shown in fig. 6.1.
Type of Solid wastes Final residues

Scrap tyres

Polyethylene

PVC pipes

MSW
Fig. 6.1 Types of solid wastes and final residues after pyrolysis

18
6.2 Heating without any charge:
Without taking any solid wastes in the pyrolyser, the temperature rise of the
reactor when it had been heated was observed. The temperature Vs time graph for that
case is shown in fig.6.2.

Pyrolyser without charge

700

600

500
Temperature (C)

400

300

200

100

0
0 5 10 15 20 25 30 35
Time (min)

Fig. 6.2 Plot of temperature Vs time for pyrolyser without charge

It is observed from the graph, that the temperature rise is faster initially up to a
temperature of 400°C; after which it becomes slower due to increased heat loss by
radiation.
6.3 Pyrolysis of scrap tyre:
The temperature variation of the pyrolyser with respect to time in the case of
scrap tyres when all the three heaters were ON is shown in fig.6.3. The rate of
temperature rise is higher in the case of scrap tyre pyrolysis than that for uncharged
condition of the pyrolyser. This may be due to certain exothermic reactions occurring
during pyrolysis of scrap tyres.

19
 Tyre Pyrolysis

800
700
600

Temperature (C)
500
400
300
200
100
0
0 5 10 15 20 25 30 35
Tim e (m in)

Fig.6.3 Plot of temperature Vs time for scrap tyre pyrolysis

6.4 Pyrolysis of LDPE:
Low Density Poly Ethylene sheets of virgin grade were pyrolysed in the
reactor. It was observed that the rate of temperature rise was slower for LDPE. This
may be due to the occurrence of a number of endothermic reactions. The temperature
Vs Time chart is shown in fig.6.4.

LDPE Pyrolysis

800
700
600
Temperature (C)

500
400
300
200
100
0
0 20 40 60 80 100
Tim e (m in)

Fig.6.4 Plot of temperature Vs time for LDPE pyrolysis

6.5 Pyrolysis of PVC:
The pyrolysis of Poly Vinyl Chloride was carried out under the same
conditions similar to LDPE. The temperature rise is faster when compared to LDPE.
The variation of temperature Vs time for PVC pyrolysis is shown in fig.6.5. But the
evolution of HCl vapours contributes very much to environmental pollution. It also

20
converts the water in the pan through which the gases are bubbled out to become
strongly acidic.

PVC Pyrolysis

800
700
600

Temperature (C)
500
400
300
200
100
0
0 10 20 30 40 50 60
Tim e (m in)

Fig.6.5 Plot of temperature Vs time for PVC pyrolysis

6.6 Products yield:

The products of pyrolysis are solid residue, liquid pyrolytic oil and gaseous
volatiles. Better the cooling of gases, more the quantity of oil collected. The typical
yield of products of pyrolysis for a) scrap tyre, b) LDPE and c) PVC are shown in
fig.6.6.

Yield

100%

80%
% b y weight

60% Gas
Oil
40% Char
20%

0%
Tyre LDPE PVC
Material

Fig.6.6 Yield of pyrolysis products

21
6.6 Reactivity of feed stocks:
In order to analyze a more practical kind of waste, a type of MSW was
obtained from Garbage Compost Production Centre, Arasur, Villianur Commune,
Pondicherry. The Centre is run by PASIC an Undertaking of Pondicherry
Government. In this centre, raw MSW from Pondicherry Municipality is segregated
mechanically in the process of composting. One of the segregations is the MSW
containing more amount of plastics; this segregation is dumped in landfills. This type
of MSW which is rich in plastics called hereinafter as ‘screened MSW’ was collected
from the centre and analysed in the pyrolyser.
Experiments were also conducted to determine the average reactivity of
different feed stocks such as scrap tyres, LDPE, PVC, screened MSW and dry leaves.
The average pyrolytic reactivity ‘r’ of a feedstock during a time period of ‘t’ minutes is
given by
r = W1-W2 x 1 min-1
W1 t
Where W1 = initial weight of raw feed stock taken in the pyrolyser
W2 = final weight of residue after pyrolysis
The average reactivities of various types of feedstock are shown in table 6.1.
Table 6.1 Average pyrolytic reactivities of different wastes
Sl. Solid wastes Avg. pyrolytic
No. reactivity (min-1)
1 Scrap tyre 0.01843
2 LDPE 0.019
3 PVC 0.02201
4 MSW 0.00909
5 Dry leaves 0.02105

6.7 Nature of collection water after pyrolysis:

The non-condensable pyrolysis gases coming from the gas-liquid separator are
bubbled through water kept in a pan. This was done to prevent ingression of outside
air into the reactor. As a result of passage of gases through water, it gets contaminated
and its nature changes. The pH value of the pan water was measured after pyrolysis of
each feed stock. The results are shown in table 6.2.

22
Table 6.2 pH values of water after pyrolysis of different wastes
Sl.
Solid wastes pH value of water
No.
1 Scrap tyre 9.2(Moderately alkaline)
2 LDPE 2.78 (Acidic)
3 PVC 0.1 (Strongly acidic)
4 MSW 3.9 (Moderately acidic)
5 Dry leaves 3.8 (Moderately acidic)

23
 Chapter 7
CONCLUSIONS

It is very much essential to scientifically dispose the ever increasing solid

wastes generated by the growing population. Pyrolysis of solid wastes is one of the
safe methods of disposal. From the experiments conducted on various types of solid
wastes, the following conclusions are derived.
• The hydrocarbon part of any solid wastes can be pyrolysed.
• Pyrolysis of solid wastes will yield solid char, liquid oil, and gases; all of them
have considerable heating values.
• The pyrolysis of scrap tyres has produced solid char containing steel wires
which can be recycled and the percentage of liquid oil collected is more than
that of gases. The temperature rise of the pyrolyser is faster due to better heat
transfer inside the reactor.
• The pyrolysis of LDPE has produced only a little char, but the percentage of
volatiles is high which can be largely converted to liquid oil, theoretically up to
100 %. The temperature rise is slower when compared to that of scrap tyres
and PVC due to poor heat transfer characteristics and drastic physical changes
taking place during pyrolysis.
• The pyrolysis of PVC has produced more solid char than LDPE, but the
evolution of HCl vapours requires pretreatment as they are strongly acidic. The
temperature rise of the pyrolyser is faster than that for LDPE.
• The average specific reactivity of screened MSW is very low when compared
to that of scrap tyres, LDPE, PVC and dry leaves due to the presence of inert
materials in it.
• The specific electrical energy consumption during pyrolysis is lowest for scrap
tyre, and highest for PVC.
• The pyrolysis of PVC can be safely done only with the integration of a
downstream treatment process for HCl vapours.
• A real pyrolyser plant can be operated by deriving heat from a portion of the
feed stock itself, instead of the electrical heating practiced in the case of lab
scale pyrolyser.

24
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27