Project Thesis

PRODUCTION OF INDUSTRIAL FUEL BY CO-PYROLYSIS OF
WASTE SLUDGE AND WASTE PCBs

A PROJECT REPORT

Submitted by

DHARMIK JOSHI (200305103704)
DHRUMIL SONI (200305103728)
HIREN THESIYA (200305103766)

In fulfilment for the award of the degree

Of

BACHELOR OF TECHNOLOGY

In
CHEMICAL ENGINEERING

Under the Guidance of

Prof. Priyeshnath Rathod
Assistant Professor
Chemical Engineering Department
Parul Institute of Technology
Parul University, Vadodara

March -2023
FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page I

PARUL UNIVERSITY
CERTIFICATE
This is to certify that Project-I -Subject code 203103408 of 8th Semester entitled
“PRODUCTION OF INDUSTRIAL FUEL BY CO-PYROLYSIS
OF WASTE SLUDGE AND WASTE PCBs” Of Group No.PUCH_39 has
been successfully completed by
DHARMIK JOSHI (200305103704)

DHRUMIL SONI (200305103728)
HIREN THESIYA (200305103766)
under my guidance in fulfillment of the Bachelor of Technology (B.TECH)

inChemical Engineering of Parul University in Academic Year 2022-2023
Project Guide Project Coordinator

Prof. Priyeshnath Rathod Prof. Priyeshnath Rathod
Head of Chemical Department, External Examiner

Dr. Vishal Sandhwar
FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page II

PARUL UNIVERSITY
ACKNOWLEDGEMENT
Behind any major work undertaken by an individual there lies the contribution of
the people who helped him to cross all the hurdles to achieve his goal.
It gives us the immense pleasure to express our sense of sincere gratitude towards
our respected guide Prof. Priyeshnath Rathod, Assistant Professor of
Chemical Engineering Department, for his persistent, outstanding, invaluable co-
operation and guidance. We gained a lot of valuable guidance and prompt
suggestions from him during entire project work. We will be indebted of him
forever and we take pride to work under him.
The journey to accomplish the work was too long. There were so many pillars who
helped us to reach here. So, we would like to show our sincere gratitude to them,
Mrs. Zarna Patel and Miss. Jinal Patel, Research scholars of Petroleum
engineering department for their constant help during lab scale experiment and
Handling the Nitrogen gas.
Mrs. Priya Patel, Mr. Akshay Jayswal and Mr. Jaydeep Parmar, Lab
assistants of Chemical engineering Department thanks for constant help.
FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page III

We also express our deep sense of regards and thanks to Dr. VishalSandhwar,
Head of Chemical Engineering Department. We feel very privileged to have their
precious advices, guidance and leadership.
Last but not the least, our humble thanks to the Almighty God.
Place: Vadodara
Date: 15/03/2023
FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page IV

ABSTRACT
This research work designed, developed and assessed the performance of a co-
pyrolysis system generating industrial fuel by the use of E-waste (PCB) & waste
jatropha sludge. Due to massive amount of both waste in different dumpsites, our
community suffers and also the environment. Thus, affects nearby people with
problems with E-waste. Demand for PCB is increasing day by day which pose a
tremendous threat to the environment. Pyrolysis process becomes an option to
waste –to- energy technology deliver fuel to replace the fossil fuel. Design and
fabrication of machine to convert the E-waste into Fuel as an effort in finding
environment friendly means of waste recycling by means of Co - Pyrolysis. In this
effort we design and develop a Co - pyrolysis process to conversion of E-waste and
waste jatropha sludge into fuel. One of the processes to lessen these wastes is
through pyrolysis of which fuel can be produced. The study involved the
production of fuel from E-waste taken from the dump site. Jatropha Sludge
commonly dump in the land and also the designing of the Co - pyrolysis setup
which is suitable for the high temperature about 600 to 700 °C and in this process
multiple feedstocks are available. We do the TGA test for our raw material because
of the check the degradability of the raw material which is the E-waste and waste
jatropha sludge and other test we do the final product test like the FTIR. Design
and fabrication of machine to convert the plastic into oil as an effort in finding
environment friendly means of waste recycling by means of plastic pyrolysis.
Keywords: Waste Plastics, Sludge Jatropha, Thermogravimatric Analysis Test,

Designing of Co-Pyrolysis system, Characterisation of Pyrolytic Oil, Phenolic
Compound.
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TABLE OF CONTENTS
Title Page I
Certificate II
Acknowledgement III
Abstract IV
Table of Contents V
List of Tables VII
List of Figures VIII
List of Abbreviations IX
Chapter : 1 Introduction
1.1 Overview 1
1.2 Process Description 1
1.3 Process Overview 3
Chapter : 2 Literature Survey
2.1 Literature Survey With Summary 4
Chapter : 3 Research Methodology
3.1 Overview of Methodology 11
3.2 Pyrolysis Methods 11
3.3 Proposed methodology 12
3.3.1. Co - Pyrolysis method 12
3.3.2.Process Description 13
Chapter : 4 Experimental Work
4.1 Experimental Steps 14
4.1.1.Selection & Preparation of Raw Material 14
4.1.2.Pre-Treatment Steps 15
4.1.3.Experimental Setup 16
4.1.4.Pyrolysis 16
4.1.5.Separation of Fuel 17
4.1.6.Bio Char 18
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Chapter : 5 Kinetic Model
5.1 Kinetic Modeling. 19
5.2 Model Free Methods. 20
5.3 Global Kinetic Models. 23
5.4 Pyrolysis Kinetic Models. 24
Chapter : 6 Application of Products
6.1 Application of Industrial Fuel 31
6.2 Application of Bio Char 31
Chapter : 7 Result Analysis 32
Summary 40
References 41
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LIST OF TABLES
Table No Table Description Page No
Table 7.1 TGA Summary Sample 1-28 35
Table 7.2 TGA Analysis of sample 1-28 36
FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page VIII

LIST OF FIGURES
Figure No Figure Description Page No
1.1 Printed Circuit Board 2
1.2 Jatropha seed 2
1.3 Pyrolysis Setup 3
3.1 Proposed Experimental Setup 12
4.1 Printed Circuit Board 14
4.2 PCBs in Shredded form 14
4.3 Jatropha Seed 15
4.4 Jatropha Seed cake after the extraction of oil 15
4.5 Drying of Jatropha sludge 15
4.6 Experimental Setup of Pyrolysis 17
4.7 Separating Funnel 17
4.8 Industrial fuel in liquid form 17
4.9 Bio char 18
7.1 TGA plot Sample 1-28 33
7.2 Sample 1 Activation Energy graph 38
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LIST OF ABBREVIATIONS
Sr. No. Symbol/Abbreviations Name

1 TGA Thermogravimetric Analysis
2 PCB Printed Circuit Board
FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page X

CHAPTER 1: INTRODUCTION
1.1 OVERVIEW:
Now days as we know day by day many industries are used a Jatropha to obtain
the Industrial Fuel. Where industries get the Industrial Fuel as a main product and
Bio-char as a by-product. Jatropha sludge is the totally non usable and waste
material for all Bio-fuel industries because they dump that sludge on land. That’s
why it is non usable and waste.
The day by day as we know that the increasing the level of both waste in
environment. Which is harmful for the environment as well as human being. Also,
it will not possible to recycle and reuse. That’s why we are trying to use the both
waste material as a feed stock to obtain the industrial fuel. So, by the use of it we
reduce the level of waste.
1.2 PROCESS DESCRIPTION:
Now we have three unknown words in our project title which is follow: -
1. Jatropha:
 Jatropha is a low-cost biodiesel feedstock with good fuel properties and
more oil than other species. It is a non-edible oilseed feedstock.
2. Co-Pyrolysis:
 Co-pyrolysis is a process which involves two or more materials as
feedstock. Many studies have shown that the use of co-pyrolysis is able to
improve the characteristics of pyrolysis oil.
3. Printed Circuit Board (PCB):

 Printed circuit boards are integral to any electronic product But recycling
PCBs in an efficient & environmentally friendly way can be an enormous
challenge.
 They also contain high-grade precious metals such as palladium, silver,
copper and gold.
Plastic waste problems have worsened year by year and with so many
environmental methods were developed for the recycling of waste plastics, still
millions of tonnes were dumped instead of just doing the recycling process [01].
FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page 1

One of the methods that was known today were recycling and energy recovery
methods such as incineration, gasification and chemical processing. Recycling
method was considered an alternative in solving the crowded landfill areas. But
plastic recycling was proven difficult and labor intensive, and can also costly for
separation methods. A promising technique of plastic waste energy recovery was
developed by converting the waste materials into fuel source [02][03].
Figure 1.1 PCB Figure 1.2 Jatropha Seed

(Printed Circuit Board)
A more reliable and sustainable way was developed instead of reduction of the
plastic waste by way of plastic recycling[04]. Pyrolysis was introduced as a more
sustainable method than recycling, for the conversion of the plastic waste and
produced a liquid in high calorific values. Pyrolysis is a thermal degradation
process in which a long chain of hydrocarbons was converted into shorter one.
[05]
Traditionally, the production of liquid fuels, organic chemicals and energy, has
relied heavily on the gasification of coal, distillation of crude oil and hydro-
power. As our natural resources are becoming depleted, and continue to do so due
to the exponential growth of our population, the need to look elsewhere for
sources of alternative raw materials and processes is imperative. Domestic and
industrial plastic solid waste (PSW) collection and disposal systems in Botswana
are not as efficient as those in other developing African countries. Specifically,
the mode of disposal of PSW in smaller cities and villages in Botswana is a major
concern.[06][07]

Although the rate of reaction associated with the biodegradation process of plastic
waste is said to be slow that it is kinetically approximated not to be taking place,
it is however thermodynamically feasible. Some chemical engineering reaction-
based researchers have argued that pigments used in plastics as well as plastics
can be broken down by acidic leachates under certain harsh conditions of
temperature and pressure to give products that are both deleterious and obnoxious
to the environment and to the underground water sources which in some areas
serve as drinking water for livestock, wildlife and even the rural folk.[08]
1.3 PROCESS OVERVIEW:
 The Co - Pyrolysis method can be used to upgrade the pyrolytic oil where two or
more feedstock materials are involved.
 The calorific value and oil yield in the Co-Pyrolysis method are higher than
pyrolytic oil. Also, the upgraded oil in the Co-Pyrolysis method contains low
water that can improve the fuel property.
 Different Biomasses, solid waste is significantly used as feedstock in the Co-

Pyrolysis method.
 Many studies have shown that the use of co-pyrolysis is able to improve the
characteristics of pyrolysis oil.
Figure 1.3 Pyrolysis Setup

CHAPTER 2: LITERATURE SURVEY
In year of 2021, the Journal of American Journal of Engineering and Applied

Sciences with title Design, Fabrication and Operational Evaluation of a Co-
Pyrolysis System for Waste-Plastics Derived Fuels: A Study of Edo North And
Author Kevin Otoikhian, Ubani Oluwaseun Amune, 1Kennedy Edogamhe,
Emmanuel Aluyor with Vol: 25, said that This research work designed,
developed and assessed the performance of a co-pyrolysis system generating
waste-plastic extract fuels from mixed Municipal Waste Plastics (MWP) while
evaluating High-Density Polyethylene (HDPE), Polypropylene (PP) and
Polystyrene (PS) as the main municipal waste plastic sources. The materials
selected for the reactor were carefully studied to meet the pyrolysis system's
strength, operability and safety requirements. The equipment was put through
its paces in three trials, using 2kg of mixed municipal waste plastics each. The
temperature was optimally constant at 450°C for three hours. The equipment
had a functional conversion efficiency (wt %) of 73.17%, a waste reduction
efficiency (wt %) of 86.3% and oil recovery of 0.90L oil/kg MWP, according to
the test results. As a result of its re-cracking process, which recycles heavy
molecular weight compounds back into the reactor, this reactor was built in
such a manner that only compounds in the carbon range of C1 20 may be
created. This process was discovered to have a major impact on the product's
distribution. Plastic fuels generated from co-mingled municipal waste plastics
had similar characteristics with diesel and based on the characterization and
comparative research done in this study
In year of 2121, the Journal name is Journal of Xi'an University of Architecture

& Technology Title ofDesign, Fabrication and Operational Evaluation of a Co-
Pyrolysis System for Waste-Plastics Derived Fuels: A Study of Edo North
with Author Kevin Otoikhian, Ubani Oluwaseun Amune, 1Kennedy
Edogamhe, Emmanuel Aluyor and Vol: 25, id published that The gradual
increasing of energy demand pressurize find out new alternative technique and
available source that can mitigate current fuel crisis. Pyrolysis is one of the
latest renewed interesting and reliable thermo chemical technique to recover
energy from any kind valuable source. It is the process of heating the feed
stocks at an oxygen free atmosphere and the products are pyro-oil, char, and
gas. These pyro oil can be used as a fuels and char for the manufacture of

activated carbon (Kumaravel, Murugesan, & Kumaravel,2016). A pyrolysis
reaction scheme is shown in Fig. 1. Due to the simple operation and low
operating cost, pyrolysis is widely used For the production of pyro oil or char
(Ly, Kim, Choi, Woo, & Kim, 2016). A lot of works have been developed on
pyrolysis in traditional reactors such as fluidized-bed (Ly et al., 2015; Yanik,
Stahl, Troeger, & Sinag, 2013), fixed bed (Aguiar, M_arquez-Montesinos,
Gonzalo, S_anchez, & Arauzo, 2008; M. R.; Islam, Tushar, & Haniu, 2008;
Quan, Gao, & Song, 2016), rotary kiln (A. M. Li et al., 1999),vacuum (De
Jongh, Carrier, & Knoetze, 2011), free-fall (Zhang, Xu,Zhao, & Liu, 2007)
reactors etc. regarding product distribution atdifferent operating conditions.
Whilst recently the pyrolysis ofterrestrial biomass has received a great deal of
attention at variousexperimental conditions from rice husk and rice straw (Fu et
al.,2011), palm (Abnisa, Arami-Niya, Daud, & Sahu, 2013), orange peel
(Aguiar et al., 2008), tamarind seed (Kader, Islam, Parveen, Haniu, & Takai,
2013), and jute dust (Choudhury, Chutia, Bhaskar, & Kataki, 2014).
In year of 2020, the Journal name is Proceedings of IOE Graduate Conference,

with Titleof Design, Fabrication and Testing of Waste Plastic Pyrolysis Plant
with Author is Ajay Jayswal, Arbind Kumar Sah with Vol: 5 , is published that
In recent decades, there has been a dramatic increment in plastic consumption.
Used plastic is one of the major wastes in many countries including Nepal. A
lot of money is spent in land filling to process plastic wastes which can pose a
threat to environment in long run. The incineration of plastic wastes leads to
severe air pollution. Plastic pyrolysis process is a widely used technique to
handle plastic wastes in many foreign countries. It is a new technology in
Nepalese context. It involves melting plastic wastes, vaporizing them,
condensing the vapour and distilling to obtain fuel. In the pyrolysis reactor,
plastics are heated, vaporized and the vapour thus produced is passed to shell
and tube condenser for condensation. The liquid thus obtained is called
pyrolysis oil and char remains in pyrolysis reactor as residue. The yields
depend on various factors like plastic type used, cracking temperature of plastic,
rate of heating, operation pressure of reactor, type of reactor, residence time,
use of catalyst, etc. The plant was designed and modelled in 3D CAD software,
Solid works. Batch reactor was employed to pyrolyse Low Density
Polyethylene at reactor base temperature of about 600°C and the vapour
produced was directed to horizontal, counter-flow shell and tube condenser.
From 10 kg of plastics, the plant yielded 6.63 litters of pyrolysis oil and 2.236
kg of char, on average, in the cost of 3.169 kg of LPG gas.
In year of 2019, the Journal name is The Italian Association of Chemical
Engineering with Title of Characterization of Pyrolytic Oil Produced from
Waste Plastic in Quezon City, Philippines using Non-Catalytic
Pyrolysis Method and Author Joselito A. Olalo with VOL. 86, is published
that Due to massive amount of waste plastics in different dumpsites, our
community suffers and also the environment. Thus, affects nearby people with
problems with plastic wastes. One of the processes to lessen these wastes is
through pyrolysis of which fuel oil can be produced. The study involved the
production of fuel oil from waste plastics taken from the Payatas dump site in
Quezon City, Philippines. After thorough cleaning, the waste plastics were
shredded thru mechanical means and underwent pyrolysis. Given the available
thermal chamber facility in ITDI-DOST in Taguig City, Philippines, pyrolysis
of waste plastics produced fuel oil in varying per cent yield from the different
types of plastic. Characterization of the oil sample was conducted such as ash
content, carbon residue, copper corrosion strip, flash point, pour point, sulphur,
kinematic viscosity, specific gravity water and sediments that were based from
the PNS/DOE QS 006-2005. The oil sample was analyzed using different
laboratory tests following the methods of the American Society for Testing and
Materials (ASTM). Using this standards, the analysis of the oil sample gave the
positive results in comparison to the specifications set by the Philippine
National Standard and was classified as fuel oil. Pyrolytic oil from waste plastic
can be an alternative fuel source
In year of 2019, the Journal name isAnatolian University Libraries

Consortium with Title of Continuous pyrolysis of sewage sludge in a screw-
feeding reactor. And Author is Ningbo Gao, Cui Quan, Baoling Liu, Zongyang
Li, Chunfei Wu, and Aimin Li with Vol: 5 is published that Pyrolysis of dried
sewage sludge is regarded as an effective treatment method as well as a
promising technology for energy/fuel production. In this work, thermo-
chemical conversion of dried sewage sludge in a continuous reactor at different
pyrolysis temperatures (400–800 °C) and solid residence time (6–46 min) was
conducted. The pyrolysis products obtained using different pyrolysis conditions
were extensively investigated. It is indicated that high pyrolysis temperature
(>700 °C) and long solid residence time (> 23 min) could enhance secondary
reactions and decrease the yield of bio-oil. The maximum yield of bio-oil of
16.69% was achieved at reaction temperature of 700 °C and solid residence
time of 23 min. The FTIR and GC-MS analyses of the bio-oil obtained at
optimum condition indicated that it contained large amounts of phenols and
esters. H2 and CO2 were the main components of pyrolysis gas, with a total
amount that exceeded 52.18%. The characteristics of the char, including
elemental.
In year of 2020, the Journal name is Journal of Radiation Research and Applied
Sciences with Title of Design, fabrication and performance test of a fixed bed
batch type pyrolysis plant with scrap tire in Bangladesh and AuthorMohammad
Abdul Aziz, M.A. Rahman , Halim Molla with volume 15 , is published that
The gradual increasing of energy demand pressurize find out new alternative
technique and available source that can mitigate current fuel crisis. Pyrolysis is
one of the latest renewed interesting and reliable thermo chemical technique to
recover energy from any kind valuable source. It is the process of heating the
feed stocks at an oxygen free atmosphere and the products are pyro-oil, char,
and gas. These pyro oil can be used as a fuels and char for the manufacture of
activated carbon (Kumaravel, Murugesan, & Kumaravel,2016). A pyrolysis
reaction scheme is shown in Fig. 1. Due to the simple operation and low
operating cost, pyrolysis is widely used for the production of pyro oil or char
(Ly, Kim, Choi, Woo, & Kim, 2016). A lot of works have been developed on
pyrolysis in traditional reactors such as fluidized-bed Gonzalo, S_anchez, &
Arauzo, 2008; M. R.; Islam, Tushar, & Haniu, 2008; Quan, Gao, & Song,
2016), rotary kiln (A. M. Li et al., 1999),vacuum (De Jongh, Carrier, &
Knoetze, 2011), free-fall (Zhang, Xu, Zhao, & Liu, 2007) reactors etc.
regarding product distribution at\ different operating conditions. Whilst recently
the pyrolysis ofterrestrial biomass has received a great deal of attention at
various experimental conditions from rice husk and rice straw (Fu et al., 2011),
palm (Abnisa, Arami-Niya, Daud, & Sahu, 2013), orangepeel (Aguiar et al.,
2008), tamarind seed (Kader, Islam, Parveen, Haniu, & Takai, 2013), and jute
dust (Choudhury, Chutia, Bhaskar, & Kataki, 2014).
In year of 2019, the Journal name isHindawi Journal of Nano materials with
title of Individual and Catalytic Co-Pyrolysis of Agricultural Outcomes and
Polymeric Materials over Nano-HZSM-5 Zeolite: Synergistic Effects and Yield
Analysis for Heating ApplicationsAuthor is C. Sowmya Dhanalakshmi ,N.
Ahalya,P. Vidhyalakshmi ,C. Krishnaraj ,N. Selvam,Pravin P. Patil,S.
Kalippan,and S. Prabhakar with Volume, 8 is published that the increased
energy demand and rapid industrialisation due to the population and modern
lifestyle force researchers to find alternative sources for conventional fuels.
According to the survey conducted in the middle of 2020, the need for global
energy is expected to increase by 30% over the next two decades in order to
sustain rapid urbanisation [1]. Every living being requires a healthy atmosphere
in order to thrive and develop. One of the biggest issues is the degradation of
ecosystems caused by the discharge of inorganic and organic pollutants from
various industries and automotive engines [2, 3]. There has been considerable
demand around the world to investigate the production and use of bio-fuels for
heat and power applications [4]. Fossil fuels have played a major part in
satisfying current energy demands, but their widespread usage has aggravated
serious environmental challenges, including global warming. Utilising bio-fuels
for power production has increased nowadays due to flexible conversion
methods and increased fuel properties. It is an alternative energy source that can
replace fossil fuels by up to 30% to 40% in the near future [5]. The augmented
solid waste output by the growing population provides carbon rich energy
resources and gives a widespread option for the production of energy. This
could also help with the waste disposal problems.
In year of 2019, the Journal name is Journal of applied science with Titleof
Evaluation of Waste Blends with Sewage Sludge as a Potential Material Input
for Pyrolysis and Authoris Lenka Kubonova , Iva Janakov 2,* , Petra Malikova
, Silvie Drabinova, Milan Dej, Roman Smelik , Pavel Skalny and Silvie
with volume 9 , is published that The large quantities of waste and waste
packaging produced by consumer society are a risk factor for both human
health and ecosystems. During waste production and its disposal, secondary
substances may escape into the environment, the constituents of which may be
contaminated. The substances contained in waste and packaging can enter the
human body through the food chain, and thus negatively affect human health
[1,2]. In the Czech Republic (an EU country with 10 million inhabitants), the
annual production of corporate waste has been around 22 million tons. In terms
of the origin of this waste, a constant trend can be observed in the increasing
production of waste particularly by companies engaged in the treatment,
collection, and processing of industrial or municipal waste. This includes waste
from municipal waste treatment facilities and wastewater treatment plants (so-
called secondary waste). However, these materials are not perceived as waste
only, but represent secondary raw materials due to their energy potential. At
present, the key waste management trend is to move towards a circular
economy [3], product reuse, recycling, and the conversion of waste to energy
[4], instead of mining.
In year of 2018, the Journal name is International Conference on Clean and

Green Energy with Titleof Co-pyrolysis of biomass and plastic wastes:
investigation of apparent kinetic parameters and stability of pyrolysis oils and
Authoris B. Fekhar1, N. Miskolczi1, T. Bhaskar2, J. Kumar2 and V. Dhyani
with volume 6, is published that This work is dedicated to the co-pyrolysis of
real waste high density polyethylene (HDPE) and biomass (rice straw) obtained
from agriculture. Mixtures of raw materials were pyrolyser in their 0%/100%,
30%/70%, 50%/50%, 70%/30%, 100%/0% ratios using a thermograph. The
atmosphere was nitrogen, and a constant heating rate was used. Based on
weight loss and DTG curves, the apparent reaction kinetic parameters (e.g.,
activation energy) were calculated using first-order kinetic approach and
Arrhenius equation. It was found that decomposition of pure plastic has
approximately 280 kJ/mol activation energy, while that of was considerably less
in case of biomass. Furthermore, HDPE decomposition takes by one stage,
while that of biomass was three stages. The larger amount of raw materials (100
g) were also pyrolyser in the batch rig at 550°C to obtain products for analysis
focussing to their long term application. Pyrolysis oils were investigated by
Fourier transformed infrared spectroscopy and standardized methods, such as
density, viscosity, boiling range determination. It was concluded, that higher
plastic ratio in raw material had the advantageous effect to the pyrolysis oil
long-term application. E.g., the concentration of oxygenated compounds, such
as aldehydes, ketones, carboxylic acids or even phenol and its derivate could be
significantly decreased, which had an advantageous effect to their corrosion
property. Lower average molecular weight, viscosity, and density were
measured as a function of plastic content
In year of 2019, the Journal name is Journal of ORIGINAL RESEARCH with

Titleof Catalytic Pyrolysis of Plastic Waste Moving Toward Pyrolysis Based
Bio refineries and Authoris Rashid Miandad1, Mohammad Rehan2*,
Mohammad A.Barakat 3,4, Asad S. Aburiazaiza3,izbullah Khan1, Iqbal M. I.
Ismail 2, Jeya Dhavamani 2, Jabbar Gardy 5, Ali Hassanpour 5 and Abdul-
Sattar Nizami with volume , 3 is published that Plastic waste production and

consumption is increasing at an alarming rate, with the increase of the human
population, rapid economic growth, continuous urbanization, and changes in
life style. In addition, the short life span of plastic accelerates the production of
plastic waste on a daily basis. The global plastic production was estimated at
around 300 million tons per year and is continuously increasing every year
(Miandad et al., 2016a;Ratnasari et al., 2017). Plastics are made of
petrochemical hydrocarbons with additives such as flame-retardants, stabilizer,
and oxidants that make it difficult to bio-degrade (Ma et al.,2017). Plastic waste
recycling is carried out in different ways, but in most developing countries,
open or landfill disposal is a common practice for plastic waste management
(Gandidi et al., 2018). The disposal of plastic waste in landfills provide habitat
for insects and rodents, that may cause different types of diseases (Alexandra,
2012). Furthermore the cost of transportation, labor and maintenance may
increase the cost of recycling projects (Gandidi et al., 2018).In addition, due to
rapid urbanization, the land available for landfills, especially in cities, is
reducing. Pyrolysis is a common technique used to convert plastic waste into
energy, in the form of solid, liquid and gaseous fuels.

CHAPTER 3: RESEARCH METHODOLOGY
3.1 Overview of Methodology: -
As per our Final product we get the various process, but every method does not suitable
for the final product. That’s why, we are using the Co-Pyrolysis method which suitable
for our final product. We get the good efficiency by use of that process.
3.2 Pyrolysis Methods: -
 There is various method that are developed and uses to convert plastic waste,
Biomass & other types of waste material into reusable components like fuel, gases,
char that processes mentioned below: -
Intermediate Pyrolysis: - Intermediate pyrolysis is the pyrolysis which is

between fast pyrolysis & slow pyrolysis. Intermediate pyrolysis is good
distribution of product and hence can be used in the coproduction of bio-char, bio-
oil, and gas but it requires additional energy for that biomass collection is its main
problem of industrialization.
Hydrodeoxygenation Method (HDO): - Hydrodeoxygenation (hydro-treating) is

a high-pressure and moderate-temperature process in which oxygen is rejected by
a catalytic reaction with hydrogen. selecting the heterogeneous catalyst and the
process conditions is crucial. Industrial hydro treating catalysts such as sulphide
cobalt/molybdenum and nickel.
Bio-mass Pyrolysis Method: - Biomass pyrolysis is defined as a Thermochemical

process that undergoes in complete absence of oxygen. It is very lengthy process
and time consuming.

3.3 Proposed Methodology
3.3.1 Co – Pyrolysis Method: -
 This method is to involve two or more material as feedstock.
 It is able to improve the characteristics of pyrolysis oil increase the oil yield
reduce the water content and increase the calorific value of oil.
 By using this method, the volume of biomass wastes can be easily controlled.
Moreover, in pyrolysis method, biomass feedstock materials are decomposed in
pyrolytic oil by the following reaction mechanism Equations [18]
Figure - 3.1Proposed Experimental Setup
3.3.2 Process Description :

 To obtain the industrial fuel , we use a Jatropha sludge & PCB as a feed
stock for Co-Pyrolysis process.
 We have a apparatus like follows.

A. Burner : For heating Purpose.
B. Pyrolyser : For mixing purpose.
C. Temperature sensor : For temperature measurement .
D. Condenser : For cooling purpose .
E. Storage : For product storage purpose.

 First we start the process from Pyrolyser. We feed our raw material in
pyrolyser column.
 Then we start the heating by use of burner at high temperature. And then
we wait for some hrs for mixing.
 After the mixing the product gone to the condenser. Their we set the lowest
cooling temperature for cool material. We set some minutes for cooling
material.
 After the cooling our product Industrial fuel will ready to use.
 We store our product in storage tank. And then we can easily used it for our
main purpose.
 We get the fuel which is usable for Aqua-regia, and reagents like cynide,
thiourea, thiosulphate,phenolic compounds.
 Also we get the Bio-Char which is usable for Bio char will be use as
adsorbate in adsorption process.

CHAPTER 4: EXPERIMENTAL WORK
4.1 Experimental Steps : -

We have conducted no. of experiments with various feed compositions and conditions, in
which we have taken Printed Circuit Board & Jatropha Seed Cake. After conducting
experiments with Printed Circuit Board, we have observed that we are not able to
obtained Industrial fuel as our products. So, after thorough literature reviews we found
that blending of Printed Circuit Board with Jatropha seed cake helps to increase the
Industrial-fuel yield and increase the production of bio-char as well.
4.1.1 Selection & Preparation of Raw Material :-
As, India Generates high amount of Electronic Waste annually with very less % of
Recycle ratio. In E-waste Major key component in that is the Printed Circuit Board that is
our main Feed stock. So we are utilizing the Printed Circuit Board Without any
hazardous metal like Copper, Zinc,Etc.
We have reduced the size of the Printed Circuit Board because thorough literature
reviews shows that the amount of fuel yield is directly proportional to the size of raw
material. Thus, we reduced the size of PCB by Shredding it into a small particles as
shown in figure.
Jatropha is a low-cost bio dieselfeed stock with good fuel properties and more oil than
other species. It is a non edibleoil seedfeed stock.We are Blending PCB with Jatropha
Sludge to Improve the Characteristic Bio char. We are Converting that seed cake into
powder form with the help of mixture.
Figure 4.1 - Printed Circuit Board Figure4.2 - PCB In Shredded form

Figure 4.3 - Jatropha Seed Figure 4.4 - Jatropha Seed Cake After
the Extraction of oil
4.1.2 Pre Treatement Step :-
After Size reduction, as a Pre-treatment step, we dry the our Jatropha Sludge up to 60-
70°c for around 30-35 minutes to remove the moisture contain from the Jatropha Sludge.
Because in order to get higher fuel yield, Jatropha Sludge must contain very less amount
of moisture.
Figure 4.5 - Drying of Jatropha Sludge

4.1.3 Experimental Setup :-
For Experiment purpose we have developed a prototype model and did our first
experiment with Following Equipment Like Pyrolyser, Condenser, Collection System,
Thermometer. We are using burnable wood to heat the Pyrolyser. For better heat transfer
co-efficient, we have used Ice Water for circulation of water in Condenser &
thermometer to measure the Temperature.
4.1.4 Pyrolysis :-
The pyrolysis process is the thermal decomposition of materials at elevated temperatures,

often in an inert atmosphere. It involves a change of chemical composition. The word is
coined from the Greek-derived elements pyro "fire", "heat", "fever" and lysis
"separating". [05] Pyrolysis is defined as the thermal decomposition of any substance in
the absence of oxygen at any elevated temperature. Or simply pyrolysis is said to be the
heating of an organic material, such as biomass, in the absence of oxygen at an elevated
temperature.[09]
For Experiment we have developed a prototype model and did our first experiment with
that and received our product Industrial Fuel as well as Bio Char. For that we have taken
PCB & Jatropha Sludge both in 50-50 % with 200 gm total and did our experiment with
following method.
As shown in figure we have started our experiment with feeding our raw material in
Pyrolyser and tighten the screw. We are using a Gasket to avoid Leakage of gases that
can fire immediately if it comes with an contact of Fire.
Then we are burning the wood to heat the Pyrolyser and that heating will lead to start
forming gases that will travel through our Condenser. In condenser we are Circulating
Cold Water with and Temperature Around 8-10 ℃ and with that temperature difference
the gases will convert into Liquid form and we will get the fuel in collection system.

Figure 4.6 - Experimental Setup of Pyrolysis
4.1.5 Separation of Fuel :-
During the experiments, we collect the bio-fuel from the collector after cooling in the
condenser and bio-char after the completion of the process. The fuel obtained have high
amount of water contain so, we separate the bio-fuel using separating funnel.
Figure 4.7 - Separating Funnel Figure 4.8 - Liquid Fuel From

the collection System

4.1.6 Bio char :-
It will be obtained from the pyrolyser after the completion of the pyrolysis process it can
be After the process is completed and the Pyrolyser is cooled down properly, we collect
the solid residue which contains bio-char.
Figure 4.9 - Bio Char

CHAPTER 5 : KINETIC MODEL
5.1 Kinetic Modeling
The concept of the single-step, solid-state reactions can be represented by the Arrhenius
equation. It means that the reactant molecules are in an endothermic equilibrium with the
active molecules that are involved in the reaction.
k(T) = Ae(- ERT ) (1)
where E is the activation energy (kJ mol -1) and A is the pre-exponential factor (>1). R
refers to the gas constant (kJ mol -1 K -1). T represents the temperature in K and k (T) is
a rate constant. The value of E was supposed to be a constant for single-step reactions
and it is the energy needed to turn inactive molecules into active molecules. To describe
the kinetic expression from the mass balance of a reacting solid and the conversion
degrees for a single-phase reaction, the thermogravimetric results can be expressed as
[22]:
da /dt= k(1 - a)^n (2)
where n is reaction order. A general kinetic Equation (2) is based on assumption that the
rate of process da/dt is a function of two variables only: degree of conversion (a) and
temperature (T). Assuming that the function of two variables can be substituted by a
product of two functions variables, k(T) and f (a). Therefore, the rate of heterogeneous
solid reactions can be described as [23]:
da / dt= k (T) f (a) (3)
where k(T) and t are rate constant and time, respectively. _ is the degree of conversion,
ranging from 0 to 1. f (a) is the reaction model that represents a certain solid-state
mechanism [24]. The degree of conversion can be defined as:
a = (m0 – mt / m0 - mf ) (4)
where m0, mt, and mf are the initial, instantaneous, and final mass of the sample.
Integrating Equation (1) into Equation (3), the rate of a solid-state reaction can be
expressed as:
da / dt= Ae -E/RT f (a) (5)

where E, A, and reactionmodel f(a) are called kinetic triplets [23]. If the reaction is
studied under non-isothermal conditions at a linear heating rate, b = dT/dt. In which
Equation (5) becomes:
da / dT = A/β e - E/RT f (a) (6)
Actual solid-state reaction is complex, which includes multiple solid–gaseous reactions

with different rates, such as adsorption, desorption, sublimation of gaseous products or
reactants on the surface of a reacting solid, and diffusion of gaseous products or reactants
through a solid [24,25].
Therefore, the effective activation energy derived from the overall kinetic data is a
composite number determined by the activation energies of the individual stages and their
relative contributions to the overall reaction rate. As a result, the effective activation
energy is usually a function of either temperature and conversion, or merely temperature.
That is why the concept of variable activation energy Ea is more suitable to the non-
elementary nature of heterogeneous solid-state reactions. It should be used to explain
how overall reaction rates are affected by temperature [26]. According to the previous
studies, this obtained activation energy is the apparent one and does not have any
mechanistic significance [27].
5.2 Model-Free Methods
There are two basic methods to calculate the kinetic triplets of complex solid-state
reactions, namely model-fitting and model-free (or iso-conversion) methods. The
modelfitting approaches use a single unpredictable heating rate [26], whereas the
modelfree method uses several heating rates, which eliminates mass transfer constraints.
Dhaundiyal et al. [15] employed a model-fitting approach (Coats Redfern method [28]) to
test the validity of the model-free method and produce the best appropriate reaction
model for the decomposition of weed and lignocellulosic materials, respectively. They
observed that kinetic parameters derived at various heating rates for models, differed
significantly from those computed using the model-free method.
The force-fitting of non-isothermal data to a hypothetical reaction model is the initial

cause of disagreement between model-free and model-based runs. Arrhenius parameters
are calculated in the form of g(a) in the model fitting of Coats Redfern method, which is
previously assumed and not able to discriminate separately temperature dependence of
rate constant and conversion resulting in erroneous estimates of Arrhenius parameters.
The possibility of multi-reaction pathways is another key cause of disagreement, as the
activation energy determined using the model-based method is a function of T and a.
However, the calculated value of activation energy represents the average value for the
overall process. It is derived in such a way that it is invariant with the reaction
mechanism and kinetics that depend on the change in temperature and degree of
conversion. With model-free methods, there is an opportunity for estimating the relative
reactivity of solids by comparing the respective consumed time to accomplish the same
extent of conversion at the same temperature. Therefore, these are called the iso-
conversion method, and the parameters are calculated as a function of the conversion rate
[25,27]. In other words, these methods used the rate data associated with a constant
conversion to eliminate the reaction rate dependency on the conversion [27]. Therefore,
iso-conversional approaches, as recommended by [27,29], are more realistic and exact
when modelling non-isothermal pyrolytic kinetics.
By integrating Equation (6), replacing E/RT by x, and making rearranging Equation (7)
can be written.
(7)
where p(x) is a function known as the Arrhenius integral, which can be calculated
numerically or by using various approximations. When we utilize Doyle’s estimate
[29,30] for p(x), we get the popular equation proposed by Ozawa [31] for determining the
activation energy by iso-conversion methods from Equation (3). Doyle [29,30] reported
that for 20 < E/RT < 60, logp (E/RT) may be closely approximated by Equation (8) [32]:
Log p (E/RT) = -2.315 - 0.457 (Eα/RT) (8)
That can be reduced to Flynn–Wall–Ozawa equation [33]:
ln β = ln AEa / g(a)R - 5.330 - 1.052 Ea / RT (9)

where Ea is the apparent activation energy or can also be called variable activation
energy. The plot of ln b against 1/T at different heating rates gives a straight line with the
slope -1.052 Ea/R. Finding the slope for different (a) reveals the dependency of Ea on a
[33].
Murray andWhite [34,35] provided a more precise estimate for 20 < E/RT < 50 in the
form of Kissinger, sometimes known as the Kissinger–Akahira–Sunose (KAS) equation
[15,36].
(10)
For a constant value of _, plotting ln (b/T2) vs. 1/T will give a straight line with a slope
of Ea/R. The profile of apparent activation energy can be generated for the different
conversions [37]. Starink approximated the expression of FWO and KAS method, which
can be transformed into the same general formula as [38]:
(11)
where s = 0 and B = 0.4567 for FWO method, and s = 2 and B = 1 for KAS method.
According to Starink, both parameters can be adjusted to s = 1.8 and B = 1.0033. As a
result, the Starink equation can be rewritten as [30,31]:
(12)
where C = ln AEa Rg(a) _ , for a given conversion fraction a, the points of ln (b/T1.8)
versus 1/T at different heating rates can be fitted to a straight line and the slope of the line
corresponds to 1.0037_ Ea RT _ . As a result, the slope of the straight line can be used to
estimate the value of Ea.

5.3 Global kinetic model
In the previous section, the models were developed for the over all process. There has
been significant work on focusing on the kinetics in pyrolysis process. Many researchers
[45–48] have studied the pyrolysis of woody bio mass and saw mill residue by
thermogravimetry analysis (TGA) . In TGA the weight loss as temperature is increased is
used to determine decomposition reactions. The studies in dicate the thermal
decomposition of biomass occurs in three main stages: in the first stage (<200 C) water ,
carbonmonoxide and carbondioxide are released from the matrix, in the second stage
(475 to 655 C) the main decomposition occurs , and in the third stage (above 600 C) the
decomposition reaction slows down.
The first decomposition takes place for cellulose and hemicelluloses under the
temperature range of 475–655C (these condstage) while the decomposition of lignin
initiates at 455 up to1175C as shownin In recent TGA analysis [36–38], an over all
kinetic model of multi component has been developed to describe the mass loss or
thermal degradation of woody biomass. The proposed model is shown below. Woody
biomass-Volatile gases bio Char dα dt ¼ kf ðαÞ ð2Þ Sloepic ka etal. [39] compared three
methods for predicting kinetic parameters the Kissinger model [37], Kissinger– Akahira–
Sunose (KAS) [39], and Flynn–Wall–Ozawa(FWO) [38].
The Kissinger method is based on the following expression:
13
where biomass conversion is defined as below: Conversion ¼ α ¼ Mt_M1 M0_ M1 ð4Þ

Mt is mass of feed stock at time of t, M0 and M1 are the masses of feed stock at the
beginning and endofthereaction, respectively, β is heating rate, and α is conversion. The
KAS method is out lined in Eq. ln βi T2αi !¼ Ln AαR Eαgα Eα RTαi ð5Þ The FWO
model is based on the following expression: ln βiÞ ¼ ln Aα Eα Rg ðα Þ -5:331-1:052 Eα
RTα i ð6Þ.
The FWO and KAS models show a variation in the Ea, demon- strating the changing
reaction mechanisms.

5.4 Pyrolysis Kinetic Modeling.
DAEM was implemented in this work to explain the pyrolysis of each sample. DAEM
contains multiple parameters such as activation energies (E) and preexponential factors
(k0) to explain the irreversible parallel reactions which occurs according to the
distribution function as presented in above Eq.
14
Here, R is the ideal gas constant, T is temperature, β is the heating rate, and x is the mass-
based conversion degree as described in above Eq.
X= (m0 – m) / (m0 _ m∞) 15
whereas m0 is the initial mass of the sample, m∞ is the remaining mass of the sample at
the end of the experiment, and m is the temporal measured mass. In addition, FðEÞ
describes the distribution model of activation energy and here we have proposed to use 4
types of distribution models namely Gaussian, Logistic, Gumbel, and Cauchy. The
Gaussian function is described by journals.
16
In addition, we have also proposed the use of the following Logistic (17), Gumbel (18),
and Cauchy function (19) as follows:
17

18
19
The comparison of these 4 distributions is presented in Figure 1. As seen in Figure 1a, the
use of the same parameters of Ei and σi generate different behavior. Here, the value of Ei
and σi were set to 180 kJ mol_1and 2 kJ mol_1, respectively. In general, it could be
inferred that the Logistic distribution generated the lowest peak distribution value.
However, the Logistic distribution also provides the highest variance of activation
energy. On the other hand, the Gaussian distribution resulted in the highest peak value
among the 4 provided distributions.
Where as the Cauchy and Gumbel distribution tend to have moderate peaks and small
variances which lies between the Logistic and Gaussian distributions. Additionally, a
sensitivity test of these distributions was also made to generate the same peak as
represented in Figure 1b. Here, the value of σi was manipulated to obtain the same peak.
As seen in Figure 1b, the Logistic distribution gave a larger area of the chart than the
other three distributions. Hence, it infers that each distribution function has specific
characteristics for later use in adapting DAEM on biomass pyrolysis. Identification of
pseudo-components was made by introducing a multidistribution factor to represent each
pseudo-component (ci) which totals to the amount of dx=dT.
20
Each pseudo-component has its contribution fractions (ci) which sums up to 1. In

addition, each component also possesses a certain preexponential factor (k0), activation
energy (E), and standard deviation (σ). To obtain these parameters, Eq. (1) through (7)
were numerically solved in Spyder (Python IDE). This method is a refinement method
from the previous work of Günes¸ and Günes¸ [38].

The objective function (8) was used to estimate parameters in DAEM by taking residuals
from subtracting the dx=dT from the experimental data and simulation. The value
generated by Eq. (8) was minimized in Spyder (Python IDE) by using the
scipy.optimize.least_square module to minimize the residual between simulated and
experimental data.
21
The non-linear regression was used to estimate 3 parameters: the contribution fraction
(ci), activation energy (E), and standard deviation (σ) while the preexponential factor (k0)
was set at a constant value of 1.67 _ 1013 s_1. For comparison, we also calculated the
coefficient of determination (R2) for each result.
Chemical kinetics play a key role in explaining the characteristics of pyrolysis reactions
and developing mathematical models. There have been extensive studies on biomass
pyrolysis kinetics in the past decades for developing various kinetic models [34–36].
Most of kinetic models are considered as lumped models, because the kinetics are based
on the yields of lumped products (i.e. char, tar and gas). The recent advances in kinetic
models have been well reviewed in the literature [32,37–41]. Table 1 summarises the key
findings of some recent review articles on the kinetic models.
Kinetic models typically include one-step global kinetic model, parallel and competitive
reactions model, models with secondary tar cracking, detailed lumped kinetic model,
distributed activation energy model (DAEM) and nucleation growth model. Some typical
models with respective reaction mechanisms are presented in Table 2, together with
kinetic data (first order) for different reaction schemes determined experimentally and
validated through modelling.
One-step global kinetic models are the simplest models available which represent the
conversion of biomass to the volatiles and char as a first order single-step reaction. Since
pyrolysis products only consist of char and volatiles [48], most of the researchers have
used the global reaction model coupled with appropriate heat transfer and volume
reaction models [40,49]. Kinetic parameters of these models can be estimated either
experimentally or using different models such as Kissenger Model, Kissenger-Akahira
Sunose (KAS) and Flynn-Wall-Ozawa (FWO) [32].

However, global kinetic models have certain limitations as they donot include elaborate
reaction mechanism and only consider the primary reactions. Hence, other kinetic models
were later formulated to include the secondary reactions [50]. The formation of gases
from tar decomposition and the conversion of tar to char by polymerization were
included in the kinetic model as secondary reactions [49].
Shafizadeh and Bradbury model [23] included both primary and secondary
decomposition reactions. In this model, cellulose was first converted to active cellulose,
which is further decomposed to other secondary products. This model gave good
predictions for the product yield, but the determination of activation energy was difficult
for this model as the composition of the active material was unknown. This model has
been used extensively by researchers in its original form as well as extended forms
[4,17,41].
A detailed lumped kinetic model for biomass pyrolysis was proposed by Cuoci et al. [43].
This mechanism included 15 reactions with 30 lumped species. Ranzi et al. [20] extended
this mechanistic model to describe the biomass pyrolysis, devolatilization and gas phase
reaction of the released gas species from the three reference components of biomass.
Generalized form of this model for cellulose is presented in along with the feed and
kinetic parameters, while the detailed mechanism proposed for hemicellulose and lignin
can be found in the literature [20]. The recent development in this regard is given by
Corbetta et al. [22]. The previous multi-step model [20] has been revised with new
experimental data and modelling of secondary gas phase reactions has also been
included. These reactions have been discussed by Couce et al.
Recently, distributed activation energy model has also been employed to better
understand the complexity of biomass pyrolysis, as it takes into consideration the
decomposition of species over a large number of independent parallel reactions with
different activation energies, represented by a continuous distribution function usually
Gaussian distribution [55]. In some cases, when there exist auto-accelerated reactions
during cellulose pyrolysis such as random nucleation or nuclei growth, first order
reaction kinetics are not enough to model the process [36].
Hence, nucleation growth model using either Avrami-Erofeev or Prout-Tompkins

equation is used. This model was first formulated for the decomposition kinetics of
potassium permanganate, and later used for other solid materials like cellulose, paper,
algal kerogens, etc [27–29]. Weight loss data obtained from Thermogravimetric analysis
of cellulose fits best to the Avrami-Erofeev equation in the form of equation (1), with α
representing degree of degradation against time, t [22,23].

kt [ ln(1 )] n , where n=2 22
Reynolds and Burnham [32] compared the different types of kinetic models with the
experimental data for cellulose and paper. Kinetic parameters were determined using
different methods including discrete distribution, the modified Friedman, modified Coats-
Redfern, threeparameter nucleation and nth-order methods. The pyrolysis profiles for
different cellulose materials and the regression analysis indicated that the three-parameter
kinetic model shows good fitting data as compared to other methods [39,42].
These kind of models have not been addressed much for biomass and need more
attention. Kinetic models have been implemented to the whole biomass [22] as well as
the biomass constituents individually [43–45]. However, cellulose being the most
abundant component of the biomass has gained the maximum attention [36,46–48].
Xiong et al. [49] assessed different kinetic model schemes for biomass pyrolysis using
computational fluid dynamics (CFD) simulations. Three reaction schemes were
compared: Scheme I: single-component single-step, Scheme II: single-component two-
step and Scheme III: multi-component multi-step. The modelling results were then
compared with the experimental data.
Kinetic models have made enormous contribution to biomass pyrolysis modelling.

However, there are certain limitations in their applications. Thermogravimetric analysis
has been widely used to determine the reaction kinetics at low heating rates, but the
kinetics under slow pyrolysis conditions may not be applicable to pyrolysis at higher
heating rates. Biomass pyrolysis performed at high heating rates may give appropriate
reaction kinetics but come with a challenge of limitations in heat transfer. Also except
detailed kinetic schemes, all the other models give lumped product compositions (tar,
char and gases) which are not sufficient to explain the complex heterogeneous reactions
taking place during biomass pyrolysis and formation of hundreds of species. Therefore,
other types of models (i.e., network models) have been employed to address the issues
related to kinetic models.
Pyrolysis is also referred as devolatilization, which is a term for removing volatiles from
coal. Devolatilization generally involves reactions such as molecular-level
deploymerization and repolymerization [8,10], and its mechanisms [31,38] can be
divided into 4 stages as shown in Fig. 1. These 4 steps are the basics of network models.
Network models were first proposed for coal devolatilization and later modified for
biomass pyrolysis. Reviews on network models of coal devolatilization are available in
literature [22–26]. Network models consider the detailed structural changes of material
during pyrolysis, thus they are also known as structural models.

The typical network models for biomass are Bio-FG-DVC (Functional Group
Depolymerization Vaporization Crosslinking) model [45], Bio-FLASHCHAIN model
[46] and Bio-CPD (Chemical Percolation Devolatilization) model [47].
FG-DVC model consists of two sub-routines, one is FG (Functional Group or species

evolution model) and the other is DVC (Depolymerization, Volatilization, and Cross-
linking or tar formation model) [48,49]. It comprises of six important concepts:
functional groups, macromolecular network, network co-ordination number, bridge
breaking, cross-linking and mass transport of tar. The whole concept can be defined as
the formation of light gases as a result of decomposition of functional groups and at the
same time depolymerisation of macromolecular network due to breakage of bridges and
formation of some new fragments which are transported to form tar.
The composition of volatile species can be analysed using functional group (FG) model,
while DVC determines the amount and molecular weight distribution of tar and char
formed [40,41]. Solomon and co-workers [32,42–44] have made significant contributions
to the development of FG-DVC model for coal.
FLASHCHAIN model includes a four-step reaction mechanism which depicts the chain
structure and its analogy with flash distillation. Niksa [45–38] proposed the
FLASCHAIN model for the rapid coal pyrolysis. The same model was modified for
biomass pyrolysis, named Bio-FLASHCHAIN [39]. Three concepts were used to
formulate this model from previous research, i.e., DISCHAIN, DISARAY and
FLASHTWO theory. DISCHAIN theory includes the straight chain configuration model
to determine the qualitative impact of the macromolecular configuration [40,45].
This is explained by two different phenomena: depolymerisation and cross-linking.

Depolymerization indicates the evolution of tar from the main reactant chains to small
fragments. The monomers may reattach to the long fragments forming tar precursors by
cross-linking to char. DISARAY theory is same as that of DISCHAIN theory.
The only difference is, instead of straight chains, it is implemented to the two
dimensional structures, i.e., bethe lattice [50]. FLASHTWO theory depicts the pressure
effects which have not been included in the previous models. It does not include any
network statistical measurements. CPD model considers the biomass as a
macromolecular structure of aromatic clusters connected through chemical bridges, when
biomass is heated the labile bridges break to form light gases and tar, while other bridges
remain intact and form char.

The model was developed to calculate the tar, char and gas yield based on structural
properties. Residence time, temperature, pressure and heating rate were the key
parameters for predicting product yield. Fletcher and co-workers [43–47] proposed a
chemical model for coal pyrolysis using Percolation Lattice statistics instead of Monte
Carlo techniques (proposed by Solomon et al. [33]).
They extended their research for black liquor and biomass as well [48,49]. Sheng and
Azevedo [47] proposed the CPD model for the main components of biomass. Lewis et al.
[50] assumed that yield of biomass pyrolysis is calculated as a sum of the weighted
average yield of its main components, i.e., cellulose, hemicelluloses and lignin and used
CPD model for all three components individually and then calculated the overall product
yields.

CHAPTER 6 : APPLICATION OF PRODUCTS
After a Co-Pyrolysis Process we get the Industrial fuel as a main product and & Bio Char
as a by product. The obtained products have numerous applications in various fields. In
this chapter, we will see the applications of bio-fuel and bio-char in various industries.
6.1 Application of Industrial Fuel.
 Combustion of Boiler.
 Combustion of Furnace.
 Fueling in engines and turbines.
 Upgrading to transportation fuels or as a renewable feed stock for chemicals and
materials.
6.2 Application of Bio Char.
 As bio-fertilizer
 Water Treatment in fish Farming.
 Feed Supplement to plants.
 As an Adsorbent to adsorb toxic gases from the environment.
 As an Electrode material in Energy Storage Devices.

CHAPTER 7 : RESULT ANALYSIS
Thermogravimetric analysis (TGA) is one of the members of the family of thermal

analysis techniques used to characterize a wide variety of materials. TGA provides
complimentary and supplementary characterization information to the most commonly
used thermal technique, DSC.TGA measures the amount and rate(velocity) of change in
the mass of a sample as a function of temperature or time in a controlled atmosphere.
The measurements are used primarily to determine the thermal and/or oxidative stabilities
of materials as well as their compositional properties. The technique can analyze
materials that exhibit either mass loss or gain due to decomposition, oxidation or loss of
volatiles (such as moisture). It is especially useful for the study of polymeric materials,
including thermoplastics, thermo sets, elastomers, composites, films, fibbers, coatings
and paints. TGA measurements provide valuable information that can be used to select
materials for certain end-use applications, predict product performance and improve
product quality. Our purpose behind the TGA is For designing of kinetic model.For
kinetic model designing we need Activation Energy and order of Reaction Based on
TGA data we calculate Activation Energy because We need it to find out the order of
reaction. After that we get the order of reaction. Based on order of reaction. we get the
kinetic parameters which is used to design the kinetic model.
 Formula Of Activation Energy :
 Method 01 : Coasts Redfern Method.

Formula (Graph) : log[ -log(1- α) /T^2] vs 1000/T.
 Method 02 : By Arrhenius Eq.
Formula ( graph) : log[-log(1- α)/T^2] vs 1/T.
Where ,
α = W0-Wt/ W0-Wf
W0= Initial weight of particular sample
Wt= Represent weight of sample at any Random Given
Temperature
Wf= Final weight of particular sample.

10.000
9.000
8.000
S-1
7.000 S-2
S-3
6.000 S-4
S-5
Mass Loss %
5.000 S-6
S-7
4.000 S-8
S-9
3.000 S-10
S-11
2.000
S-12
S-13
1.000
S-14
0.000
0 100 200 300 400 500 600 700 800
Temperature (⁰C)
8.000
7.000
6.000
5.000
Mass Loss %
4.000
3.000
2.000
S-15 S-16 S-17
S-18 S-19 S-20
1.000
S-21 S-22 S-23
S-24 S-25 S-26
0.000 S-27 S-28
0 100 200 300 400 500 600 700 800
Temperature (⁰C)
Plot 7.1 shows the TGA results generated on Our material PCB and Jatropha Sludge.. The plot shows the percent mass as a
function of sample temperature for the PCB & Jatropha Sludge bristles under a nitrogen purge.

Table 7.1 TGA Summary sample 1-28
Activation Energy ( kj / mol )
Order of Reaction
Temperature Method 1 Method 2 Activation Energy in
Sample No. Materials %
Gradient Fraction (J/Mol)
Coasts Redfern By Arrehenius Malek
n=Ar/Aw
Method Eq. Method
1 J 100 % 10 °C 0.425 0.425 23.400 42.600 53.400 1.66 1.17
2 P 100 % 10 °C 0.611 0.611 73.800 124.500 151.050 1.69 1.00
3 J 10 % P 90 % 10 °C 0.634 0.634 69.300 100.700 155.700 1.55 0.95
4 J 20 % P 80 % 10 °C 0.520 0.520 48.200 92.400 123.500 3.27 1.08
5 J 30 % P 70 % 10 °C 0.661 0.661 71.900 127.100 124.400 1.40 0.97
6 J 40 % P 60 % 10 °C 0.501 0.501 39.100 88.900 118.700 1.45 1.10
7 J 50 % P 50 % 10 °C 0.462 0.462 42.200 83.800 108.200 5.98 1.14
8 J 100 % 20 °C 0.441 0.441 35.040 57.390 106.330 1.05 1.14
9 J 100 % 30 °C 0.440 0.440 35.700 63.450 107.070 1.43 1.14
10 J 100 % 40 °C 0.421 0.421 33.520 50.600 105.300 1.70 1.20
11 P 100 % 20 °C 0.914 0.914 7.147 51.260 131.000 1.79 0.93
12 P 100 % 30 °C 0.900 0.900 5.500 36.815 132.000 2.31 0.93
13 P 100 % 40 °C 0.975 0.975 5.320 39.420 147.200 2.90 0.90
14 J 10 % P 90 % 20 °C 0.954 0.954 6.700 51.000 138.900 1.89 0.92

15 J 10 % P 90 % 30 °C 0.927 0.927 60.800 75.400 183.300 2.29 0.93
16 J 10 % P 90 % 40 °C 0.735 0.735 4.260 12.500 105.500 2.27 0.99
17 J 20 % P 80 % 20 °C 0.739 0.739 5.140 26.700 104.200 1.40 1.01

18 J 20 % P 80 % 30 °C 0.746 0.746 4.600 17.300 106.800 1.92 1.00
19 J 20 % P 80 % 40 °C 0.781 0.781 4.900 39.800 112.400 2.38 0.97
20 J 30 % P 70 % 20 °C 0.793 0.793 6.300 33.900 111.000 1.52 0.98

21 J 30 % P 70 % 30 °C 0.846 0.846 6.100 25.200 120.300 2.16 0.95
22 J 30 % P 70 % 40 °C 0.650 0.650 5.500 24.700 128.100 2.03 1.05
23 J 40 % P 60 % 20 °C 0.775 0.775 5.600 40.100 109.500 1.48 0.99

24 J 40 % P 60 % 30 °C 0.730 0.730 4.200 22.500 104.900 1.89 1.00
25 J 40 % P 60 % 40 °C 0.552 0.552 4.300 19.600 101.500 2.17 1.01
26 J 50 % P 50 % 20 °C 0.645 0.645 7.300 25.700 85.100 1.18 1.06

27 J 50 % P 50 % 30 °C 0.721 0.721 4.700 30.300 101.800 1.87 1.01
28 J 50 % P 50 % 40 °C 0.766 0.766 6.100 30.000 106.400 2.32 0.99

We done the 28 samples Thermogravimetric Analysis test in Table which shows the summary of
All Thermogravimetric analysis samples data with different ratio of feed stock with different

heating rate. We also find the Activation energy with two different methods which is Coast
Redfern method & Arrhenius method. Also find the order of reaction with different methods like
Malek method.
Table 7.2 TGA Analysis of sample 1-28
Sample No. Order Temp. Range Slope Activation Energy, J/mol
No.
S1 n=1/2 25-700 °C 138.71 1153.23494
n=1/3 25-700 °C 165.96 1379.79144
n=2/3 25-700 °C 186.8 1553.0552
S2 n=1/2 25-700 °C 76.06 632.36284

n=1/3 25-700 °C 36.993 307.559802
n=2/3 25-700 °C 7.1182 59.1807148
S3 n=1/2 25-700 °C 93.214 774.981196

n=1/3 25-700 °C 57.644 479.252216
n=2/3 25-700 °C 30.474 253.360836
S4 n=1/2 25-700 °C 121.74 1012.14636

n=1/3 25-700 °C 155.63 1293.90782
n=2/3 25-700 °C 88.601 736.628714
S5 n=1/2 25-700 °C 105.2 874.6328

n=1/3 25-700 °C 137.15 1140.2651
n=2/3 25-700 °C 75.136 624.680704
S6 n=1/2 25-700 °C 123.47 1026.52958

n=1/3 25-700 °C 155.38 1291.82932
n=2/3 25-700 °C 93.498 777.342372
S7 n=1/2 25-700 °C 135.08 1123.05512

n=1/3 25-700 °C 143.99 1197.13286
n=2/3 25-700 °C 95.298 792.307572
S8 n=1/2 25-700 °C 97.995 814.73043

n=1/3 25-700 °C 69.246 575.711244
n=2/3 25-700 °C 125.05 1039.6657
S9 n=1/2 25-700 °C 110.69 920.27666
n=1/3 25-700 °C 85.168 708.086752
n=2/3 25-700 °C 134.72 1120.06208

S10 n=1/2 25-700 °C 103.42 859.83388
n=1/3 25-700 °C 75.536 628.006304
n=2/3 25-700 °C 129.67 1078.07638
S11 n=1/2 25-700 °C 112.07 931.74998

n=1/3 25-700 °C 140.8 1170.6112
n=2/3 25-700 °C 82.032 682.014048
S12 n=1/2 25-700 °C 94.718 787.485452

n=1/3 25-700 °C 121.48 1009.98472
n=2/3 25-700 °C 69.529 578.064106
S13 n=1/2 25-700 °C 71.9 597.7766

n=1/3 25-700 °C 102.39 851.27046
n=2/3 25-700 °C 43.204 359.198056
S14 n=1/2 25-700 °C 111.09 923.60226

n=1/3 25-700 °C 134.44 1117.73416
n=2/3 25-700 °C 89.116 740.910424
S15 n=1/2 25-700 °C 91.046 756.956444

n=1/3 25-700 °C 119.04 989.69856
n=2/3 25-700 °C 64.696 537.882544
S16 n=1/2 25-700 °C 89.89 747.34546

n=1/3 25-700 °C 114.65 953.2001
n=2/3 25-700 °C 66.584 553.579376
S17 n=1/2 25-700 °C 101.62 844.86868

n=1/3 25-700 °C 130.05 1081.2357
n=2/3 25-700 °C 74.861 622.394354
n=1/2 225-700 °C 91.855 763.68247

S18
n=1/3 25-700 °C 121.19 1007.57366
n=2/3 25-700 °C 64.246 534.141244
S19 n=1/2 25-700 °C 82.838 688.715132

n=1/3 25-700 °C 54.087 449.679318
n=2/3 25-700 °C 109.9 913.7086

S20 n=1/2 25-700 °C 102.01 848.11114
n=1/3 25-700 °C 72.248 600.669872
n=2/3 25-700 °C 136.02 1130.87028
S21 n=1/2 25-700 °C 108.13 898.99282

n=1/3 25-700 °C 79.783 663.315862
n=2/3 25-700 °C 134.8 1120.7272
S22 n=1/2 25-700 °C 111.98 931.74998

n=1/3 25-700 °C 77.98 792.307572
n=2/3 25-700 °C 132.69 359.198056
S23 n=1/2 25-700 °C 113.55 944.0547

n=1/3 25-700 °C 85.799 713.332886
n=2/3 25-700 °C 139.66 1161.13324
S24 n=1/2 25-700 °C 81.517 677.732338

n=1/3 25-700 °C 82.657 687.210298
n=2/3 25-700 °C 31.238 259.712732
S25 n=1/2 25-700 °C 97.827 813.333678

n=1/3 25-700 °C 69.606 578.704284
n=2/3 25-700 °C 124.39 1034.17846
S26 n=1/2 25-700 °C 101.16 841.04424

n=1/3 25-700 °C 72.119 599.597366
n=2/3 25-700 °C 126.5 1051.721
S27 n=1/2 25-700 °C 78.003 648.516942

n=1/3 25-700 °C 48.076 399.703864
n=2/3 25-700 °C 106.17 882.69738
S28 n=1/2 25-700 °C 96.584 802.999376

n=1/3 25-700 °C 64.568 536.818352
n=2/3 25-700 °C 126.75 1053.7995

TGA analysis is helpful to design the kinetic models and also used full to find the weight
loss with respect to temperature. We get exact value that how much weight loss will be
happen in reaction time from TGA analysis.
Plot 7.2 – Sample 1 Activation energy Plot 7.3 – Sample 2 Activation energy

Plot 7.8 – Sample 7 Activation energy
We have a 28 samples TGA/DTG graph. Which shows the The data obtained in TGA is
useful in determining purity and composition of materials, drying and ignition
temperatures of materials and knowing the stability temperatures of compounds. The data
obtained in DTA is used to determine temperatures of transitions, reactions and melting
points of substances.

CONCLUSION
We are conclude that waste management is becoming more difficult day by day to
reduce waste with time consuming processes due to long time of degradation time
it takes for material that involves plastic. For that the pyrolysis becoming more
useable to convert plastic into fuel. In this regard we are using Co-Pyrolysis
method to convert printed circuit board (PCB) & Jatropha into fuel. By converting
PCB & Jatropha to fuel, we solve two issues ,reducing the waste of jatropha sludge
& PCB & another one is shortage of fuel. The dual benefit, it will surely provide a
strong platform for us to build a clean and green future. The calorific value of
product yield in the co-pyrolysis process is higher than the pyrolysis process and
comparable with conventional fuel, such as diesel. By use of this we reduce the
level of Jatropha sludge and also level of E-waste in the market and also provide
the Industrial fuel as well as Bio-Char to market. We also try to reduce the level of
Air and Land pollution itself. It is also eco friendly process which is not harmful to
environment as well as human being.

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PRODUCTION OF INDUSTRIAL FUEL BY CO-PYROLYSIS OF

WASTE SLUDGE AND WASTE PCBs

Parul University, Vadodara

FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page I

DHARMIK JOSHI (200305103704)

under my guidance in fulfillment of the Bachelor of Technology (B.TECH)

Project Guide Project Coordinator

Head of Chemical Department, External Examiner

FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page II

our respected guide Prof. Priyeshnath Rathod, Assistant Professor of

Chemical Engineering Department, for his persistent, outstanding, invaluable co-

operation and guidance. We gained a lot of valuable guidance and prompt

forever and we take pride to work under him.

Handling the Nitrogen gas.

assistants of Chemical engineering Department thanks for constant help.

FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page III

Head of Chemical Engineering Department. We feel very privileged to have their

precious advices, guidance and leadership.

FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page IV

Keywords: Waste Plastics, Sludge Jatropha, Thermogravimatric Analysis Test,

FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page V

FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page VI

FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page VII

Table No Table Description Page No

Table 7.1 TGA Summary Sample 1-28 35

Table 7.2 TGA Analysis of sample 1-28 36

FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page VIII

Figure No Figure Description Page No

1.1 Printed Circuit Board 2

1.2 Jatropha seed 2

1.3 Pyrolysis Setup 3

3.1 Proposed Experimental Setup 12

4.1 Printed Circuit Board 14

4.2 PCBs in Shredded form 14

4.3 Jatropha Seed 15

4.4 Jatropha Seed cake after the extraction of oil 15

4.5 Drying of Jatropha sludge 15

4.6 Experimental Setup of Pyrolysis 17

4.7 Separating Funnel 17

4.8 Industrial fuel in liquid form 17

4.9 Bio char 18

7.1 TGA plot Sample 1-28 33

7.2 Sample 1 Activation Energy graph 38

7.3 Sample 2 Activation Energy graph 38

7.4 Sample 3 Activation Energy graph 38

7.5 Sample 4 Activation Energy graph 38

7.6 Sample 5 Activation Energy graph 39

7.7 Sample 6 Activation Energy graph 39

7.8 Sample 7 Activation Energy graph 39

FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page IX

Sr. No. Symbol/Abbreviations Name

FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page X

1.2 PROCESS DESCRIPTION:

3. Printed Circuit Board (PCB):

FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page 1

Figure 1.1 PCB Figure 1.2 Jatropha Seed

FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page 2

1.3 PROCESS OVERVIEW:

 Different Biomasses, solid waste is significantly used as feedstock in the Co-

Figure 1.3 Pyrolysis Setup

FACULTY OF ENGINEERING AND TECHNOLOGY, PARUL UNIVERSITY Page 3

In year of 2021, the Journal of American Journal of Engineering and Applied