EXPERIMENTATION AND OPTIMIZATION OF

CASCADE PYROLYSIS REACTOR

A thesis (Phase II) submitted in partial fulfillment of the

requirements for the award of the degree of

M.Tech

in

Thermal Power Engineering

By

ARUL M (211317026)

DEPARTMENT OF MECHANICAL ENGINEERING

NATIONAL INSTITUTE OF TECHNOLOGY
TIRUCHIRAPPALLI – 620 015

JUNE 2019
 BONAFIDE CERTIFICATE

This is to certify that the project titled “EXPERIMENTATION AND

OPTIMIZATION OF CASCADE PYROLYSIS REACTOR” is a bonafide
record of the project work done by

ARUL M (211317026)

in partial fulfilment of the requirements for the award of the degree of Master of
Technology in Thermal Power Engineering of the NATIONAL INSTITUTE
OF TECHNOLOGY, TIRUCHIRAPPALLI, during the year 2018 -2019.

Dr. R. Anand Dr. S.P. Sivapirakasam

Project Guide Head of Department
Associate Professor Professor
Department of Mechanical Engineering Department of Mechanical Engineering
National Institute of Technology National Institute of Technology
Tiruchirappalli Tiruchirappalli

Project Viva - Voce held on

Internal Examiner External Examiner

ii
 ABSTRACT

The industrialization and growth of the population increases the demand for energy, one of
the best alternative is to meet rising energy demand by converting waste into worthwhile
products. Experiment was conducted on microwave pyrolysis reactor to convert e-waste
ABS plastic into energy which yields oil (66.9%), gas (26.16%) and char (6.94%). In this
work, the production of pyrolysis fuel from e-waste ABS plastic is simulated. e-waste is
an excellent renewable resource to produce fuel oil. It is of utmost importance to make
effective use of e-waste resources. There are different methods available for the production
of fuel oil from waste. One of the best methods is pyrolysis to convert waste into fuel oil.
This is due to the fact that pyrolysis is an efficient conversion method compared to other
thermochemical conversion practices. Pyrolysis is the process of decomposing waste in an
inert atmosphere to convert it into worthwhile products. The production of fuel oil from e-
waste ABS plastic via pyrolysis was simulated using Aspen HYSYS because of its ability
to solve chemical as well as energy problems. To simulate the microwave assisted pyrolysis
reactor, an Aspen HYSYS model was developed. The model is based on Gibbs free energy
and it has been calibrated using the restricted equilibrium method. The model was validated
and foresees the percentage of yield, the predicted values very well agreed with the
available data. Important parameters of the pyrolysis process such as pyrolysis temperature,
sweeping nitrogen gas flow rate, heating rate, moisture content was varied. It was found
that pyrolysis temperature, nitrogen flow rate, heating rate have a very profound influence
on the pyrolysis process and yield, while the moisture content had a lesser impact.

Keywords: ABS plastic; GCMS; Aspen HYSYS; pyrolysis

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 ACKNOWLEDGEMENT
At the outset, I take this opportunity to thank our beloved Director of National
Institute of Technology, Tiruchirappalli (NITT) for directing us and enabling us to enhance
focus towards research and development.
I wish to express my sincere thanks to Dr. S.P. Sivapirakasam, Professor and
Head of Department, Department of Mechanical Engineering, for providing me with
this opportunity and for his constant support and encouragement throughout the project.
I take this opportunity to express my deep sense of gratitude and indebtedness to
my guide, Dr. R. Anand, Associate Professor, Department of Mechanical Engineering
for his valuable support, suggestions and constructive criticism throughout this project.
I sincerely thank my project head coordinator, Dr. V. Mariappan, Associate
Professor, Department of Mechanical Engineering for his valuable suggestions during
project reviews.
I would like to thank Mr. M. Dinesh kumar, Mr. A. Santhosh kumar Ph.D.
Scholars in mechanical department for their continuous support and guidance for the
completion of the project.
I would like to thank the Computer Support Group of NITT for providing simulation
facilities.
I would like to thank Mr. L. Durairaju, lab technician of Thermal lab for his
continuous support and guidance for the completion of the project.
I take this opportunity to thank all the faculty members and staff of Mechanical
Engineering Department for their support and encouragement in accomplishing this work.
I would like to place on record the continuous support, encouragement, advice and
help that my parents and friends have given me throughout the duration of this project,
and I shall always be grateful to them for this.
Finally, I thank everyone who has contributed in any way for the successful
completion of the project work.
Arul M (211317026)

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 TABLE OF CONTENTS

Title Page No.

BONAFIDE…………………………………………………………………… ii
ABSTRACT…………………………………………………………………… iii
ACKNOWLEDGEMENTS…………………………………………………... iv
TABLE OF CONTENTS……………………………………………………... v
LIST OF FIGUERS …………………………………………………………... viii
LIST OF TABLES…………………………………………………………… ix
ABBREVIATIONS…………………………………………………………… x

CHAPTER 1 INTRODUCTION
1.1 General……….……………………………………………. 1

1.2 Energy Scenario and Waste Management……………….… 1

1.3 Aspen HYSYS Simulation………………………………… 3

1.4 Objective ……………………….…….......…….......……... 4

1.5 Scope of the Present Work………………………………… 4

1.6 Methodology ………………………………....………….... 5

1.7 Organization of the Thesis………………………………… 6

CHAPTER 2 LITERATURE REVIEW

2.1 General……………………………………………………. 7

2.2 e-waste Management …….…………………………….…. 7

2.3 Thermo Chemical Conversion for Waste Treatment……... 9

2.4 Pyrolysis Fuel is a Source of Energy ……………………… 11

2.5 Factors Affecting the Pyrolysis Process…………………… 11

2.6 Aspen Simulation…………………………………………... 14

2.7 Summary…………………………………………………. 15

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CHAPTER 3 EXPERIMENTAL INVESTIGATIONS
3.1 General……………………………………………………. 16

3.2 Collection and Separation e-waste Plastic ………………... 16

3.3 Sample Preparation for Ultimate & Proximate Analysis… 16

3.4 Ultimate and Proximate Analysis ………………………… 17
3.5 Pyrolysis Process and Reactor Design……………………. 17

3.5.1 Microwave Pyrolysis……………………………………… 18

3.6 Gas Chromatography Mass Spectrometry (GC-MS) ……. 18

3.7 Summary………………………………………………...... 18

CHAPTER 4 ASPEN HYSYS SIMULATION

4.1 General……….……………………………………………. 19

4.2 Assumptions ……………….……………………….......... 19

4.3 Selection of Reactor …………………………………......... 20

4.4 Simulation Flowsheet ………………….......…….......……... 21

4.5 Aspen HYSYS Model …………………………................ 21

4.5.1 Pyrolysis Reactor ………...................................................... 21

4.5.2 Condensation......…………………………………................ 22

4.5.3 Separation Column………………………………................ 22

4.6 Sequence and Kinetics of ABS Pyrolysis Reaction............... 22

4.7 Fluid Package and Components……………....................... 23

4.8 Summary 24

CHAPTER 5 RESULT AND DISCUSSION

5.1 General……….……………………………………………. 25

5.1.1 Microwave Pyrolysis Yield ……….......…….......……....... 25

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5.1.2 NCG Composition ……………………………................ 26

5.1.3 Pyrolysis Oil Composition …........................................... 27

5.2 Simulation Results. . . . . . . . . . . . . . . . . . . . . . . . . . . . . .. 29

5.2.1 Sensitivity Analysis; Pyrolysis Temperature. . . . . . . . . . . 29

5.2.2 Sensitivity Analysis; Nitrogen Flow Rate . . . . . . . . . . . . . 30

5.2.3 Sensitivity Analysis; Heating Rate. . . . . . . . . . . . . . . . . . . 30

5.2.4 Variation of Gas Composition. . . . . . . . . . . . . . . . . . . . . . 31

CHAPTER 6 CONCLUSIONS AND SCOPE FOR THE FUTURE

WORK

6.1 Conclusions 33

6.2 Scope of Future Work 34

APPENDIX 1 35

REFERENCES 37

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 LIST OF FIGURES
Figure Title Page No.
No.
1.1 Research Outline………………………………………………………………………………………… 5
3.1 Schematic Diagram of Cascade Pyrolysis Reactor………………………………………… 17
4.1 Flow Sheet of a Thermal Pyrolysis Reactor ………………………………………………… 21
5.1 Microwave Pyrolysis Various Yield Percentage At 450oc………….….….….……. 25
5.2 Chromatograph for NGC From the Microwave Pyrolysis Reactor.……….……… 26
5.3 Chromatograph for Oil from The Microwave Pyrolysis Reactor……………………. 29
5.4 Variation of Yield Percentage with Pyrolysis Temperature (Oc).…………………… 30
5.5 Variation of Yield with Nitrogen Flow Rate ……………………………….….….….….…. 30
5.6 Pyrolysis Oil Yield for Different Heating Rates……………………………………………… 31
5.7 Gas Compositions from Simulation of E-Waste Pyrolysis …………………………… 32

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 LIST OF TABLES
Table Title Page No.
No.
4.1 Summary of Reactor Models in Aspen HYSYS ………………………………………… 20
4.2 Feedstock Conditions ………….….….….……...…….…….…….…….…….…….…….…… 24
5.1 Composition of NCG Obtained By GCMS.……….……………………………………… 26
5.2 Composition of Pyrolysis Oil Obtained by GC …………………….….….….….….…. 27

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 LIST OF ABBREVIATIONS

ABS Acrylonitrile Butadiene Styrene

ASTM American Society for Testing And Materials
CH4 Methane
C2H6 Ethane
C2H2 Acetylene
CO Carbon Monoxide
CO2 Carbon Dioxide
e-waste Electrical and Electronic Waste
GCMS Gas Chromatography- Mass Spectrometry
HIPS High Impact Polystyrene
H2 Hydrogen
N2 Nitrogen
NCG Non-Condensable Gas
NOx Oxides of Nitrogen
PAH Polycyclic Aromatic Hydrocarbons
PC Personal Computer
PP Polypropylene
PS Polystyrene
PSW Plastic Solid Waste
RSTOIC Stoichiometric Reactor
RYIELD Yield Reactor
REQUIL Equilibrium Reactor
RGIBBS Gibbs Reactor
RPLUG Plug Reactor

x
 CHAPTER 1
INTRODUCTION

1.1 GENERAL
The usage of conventional energy sources like fossil fuels for power generation are
having huge negative impacts on environment. Since the world demand for energy is
increasing rapidly, new sources of energy which will replace fossil fuels are required.
E-waste is gaining popularity in research for development of new renewable and eco-
friendly energy sources. The thermochemical conversion process is one of the best
alternatives to meet rising energy demand by converting waste into worthwhile
products.
The world started depending on fossil fuels the moment it was introduced. Coal, oil and
natural gas are fossil fuels which are non-renewable source of energy, were introduced
to the world to develop power for various applications like electric power generation,
automobile engines etc. Due to the ill effects of fossil fuels there is a need of new
renewable and reliable fuel on which we can depend on. The consumption of petroleum
products and the elimination of electronic waste have been illustrated in the energy
scenario.

1.2 ENERGY SCENARIO AND WASTE MANAGEMENT

The increase in production and application plastics has led to plastic waste making up
a significant portion of municipal solid waste [1]. After food waste and paper waste,
plastic waste is the major constituent of municipal and industrial waste in cities [1]. The
steady increase in energy demand, in addition, the recent figures of 2018 unveiling the
increase in fossil fuel consumption since 1998, has made energy research more up to
date than ever before (Panagiotis Evangelopoulos et al. 2017). In the meantime,
mainstream researchers are concentrating on the look for new fuel options relative to
population growth to meet the society’s increasing energy demand. The generation of
waste is usually proportional to the population, since some fractions of waste are tough
to recycle, fractions that have got to be studied in larger detail for energy purposes
(Statistical Review of World Energy, June 2016). In recent decades, it’s been a
transformation in info technology and thus the demand for electrical and electronic

1
equipment is increasing worldwide, whereas at the same time its total useful life is
decreasing (Sohaili J et al., 2012). Together with the amount of waste, the fraction of
electronic and electronic equipment has magnified and can still increase by about 49.8
Megatons in 2019, according to recent forecasts (Sohaili J et al., 2012). The steady
decline in the number of open petroleum derivatives, worries about ecological pollution
and fuel-supply demand (Selim Ceylan et al 2014).
Plastic consumption has increased rapidly in recent years due to its light weight, its
ability to form easily and its non-corrosive behavior (Mochamad Syamsiro et al. 2014).
The importance of metals and wood is replaced by these excellent properties.

In Indonesia, like many developing nations, plastic consumption has also increased due
to economic development and rapid urbanization. Annual utilization of plastics during
the 1950s has been magnified by approximately twenty times to almost a hundred
million tonnes from five million tonnes (Mochamad Syamsiro et al. 2014). In Indonesia,
in the same way as other developing countries plastic consumption
has conjointly accrued because of economic development and fast urbanization. In
2011, Indonesia consumed ten kg of plastics capita p.a. However, the numerous-range
of consumptions would increase the production of plastic waste. Which prompted
ecological issues. As a result of their slow degradation rates, landfills cannot be an
important way to remove plastics from electronic waste (Aguado J et al. 2007).
Incineration generates pollutants such as organic brominated compounds in the
environment, causing environmental problems. Along these lines, recuperation and
reusing strategies have been utilized to lessen landfills and limit the ecological effect
of electronic waste.

The pyrolysis is the process of thermochemical decomposition to extract gaseous fuel,

liquid oil and solid carbon in the inert atmosphere (Demirbas A et al. 2004). The
performance of these three products varies according to the change in the operational
parameter (BridgwaterAV et al. 1999). In attendance be situated several approaches
available for heating waste. Among these, unadventurous heating and microwaves are
made. Factual world wastes are preserved terribly expeditiously in microwave pyrolysis
when contrasted with the ordinary pyrolysis (Su Shiung Lam et al. 2012). The
customary method of pyrolysis heating is founded on conveyance and convection, so
the heating is less efficient and slower, while in microwave pyrolysis because of the
verbose charisma of the electro attraction field, it warms all materials correspondingly.

2
Along these lines, microwave pyrolysis gives reasonable dissemination of heating and
productive heat exchange and warming techniques can be effortlessly controlled. Just
heat the dipole material. In this manner, heat has been made in the significant sign and
the productivity of the procedure is more noteworthy than traditional warming (Su
Shiung Lam et al. 2012). Techniques of chemical recycling of waste includes pyrolysis,
gasification, hydro-cracking catalytic cracking, coking and vis-breaking. A popular
process for the recycle of plastics in general and waste ABS is pyrolysis. The pyrolysis
process involves the thermal breakdown of waste in the absence oxygen/air [5]

1.3 ASPEN HYSYS SIMULATION

(Xianjun et al 2015) Simulated the variation of biomass pyrolysis yield using
Aspen plus and compared the simulated value with experimental results.
Several researchers used Aspen HYSYS process simulator to simulate the
pyrolysis reactor [5]; Even so, the simulation made on the production of methanol from
biomass pyrolysis is limited. An Aspen HYSYS model was used by Mansaray et al. [6]
to predict the pyrolysis of biomass based on chemical equilibrium, energy equilibrium
and equilibrium of components. Due to the presence of highly volatile material in
biomass and the intricacy of kinetics in the biomass reaction rate in fluidized beds, they
disregarded the formation of char and analyzed the process on the assumption of
biomass pyrolysis tends to follow Gibbs equilibrium.
The ultimate purpose behind this research is to incorporate simulation to
accurately predict the steady-state performance of a microwave assisted pyrolysis
process by considering the reaction rate kinetics. Gibbs equilibrium defines the
products of homogeneous reactions and kinetics are used to define exactly the pyrolysis
products. This article illustrates the specifics of modelling strategies taken to
acquire process computation for e-waste pyrolysis in a microwave assisted pyrolysis
reactor. Pavel Lestinsky et al (2016) Modelled the thermal pyrolysis of spruce sawdust
into a hydrogen plasma descending reactor. The objective of this research was to
simulate the production of methanol from sugarcane bagasse by microwave assisted
pyrolysis process. The Aspen HYSYS flowsheet of the pyrolysis process for pyrolysis
fuel oil production is portrayed in Fig. 1. The model is constructed based on the
following key premises: Stable operation; zero-dimensional; ambient pressure; ideal
gases; negligible drop of pressure; char is purely of carbon (C); pyrolysis process is

3
 prompt; the formation of tar is not taken into account; Pyrolysis reactor heat loss is
neglected.

1.4 OBJECTIVES
1. To produce diesel-like fuel from the e-waste ABS plastics.
2. To improve the process efficiency by recovering the energy from non-condensable gas
obtained in the microwave pyrolysis.
3. To optimize the various process parameters like temperature, nitrogen flow rate and
heating rate of the pyrolysis reactor to get maximum pyrolysis oil yield from e-waste
ABS plastic.

1.5 SCOPE OF THE PRESENT WORK

1. Optimize the various process parameters of the microwave pyrolysis reactor using
Aspen HYSYS to get maximum yield.

4
1.6 METHODOLOGY

Fig. 1.1 Research outline.

The disposal of electronic waste is increasing rapidly, and some of the waste is still
recycled residual value residues even after recycling. Accordingly, the best choice is to
renovate electronic left-over obsessed by the foremost treasured products through the
use of updraft renovation processes. Plastic samples from electronic waste were
collected from a dumpster and the ABS plastic was separated. The raw material was
prepared using a mechanical crusher to grind the plastics into small pieces. In addition,
they have become a powder form for thermogravimetric analysis. The thermal analysis
of ABS plastic has been studied using a thermogravimetric analyzer in an inert
atmosphere. The pyrolysis thermal reactor is designed based on the properties of non-
condensable gases that leave the microwave pyrolysis reactor and ABS plastic. And the
simulation of the thermal pyrolysis reactor was performed using an Aspen HYSYS.

5
1.7 ORGANISATION OF THE THESIS
The details of the research work carried out in this present study are given in six
chapters as follows.
Chapter 1 gives a brief introduction to the present energy crisis around the world. It
tells about the depletion of fossil fuel and significance of pyrolysis process for
conversion of e-waste plastics to pyrolysis oil. It also describes the advantages of the
pyrolysis process compared to the other thermochemical conversion processes.

Chapter 2 deals with a literature review on pyrolysis oil production from e-waste. This
chapter explains the type of pyrolysis process and factors affecting the pyrolysis process
and type of heating mechanism for the pyrolysis process and comparison between
thermal and microwave heating. It includes the simulation of thermal pyrolysis reactor
using Aspen HYSYS.

Chapter 3 gives the details of the various instruments used in studying pyrolysis
thermal degradation of e-waste plastic for kinetic parameters determination and the
microwave assisted pyrolysis set-up for experimental analysis.

Chapter 4 gives the information regarding the various elements of Aspen HYSYS such
as components, property package, flow sheet. Role of Aspen HYSYS in pyrolysis
reactor optimization.

Chapter 5 It provides the different results obtained during the work and a detailed
discussion about it. The effect of temperature, nitrogen flow rate, heating rate on the
pyrolysis reactor yield was discussed.
Chapter 6 presents the conclusion of the thermal pyrolysis reactor simulation and
suggests the scope for future work.

References and Appendices are provided at the end of the thesis.

6
 CHAPTER 2
LITERATURE REVIEW

2.1 GENERAL

Currently, fossil fuels are extensively used in power sectors as well as in the automotive
industry, but at the cost of harming the environment by increasing the amount of carbon
secreted into the atmosphere. Pyrolysis does have the potential to switch e-waste ABS
solid waste into fuel oil that could be used to leverage certain industrial sectors. The
management of plastic waste is a cause of growing concern all over the world. Every
year, around 300 million tonnes of plastic are produced worldwide, around 10% is
recycled. Among all, India is that the fifth largest producer of electronic waste.
Consistently, India is dumping 2.2 million tonnes of electronic waste, of which 12%
are telecommunications equipment and 70% is electronic waste devices. electronic
waste Polymers are one of the most difficult fractions of solid electronic waste linked
to recycling due to their complexity and diversity. In this project the aim is to find a
cascade pyrolysis reactor to recover the e-waste heating value which can be used to
produce high amount of combustible fuel.

2.2 e -WASTE MANAGEMENT

In scientific India, the national scenario on electronic waste reported that (29
May 2014) the "Basel Convention" recognized that electronic waste is dangerous.
Furthermore, it created a framework to monitor the cross-border momentum of such
electronic waste. The Basel ban is an amendment to the Basel Convention that prohibits
the export of electronic waste from developed countries. In India for the year 2005, the
electronic waste inventory showed around 1.46.180 tons and is expected to exceed
8.00.000 tons for 2012.
Electronic waste contains many constituents and components, making a posh
and heterogeneous waste that are plastic, metals, and ceramics. significant metals are
as yet present in the residual material that is generated by conventional recycling
methods discussed in H.T et al. (2007); they frequently result in landfills. Schlummer.
M. et al. (2005) stated that the reprocessing of electronic leftover likewise roots

7
ecological issues due to the existence of several halogenated and non-halogenated fire
resistants. Alston S.M. et al. (2011) The identification of different polymers in
electronic waste has been used as high impact PS, ABS, PS, polyvinylchloride,
polycarbonate, and PP.
Regardless of technological and sustainability developments, the awareness of
solid plastic waste (PSW) extends its opportunities for meeting with companies. The
current development in the recovery and recycling of PSW has been declared by S.M.
Al-Salem et al. (2009). The importance was centered on waste produced from
polyolefin sources, that generated a significant fraction of our plastic products within
the standard of the living cycle. Four forms of management of the PSW have been
discussed and detailed by H. Kang et al. (2005) are the systems of re-extrusion
(primary), mechanical (secondary), chemical (tertiary) and energy recovery
(quaternary). re-extrusion comprises the revived outline of a hygienic waste of a
polymer in the extrusion cycle to yield crops of the similar sort of substantial, generally
used in the dispensation industry itself nevertheless seldom practical midst recyclers,
since plastic salvaging seldom happens possesses the essential superiority mentioned
by Toloken S et al. (1998).

Mastellone. M.L et al. (1998) has stated that many of the waste produced,
consisting of waste from production waste or at the end of its useful life, is the raw
material of secondary methods, therefore generally more in demand and reduced in
sizes, such as scales or powders, pellets, dependent source, usability, and shape. In
recent days, chemical treatment plans have subsidized significantly to the reusing status
of PSW. progressed thermochemical process technologies refuge a extensive
assortment of modern innovations and harvest raw materials or petrochemical fuels. As
of late, thermal dissociation (non-catalytic thermal de-composing) is acquiring revived
heed, for example, the way that the additional estimation of petroleum derivatives and
their valuable potential items. However, the modern thermochemical reprocessing of
PSW (ie, polyolefins) remains essential for accurate design and kinetic observations to
obtain chemicals and specific potential chemicals. It was found that energy recovery
was a possible solution for PSW that was discussed by U. Arena et al. (2003).

Martinho et al. (2012) characterized, developed and studied various components of

electronic plastic waste. many waste products have been considered, such as
refrigerators, small electronics, such as writers, printers, central processing units,

8
televisions, computer cases, keyboards, and printers. the amount of plastics present in
different types of electronic equipment is discussed, which shows that most of the
electrical components comprise a 9-32% waste of plastic-type polymers. different kinds
of plastics in the tested electronic component are delivered Graca Martionho et al.
(2011) as disclosed that the most influential polymers were shock-resistant PS (HIPS),
polycarbonate (PC / ABS) mixtures, polypropylene (PP), acrylonitrile butadiene
styrene (ABS) and polystyrene (PS). With reference to CRT televisions, large
refrigeration and cooling and screens had the least number of different polymers, with
11 different types, typewriters, whereas copiers, processing mainframes, and computers
exceeded fourteen different polymers. In the case of small electronic equipment, the
number has reached twenty diverse sorts. Furthermore, metals, coloured essences and
halogenated fire resistant’s have also been found in electrical and electronic
components.

2.3 THERMOCHEMICAL CONVERSION FOR WASTE TREATMENT

Every year waste materials are generated all over the world, such as biomass, used
oil, electronic waste, plastic waste reported by Su Shiung Lam and others (2012). Some
of these wastes are simply disposed of in a way that can contaminate the environment,
while others are collected and recovered for use as an energy source or other more
valuable products. Improper disposal of these waste materials (for example, municipal
solid waste, PVC and used motor oil) can pose a danger to the environment owing
towards the existence of undesirable species like polycyclic pungent hydrocarbons
(PAH), soot and metal. Thermochemical conversion processes such as incineration,
gasification, and pyrolysis were well known methods for waste management.
Incineration and gasification will end up with secretions of brominated dioxins, heavy
metals, hydrocarbons, and polycyclic aromatic hydrocarbons. Ramasamy, K.K et al.
(2007) indicated pyrolysis is the best way to recover the chemical and energy value of
waste without releasing any toxic oxidized species (ie, NOx, dioxins) into the
environment.

M. J. Antal et al. (1990) have investigated that slow pyrolysis is the most efficient
process for creating coal in dry conditions and slow pyrolysis. This technique is
obtained from the strategies for a generation of coal. Slow pyrolysis uses direct heating
rates over a prolonged period and, in the latest warnings, 30-45% of the carbon yield as

9
biochar. This process is not reasonable for the carbonization of most agricultural waste
due to the need to dry the previous raw material and during the reaction. AV.
Bridgewater et al. (2012) have investigated that intermediate pyrolysis occurs at an
average temperature (450-500 ° C). Hot steam residence time from 10 to 30 sec.
Generally, water or hydrogen is used.
A. Demirbas et al. (2002) have investigated that instant pyrolysis is described by
direct temperatures (400-600 ° C) and a rapid heating rate (> 2 ° C / s). Steam retention
times are typically less than two seconds. In contrast to slow pyrolysis, much gas and
tar are supplied. The situations in which rapid pyrolysis translates into the generation
of bio-oil with low carbon and water inclusion, with the estimate of the augmented
energy. speedy cooling of pyrolysis vapors to provide pyrolysis oil. F. Morasemi et al.
(2013) reported, in electric heating, heat transmission occurs by convection and
conduction, but in microwave heating, heat transmission occurs only by irradiation and
is volumetric heating. In the electric pyrolysis occurs the transfer of energy, but in the
pyrolysis of the microwaves, the conversion of energy takes place. Therefore,
microwave assisted pyrolysis is much faster and more energy efficient than electric
heating. Rapid pyrolysis can only be performed with the help of microwave-assisted
heating.
Appleton. T.J et al. (2005) have mentioned that in the field of pyrolysis, microwave
pyrolysis is a productive procedure that offers few merits over the standard pyrolysis
process; for example, Heating efficiency is high because of volumetric heating.
Microwave assisted pyrolysis of electronic wastes were studied using 2 kinds of
absorbers (for example carbon based, iron based) were used to study and diverse trial
arrangements cast-off to build the superiority and amount of the liquid portion and to
cut back solid waste.

Yu-Fong Huang et al. (2016) states that microwave heating is better than
conventional heating due to numerous advantages. Solid microwave pyrolysis at fitting
microwave control levels can have high warming qualities and explicit surface
territories with higher gas and strong yields however bring down fluid yield than
ordinary pyrolysis. Utilizing microwave pyrolysis, half of the lignocellulosic biomass
can be changed over into a vaporous item, mainly composed of CH4, H2, CO2, and CO
with a lot of bioenergy because of the significant returns of CO and H2. The inclusion
of suitable catalysts provides a considerable influence on the property of the microwave

10
transmutation product. Gas and liquid yields, further because the presentation of
microwave transmutation heating, can be significantly advanced by including catalysts.

2.4 PYROLYSIS FUEL IS A SOURCE OF ENERGY

Ioannis Kalargaris et al. (2016) have considered that residual plastics can be a
sustainable power source since they have a higher calorific value. It very well may be
renewed into beneficial oil by a transmutation procedure and used in an IC engine to
generate mechanical and low-grade energy. The oil is delivered by the fast technique
of pyrolysis and the possessions of this emollient are like those of diesel. Pyrolysis lard
got from plastics was utilized as added substance on the way to diesel and was utilized
in a propelled infusion minute in the diesel motor, which brought about warm
proficiency of the brake and discharges were moved forward. The qualities of motor
start, execution, and fumes emanations have been hindered and identified with the
activity of diesel. The results showed that the locomotive could continue to work with
high-ply plastic pyrolysis oil by introducing a diesel-like performance.

Brebu et al. (2005) have mentioned that pyrolysis is an important method among
other thermochemical conversion processes that aims to produce valuable gasoline
hydrocarbons or other valuable chemicals declared by Bagri and Williams (2006). On
the other hand, it is the most appropriate form of plastic waste processing process
reported by Sakata and Luda et al. (2002).

Sharuddin S.D.A et al. (2015) said that the pyrolysis procedure can most likely be
exploited to change over plastics into diesel-like fuels or further increasingly significant
items and will positively be viewed as a basic procedure to re-establish and reuse the
polymeric substance of electronic waste, Muhammad said. C et al. (1999).

2.5 FACTORS AFFECTING THE PYROLYSIS PROCESS

One of the most important factors of government that influences pyrolysis was the
retention time of the raw material inside the pyrolysis reactor, according to Mastral et
al. (2002) The yields of the products were influenced by the average time spent by a
particle in the pyrolysis reactor. The results of isothermal pyrolysis of high density
polyethylene examined by Lettieri and Al-Salem (2010) using TG analysis between the

11
temperature range of 500-600 ° C. Both the residual carbon and the aromatic production
rate were lower in Comparison with liquids and gases that are not condensable. Ludlow-
Palafox and Chase (2001) claimed that the increase in residence time increases the yield
of non-condensable gases. From plastic, from the increase in the conversion of primary
products that produce more products that are thermally stable, which favors the increase
in the production of liquids, this can be recognized by Mastral et al. (2003).

The reaction can be increased by improving the thermal degradation that can be
performed using higher heating rates. noted that the degradation of HDPE began above
598 K and shows total decomposition at temperatures above 740 K of temperature. This
is different for LDPE, where the decomposition was started at a temperature of 633 K
observed by detailed that the disintegration of PP started at a temperature beneath 673
K, implying that the PP decomposes under PE. Among the common plastic materials,
the PS starts to degrade up to about 573 K, which was even before the initial degradation
of PET investigated by Onwudili et al. (2010). Therefore, the pyrolysis temperature
controls the breaking of the carbon chains to a higher level.

In polyethylene pyrolysis, no wax was delivered over 873 K in connection to the

most reduced temperatures appeared by Williams and Williams (1997). He
demonstrated that the lighter segments were created by flouting the enormous
honeycomb. The number of gas increments with the expansion in temperature. A vast
assortment of littler natural atoms has been created because of high temperatures, which
increment the arrangement of blast when the particles break down. The measure of oil
and wax diminishes with expanding temperature because of the propensity of a more
noteworthy number of optional concoction responses with the best measure of vitality.
Singh and Ruj (2016) additionally watched similar outcomes when high temperatures
cause a high gas arrangement with an expansion in the measure of hydrocarbon mixes
in the items. have discovered that splitting is decreased since of the absence of
habitation time as temperature increments in the mixes and the reactor and in addition
sweet-smelling mixes as wax that have substantial atomic chains that have been
acquired in the oil-based good.
Yu-Fong Huang et al. (2012) Corn stubble, which is one of the most abundant
rural reserves in the world, could be transformed into meaningful biofuels and
biologically based elements through a microwave pyrolysis method. After the response
to the 500 W microwave control level during the 30 minutes of preparation, the

12
response performance in the N2 environment was mostly higher than those of the low
CO2 climate. This could be due to the better heat absorption capacity of CO2 particles
to reduce the heat of pyrolysis. The most significant portion of metal oxide impulses
exponentially expanded the most extreme percentage of temperature and mass drop,
however, reduced the calorific estimates of massive deposits. The most created gas was
CO under air N2 and CO2 in a CO2 atmosphere. The expansion of the catalyst reduced
the arrangement of polycyclic aromatic hydrocarbons and in this way made the fluid
articles less dangerous.
Chiara Santella et al. (2016) The review concerns hot and catalytic pyrolysis
containing certain excess plastics, illustrating the polymers contained in low- squander
electrical and electronic equipment (WEEE). The H-style H (HUSY) ultra-stable H and
Zeolite Socony Mobil-5 (HZSM-5) H-style are the two zeolite-based catalysts that have
been used at 400 ° C, with a high content of silica, while three Different temperatures
were taken for the hot break: 400, 600 and 800 ° C. Returns ranging from 82% to 92%
were acquired when pyrolysis was completed with HZSM-5 at 400 ° C. Forte
(approximately 13%) is observed using HUSY.
Xiqiang Zhao et al. (2012) expressed thought about in the examination office
utilizing a steady bed. The temperature impacts and the nearness of the additional
substances in the properties and yields of the articles and the pyrolysis rehearses are the
groupings of this exertion. The outcomes demonstrated that, at a consistent temperature
(500°C), pyrolysis, the execution of the strong components diminished with the
development of the microwave control amidst the warming stage, while the execution
of the gas components was the switch; The H2 approach is expanded by about 20%.
With the expansion of microwave control, which caused a high rate of warming. The
littlest CO2 combination was accomplished by including have extended with the
development of gasification reactions among carbon and CO2 and the change and dry
division reaction of CH4 to a pinnacles of fumes gas happened example kept on being
warmed after pyrolysis at a steady temperature.
The main types of plastics present in electronic waste were styrene-butadiene
(ABS) and high impact polystyrene (HIPS) acrylic treated in the presence of zeolite
catalysts were cited by Ribeiro. R et al. (2012). Pyrolysis was a minor amount of oil
estimated at 80% by weight zeolite Y, 77% by weight using ZSM-5 catalyst without a
catalyst, plastics produced an oil yield of 84% by weight. Hall W.J et al. (2008) reported
an increase in ethylene and propene gases and other gases were observed alkenes. The
13
raw material recovered from the polymers of the refrigerator showed similar results.
Pyrolysis non-catalysed plastic oils Electronic waste consisting primarily of aromatic
with large amounts of styrene, resulting from the degradation of ABS and HIPS, while
the use of the zeolite catalyst in pyrolysis caused a high amount of toluene, benzene,
and ethylbenzene in oil, but in quantity minors of styrene. A significant amount of
polycyclic aromatic compounds such as organic phenanthrene, pyrene, and naphthalene
were obtained according to Yafei Shen et al. (2015) in oils produced by thermal and
catalysed pyrolysis.
An exhausted catalyst can transform the used oil into diesel fuel. Donny
Lesmanaa et al. (2015). The pyrolysis of spent oils in front of the exhausted pulse was
reported, as well as momentum, for example the type of recovery The pyrolysis of spent
oils in front of the exhausted pulse was reported, as well as the recovery properties of
the spent momentum, ( in situ and ex situ) and the time and temperature ( in situ and ex
situ) and recovery of the amount of money spent. Similarly, the effect of the devoured
energy, the sort of depleted oil, the load proportion of the energy devoured by the waste
oils, and the power of the force expended. The profit of pyrolysis emollient was above
60% when the utilized oil.
The decomposition of the sample was completely stable at 500 ⁰C with the
residual weight of 6.7%, 7.7%, and 2.7% corresponding to 10 K/min, 20 K/min and 30
K/min heating rates. It was observed that the initial weight loss for ABS was happened
in the range of 100-350 ⁰C because of volatile removal. Depolymerization happened in
the range of 350-500 ⁰C. No residual mass left after 600 ⁰C because of evaporation of
carbon.

2.6 ASPEN SIMULATION

Shu et al (2016) Displayed coal pyrolysis in a downstream reactor and talked

about the commitments of different heat exchange systems to the increase in molecule
temperature. Iavarone et al. (2016) surveyed the precision of a few single-step response
models to anticipate the unpredictable execution of bituminous coal in a drag-stream
reactor dependent on Aspen HYSYS displaying results.

Ma J et al (2017) Modelled the hydraulic pyrolysis of pulverized coal into a

hydrogen plasma descending reactor with magnetic rotation. Yan et al. (2012)
reproduction of warming and devolatilization of particles amid fast carbon pyrolysis in

14
a warm plasma decrease reactor utilizing the Euler-Lagrange demonstrate. As of late,
with a comparable methodology, Ma et al. (2017) displayed the pressure driven
pyrolysis of pummelled coal into a hydrogen plasma sliding reactor with the attractive
turn. Polesek Karczewska et al. (2015) developed a transient three-dimensional three-
dimensional model for the wet pyrolysis of coal and examined the impact of the low
penetrability of coal in its plastic stage in the Internal weight spikes. Xing Xianjun et al
(2015) Simulated the variation of biomass pyrolysis yield using Aspen plus and
compared the simulated value with experimental results.

2.7 SUMMARY

A comprehensive literature search has already been carried out, and further
studies are needed during the stay of the complete project to be refreshed with the flow
explore in the proposed region. Traditional electronic waste reusing strategies create a
waste material that still contains profitable waste; they regularly result in landfills. The
polymers have been distinguished in deposits of electronic waste, for example,
polyvinylchloride, high effect polystyrene, polypropylene ABS, polystyrene, and
polycarbonate. Flow look into demonstrates that the warm transformation process
called pyrolysis is a successful method to recoup vitality from electronic waste.
Aspen HYSYS simulation is the analysis of multiphase models that incorporate
physical and chemical reactions and momentum of the interface, heat transfer and mass
in the fixed bed thermal pyrolysis reactor to realise the variation of pyrolysis yield with
respect to temperature, nitrogen flow rate, heating rate and moisture content of
feedstock inside the pyrolysis reactor.

15
 CHAPTER 3
EXPERIMENTAL SETUP AND MEASUREMENTS
3.1 GENERAL

The experimental analysis includes a collection of e-waste and separation of

plastics from collected e-waste and ground them into smaller particles to prepare
feedstock. Selected plastic (i.e., ABS) which comprises a huge percent of e-waste
plastics. The powdered sample has been prepared for ultimate and proximate analysis
to find the various properties like density, enthalpy of the selected plastics. Variable
heating rate or isoconversional and single heating rate or autocatalytic models were
used for this study. Finally, the microwave assisted pyrolysis experiment was
conducted and non-condensable gases are collected. CGMS test was taken for non-
condensable gas.

3.2 COLLECTION AND SEPARATION OF e -WASTE PLASTICS

Electrical and electronic waste was collected from WEE recycling centers,
Then, plastics were separated manually from other metal components of e-waste and
different sorting methods were employed to separate plastics, and ABS plastics were
even differentiated by its applications of use in different parts of e-waste. A mechanical
shredder was used to ground and reduce the size of the ABS plastic into smaller
particles.

3.3 SAMPLE PREPARATION FOR ULTIMATE AND PROXIMATE

ANALYSIS

The sample was prepared in the solid form, the size should be less than 4 mm
in diameter, and 3 mm thickness is the requirements for the thermogravimetric study.
The grinder was used to reduce the shredded plastics into the required size of the
grounded form.

In current study NETZSCH, STA 449F3 model instrument was used, and the
thermal behavior of e-waste plastics (ABS & HIPS) was calculated within the
temperature vary 77–1832 °F. Sample mass required for study can range from 1 mg to
150 mg. Currently, 10 mg mass of a powdered sample of e-waste plastic was analyzed
because of the optimality of the 10 mg weight. Prepared sample powder was placed in

16
an alumina crucible with an N2 flow rate of 20 mL/min are the operating conditions
employed for the analysis.

3.4 ULTIMATE AND PROXIMATE ANALYSIS

In the present survey, the ultimate and proximate analysis were employed to
check enthalpy and mass variety as a function of temperature, time and atmosphere.
Thermal stability and composition of the materials are predicted by this study. The
technique will characterize materials that show weight loss or gain because of
ingestion/desorption of unpredictable mixes, disintegration, oxidation and decrease.
The variable heating rate strategies are utilized to decide the kinetic parameters without
knowing the kinetic mechanism of pyrolysis and the hypothesized reaction rate depends
solely on the temperature for constant conversion no matter the heating rate.
Furthermore, it assumes the reaction order as one and the conversion of plastic
electronic waste into products is a one-step process.

3.5 PYROLYSIS PROCESS AND REACTOR DESIGN

Schematic view of the cascade pyrolysis reactor is shown in the below figure.
Initially, microwave pyrolysis of e-waste ABS plastic was done and produced oil, NCG,
and char. Using properties of ABS plastic and non-condensable gases thermal pyrolysis
reactor was designed as APPENDIX 1.

Fig.3.1 Schematic diagram of the cascade pyrolysis reactor.

17
3.5.1 MICROWAVE PYROLYSIS

The pyrolysis tests were completed in a lab scale microwave pyrolysis reactor. The
reactor is outfitted with four magnetrons, the reactor is provided with 1kW power and
that encompasses a fixed frequency of 2495MHz. In the investigations, a consistent
intensity of 1 kW was utilized for the test. For the material test, the execution was
performed with a pair of hours shift time. The temperature was measured by a
thermocouple positioned inside the reactor. For the performance test, the material used
was 1 kg, which was weighed before and after pyrolysis. To ensure that the packaging
was not a problem, the weight of each material remained constant the initially. In
addition, the oil that was produced during pyrolysis was weighed.

3.6 GAS CHROMATOGRAPHY MASS SPECTROMETRY

In this work, Gas chromatography-mass spectrometry is used to study

the non-condensable gases that are coming out from the microwave pyrolysis reactor.
The GC-MS analysis of non-condensable gases has been performed at Karunya Institute
of Technology and Sciences, Department of Mechanical Engineering, Coimbatore.
And, GC-MS analysis of pyrolysis oil has been done at NITT. The non-condensable
gases consist of H2 (17.897%), CO (2.15%), CH4 (35.428%), CO2 (27.2%), C2H2
(5.189%), C2H6 (12.133%).

3.7 SUMMARY

Microwave assisted pyrolysis experiment was conducted, the non-condensable gases

and pyrolysis oil were collected and GC-MS analysis for pyrolysis oil and non-
condensable gases were carried out various properties of the material was predicted.
The obtained parameters of oil and NCG is explained in results and discussion part are
also given in chapter 5.

18
 CHAPTER 4
ASPEN HYSYS SIMULATION

4.1 GENERAL
ASPEN HYSYS simulator has been used to design and envisage the reliability
of a system which encompasses the excretion of the system into its chemical makeup
for distinct learning of concert. It is widely used to study and investigate the effect of
various operating parameters on various reactions Aspen HYSYS because of its ability
to solve chemical as well as energy problems. To simulate the microwave assisted
pyrolysis reactor, an Aspen HYSYS model was developed. The model is based on
Gibbs free energy and it has been calibrated using the restricted equilibrium method.
Equations are obtained from the conservation of extensive properties such as mass,
time, energy and species concentration both locally and globally. Aspen HYSYS offers
various advantages over experiments like less overall cost better performance of the
parametric study. Moreover, the cost of prototyping also reduces substantially. Because
of the speed, quick and systematic screening of many design concepts can be carried
out, before a prototype of the design is ever built.

4.2 ASSUMPTIONS

The model is constructed based on the following key premises:

➢ Steady state operation,

➢ Negligible drop of pressure,

➢ Char is purely of carbon (C),

➢ The reaction in the pyrolysis reactor had reached a chemical equilibrium,

➢ Pyrolysis reactor heat loss is neglected,

➢ Property of the biomass was entered as non-conventional component.

➢ All the gases are homogeneously disseminated within the blend stage.

19
4.3 SELECTION OF REACTOR
There are 7 built-in reactor models, RSTOIC, RYIELD, REQUIL, RGIBBS,
RPLUG, RCSTR and RBATCH, in Aspen HYSYS. RPLUG, RCSTR and
RBATCH are rigorous models for plug flow, CSTR and batch reactors,
respectively. If both are unknown, the RYIELD reaction kinetics and stoichiometry
should be integrated into the imitations. The reactor system of preference should be
either REQUIL or RGIBBS for single phase chemical equilibrium or simultaneous
phase and chemical equilibrium calculations. REQUIL centre’s its scheming on
both the simultaneous solution of computations of stoichiometric chemical and
stage steadiness intentions, while RGIBBS resolves its prototypical by curtailing
Gibbs permitted dynamism.
Apart from RPLUG and RBATCH, all reactor models could have the Moreover,
the cost of prototyping also reduces substantially. Because of the speed, quick and
systematic screening of a large number of design concepts can be carried out, before
a prototype of the design is ever built. Custom kinetics can be defined in subroutines
from Fortran or worksheets from excel. In this work RGIBBS has been used
because it solves model by minimizing Gibbs free energy.

Table 4.1 Summary of reactor models in Aspen HYSYS.

Model Stoichiometry Kinetics Rigorous Feed

RSTOIC Yes No No Any

RYIELD No No No Any

REQUIL No No No Any

RGIBBS No No No Any

RBATCH Yes Yes Yes 1

RCSTR yes Yes Yes Any

20
 4.4 SIMULATION FLOWSHEET

Fig.4.1 Flow sheet of a thermal pyrolysis reactor

. Referring to Fig.4.1. non-traditional stream of e-waste ABS plastic stated as

‘ABS’ various properties of e-waste ABS plastics were entered. Lower heating value
of the chosen plastic was also quantified. Subsequently, the thermodynamic state of the
stream (1 atm and 28 ° C) and the mass flow rate were inputted. The pressure was set
to 1 atm for all the feed streams and unit operating blocks (i.e. There is no pressure
drop). In this simulation R-Gibbs minimum energy reactor was used and named as
‘PYRO-RE’. The different yields of the pyrolysis reactor obtained from e-waste ABS
plastic were determined using a calculator block.

4.5 ASPEN HYSYS MODEL

Three different stages were considered in ASPEN HYSYS simulation are pyrolysis
reactor, condenser, and gas liquid separation [10].

4.5.1. PYROLYSIS REACTOR

The ASPEN HYSYS yield reactor, the feeds pyrolysis process has been simulated by
the RGibbs reactor. It is used when stoichiometry of reaction is uncertain or
insignificant, kinetics of reaction is uncertain or insignificant, but distribution of yield
is notorious. RGibbs models single phase chemical equilibrium, or phase and chemical
equilibrium simultaneously. When the reactors temperature and pressure are known but

21
reaction stoichiometry is unknown it is preferred to use RGibbs model. Carbon partway
the gas phase and the remaining carbon encompasses portion of the solid phase (char)
and afterward endures char gasification. A Parting stake model was hand-me-down
before the RGibbs reactor to discrete volatiles and solids. In this step, e-waste ABS
plastic is rehabilitated into pyrolysis vapor by stipulating the configuration conferring
to its ultimate analysis.

4.5.2. CONDENSATION
Condenser was used for condensing vapor into gas and liquid. Heat exchanger type of
condenser has been used for this purpose. The technique will characterize materials that
show weight loss or gain because of ingestion/desorption of unpredictable mixes,
disintegration, oxidation and decrease. The variable heating rate strategies are utilized
to decide the kinetic parameters without knowing the kinetic mechanism of pyrolysis
and the hypothesized reaction rate depends solely on the temperature for constant
conversion no matter the heating rate.The mixture of the inert fluidizing gas together
with the non-condensable gases and the pyrolysis vapors flow into the condenser at
500oC at a flow rate of 3 L/min. Inside the inert fluidizing gas, the concentration of the
pyrolysis products is quite low and their presence does not really influence the total
volumetric flow of gas substantially. Henceforth, in measuring the gas blend velocity
within the condenser they have been disregarded to perform a significant role.

4.5.3 SEPARATION COLUMN

The ASPEN HYSYS flash separation column performs separation of pyrolysis fuel oil
and non-condensable gases by using reaction kinetics. Segregation column presumes
flawless intercourse throughout the reactor, meaning that the content reactor has the
similar possessions and configuration as the exit stream.

4.6 SEQUENCE AND KINETICS OF ABS PYROLYSIS REACTION

This model noticeably does not possess any secondary reactions since it is considered
that fast pyrolysis of plastics does not take place in enough time to involve secondary
interactions between products. The equation of reaction used for this simulation was a
modification of the one used by Alla and Ali as shown in equation 1. The reaction was
assumed to occur only in the vapour phase.
𝐴𝐵𝑆 = 𝐻2 + 𝐶1 + 𝐶2 + − − − + 𝐶25 + 20𝐶 (1)
22
The kinetics of plastic pyrolysis reactions has been previously implemented
successfully with Arrhenius equation. For this simulation, the kinetic parameters
obtained by Kayacan and Doğan for waste LDPE at a heating rate of 5 K/min was

utilised. The reported values are A = 3.367 E17 S-1 and E = 279.74 KJ/mol. The
Arrhenius rate equation is then given by the expression of equation 2
𝐸
𝐾 = 𝐴 exp(− 𝑅𝑇) (2)

Where K (s-1) is the rate constant, A (s-1) is the pre-exponential factor, E (KJ/mol) is
the activation energy, T (K) is temperature and R is the universal gas constant 8.314
KJ/molK.
Be that as it may, the Aspen examination process for the pyrolysis reactor has
been perplexing, tedious and blunder inclined. Normally, the examiner must pursue a
few stages to arrange the issue and any minor mistakes can prompt the disappointment
of the reproduction. When the investigation is designed, numerous hours or long
periods of estimation are required to acquire the arrangement and assess the outcomes.
The outcomes are very mind boggling, with substantial informational indexes, which
require time and exertion to break down and get helpful data, which can be retroactive
in the planning stage.

4.7 FLUID PACKAGE AND COMPONENTS

The Peng-Robinson (PR) property package was used in the simulation. Aspen
HYSYS Databank does not contain any polymers. Hence, the polymer is added to the
simulation as a hypothetical component. The chemical species used to model the feed
is ethylene. This information informs the software of the elemental composition of the
feedstock. However, to completely predict all other physical and chemical properties
of the feedstock, Aspen HYSYS requires the stipulation of three properties; density,
molecular weight and normal boiling point. These properties were inputted into the
hypothetical component manager and they served as the basis with which the software
estimated all other necessary information about the polymer. Before importing the
geometry, parameters are designed for the analysis. Because of the speed, quick and
systematic screening of a large number of design concepts can be carried out, before a
prototype of the design is ever built.

23
Various parameters like reactor geometry specification, simulation type, start and end
of simulation etc. are provided. Then geometry is imported into workbench and
decomposition takes place to generate a sector model.

Table 4.2 Feedstock Properties.

Parameter Value

Feed Temperature (oC) 30

Pyrolysis pressure (atm) 1

Pyrolysis temperature (oC) 450

Feed density (kg/m3) 1050
Feed rate (kg/hr) 1
Melting point (K) 383

Boiling point (K) 543

Molecular weight (g/mol) 211.308

4.8 SUMMARY
The detailed information regarding modelling and procedure adopted for the Aspen
HYSYS analysis is given in this chapter containing the settings used in the model.
Various conditions are defined like mass flow rate of feedstock and nitrogen required.
Selection of temperature-based solver with gravitational effects is used considering the
various variables like pressure, momentum, species, etc.

24
 CHAPTER 5
RESULTS AND DISCUSSION
5.1 GENERAL
In this present chapter, composition of pyrolysis oil and non-condensable gases
were exposed, and they were obtained from the thermal analysis gas chromatogram-
mass spectroscopy (GCMS) of the chosen styrene polymer ABS. The Aspen HYSYS
simulation of the designed thermal pyrolysis reactor was done and sensitivity various
parameters are discussed. To analyze the susceptibility of the primary operating
parameters with regard to pyrolysis reactor performance the evaluated model was used.
Important parameters including pyrolysis temperature, nitrogen flow rate, heating rate,
biomass moisture content. Sensitivity analysis was done by keeping input data same as
used for the model validation and at any given time a single parameter was varied.

5.1.1 MICROWAVE PYROLYSIS YIELD

80

70 66.9

60
Pyrolysis yield (%)

50

40

30 26.16

20

10 6.94

0
Pyrolysis oil NCG Char

Fig.5.1 Microwave pyrolysis various yield percentage at 450oC

Various microwave pyrolysis yields were pyrolysis oil, non-condensable gases, and
char, their proportions are oil-66.9%, non-condensable gas-26.16%, and char-6.94% of
the given amount of feedstock at the temperature of 450oC and retention time of 50
minutes with 0.5 Lit/min of nitrogen supply.

25
 5.1.2 NCG COMPOSITION

Table 5.1. Composition of NCG obtained by GCMS

Sl No. Name Percentage (%)

1 H2 17.802

2 CO 2.15

3 CH4 35.43

4 CO2 27.2

5 C2H2 5.189

6 C2H6 12.133

Fig.5.2 Chromatograph for NGC from the microwave pyrolysis reactor.

Each peak in the GCMS graph indicates a gas and using the area of the peak mass
fraction of the gases is calculated. Further several properties of the non-condensable
gas from the microwave pyrolysis reactor is calculated using a mass fraction. The
calculated gas composition is given in the below table 5.1.

26
5.1.3 PYROLYSIS OIL COMPOSITION

Table 5.2 Composition of pyrolysis oil obtained by GC

Sl No. Name Percentage (%)

1 C8H10 12.44

2 C8H8 6.12

3 C9H12 22.9

4 C9H10 10.37

5 C17H18 9.06

6 C10H12 1.32

7 C9H9 0.45

8 C10H22O 0.38

9 C10H10 0.23

10 C10H8 0.52

11 C10H11N 0.19

12 C12H10 1.81

13 C13H12 0.24

14 C14H14 0.48

15 C15H16 0.33

16 C18H22 0.25

27
 Sl No. Name Percentage (%)

17 C16H16 11.79

18 C16H18 0.27

19 C11H14 0.24

20 C16H14 0.96

21 C15H12O 0.32

22 C5H8N2 1.46

23 C16H10 0.33

24 C15H12 0.49

25 C18H18 2.68

26 C17H18 1.31

27 C16H12 2.99

28 C17H14 3.44

29 C19H40 1.02

30 C24H24 5.36

31 C21H22 0.25

Each peak in the GCMS graph indicates an element and using the area of the peak mass
fraction of the oil is calculated. Further several properties of the pyrolysis oil from the
microwave pyrolysis reactor is calculated using a mass fraction. The calculated oil
composition is given in the below table 5.2

28
 Fig.5.3 Chromatograph for oil from the microwave pyrolysis reactor.

5.2 SIMULATION RESULTS

5.2.1 SENSITIVITY ANALYSIS; PYROLYSIS TEMPERATURE

Figure shows the influence of pyrolysis temperature on the percentage of yield.
Pyrolysis temperature is varied from 300-850 °C and it shows that pyrolysis
temperature has a very strong influence on pyrolysis yield. Fixed bed e-waste ABS
pyrolysis reactor should be operated above 300 °C to ensure the yield formation. There
is no yield formation below 300oC as it can be seen from the simulation result and
maximum yield is obtained at around 450oC even if pyrolysis temperature is increased
beyond 450oC, there will be no change in yield percentage so we can conclude that
optimum temperature for the oil production from e-waste is around 450oC.

29
 80
Oil (%) Gas (%) char (%)
70

60
Pyrolysis yield (%)
50

40

30

20

10

0
300 350 400 450 500 550 600 650 700 750 800 850
Temperature (oC)

Fig.5.4. Variation of yield percentage with pyrolysis temperature (oC).

5.2.2 SENSITIVITY ANALYSIS; NITROGEN FLOW RATE
After pyrolysis temperature, flow rate of nitrogen supplied for purging the
reactor vessel to create inert atmosphere and to drive out the pyrolysis vapour has a
great influence on pyrolysis yield. When the nitrogen flow rate is low residence time of
pyrolysis vapour inside the reactor vessel increases so the oil yield will be less, on the
other hand if the flow rate increased above optimum range then also oil yield will
decrease because of less time available for the condensation. Maximum oil yield was
around 66.42 % at the nitrogen flow rate of 200 cc/min.

80
Oil (%)
70
Gas (%)
60 char (%)
Pyrolysis yield (%)

50

40

30

20

10

0
150 200 300 400 500
Nitrogen flow rate (cc/min)

Fig.5.5. variation of yield with nitrogen flow rate.

30
5.2.3 SENSITIVITY ANALYSIS; HEATING RATE
Simulation has been done for different heating rates (10 K/min, 20 K/min, 30
K/min) variation of oil yield is shown in the figure 5.6. Optimum heating rate was
found to be 10 K/min and the corresponding methanol production was 66.9 % on weight
basis.
68

67

66

65
oil yield (%)

64

63

62

61

60
0 5 10 15 20 25 30 35
Heating rate (K/min)

Fig .5.6. Pyrolysis oil yield for different heating rates.

5.2.4 VARIATION OF GAS COMPOSITION
Gas composition varies as the pyrolysis temperature changes as it can be seen
in the figure 5.7 given below the composition is mostly of hydrogen, methane, carbon
monoxide, carbon di-oxide, acetylene, ethane. Fraction those gases were different as
we change the temperature at which pyrolysis was done. Overall if we increase the
pyrolysis temperature carbon di-oxide fraction decreases whereas methane, hydrogen
and ethane fractions increase slightly, and the fractions of carbon monoxide and
acetylene decreases slightly. If we are getting more non-condensable gases means that
our oil yield decreases.

31
 70

60 H2 CH4 CO CO2 C2H6 C2H2

50
Gas composition (%)

40

30

20

10

0
300 350 400 450 500 550
Temperature(oC)

Fig .5.7. Gas compositions from simulation of e-waste pyrolysis

32
 CHAPTER 6

CONCLUSIONS AND SCOPE FOR THE FUTURE WORK

6.1 CONCLUSIONS

The objective of the research work was to develop a pyrolysis reactor model and to use
the same for investigating the impact of main operating parameters on reactor
performance. A pyrolysis reactor computer simulation model was developed using
Aspen HYSYS and results were obtained varying operating parameters.
• The findings revealed the following: pyrolysis temperature, nitrogen flow rate,
heating rate are the most important pyrolysis oil yield variables; the pyrolysis
process must be done in the temperature range of 400 – 500oC, nitrogen flow
rate of 200 cc/min, and the heating rate of 10 K/min. The simulation showed
that the maximum percentage of methanol yield from sugarcane bagasse is
around 66.42 % on the weight basis.
• Experimentally microwave pyrolysis yields were pyrolysis oil, non-
condensable gases, and char, their proportions are oil-66.9%, non-condensable
gas-26.16%, and char-6.94% of the given amount of feedstock at the
temperature of 450oC and retention time of 50 minutes with 200 cc/min of
nitrogen supply.
• GCMS analysis of non-condensable gas proportions found to be H2 (17.897%),
CO (2.15%), CH4 (35.428%), CO2 (27.2%), C2H2 (5.189%), C2H6 (12.133%).
Various gas composition also found using GCMS.
• The results from the reactor simulation model showed good agreement with
theoretical results.
• Gas flow parameters of the burned non-condensable gas were also analyzed.

33
 6.2 SCOPE FOR THE FUTURE WORK
It is evident from our study that Aspen HYSYS simulation for pyrolysis reactor
analysis is a significant tool to examine the performance of the thermal pyrolysis reactor
under different parameters. The simulation and experimental design for pyrolysis
reactor exhibited the same results. This means the same model can be utilised to study
reactor performance for different plastic properties in the simulation. Moreover, we did
simulation analysis using ABS plastic and input energy was low grade energy of non-
condensable gas from the microwave pyrolysis reactor, so the model can be extended
for the analysis of reactor with different plastics and energy input.

34
 APPENDIX 1

1.1 Volume of the reactor vessel

𝑚
𝑉= ⍴

𝑉 = 𝜋 (𝑟₃2 − 𝑟₂2 )𝐿

𝑟2 = 𝑟1 + 𝑡

𝑟₄ = 𝑟₃ + 𝑡

Where,

L-Length of the reactor,

r1 -inner radius of the inner cylinder,

r2 -outer radius of the inner cylinder,

r3-inner radius of the outer cylinder,

r4-outer radius of the outer cylinder,

1.2 Heat transfer calculation

Heat required = 𝑚ₚ𝑐ₚ (𝑇𝑝𝑦𝑟𝑜𝑙𝑦𝑠𝑖𝑠 − 𝑇𝑖𝑛𝑖𝑡𝑖𝑎𝑙 )

Total heat transferred to the cylinder wall = 𝑄𝑟𝑎𝑑𝑖𝑎𝑡𝑖𝑜𝑛 + 𝑄𝑐𝑜𝑛𝑣𝑒𝑐𝑡𝑖𝑜𝑛

In the furnace heat is transferred by radiation and convection

4
𝑄𝑟𝑎𝑑𝑖𝑎𝑡𝑖𝑜𝑛 = 𝜎 𝐴𝑖𝑛 (ɛ 𝑔𝑎𝑠 𝑇𝑔4 − ⍺𝑔𝑎𝑠 𝑇𝑖𝑤 )

𝑄𝑐𝑜𝑛𝑣𝑒𝑐𝑡𝑖𝑜𝑛 = ℎ 𝐴𝑖𝑛 (𝑇𝑔 − 𝑇𝑖𝑤 )

ɛ 𝑔𝑎𝑠 = ɛ 𝑐𝑜2 + ɛ H2 O − ∆ɛ
𝑇𝑔 𝑇𝑔
⍺𝑔𝑎𝑠 = ɛ 𝑐𝑜2 (𝑇 )0.65 + ɛ H2 O (𝑇 )0.45 − ∆ɛ
𝑖𝑤 𝑖𝑤

2𝜋𝐿𝑘 (𝑇𝑖𝑤 −𝑇𝑜𝑤 )

Heat conducted through the cylinder wall = 𝑟
ln( 𝑜 )
𝑟𝑖

Heat obtained by combustion = m CV

Total heat transferred to the cylinder wall = Heat conducted through the cylinder

𝑄𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟𝑟𝑒𝑑 = 148.1W 𝑄required = 111.66W

𝑄𝑡𝑟𝑎𝑛𝑠𝑓𝑒𝑟𝑟𝑒𝑑 > 𝑄required so, the design is feasible.

35
 where,

𝑚ₚ-mass of plastic,

𝑐ₚ-specific heat of plastic,

σ-Stefan boltzmann constant,

𝑇𝑔 –Temperature of the gas,

𝑇𝑖𝑤 –Temperature of the inner wall

𝐴𝑖𝑛 -Area of the inner cylinder,

𝑇𝑜𝑤 - Temperature of the outer wall,

h-Heat transfer coefficient,

k-Thermal conductivity,

Assumptions

Mass - 0.5kg

Material - stainless steel

The inner radius of the inner cylinder - 3.75 cm

Steps

1. Using the assumed mass and density of ABS calculated the volume.

2. Radius and length of the reactor are calculated using the volume.

3. Total heat required is calculated by equation (1).

4. Heat transferred is calculated by equation (2).

1.3 Properties of non-condensable gas.

Density = ∑𝑥𝑖 ⍴𝑖

Calorific value = ∑𝑥𝑖 𝐶𝑉𝑖

Molecular weight = ∑𝑥𝑖 𝑀𝑤𝑖

xi – Mass fraction of ith gas.

⍴i – Density of ith gas.

CVi – Calorific value of ith gas.

Mwi – molecular weight of ith gas.

36
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