PYROLYSIS OF COCONUT (Cocos nucifera) SHELLS AND THE APPLICATION OF

THE PRODUCED CHAR FOR THE TREATMENT OF FOUNDRY WASTEWATER

A FINAL YEAR RESEARCH PROJECT

PRESENTED TO

THE DEPARTMENT OF CHEMICAL ENGINEERING

BY

CHARLES DANIEL CHRIS

18CF023951

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS FOR THE DEGREE

BACHELOR OF ENGINEERING (B.Eng.) IN CHEMICAL ENGINEERING, COVENANT
UNIVERSITY, OTA

OCTOBER 2022

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 TABLE OF CONTENTS

LIST OF TABLES........................................................................................................................iv
LIST OF FIGURES......................................................................................................................iv
CHAPTER ONE............................................................................................................................1
1.1 Background of the Study........................................................................................................1
1.2 Statement of Problem.............................................................................................................3
1.3 Aims and Objectives..............................................................................................................4
1.3.1 Aim of the Study.............................................................................................................4
1.3.2 Objectives of the Study...................................................................................................4
1.4 Justification of Study.............................................................................................................4
1.5 Scope of the Study.................................................................................................................5
CHAPTER TWO...........................................................................................................................6
2.1 Overview of Biomass.............................................................................................................6
2.1.1 Biomass as a Renewable Source of Energy....................................................................6
2.1.2 Coconut as a Biomass......................................................................................................7
2.2 Conversion of Biomass..........................................................................................................8
2.2.1 Biochemical Conversion of Biomass..............................................................................8
2.2.2 Thermochemical Conversion of Biomass.......................................................................9
2.3 Classes of Pyrolysis Feedstocks...........................................................................................11
2.3.1 Pyrolysis of Coal...........................................................................................................12
2.3.2 Pyrolysis of Biomass.....................................................................................................12
2.3.3 Pyrolysis of Municipal Waste.......................................................................................12
2.3.4 Pyrolysis of Refuse Derived Fuels................................................................................13
2.4 Pyrolysis of Biomass............................................................................................................13
2.4.1 Description of Process...................................................................................................13
2.4.2 Products Formed............................................................................................................15
2.4.3 Types of Pyrolysis.........................................................................................................16
2.4.4 Factors Affecting Pyrolysis...........................................................................................16
2.5 Adsorption Process..............................................................................................................20
2.5.1 Description of Process...................................................................................................20
2.5.2 Types of Adsorption......................................................................................................20

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 2.5.3 Factors Affecting Adsorption........................................................................................21
2.5.3 Adsorption Isotherms....................................................................................................23
2.5.4 Adsorption Kinetics.......................................................................................................25
2.5.5 Adsorption Thermodynamics........................................................................................26
2.6 Methods of Wastewater Treatment......................................................................................27
2.6.1 Adsorption.....................................................................................................................27
2.6.2 Biological Digestion......................................................................................................27
2.6.3 Pressure Sand Filtration.................................................................................................27
2.7 Major Contaminants in Wastewater.....................................................................................28
2.7.1 Organic Contaminants...................................................................................................28
2.7.2 Heavy Metals.................................................................................................................28
2.7.3 Radioactive Materials....................................................................................................28
2.7.4 Potential of Coconut Shells in Wastewater Treatment..................................................29
2.8 Iron as a Contaminant in Wastewater..................................................................................29
2.8.1 Removal of Iron from Wastewater by Adsorption........................................................29
2.8.2 Effects of Iron on the Human body, Plants, Animals and Ecosystem...........................30
2.9 Review of Related Past Reports...........................................................................................32
CHAPTER 3.................................................................................................................................34
3.1 Materials and Reagents........................................................................................................34
3.1.1 Materials Used...............................................................................................................34
3.1.2 Reagents Used...............................................................................................................34
3.2 Equipment and Apparatus Used...........................................................................................35
3.2.1 Apparatus Used.............................................................................................................35
3.2.2 Equipment used.............................................................................................................35
3.3 Experimental Procedure.......................................................................................................36
3.3.1 Block Flow Diagram.....................................................................................................36
3.3.2 Pretreatment of Biomass and Physiochemical Assessment of Pretreated Biomass......36
3.3.3 Pyrolysis of Coconut Shells..........................................................................................38
3.3.4 Activation of Biochar....................................................................................................38
3.3.5 Characterization of Synthesized Adsorbent..................................................................39
3.3.6 Treatment of Raw Wastewater with Activated Carbon.................................................39
REFERENCES............................................................................................................................41

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 LIST OF TABLES

Table Title Page

2.1 Potential fuels obtained from various types of biomass and processed 7
wastes
2.2 Composition of coconut biomass 8
2.3 Typical operating parameters and products for pyrolysis process 14
2.44 Review of Past Related WorksRepresentation of Biomass Pyrolysis 29
2.5 Review of Past Related Works

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 LIST OF FIGURES
Figure Title Page
2.1 Typical Pyrolysis Process 10
2.2 Typical Gasification process 11
2.3 Classification of Pyrolysis Feedstock 11
2.4 Representation of Biomass PyrolysisVariation of properties of Biochar 17
with varying process conditions
2.5 Adsorption mechanism of Fe2+ on activated carbon 29

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 CHAPTER ONE
INTRODUCTION

1.1 Background of the Study

Thus far, petroleum and other fossil fuels such as gasoline and diesel have been able to
adequately cater for our energy needs. However, there is great concern regarding the finiteness of
fossils. Oil experts predict that with the continuous increase in population and hence, demand,
fossil fuels will eventually be depleted (White, 2012). The prices of fossils have inevitably begun
to increase due to this excessive demand. Moreover, despite the fact that roughly half of the
world’s oil reserves have yet to been exploited, there is a glaring difficulty in accessing these
resources in time to be able to meet up with global needs (Abas et al, 2015). For this reason,
research for another source of energy commenced, from which biomass was brought forward as
a promising alternative to fossil fuels.

The term "biomass" refers to biological material generated from living or recently extinct
creatures, most frequently plants or components derived from plants. The conversion of biomass
(usually a solid mass) to liquid and gaseous fuels can either be done through biochemical or
thermo-chemical means. The biochemical process such as anaerobic digestion involves the use
of micro-organisms to break down biomass, forming renewable energy such as biogas in the
process. Thermo-chemical routes involve heating biomass at extreme temperatures.
Thermochemical conversion has been found to be more efficient in converting biomass to energy
and less time-consuming than biochemical methods (Dhyani et al, 2018).

Pyrolysis is a well-recognized method of thermochemical conversion. In pyrolysis, biomass is

heated at elevated temperatures in the absence of oxygen. At the end of the pyrolysis process,
three products emerge: a gaseous product constituting of lower molecular weight compounds
unable to condense which is known as pyrolytic gas, bio-oil formed from the remainder of the
gaseous product, which was able to condense and finally, biochar, a solid carbon-rich product
which is similar to petroleum-based coal. Bio-oil can be added to petrol-diesel to increase its
cetane number, thereby reducing ignition delay and carbon dioxide emission (Yusuf et al, 2011).

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Biochar, on the other hand, can serve as a soil additive, increasing the nutrients and water
holding capacity of the soil and also has use in animal farming as a feed supplement (Schmidt et
al, 2014).

Another promising application of biochar is in wastewater treatment. The quality of natural water
bodies and in turn, water supply is declining as a result of the continuous discharge of
contaminants such as dyes, heavy metals, pesticides, and surfactants from industries into water
bodies. The presence of these pollutants can bring about adverse effects to the ecosystem and its
inhabitants. Heavy metals, for example, when amassed in the human body can incite declined
mental capability. This has necessitated the development of a wide number of technologies to
remove organic and inorganic pollutants from wastewater before it is discharged. Some of these
methods include membrane separation, ion exchange, flocculation, reverse osmosis, filtration,
etc.

Unfortunately, these processes are plagued by certain problems such as high energy requirement
and thus, high operational cost, complex design, generation of large amounts of sludge which is
toxic and leads to disposal issues (Bhatnargar et al, 2010). Adsorption has thus gained more
interest due to its relatively simpler design and economical nature and removal efficiency.
However, activated carbons, which are the most common adsorbents used in wastewater
treatment due to their high adsorption capacity are expensive. Hence, there is a dire need to
utilize readily available materials such as agricultural waste to synthesize activated carbon.
When coupled with its rich carbon content, enhanced surface area, high cation/anion exchange
capacity, and stable structure, biochar can certainly be used as an alternative to commercial
activated carbon in the treatment of wastewater (Rizwan et al, 2016).

Biochar which can be processed into activated carbon can be derived from various agricultural
waste materials such as coconut shells. Coconut yields various products among which includes
coconut oil, which is used in the manufacture of toilet soaps, cosmetics, hair products, etc. For
this reason, coconut experiences high demand virtually all year round leading to disposal (en
masse) of coconut shells and other wastes. Hence, coconut wastes in general, are a viable
feedstock for the production of biochar as they are readily available and inexpensive.
Furthermore, coconut shells in particular, are a very promising bio-adsorbent due to their low
modification requirements, lower ash content and high volatile matter content (James et al,

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2021). Using activated carbon made from coconut shells to remove organic matter is second only
to its application in removing heavy metals. In the research by Pino et al, 2006, biochar
synthesized from coconut shell was used to remove cadmium from wastewater. The adsorbent
was found to have high adsorption capacity even at low concentrations. In this research, biochar
synthesized from the pyrolysis of coconut shell will be activated, and then used to treat
wastewater from the casting section of a foundry and AAS (atomic absorption spectroscopy)
analysis will be conducted on the treated samples to determine the efficiency of the adsorbent in
removing iron in particular from the effluent.

1.2 Statement of Problem

Due to an increase in population, there is a high demand for food. As a result, food resources are
cultivated and transported on a large scale invariably resulting in the mass production of
agricultural waste. These waste products can be attributed to factors such as poor transportation
network, inadequate storage facilities and food spoilage (Adejumo et al., 2020). Agricultural
wastes include corn husks, wheat straw, banana peels, coconut pith, husk, shells, etc. They are
termed ‘waste’ as they are merely byproducts gotten during cultivation and consumption. Lack
of utilization of these organic waste leads to their accumulation, which is a major contributor to
land pollution, which is a source of GHGs and can also block water ways, leading to flooding.

There is also the problem of overdependence on wood. Wood has long been a conventional
source of fuel in the form of charcoal and firewood, especially in rural regions given its
availability. As such, there is a great need for wood resulting in the continuous felling of trees.
However, deforestation is known to bring about dastardly consequences such as soil erosion,
desertification, landslides, etc. (Prabhakar et al, 1986). Unless an alternative for charcoal and
firewood can be provided, the scenario described above is inevitable.

Furthermore, there is the need to find an effective and inexpensive means of removing pollutants
such as inorganic metals from wastewater. Activated carbon has proven to be one of the most
effective adsorbents due to properties such as high specific area and large pore volume. This is
evidenced by its high adoption in industries (Zhao, 2003). However, due to the high cost of
commercial activated carbons as a result of its non-renewable raw materials e.g. coal, the
adsorption process is expensive (Attia et al, 2008). Research has hence gone into deriving the
adsorbent from readily available and hence, low-cost materials.

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1.3 Aims and Objectives

1.3.1 Aim of the Study

The aim of this study is to activate biochar obtained from the pyrolysis of coconut shells and use
it as an adsorbent to treat foundry wastewater and determine its efficiency in removing heavy
metals from the wastewater.

1.3.2 Objectives of the Study

i. To carry out pretreatment of coconut shells.
ii. To obtain biochar from the pyrolysis of coconut shells.
iii. To activate the char using phosphoric acid and characterize resulting adsorbent.
iv. To treat raw wastewater from the casting section of a foundry using activated char as an
adsorbent.
v. To investigate the equilibrium, kinetics and thermodynamics of the adsorption process.

1.4 Justification of Study

First and foremost, this research contributes to the removal of harmful substances from raw
wastewater. When severe, water pollution can kill large numbers of fish, birds, animals and
human beings in the affected area. By utilizing readily available raw materials such as coconut
shells to produce activated carbon, this study provides a cost-effective and efficient means of
wastewater treatment. This helps to protect aquatic life and other organisms in the immediate
environment from dangerous toxins, in line with “United Nations' Sustainable Development
Goals (SDGs), specifically Goal 14: Life Below Water. The effectiveness of the adsorption
process (amount of pollutant removed) was determined to ensure the adsorbent could yield a
high removal efficiency. Also, the experimental data of the adsorption process were analyzed to
study the kinetics, adsorption, and thermodynamics of the process. This is essential as a proper
understanding and interpretation of adsorption isotherms, kinetics and thermodynamics is critical
for the overall improvement and effective design of the adsorption system.

Furthermore, studies such as this are important as they promote the utilization of the abundant
amount of agricultural waste present in the environment as against the conventional dumping of
waste. This will serve to reduce the formation of landfills which is a major source of greenhouse
gases e.g. methane. As a result, carbon footprints are reduced, impeding the further development

4
of climate change. Therefore, this research coincides again with the United Nations'
Sustainable Development Goals (SDGs), specifically Goal 13: Climate Action.

1.5 Scope of the Study

This study encompasses the treatment of raw wastewater from the casting section of a foundry
by using biochar, a solid product gained after pyrolyzing coconut shell as an adsorbent after it
has been activated. This research also includes the conduction of AAS analysis on the raw water
before and after treatment to determine the removal efficiency of the treatment process. The
surface morphology of the activated char is also studied by running tests such as SEM (Scanning
Electron Microscope), XRD (X-ray diffractomer) on a sample. The adsorption process was
thoroughly studied. This included investigations into the kinetics, equilibrium, and
thermodynamics of the process.

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 CHAPTER TWO
LITERATURE REVIEW

2.1 Overview of Biomass

2.1.1 Biomass as a Renewable Source of Energy

Biomass, just like fossil fuels originate from the remains of plants and animals. However,
biomass is formed from remains that have only been present for a much shorter period of time.
This is in contrast to fossil fuels which are formed over an extensive period of time. It is due to
this long duration that these resources are seen as non-renewable as they cannot be easily
replenished. Consequently, biomass is a highly practical substitute for fossil fuels in the energy
industry. Biomass, especially ones with high calorific value such as coconut waste can generate
more than ten times the amount of power generated by solar and wind energy (Posibi, 2021).

However, the contribution of biomass to the total power generated in Nigeria is infinitesimal.
This is due to factors such as large area of land required, location of processing facility, etc (Diji,
2013). Biomass contains chemical energy, which is originally gotten from the Sun through
photosynthesis. The use of biomass does not only provide a carbon-neutral and renewable source
of energy but is also a means of turning waste into energy, reducing landfills and invariably
amount of greenhouse gases (most especially methane) into the atmosphere. Biomass
encompasses a large variety of resources, but can be categorized into the following:

i. Energy crops: These are crops grown specifically for the purpose of serving as fuel
for energy production. These are usually trees, grasses, and oil crops, some of which
include rapseed, canola, etc.
ii. Forest sources: These are residues gained from lumbering operations such as wood
chips, sawdust, mill scrap, etc.
iii. Agricultural wastes: These are wastes left after the cultivation or harvesting of
agricultural products e.g. bagasse, corn straw, coconut husks, bean husks etc.
iv. Municipal wastes: These refer to wastes products from household, and industrial
sources. These include sewage sludge, refuse-derived fuel (RDF), food waste,
wastepaper, yard clippings, etc.

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Table 2.1 shows the potential fuels obtained gotten from different biomass and processed wastes.

Table 2.1: Potential fuels obtained from different biomass and processed wastes
(Diji, 2013)

Biomass Processed Waste Fuel Produced

Bamboo Sawmill waste Producer gas
Crops such as sugar cane, corn, Cereal straw and cobs Bioethanol
soyabean
Soft stems, such as those of Industrial wood bark and Biogas
potatoes logging wastes, swamps and
water plants, black liquor
from pulp mills, municipal
wastes
Shrubs and tress Bagasse Charcoal

2.1.2 Coconut as a Biomass

Biomass from coconut (Cocos nucifera) plant comes in various forms: as coconut shell, pith,
husk, etc. Coconut waste is an attractive source of biomass. Being that coconut is constantly in
high demand all year round, a constant supply of biomass is guaranteed. As a result, large
amounts of coconut waste products are generated. Coconut wastes possess a relatively high
amount of lignin (41-45%), cellulose (36-43%) and hemicellulose (0.15-0.25%) compared to
other agricultural wastes (Becker et al, 2016).

Both coconut shells and husks have high heating values due to their high lignin and cellulose
content. For this reason, coconut shells and husks are ideal for energy generation and conversion
(Tsai et al, 2006). Coconut shells, however are more suitable for the pyrolysis process than
coconut husks due to their lower ash content and high carbon content. Ash content is an
important factor to consider as it can cause fouling of equipment. Higher carbon content results
in better ignition during the thermochemical process and a solid residue (biochar) of higher
quality (Abrahim et al, 2019).

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 Table 2.2: Composition of coconut biomass (Azeta et al. 2021)

2.2 Conversion of Biomass

Biomass in its ordinary solid form is more difficult to transport when compared to liquid and
gases. Hence, biomass is converted to liquid and gaseous fuels by one of the following routes:

i. Biochemical conversion
ii. Thermochemical conversion

2.2.1 Biochemical Conversion of Biomass

In this process, microbes are utilized to convert biomass into fuels. Although this route may take
more time, it is less energy-intensive (requires less energy input) than the thermochemical
conversion route. The primary methods of biochemical conversion of biomass are as follows:

2.2.1.1 Fermentation

In the fermentation process, initial pre-treatment is first done on the biomass to isolate cellulose
from other constituents such as hemicellulose and lignin (Lee & Lavoie, 2013). The cellulose is
broken down into simpler sugars (hexose and pentose) in a process known as hydrolysis which
involves the use of either acid or enzymes. The sugars are then broken down resulting in the
formation of ethanol (formally called bioethanol) with the aid of micro-organisms such as yeast.

2.2.1.2 Anaerobic and Aerobic Digestion

In this process, microorganisms break down the complex units present in biomass, which is a
biodegradable matter such as proteins, polysaccharides into much simpler forms under anaerobic
or aerobic conditions. Anaerobic digestion is a series of processes that culminates in the

8
production of methane (CH4) in addition to carbon dioxide (CO2) and hydrogen sulphide (H2S)
which are produced in smaller amounts. The gas produced can be further processed to yield a
clean energy source known as biogas. A common source of anaerobic bacteria is cow dung.

In aerobic digestion, the microbes require oxygen to decompose the organic matter. This of
course, means that different organisms from the anaerobic digestion are used in this process.
Aerobic digestion is a much simpler process because most naturally occurring microorganisms
are aerobes. The introduction of air, which contains oxygen is enough to facilitate the growth of
these bacteria. At the end of the process, carbon dioxide, heat and a solid residue are produced
(Shammas & Wang, 2007)

2.2.2 Thermochemical Conversion of Biomass

The thermochemical route involves heating the carbon-based materials at high temperatures.
This process can be conducted in the absence or presence of oxygen. As stated earlier,
thermochemical conversion methods are faster but require large amounts of energy due to the
extreme temperatures needed for the process. The primary methods for the thermochemical
conversion of biomass are as follows:

2.2.2.1 Combustion

Combustion involves the direct burning of biomass in excess air to produce heat which can be
used to generate steam and power steam turbines and also carbon dioxide.

2.2.2.2 Pyrolysis

Pyrolysis is an oxygen-deficient process. The biomass is heated at temperatures of about 400–

500 oC in an enclosed vessel with little or no oxygen present. The temperatures used in pyrolysis
are relatively low compared to other thermochemical processes. At the end of the process, gas
and a solid residue are found. A portion of the gas is able to condense and upon cooling, forms
pyrolysis oil, also called bio-oil. The solid product is known as biochar.

9
 Figure 2.1: Typical Pyrolysis Process
Source: Meier et al, 2013

2.2.2.3 Gasification

Gasification involves the use of a medium such as oxygen to convert a raw material e.g biomass
into carbon monoxide (CO) and hydrogen (H2), otherwise known as syngas.

Although gasification and combustion are firmly related, there is a huge distinction between
them. In gasification, energy is stored in the bonds present in the gas formed whereas in
combustion, bonds are broken leading to the evolution of energy. Gasification also generates
gases with lesser amounts of carbon. (Probstein & Hicks, 2006)

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 Figure 2.2: Typical Gasification process
Source: Probstein & Hicks, 2006

2.3 Classes of Pyrolysis Feedstocks

Various substances can be fed into a pyrolizer. These are classified as either non-renewable or
renewable sources. The non-renewable feedstocks include coal majorly, whereas renewable
feedstocks comprise of lignocellulosic biomass, municipal waste and refuse derived fuels. These
classes are discussed in subsections below.

Figure 3.3: Classification of Pyrolysis Feedstock

Source: Rajasekhar et al., 2017

2.3.1 Pyrolysis of Coal

Coal is the primary non-renewable feedstock and is major fuel due to its high calorific value.
Coal occurs in different forms such as anthracite, peat, lignite, etc. Coal in its various forms
possesses different thermal stabilities due to their individual volatile matter content. They are
ranked by the energy expended during their decomposition and as such, are arranged in the
following order: anthracite>bituminous>sub-bituminous>lignite. Similar to pyrolysis of other
fuels, the pyrolysis products of coal are coke/char, bio-oil and syngas. The particular form of
coal used as a feed is a major determinant of the product ratios of the process. Tar is the primary
volatile product of pyrolysis for bituminous coals. As bituminous coals are replaced by lignite

11
and subbituminous coals, the volatile products' composition shifts away from tar towards
hydrocarbon gases, water, and carbon oxides (Rađenovic et al., 2006).

2.3.2 Pyrolysis of Biomass

Lignocelluosic biomass can be classified into woody biomass and agricultural residue. Examples
of woody biomass include sawdust, wood chips, etc. Agricultural waste products or agro-
residues include corn husk, wheat straw, coconut shells, bagasse, etc. These are an attractive
feedstock as they are inexpensive and readily available. In 2019, Nigeria generated an estimated
6047.02 tons of residue (Alhassan et al., 2019). Biomass comprises of three main components,
namely: cellulose, hemicellulose, and lignin, alongside inorganic and extractives which
constitute a much smaller fraction. The exact composition of the feedstock varies for different
parts and species of the plant. For example, lignin typically makes up 30% of softwood by
weight and 20-25% of hardwood (Rajasekhar et al., 2017).

This knowledge is very crucial as the chemical composition is one of the parameters that governs
the yield of the process. The respective constituents have distinct thermal stabilities, (much like
the variants of coal) and react differently to high temperatures. The carbohydrates (cellulose and
hemicellulose) break down at the glycosidic link to provide lower-molecular-weight volatile
pyrolysis products, whereas lignin is mainly charred to a carbonaceous residue. The relationship
between these constituents and products is explained in further detail later in this literature.

2.3.3 Pyrolysis of Municipal Waste

Municipal solid waste (MSW) typically includes domestic refuse such as kitchen waste,
recyclables such as paper and plastic products from stores and offices, garbage and also
industrial waste. MSW is composed mainly of combustible matter and as such has a calorific
value (about 7,000-14,000 kJ/kg) suitable for energy generation (McIntyre et al., 1974).
Pyrolysis, has gained interest as a method of treating MSW due to the increase in generation of
MSW and numerous drawbacks of conventional methods such as composting, incineration,
ocean dumping, etc.

Due to the complexity in composition of MSW, the exact mechanism of pyrolysis is not known
(McIntyre et al, 1974). Metals and glass, which are non-combustible have to be first separated.
The remainder can then be further categorized into polymers such as polyethylene (PE),
polyethylene terephthalate (PET), polystyrene (PS), organic waste, paper, etc. (Younan et al.,

12
2016). The composition of MSW vary according to geographical location. Hence, the products
obtained from the pyrolysis of MSW cannot be generalized. However, polymers are known to be
a major component in any sample of MSW. Various studies have been carried out to investigate
the yield from different plastics. In a study by Miandad et al., 2017, polystyrene was pyrolyzed at
high temperatures and heating rates, Bio-oil was found to be the major product (80%). On the
other hand, when polyethylene was subjected to the same conditions, pyrolytic gas was the major
product (~65%) (Miandad et al., 2017).

2.3.4 Pyrolysis of Refuse Derived Fuels

Refuse Derived Fuels (RDF) are a modified form of MSW. MSW undergoes densification
processes which can include drying and pelletizing. RDF has a higher calorific value, more
homogeneity and is more easily transported than MSW. The pyrolysis of MSW faces a major
challenge which is the incoherent nature of MSW. This leads to inconsistent energy
characteristics and lack of uniform thermal behaviour. Thus, RDF is a better feedstock as they
are homogenous (Wang et al., 2001). According to Efika et al., 2015, a fluidized bed reactor is
suitable for the pyrolysis of RDF due to the high heat transfer rates, better mixing capabilities,
and improved heat transfer capabilities of smaller-sized particles in this reactor.

2.4 Pyrolysis of Biomass

2.4.1 Description of Process

Pyrolysis is a thermal process (involves the addition of heat) whereby organic matter is broken in
the absence of oxygen. The yield of the pyrolysis process and composition of the products are
affected by certain factors which include: the type of biomass and the conditions for the
pretreatment, pyrolysis temperature, heating rate, reactor type and the carrier gas type. The
choice of reactor has been found to have a major effect on the process Ismadji et al, 2005.
Nonetheless, many other factors such as the heating rate and temperature influence the product
yield.

13
Table 2.3:Typical operating parameters and products for pyrolysis process (Jahirul et al, 2012)…
wk
Pyrolysis Solid Heating Particle Temperature Product yield (%)
process residence rate (K/s) size (K)
Oil Char Gas
time (s) (mm)

Slow 450-550 0.1-1 5-50 550-950 30 35 35

Fast 0.5-10 10-200 <1 850-1250 50 20 30

Flash <0.5 >1000 <0.2 1050-1300 70 12 13

Pyrolysis involves certain reactions before the final products are formed. These reactions can be
categorized as follows:

2.4.1.1 Primary Reactions

These are the initial reactions that take place leading to the formation of final products. They
include:

 The coupling or condensation of benzene rings to form char.

 Depolymerization: In this process, monomers are disassociated from one another. This
leads to the formation of volatiles and gases.
 Fragmentation: Here, the covalent links between the unit monomers and polymers are
broken. As a result, the incondensable gases are formed.

2.4.1.2 Secondary Reactions

Products formed by the primary reactions may undergo further reactions such as cracking and
recombination to produce lighter and heavier compounds respectively.

2.4.2 Products Formed

At the end of the pyrolysis process, three products are formed: the gas phase which remains
incondensable known as pyrolytic gas, liquid known as bio-oil and a solid residue known as
biochar. These three products are discussed in the following subsections.

(2.1)

14
2.4.2.1 Pyrolytic Gas

Pyrolytic gas comprises of mainly of carbon dioxide, carbon monoxide and hydrogen, in addition
to much lesser amounts of methane, ethane, ethylene, etc. The oxides of carbon are formed via
the decomposition of carboxyl and carbonyl groups, whereas hydrogen is generated by the
decomposition of C-H bonds. The higher the pyrolytic temperature, the more secondary reactions
such as cracking take place resulting in the formation of more pyrolytic gas.

2.4.2.2 Bio-Oil

Bio-oil possesses a darkish-brown colour. Its principal constituents are oxygen-containing

compounds, which contributes to its easy decomposition on heating and poor calorific value,
making it unsuitable for use as a fuel. Bio-oil is synthesized by simultaneously fragmenting and
depolymerizing major constituents of the feedstock through rapid pyrolysis. High heating rates
observed in fast pyrolysis promotes the formation of of bio-oil. Bio-oil typically comprises of a
large amount of water alongside carbonaceous compounds such as alkanoic acids, aldehydes,
etc.

2.4.2.3 Biochar

Biochar is the solid product of the pyrolysis process. It is a charcoal-like material and has the
most carbon-content out of all the products. Although, the amount of carbon present may vary
due to process conditions. Due to its stable and porous nature, it can be used to manufacture
activated carbon (Jahromi, 2019).

2.4.3 Types of Pyrolysis

Based on the rate at which heat is supplied, pyrolysis can be classified into the following:

i. Slow pyrolysis
ii. Fast pyrolysis
iii. Ultra-fast pyrolysis

2.4.3.1 Slow Pyrolysis

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This is the oldest method of pyrolysis. In this process, biochar is the desired product. The
biomass is slowly warmed in the reactor at moderate temperatures of about 400℃ over a long
period of time. This results in a decreased amount of gas and oil generated. Biochar is the least
product found here as indicated in table x. Due to the long duration of time, condensable gas is
converted to pyrolytic gas and biochar (Omulo et al, 2019).

2.4.3.2 Fast Pyrolysis

Fast pyrolysis, the term for the thermal decomposition of organic matter which takes place in an
oxygen-deficient environment at temperatures above 500°C. It is the most widely used method of
pyrolysis. The biomass is rapidly heated until it reaches the peak temperature and then begins to
decompose.

2.4.3.3 Ultra-fast Pyrolysis

Ultra-fast pyrolysis, also known as flash pyrolysis, is a kind of pyrolysis with an exceptionally
quick thermal breakdown and a high heating rate. The main products are gases and bio-oil. The
rate of temperature increase can range from 100 to 10,000° C/s, and residence times are brief.

2.4.4 Factors Affecting Pyrolysis

2.4.4.1 Effect of Biomass Composition on Pyrolysis Process

Biomasses comprise mostly of cellulose, hemicellulose, and lignin, together with smaller
amounts of extractives and minerals. These components are available in different ratios and this
ratio can be as a result of the particular feedstock, pyrolysis condition, etc. (Antal & Grønli,
2003). During pyrolysis, the carbohydrates are broken down into partly-condensable fumes (bio-
oil) and gas. Lignin is broken down into mianly into char. Extractives increase the amount of
liquid and gaseous products formed. Figure 2.4 below describes the contribution by each
constituent of biomass to the product ratio obtained.

Cellulose, hemicellulose, and lignin are the three polymeric substances that make up most
biomasses. Other common components are obtained as minerals and "extractives," which are
often more subdued natural atoms or polymers (inorganic mixtures). These are present in distinct
extents for different forms of biomass, and these extents have an effect on the ratio of pyrolysis-
produced products (Antal & Grønli, 2003). The basic components significantly increase the

16
product yields when they are heated to adequate temperatures. Condensable fumes (hence fluid
products) and gas are crucial byproducts of hemicellulose and cellulose degradation. The
breakdown products of lignin include fluid, gas, and intense char Either directly via volatilization
or by decay, extractives add to fluid and gas products. The schematic representation of this
distribution of components into products is provided in Figure 2.4 below.

Figure 2.4: Representation of Biomass Pyrolysis

Source: (Zaman, 2017)

2.4.3.2 Effect of Carrier Gas on Pyrolysis Process

The pyrolysis process requires an inert environment, and this is achieved by the use of carrier
gases such as Nitrogen (N2), oxides of carbon, methane (CH4), etc. Carrier gases are able to alter
the reaction mechanisms of the process, thereby affecting the amount of individual product
formed. For example, steam promotes the formation of bio-oil by preventing secondary reactions
such as cracking. In a research by Zhang et al, 2011, the following carrier gases were used: N2,
H2, CO, CO2 and CH4. The use of CO2 resulted in the least formation of char than when other
carrier gases were used. According to Guizani et al, 2014, methane results in a high formation of
bio-oil. Hence, the carrier gas chosen must be carefully selected to be in line with the desired
product.

2.4.3.3 Effect of Temperature on Pyrolysis Process

17
The temperature of the reactor is a measure of the heat available in the reactor to decompose the
biomass. Before products can even be formed, enough heat needs to be supplied to remove water
and facilitate the primary reactions such as disassociation of bonds and formation of carboxyl
and carbonyl compounds. At different temperatures, certain reactions are favored more than
others leading to formation of more products more than others. For example, the
depolymerization process is favoured at the temperature ranges of 250 to 500℃. Thus, larger
amounts of bio-oil are produced at this temperature (Noor et al, 2019).

2.4.3.4 Effect of Heating Rate on Pyrolysis Process

The rate at which heat is supplied is one of the primary factors that determine the different ratios
of products obtained. Slow pyrolysis involves mild temperatures and longer residence times
resulting in higher amounts of stable solid residue formed. This is also attributed to the fact that
slower heating times will facilitate formation of more bonds between organic functional groups.
Faster heating rates (≥1000℃/minute) as seen in fast and flash pyrolysis are characterized by
short residence times. Under these conditions, depolymerization of cellulose and hemicellulose
accelerated resulting in more volatiles being formed (Qureshi et al, 2018).

2.4.3.5 Effect of Vapour Residence Time on Pyrolysis Process

The residence times of vapour inside the reactor is another significant factor affecting the
product yields. Residence time simply refers to the duration during which vapours remain in the
reactor before they are removed. When vapours are only allowed to remain for a short period of
time, it promotes bio-oil formation by limiting the extent to which cracking reactions occur (Kan
et al, 2016).

2.4.3.6 Effect of Pre-treatment of Biomass on Pyrolysis Process

Pretreatment of biomass is required to improve the efficiency of the pyrolysis process.

Pretreatment can improve process efficiency by destroying the lignocellulosic structure, allowing
for better heat transfer rates. The most common methods for pretreatment of biomass include:

i. Physical Pre-treatment: This involves methods such as grinding and crushing so as to

reduce the particle size of the biomass. Biomass is a poor conductor of heat, and so, has
to be reduced to allow for better heat transfer. However, the extent to which the particles

18
 are reduced is based on the desired product. Generally, smaller particle size promotes
heat and mass transfer, resulting in increased production of bio-oil and lesser amounts of
char (Ishak et al, 2012). Particle shape is another parameter to consider. Spherical-shaped
biomass were found to produce less volatiles than cylindrical and plate shaped biomass
(Lu et al, 2010). Physical treatment is applied in the pyrolysis of coconut biomass.
According to Abrahim et al, 2019, coconut biomass is first dried. The method of drying
chosen was sun-drying and so the duration was up to a week. The biomass is then grated
and ground into small pieces before being sieved.
ii. Chemical Pretreatment: This involves the use of chemicals to prevent the inorganic
compounds present in biomass from interfering in the process. Some of these substances
include metals such as sodium which can cause corrosion of the reactor and inhibit bio-
oil formation. Although, the presence of cations can catalyze the formation of char
(Wang et al, 2011). Alkaline solutions such as NaOH and acid solutions such as sulphuric
acid are the usual reagents.
iii. Thermal Pretreatment: By evaporating the water present in the biomass, less energy is
used up during pyrolysis to remove moisture. This saves time as it allows the process
temperature to be achieved at a much faster pace. As shown by Wang et al, 2011, water
has a major effect on product ratios. The study showed that the more water was removed,
the more bio-oil and char and char that were produced and the less pyrolytic gas were
formed.
iv. Biological Pretreatment: The use of micro-organisms such as rot fungus to pre-treat
biomass is another viable option. These microbes decompose the lignin and
hemicellulose giving off water and carbon dioxide as byproducts. The use of
microorganisms not only make the biomass more compact but also reduce the emission
of sulphur dioxide.

2.5 Adsorption Process

2.5.1 Description of Process

Adsorption is the process whereby specific molecules (liquid or gas) in a mixture or solution
adhere to the surface of a porous substance, known as an adsorbent, which is usually a solid. This
phenomenon can either be as a result of physical or chemical interactions between the gas or

19
liquid molecules (called adsorbate) and the adsorbent. Adsorption differs from absorption
whereby there is mas transfer of molecules from the gas phase to the liquid phase. Every
separation process requires a driving force. In the distillation process, the difference in the
composition of a component across the liquid and vapor phases facilitates the separation.
Similarly, the uneven distribution of a component across the adsorbate phase (liquid solution or
gaseous mixture) and the adsorbent phase is responsible for the mass transfer (Ujile, 2015).
“Again, there is also a need for a difference in a property among the components to be separated.
Distillation requires a difference in the boiling points of components; absorption requires a
difference in the extent to which components are soluble in the absorbing medium, and
adsorption requires that a specific component be more readily transferred to the adsorbent phase
(Coulson et al, 2002)

Adsorption is an important separation process that can be used for the recovery of valuable gases
such as the capture of carbon dioxide from flue gases, the removal of moisture from air, etc.
Typical adsorbents include zeolite, activated carbon, silica gel, etc. Adsorption is not a complex
process and thus, even common solids can serve as adsorbents, albeit to a poor extent. However,
only very few adsorbents can give adequate selective adsorption of a particular substance. For
instance, while there are numerous adsorbents. silica gel is the principal adsorbent in the drying
of air (Treybal, 2011).

2.5.2 Types of Adsorption

As stated in the section above, the interactions between the two phases can either be as a result of
physical forces or chemical forces. The process is then termed physisorption or chemisorption
respectively.

2.5.2.1 Physical Adsorption

In physical adsorption process or physisorption, the molecules are bound together by weak,
physical forces known as Van der Waals forces. This involves an attraction between the atoms of
the adsorbate and atoms on the surface of the adsorbent. As a result of such weak intermolecular
forces, physisorption is easily reversible and evolves a relatively low amount of heat when the
bonds are formed (Scharm, 1972). Unlike chemisorption, physical adsorption can occur
spontaneously on multiple layers, and the molecules adsorbed are able to move within a fixed
perimeter (Mhemeed, 2018).

20
2.5.2.2 Chemical Adsorption

Chemical adsorption or chemisorption involves the formation of chemical bonds, in addition to

physical forces between the adsorbate and molecules on the surface of the adsorbent. Thus, the
bond between the molecules is much stronger than in physisorption, and the process is less easily
reversed. In most cases, the process is irreversible and evolves a higher amount of heat following
the formation of bonds. Chemisorption is less specific than physisorption. In other words,
adsorption may place on the surface of an adsorbent but not occur on another adsorbent, even
when it is subjected to the exact conditions of the former. Chemisorption occurs on a single layer
of the adsorbent and requires activation energy in order to proceed.

2.5.3 Factors Affecting Adsorption

Certain factors inhibit or promote the rate and extent to which the adsorption of a substance takes
place. These factors are discussed below.

2.5.3.1 Effect of Temperature and Pressure on Adsorption

Adsorption is accompanied by the evolution of heat, i.e. it is an exothermic process. Hence, the
addition of heat will retard the extent of adsorption. This is because the increase in temperature
will favor the reverse process, known as desorption. This involves the release or escape of
previously adsorbed molecules due to the energy gained from increasing temperature. This is
more pronounce in physical adsorption. There is a delay in its effect on chemical adsorption due
to its high activation energy and so, high temperature initially favours chemical adsorption. As
time elapses, desorption begins to occur.

Pressure, however, results in an increased rate of adsorption. Increased levels in pressure would
mean a larger amount of adsorbate molecules are coming onto the surface of the adsorbent, thus
increasing the rate at which these molecules form bonds with the adsorbent surface. However,
this increase eventually comes to a halt due to the saturation of the pores of the adsorbent. At this
point, no amount of increase in pressure would promote the process (Treybal, 2011).

2.5.3.2 Effect of Adsorbent Dosage on Adsorption

The increase in the concentration or amount of adsorbent invariably yields an increased extent of
adsorption. This is due to the fact that more adsorbent present in the process means there are

21
more active sites available for bonding. However, an optimal dosage needs to be determined.
According to Torab-Mostaedi et al, 2015, the addition of more adsorbent results in no increase.
At this point, bonding between all adsorbate molecules and the adsorbent has already occurred.

2.5.3.3 Effect of Nature of Adsorbent on Adsorption

Being that adsorption occurs on the surface, an important and required feature of any adsorbent
is high surface area. Adsorbents with large surface area possess more active sites available for
adsorption. For this reason, commercial adsorbents are usually finely divided or granular in
nature.

2.5.3.4 Effect of Contact Time on Adsorption

The more time made available for adsorption to take place, the higher the adsorption efficiency
recorded. This trend of increase in adsorption with time will continue until equilibrium is
reached.

2.5.3.5 Effect of Initial Concentration on Adsorption

As larger concentrations of adsorbate are exposed to the solid phase, the rate at which adsorption
takes place is increased.

2.5.4 Adsorption Isotherms

Adsorption isotherms are graphs which depict the relationship between the amount of adsorbate
adsorbed on the surface of an adsorbent and the equilibrium pressure or concentration at constant
temperature (Dermibas et al, 2002). Adsorption isotherms are necessary information in the
optimization of an adsorption process.

2.5.4.1 Langmuir Isotherm

When adsorption is confined to one layer, the Langmuir isotherm is the conventional method for
studying the equilibrium of the process. Several assumptions are involved in the development of
this model. An example of such assumptions is that adsorption takes place on a single layer.

The Langmuir equation is given below:

22
 (2.2)

where:

qe (mg/g) = quantity of adsorbate on surface of adsorbent at equilibrium,

Ce (mg/L) = concentration of adsorbate in solution at equilibrium

qm (mg/g) = maximum adsorption capacity

Ke = Langmuir constant that is a measure of the energy of adsorption.

The separation factor, RL is another significant information provided by the Langmuir isotherm.
It is given as:

(2.3)

where CO = initial concentration of the adsorbate (mg/L); KL (L/mg) = Langmuir constant.

The value of RL indicates the feasibility of the adsorption process, where a value of:

RL > 1: unfavorable; RL = 1: linearity; RL = 0: irreversibility, 0< RL < 1: favorable.

2.5.4.2 Freundlich Isotherm

While the Langmuir isotherm is suited to monolayer adsorption, the Freundlich isotherm is
tailored for heterogenous adsorption or multilayer adsorption processes. The linear form of the
isotherm is written as follows:

(2.4)

Where:

qe (mg/g) = quantity of absorbed material on absorbent surfaces

KF (mg/g) = adsorption capacity

23
n = feasibility of adsorption process. Avalue of 1/n (g/L) indicates a variable adsorption process.
n > 1 indicates the feasibility (Poots et al., 1978). The values of KF and n are derived from
determining the intercept and slope respectively of a plot of ln (qe) against ln (Ce).

2.5.4.3 Temkin Isotherm

This model assumes that all molecules' adsorption heat is inversely proportional to extent of
adsorption. Along with Langmuir and Freundlich, it has gained popularity because it considers
the effects of indirect adsorbate/adsorbent interactions. The isotherms is given by the equation:

(2.5)

where

KT = maximum binding energy,

b = measure of adsorption heat,

R = universal gas constant (8.314 J K−1 mol−1)

T = temperature (K).

2.5.5 Adsorption Kinetics

Adsorption Kinetics is another important factor that yields important information concerning an
adsorption process. The information provided by the kinetic models on adsorption routes and the
likely mechanism at play is crucial for the improving the process. Adsorption kinetics essentially
explains how quickly a solute is absorbed and how long adsorbates remain at the solid-liquid
interface. The model that best describes the process is chosen using the goodness of fit index
(Musah et al, 2018). Major kinetic models are discussed below:

2.5.5.1 Pseudo First Order Model

The pseudo first-order model assumes that the adsorption rate increases linearly with the
difference in saturation concentration and the amount of solid uptake with time (Sahoo, 2020).
The model is expressed by the equation below:

24
Where

qe (mg/g) = quantity of absorbed material on absorbent surfaces

qt (mg/g) = instantaneous quantity of absorbed material on absorbent surfaces.

k1 (min−1) = rate constant.

The values of k1 and qe are gotten from the slope and intercept of the plot of ln (qe − qt) against
t.

2.5.5.2 Pseudo Second Order Model

The pseudo second order model assumes that the rate limiting step to be chemisorption (Wang,
2008). Unlike the pseudo-first order model, it is able to provide the equilibrium adsorption
capacity. The model is expressed as:

(2.7)

where

qt (mg/g) = instantaneous quantity of absorbed material on absorbent surfaces.

k2 (g/(mgmin)) = rate constant.

Values of qe and k2 can be obtained from the slope and intercept of a plot of t/qt against t.

2.5.5.3 Intraparticle Diffusion

This model was proposed to study the diffusion mechanism in adsorption. It is given by the
expression below:

(2.8)

where ki is the intraparticle diffusion rate (mg/g min-1/2). A linear plot of qt against ki indicates
intraparticle diffusion. However, when non-linearity is observed, this shows that there is more
than one rate-limiting step (Belessi et al, 2009).

25
2.5.6 Adsorption Thermodynamics
This involves determining the following parameters: enthalpy (ΔH), entropy (ΔS) and Gibbs free
energy (ΔG). The enthalpy values indicate the nature of the adsorption process – chemisorption
or physisorption. Enthalpy values lower than -40KJ/mol generally indicate chemical adsorption
(Crini et al, 2008). This is confirmed by the values of ΔG obtained at different temperatures. For
an exothermic process, values of Gibbs free energy will increase with increasing temperature.
Hence, values of ΔG show the temperature above which a process is no longer favourable. It can
be evaluated by the equation below

(2.9)

Where KD is the thermodynamic equilibrium constant (Lg-1). KD can be obtained by evaluating

qe/ce (Maiti et al, 2008). The values of entropy and enthalpy can be obtained from Hoff’s plot
given by:

(2.10)

Where R = universal gas constant (8.314 J mol−1 K−1) and T = temperature (K).

2.7 Methods of Wastewater Treatment

2.7.1 Adsorption
Adsorption is one of the most employed treatment processes due to its low cost, easily
operability and simple design. It involves the use of a substance known as an adsorbent to
remove undesirable pollutants from wastewater. Examples of such adsorbents include zeolite,
activated carbon, etc. Activated Carbon is commonly used in wastewater treatment and is known
to yield high removal efficiency. Initial oxygen treatment is applied to activated carbon. This
aids in the millions of small pores on the charcoal opening up. Micropollutants including
chlorine, methane, organic molecules, and even the flavor and odor of water are all absorbed by
carbon.

2.7.2 Biological Digestion

In this process, organic contaminants present in the wastewater are broken down into simpler
forms - methane and carbon dioxide. This process is facilitated by anaerobic bacteria, and as

26
such, operates under anaerobic conditions. The bacteria inhabit large amounts of cow manure
that usually serve as the reactor's foundation.

2.7.3 Pressure Sand Filtration

Water is passed through multiple layers of filters to remove impurities. The pollutants present in
the water are trapped by the filters and the clean water flows through the base of the tanks.
Backwashing enables the renewal of the filter bed when the precipitate clogs the sand (shown by
a decreased filtering rate.

2.8 Major Contaminants in Wastewater

The major pollutants observed in wastewater are discussed in the following subsections below:

2.8.1 Organic Contaminants

Major organic contaminants include dyes, pesticides, phenols, pharmaceutical compounds, etc.
Water with high organic content can lead to adverse health problems such as nervous system
disorder, cancer, etc. Furthermore, organic matter will incite microorganisms present to utilize
the oxygen to breakdown organic contaminants, leading to a condition known as eutrophication.
With reduced oxygen levels, sustenance of aquatic life is limited. Various biomass have been
utilised to make biochar, which has then been used extensively and efficiently as an sorbent for
removing organic pollutants from wastewater.

Using coconut shell-synthesized activated carbon to remove organic matter is second only to its
application in removing heavy metals. In the research by Farouk et al, 2021, biochar synthesized
from coconut shell and barley straw was used respectively to remove methylene blue, one of the
most common organic contaminants. Coconut shell-based biochar yielded a much higher
maximum capacity.

2.8.2 Heavy Metals

The rapid rate of industrialization has led to the widespread of toxic inorganic substances in
rivers, lakes, groundwater, and other water sources. These industrial effluents include heavy
metals such as arsenic, cadmium, iron, etc. Not only are these substances toxic to the human
body, they are also non-biodegradable and harmful to the ecosystem. Lead, for instance causes
anemia when its concentration is beyond regulated levels (Khayat, 2013). Biochar as an
adsorbent has been found to be effective in removing inorganic pollutants from wastewater. This

27
is as a result of the numerous functional groups present on the surface and also the large size of
its pores (Chen et al, 2014). Various coconut wastes have been used to remove heavy metals
from wastewater e.g. coconut husk in the removal of chromium (III), coconut pith in the removal
of chromium (VI), etc. Coconut shell was modified with chitosan and used to remove zinc ion
from the wastewater of beverage production and gave impressive adsorption capacities (Amuda
et al, 2007).

2.8.3 Radioactive Materials

Although not as common as the previously discussed contaminants, radioactive materials can
also be found in wastewater and pose a great threat to human health. They may originate from
the mining and processing of ores, testing and use of nuclear weapons, etc. Uranium was
successfully removed from an aqueous solution by coconut pith in a study by Anirudhan et al,
2009.

2.8.4 Potential of Coconut Shells in Wastewater Treatment

As earlier stated, coconut shell is a very promising bio-adsorbent now being used due to its
abundance, physical structure, and low modification requirements. Following various
experiments by researchers, removal efficiency has been found to be much higher when coconut
shells are processed into activated carbon using reagents such as phosphoric acid (H3PO3). Thus,
activation is a very necessary step in order to achieve desired results. Sarkingobir et al, (2020)
demonstrated this by treating wastewater containing lead, copper and polyethylene glycol using
unprocessed coconut shell and activated carbon. Modification of biochar has also been
investigated to further improve its already significant efficiency. At the following conditions
when concentration = 12µ/ml, dosage = 0.2g, pH = 4.0, the removal efficiency of iron-modified
coconut shell biochar is almost perfect (Bu et al, 2021). Aside modification by elements,
undergoing size reduction processes to increase surface area is another way to further improve
efficiency. Activated carbon from coconut shell has also been found to be efficient in reducing
organic matter in wastewater (Yasdi et al, 2021).

2.9 Iron as a Contaminant in Wastewater

2.9.1 Removal of Iron from Wastewater by Adsorption

Iron is a very common pollutant found in water. Not only is it introduced into water bodies by
from industrial effluents, but iron is also a natural constituent of the Earth’s crust and hence

28
occurs easily in groundwater (Moreira et al, 2004). Removal of iron can be done by various
means such as aeration and sand filtration. The use of an adsorbent to separate iron from
wastewater is another viable option. It involves the adsorption of Fe2+ ions onto the surface of the
adsorbent alongside oxygen. Oxygen receives electrons from the Fe2+ ions and reacts with
radicals present on the surface such as hydronium ion to form a water molecule. The mechanism
and rate laws of this process was proposed in a study by Ronnholm et al, 2004.

Figure 2.5:Adsorption mechanism of Fe2+ on activated carbon

Source: Ronnholm et al., 2004

The use of an adsorbent to separate iron from wastewater is another viable option. It involves the
adsorption of Fe2+ ions onto the surface of the adsorbent alongside oxygen. Oxygen receives
electrons from the Fe2+ ions and reacts with radicals present on the surface such as hydronium
ion to form a water molecule. The mechanism and rate laws of this process was proposed in a
study by Ronnholm et al, 2004.

2.9.2 Effects of Iron on the Human body, Plants, Animals and Ecosystem
The presence of iron in water is harmful in the following ways:

2.9.2.1 Effects on Humans

i. Inflammation of stomach lining and ulcers.

29
 ii. Can result in liver cirrhosis, liver cancer or heart disease.
iii. Can lead to skin infections and clogged skin pores thus causing eczema.
iv. Can interfere with medical supplements e.g. inhibit the action of drugs meant to remedy
Parkinson’s disease.
v. Abdominal pain, constipation, nausea and vomiting.

2.9.2.2 Effects on Plants and Animals

i. Damage of structural units of the cell.

ii. Excessive amounts can retard assimilation of soil nutrients by plants soil.
iii. Retarded photosynthesis.
iv. It can lead to gastrointestinal, liver, metabolic, nervous and cardiovascular problems in
animals.

2.9.2.3 Effect on Ecosystem

i. Excessive iron can cause taste, odor, and flow problems with drinking water wells and
can precipitate and plug up in situ groundwater remediation systems.
ii. It is also harmful to aquatic life as it can block the opening in gills, thus resulting is
asphyxiation
iii. Increased toxicity of soil and thus reduced plant growth.
iv.
v.

30
31
 2.10 Review of Related Past Reports

Table 2.4: Review of Past Related Works

Author Title Work Result Gap

Oribayo et Coconut Shell- Investigated the The adsorbent was No investigation into
al., (2020) Based Activated potential of found to have a optimal amount of
Carbon as an activated carbon maximum adsorbent required;
Adsorbent for the from coconut adsorption capacity paper failed to take into
Removal of Dye shells (CSAC) as of 320.5mg/g. From consideration the
from Aqueous an adsorbent in the thermodynamics particle size of the
Solution: removing organic properties adsorbent which can
Equilibrium, pollutant, determined, it was improve adsorption
Kinetics, and methylene blue established that the capacity of adsorbent.
Thermodynamic from wastewater adsorption process
Studies was endothermic
and spontaneous.
Packialakshi Treatment of CSAC was used to The highest Study of the kinetics and
mi et al., industrial remove zinc and adsorption was thermodynamics of the
(2021) wastewater using potassium from the recorded when the adsorption was
coconut shell wastewater particle size of the excluded. These
based activated discharged from adsorbent was information are essential
carbon electroplating 150µg.The results for proper understanding
industries. The obtained from the and thus, design and
effect of particle experiments showed optimization of the
size of adsorbent a good conformity adsorption process.
was also studied, with Freundlich
comparing values adsorption isotherm.
of (150, 300, 450,
600) µg.
Ghazali et Preparation Of CSAS was used to Adsorption capacity Physical method of
al., (2012) Activated Carbon treat wastewater was higher at lower activation was used
from Coconut containing activation which is more energy
Shell to Remove Aluminium and temperatures. intensive and costlier
Aluminum and Magnesium ions. Removal efficiency than chemical activation
Manganese in The effect of was also found to and also produces
Drinking Water activation increase with adsorbents with lesser
temperatures, pH increasing pH and adsorption capacity
and initial initial concentration. (Prauchner, 2011)
concentration was
also investigated.

Adewuyi & The Use of Activated carbon An optimal amount Adsorption isotherms,
Olabanji Coconut-Shell synthesized from of dosage was kinetics and
(2014) Based Activated coconut shell was determined as thermodynamics were
Carbon as an used to treat hard beyond that amount, not determined. As such,

32
Adsorbent in the water. Its removal efficiency process cannot be
Treatment of efficiency in began to reduce. The improved upon as there
Hard Water removing Calcium, adsorbent was able is too little data to work
Magnesium and to remove 80% of with.
Total hardness was calcium, but only
determined and 60.44% and 66.71%
also the effect of of magnesium and
adsorbent dosage total hardness
and contact time. respectively.

33
 CHAPTER 3
METHODOLOGY

Coconut (Cocos nucifera) shells were sourced from a local market situated in xxx, Ogun State,
Nigeria. After the shells had undergone necessary treatment processes, the processed shells were
stored in clean PET bottles and kept in a cabinet in the research laboratory.

3.1 Materials and Reagents

3.1.1 Materials Used

Table 3.1 below gives the list of materials used in this study.

Table 3.1: List of materials used

S/ Materials
N

1 Coconut shells

2 Filter paper

3 Masking tape

4 Foundry wastewater

5 PET bottles

3.1.2 Reagents Used

The chemical regents used include the following listed below

Table 3.2: List of reagents used

S/N Reagent Chemical Formula Brand Purity

1 Concentrated Phosphoric H3PO4

Acid

34
 2 Distilled Water H2O

3.2 Equipment and Apparatus Used

3.2.1 Apparatus Used

Table 3.3: Apparatus used in the study

S/N Apparatus Calibration Quantity

1 Conical Flasks 250 ml
2 Beakers 250 ml
3 Measuring cylinder 500 ml
4 Ceramic Crucibles 150 ml
5 Glass stirring rod ___
6 Spatula ___
8 Glass funnel ___

3.2.2 Equipment used

The equipment utilized in conducting this research are enumerated in table 3.2
Table 5.4: Equipment used in the study

S/ EQUIPMENT NAME MANUFACTURER

N
1 Muffle Furnace
3 Air Oven
4 Hotplate Magnetic Stirrer
5 Weighing balance
6 Sieve Shaker
7 Mechanical grinder
8 X-ray diffractometer
9 Scanning electron microscope

35
3.3 Experimental Procedure

3.3.1 Block Flow Diagram of Experiment

After procuring the coconut shells, they were then washed to remove impurities and unwanted
particles of the husk still attached. Afterwards, they were sundried, grinded and sieved to obtain
particles of a suitable size. This ground biomass was then fed to a pyrolizer which yielded the
following products: pyrolytic gas, bio-oil and biochar.
Biochar, one of the products obtained is to be used as an adsorbent in treating wastewater.
Hence, it is first activated using concentrated phosphoric acid to form activated carbon. Distilled
water is used to wash off the acid until a neutral pH is obtained.

SEM-EDS (Scanning Electron Microscopy – Energy Dispersive Spectroscopy), FT-IR (Fourier

transform infrared spectroscopy), XRD (X-ray Diffractometer) tests were conducted on the
synthesized activated carbon to investigate the elemental composition, functional groups present
and crystalline structure of the adsorbent respectively.

The diagram below gives a summary of the experimental process:

Figure 3.1: Block Flow Diagram of Experiment

3.3.2 Pretreatment of Biomass and Physiochemical Assessment of Pretreated Biomass

3.3.2.1 Sample Preparation

Coconut shells were washed to remove impurities such as sand after coconut husks still attached
had been peeled off. The shells were dried under sunlight for xx hours to reduce moisture as it

36
could inhibit the efficiency of the pyrolysis process. Once dry, the shells were crushed and
sieved to yield a particle size of xx using a crusher and sieve shaker respectively. Once again,
they were left to dry under the sun and finally kept in a desiccator in the laboratory.

[plates: drying, grinding, sieving]

3.3.2.2 Proximate Analysis

Proximate analysis was done on the lingo-cellulosic biomass sample to evaluate the moisture
content (M), volatile matter (VM) content, fixed carbon (FC) and ash (A) present using the
ASTM D3173-75 method.

 To determine the moisture content, xx g of the biomass was loaded into weighted
crucibles and dried for xx hours at 105 °C (slightly over the boiling point of water)
without the crucible's lid. The crucible was removed, placed in a desiccator, and then
weighed. The weight difference between the crucible before and after heating was used to
determine the moisture content of the biomass. To obtain the percent moisture content,
equation 3.1 is used

%M = (Loss in weight of biomass sample/Weight of biomass taken) * 100 (3.1)

 Volatile matter was determined by heating the biomass sample with the lid of the crucible
placed on it in a muffle furnace at 950 oC for xx minutes. This was done in a vessel made
inert by the continuous passage of nitrogen gas. After heating, the crucible was placed in
a desiccator to cool down and then weighed. The difference in the weight before and after
heating is the weight of volatile matter present in the biomass sample. This is done on dry
basis.

%VM= (Loss in weight of sample at 950oC / Weight of dried biomass) * 100 (3.2)

 To obtain the ash content, the sample was oxidized at 750oC. The percentage of residue
left represents the fixed ash. same biomass sample was burnt in a crucible without the lid
with a muffle furnace.

%A = (Weight of residue left in crucible/Weight of dried biomass) * 100 (3.3)

37
  The fixed carbon content (FCC) was determined using equation 3.4, according to ASTM
D1762-84 standard:

FCC (% w/w) = 100 – [A (%w/w) + VM (%w/w) + M(%w/w)] (3.4)

 The higher heating value (HHV) of the sample was determined using equation 3.5:

HHV= 354.3*FC (%w/w) + 170.8*VM (%w/w) (3.5)

3.3.2.3 Ultimate Analysis

3.3.3 Pyrolysis of Coconut Shells

The biomass (coconut shells) was fed into the reaction tube of the pyrolyzer. After the inert gas
(Nitrogen) supply was initiated, the temperature and heating rate controllers were turned on and
set to ℃ and xx℃/min. The experiment lasted a total of xx hours. On completion, the reaction
tube was opened and the products: pyrolytic gas, bio-oil and biochar were obtained. The biochar
obtained was then used to treat wastewater from the casting section of a foundry located at
Covenant University, Ota, Ogun State, Nigeria.

[add figure here]

3.3.4 Activation of Biochar

xxg of char obtained after pyrolysis was impregnated with xx ml of conc. phosphoric acid (xM)
for xx hours. The mixture was rinsed after impregnation with distilled water until a pH of 7 was
reached. Next, the adsorbent was heated in a muffle furnace at 900 OC for x hour. It was then put
in a dessicator to cool. The activated char produced was then kept in a PET bottle to be later used
for treatment of raw wastewater.

[add figure here]

3.3.5 Characterization of Synthesized Adsorbent

Following the chemical activation process, the adsorbent obtained underwent the following tests
in order to investigate its structure and properties. These tests include SEM-EDS (Scanning
Electron Microscopy – Energy Dispersive Spectroscopy) done to understand the elemental
composition; XRD (X-ray Diffractometer) to investigate the structure on both atomic and
molecular levels; FT-IR (Fourier transform infrared spectroscopy) to identify the functional
groups and chemical bonds present.
38
3.3.6 Treatment of Raw Wastewater with Activated Carbon
Xx ml of raw wastewater from the casting section of the foundry was treated separately with 1g
and 2g of activated char. The adsorption/treatment process was done at done at temperatures of
30 ℃, 40 ℃, 50℃ and 60℃. Also, samples were taken at intervals of 15 minutes until a total of
90 minutes had elapsed. Raw wastewater was poured into a conical flask together with the
specified mass of adsorbent. The mixture was first heated to the required temperature before
being placed on a magnetic stirrer. After the experiment was over and data recorded, the mixture
was filtered, and the filtrate was kept in a PET bottle and labeled to be analyzed.

[add figures here]

3.3.7 Adsorption Isotherms, Kinetics and Thermodynamics

3.3.7.1 Adsorption Isotherms

Adsorption isotherms are used to compare the extent of adsorption on different materiuals i.e. the
adsorption capacities of different adsorbents. They are plots of adsorbate adsorbed on a surface
(g/g) against pressure or concentration for gas and liquid adsorbates respectively. There are
various isotherms, but in this study, Langmuir, Freundlich and Temkin isotherms were used. The
batch experiments involved varying dosage of adsorbent (1g and 2g) and taking samples at
intervals of 15 minutes with a total time of 90 minutes. R-square values were used to determine
the isotherm that best described the process.

3.3.7.2 Adsorption Kinetics

Adsorption kinetics is useful in the determination of the mechanism and pathway followed by the
process. Contact time, dosage and temperature were varied allowing for the generation of
necessary data to investigate the kinetics. The pseudo-first order model, pseudo-second order
model and intraparticle diffusion model were plotted and the model to which the process most
conformed to was determined using R-square values.

3.3.7.3 Adsorption Thermodynamics

By varying only the temperature of the process (30℃, 40℃, 50℃ and 60℃), thermodynamic
properties such as the enthalpy, entropy and Gibbs free energy were determined. The equations
for each property were given in the literature above. See section 2.5.5.

39
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