CHAPTER 1

INTRODUCTION

1.1 Research Background

More than two million tons of agricultural wastes are produced in Malaysia:
however, most agricultural waste is being discarded or burnt on land. For that reason,
it is important to find beneficial uses for these resources. One such potential use for
these abudant agricultural residues is their pyrolysis to produce biochar (Abdulrazzaq
et al. 2014). The use of natural fibres obtained from plants and trees as reinforcing
materials has attracted many researchers to widen their applications. Natural fibres
are low cost, low density, have specific properties, biodegradable and non-abrasive.
(Zuhri, Sapuan & Napsiah, 2009).

The major agricultural products are: palm oil, sawn logs, paddy straw and
tropical fruits. In the oil palm sector, the palm oil milling process produces oil palm
solid wastes (e.g., shell, fiber and EFB). For every ton of oil palm fruit bunche used
in the palm oil refining process, approximately 0.07 tons of palm shell, 0.15 tons of
palm fiber and 0.2 tons of EFB are produced as solid wastes (Wan et al. 2010). Oil
palm wastes (Figure 1.1.1) are high-potential biomass energy resources in Malaysia
because Malaysia is the second largest produced and exporter of palm oil in the
world. In contrast, rice husks and paddy straw are among the major agricultural
wastes that can be used for biomass-based power generation. The husk accounts for
22% of the weight of the paddy and rice accounts for 78% (Umamaheswaran and
Batra, 2008). The world annual production of rice is more than 540 million metric
tons (Paethanom and Yoshikawa, 2012). Rice husk from paddy (Oryza Sativa) is one
example of alternative material that has a great potential. Rice husk (Figure 1.1.2) is
a major by-product of the rice milling industry, is one of the most commonly

1
available lignocellulose materials that can be converted to different types of fuels and
chemical feedstocks through a variety of thermochemical conversion processes. Rice
husk is an agricultural residue abundantly available in rice producing countries.The
fibrous residue of sugarcane (Figure 1.1.3) after crushing and extraction of its juice,
know as ‘bagasse’, is one of the largest agriculture residues in the world (Pandey et
al., 2000: Trejo-Hernandez et al., 2007: Mulinari et al., 2009: Hernandez-Salas et al.,
2009). An analysis of sugarcane bagasse indicates that its main constituents are
cellulose, hemicellulose, lignin, ash and wax (Walford, 2008). This composition os
sugarcane bagasse makes it an ideal ingredient to be applied and utilized as
reinforcement fiber in composite materials for the purposes of creating new materials
which possess distinct physical and chemical properties. According to Purevsuren et
al. (2003), thermal conversion, developed for industrial applications, can also be
used on solid agricultural wastes.

Figure 1.1.1 : Oil Palm Fiber

Figure 1.1.2 : Rice Husk

2
 Figure 1.1.3 : Sugarcane Bagassse

1.2 Biomass and Biochar

Biomass is one of the renewable energy resources. Generally, biomass refers

to non-fossilised and biodegradable organice material originating from plants,
animals or microorganisms. Biomass resources include various natural and derived
materials, such as woody and herbaceous species, wood wastes, bagasse, agricultural
and industrial residues, waste proper, municipal solid waste, sawdust, biosolids,
grass, waste from food processing, animal wastes, aquatic plants and algae. The
utilisation of biomass as an energy source offers a way to reduce carbon dioxide
(CO2) from the atmosphere and help to mitigate the climate change by reducing
greenhouse gases (Shariff, Mohammad Aziz and Abdullah, 2014).

In general, biomass refer to foresty, purpose-grown agicultural crops, trees

and plants and organic, agricultural, agro-industrial and domestic wastes such as
municipal and solid wastes (Demirbas and Arin, 2012). According to Demirbas
(2009), biomass term also includes gasses and liquids recovered from the
decomposition of non-fossilized and biodegradable organic material. Biomass
excludes organic material which has been transformed by geological processes into
substances such as coal or petroleum (Aghamohammadi et al., 2011).

3
 Biomass is know as one of the major world renewable energy resource. It is a
suitable alternative to subtitute the energy dependency on fossil fuel. According to
Demirbas (2009), biomass appears as an attractive resource due to its ability to
sustainably developed in the future. It has the attributes that contribute to a healthy
environment and economy. Besides, the utilization of biomass offers great benefits
towards the nature by reducing waste management problem and help in the climate
change mitigation. It also has potential to contribute towards the positive economic
growth.

Energy from biomass can be recovered via thermal, biological and physical
process. Thermochemical conversion which includes combustion, gasification and
pyrolysis process (Őzҫimen and Karaodmanoğlu, 2004, Bridgwater, 2003) is one of
the most common routes applied to convert biomass into various energy. These
conversion processes are described and classified by the type of final product
obtained, the properties of the feedstock used and their operation parameters which
include temperature, heating rate and holding time often known as residence time.
Biomass can be converted into solid char, liquid bio-oil and gas product via pyrolysis
products.

Generally, biochar is the black carbon and porous substance formed from
slow pyrolysis. The production of biochar was inspired from fertility of black soil in
Amazon which is known as Terra Preta. Biochar can be produced either by slow
pyrolysis or fast pyrolysis, similar as the method to produce charcoal. Futhermore,
the usage of pure charcoal will cause great impact on the environment such as
greenhouse gases emission, global warming crisis, thinning of ozone layer and
eventually, altering the world climate (Ab Aziz, Mohd Nor, Abdul Manaf and
Hamzah, 2015).

4
 Recent studies has discovered that biochar might have the potential to reduce
the greenhouse gases emission produced from combustion of charcoal. Based on
several research conducted in United States of American (USA), Colombia, Kenya
and Australia, it is generally accepted that biochar has a highly stable form of carbon
and has the potential to perform the sequesteration of carbon dioxide at billion-ton
scale for 30 years time (Sohi S. et al., 2009). Another unique ability of biochar is that
it can increase cation exchange capacity (CEC) and pH of soil (Shafie et al.,2012),
thus increasing soil moisture, total nitrogen and phosphorus ions, promotes root
development (Chan et al., 2008), minimize soil erosion and nutrient leaching during
drought (Lorenz, 2007). The yield and quality of biochar is critically influenced by
the type of biomass used, chemical and structural composition of biomass, pyrolysis
temperature, process heating rate and type of pyrolysis reactor being used (Shafie et
al., 2012). More importantly, this biomass has yet to be fully utilized economically
and commercialized in Malaysia despite of its benefits to human and environment as
well.

1.3 Problem Statement

The abundance of wastes generated from the oil palm fiber, sugarcane
bagasse and rice husk in Malaysia shows a significant increment every year. These
wastes could be used as the feedstocks to produce biochar and therefore help
minimize the waste management problem. The purpose of this project is to identify
the agricultural waste made from fibre which are rice husk, sugarcane baggase and
oil palm fiber (OPF) are used in this experiment for removal of CO2. The agricultural
waste that used are made from fibre because low environmental pollution and more
cheap. Biomass char is a solid product from the pyrolysis of biomass under a
reducing atmosphere condition. Since biomass contains large amounts of volatiles, a
porous structure is formed inside and on the surface of pyrolyzed biomass (Yan et al.
2010; Xu et al. 2011). The efficiency of the char can be measure by characterization
of this materials using Fourier Transform Infra-Red (FTIR) Analysis and Particle
Size Analyzer. The FTIR to determined the changes of functional groups of the
chars and Particle Size Analyzer is to determined the effect of particle size of surface
area on char yields.

5
 The emission of carbon dioxide, one of the anthropogenic greenhouse gases
have risen by more than 3% annually (Ghani et al., 2013) and this resulted in rapid
rise in global temperature which resulted to the shift of wheather patterns. Therefore,
a new approach to maintain carbon in a stable from that can be stored outside the
atmosphere for longer periods should be developed (Rebitanim et al., 2013). The
carbon dioxide humans emit through burning fossil fuels rises high into the
atmosphere where it gets trapped and creates a layer of gas that warms the earth. The
CO2 and other greenhouse gases function like a literal greenhouse. They allow the
heat of the sun to penetrate the atmosphere, and then trap the heat where it warms the
earth’s temperature. This process is similar to what happens to a parked car left in
the sun too long. The sunlight’s heat enters the car easily, but is then trapped inside.
Some of the wastes also are useful for other economic purpose. While CO2 is
commonly found in natural gas throughout many locations, CO2 removal from gas is
necessary in order to deliver the gas to the pipeline. When CO2 is mixed with water,
the result is a corrosive carbonic acid. CO2 is also known to reduce the BTU value in
gas, ultimately making it unmarketable. Natural gas at its geological conditions in
some deposits contain some complex contaminants such as CO2, H2S, CO,
Mercaptan (Acid Gas), which constitute great environmental hazards when get to the
atmosphere and also hindered natural gas processes (Salako, 2009). The production
and utilization of biochar have been suggested as a promising way to reduce the
percentage of carbon dioxide in the atmosphere.

The yields and characteristics of biochar are depends on various factors such
as the feedstock type, chemical and structural composition of feedstock, operating
parameter, heating rate, holding time as well as the type of reactor which is muffle
furnace. The study of biochar characterization is necessary because of their potential
environmental applications such as soil amending and atmospheric carbon
sequestration. It is also necessary in order to understand the type of biochar that can
promote plant growth. This research will provide more understanding into the
properties of biochar and the influence of its feedstock from which it is produced
(Muhammad Aziz, 2014).

6
1.4 Scope Of Study

In this research the scope of study are the most important to make sure the
objective of this experiment are achieved. The parameter that will be used in this
research has identitied some of the scope . There are some paramater that will be
used :

1. The parameter are used :

 Temperature (Celcius, °C) : The temperature are used for pyrolysis in the
muffle furnace of the agricultural waste from rice husk , sugarcane
bagasse and oil palm fiber.
 Time (Hours) : The heating time of agricultural waste for pyrolysis
process convert into chars.
 Heating rate (°C/min) : The heating rate of pyrolysis process.
 Waste (Mass, g) : The mass of agricultural waste from rice husk,
sugarcane bagasse and oil palm fiber are need to convert into char by
pyrolysis process.
2. To analyze the chars after pyrolysis process :
 Fourier Transform Infra-Red (FTIR) Analysis Thermo Science.
 Particle Size Analyzer.

1.5 Objectives

1. To identify agricultural waste made from fibre.

2. To prepare char from the chosen agricultural waste at temperature 400°C,
600°C and 800°C at time 2 hours.
3. To investigate the effect of pyrolysis on char produced.
4. To analyse the char produced using Fourier Transform Infra-Red (FTIR) and
Particle Size Analyzer.

7
 CHAPTER 2

LITERATURE REVIEW

2.1 Introduction

This chapter provides background and review of biomass or agricultural

waste and its conversion technology and biochar. In this research, agricultural waste
are used made from fibre which are rice husk, sugarcane bagasse and oil palm fiber
for removal of CO2. The preparation of pyrolysis process of chars are using muffle
furnace and the characterization of chars are using Fourier Transform Infra-Red
(FTIR) to determine functional group of biochar and Particle Size Analyser (PSA) to
determine the size of surface area of biochar.

This chapter also briefs the current scenario of agricultural waste in Malaysia
and reviews the studies of the pyrolysis process. It reviews the properties, benefits,
production activities of biochar and the findings from studies of pyrolysis of biomass
for biochar production and characterization of biochar using FTIR and Particle Size
Analyzer analyzer.

8
 2.2 Agricultural Waste

Agricultural waste as source of biomass energy. J. Ronald Miner, Oregon

State University, Corvallis(1972) state that increased attention has been given to the
role of agricultural wastes and the resposibility of agriculture to control pollution. In
opening the 1970 Cornell Agricultural Waste Management Conference, Bayley
stressed the importance of planning and development of new waste disposal
techniques to meet these resposibilities. Malaysia is blessed with abundant renewable
sources of energy, especially biomass and solar. Malaysia is located in a region
where biomass productivity is high which means that the country can capitalize on
this renewable energy resource to supplements limited petroleum and coal reserves.
Malaysia, as a major player in the palm oil and sago starch industries, produces a
substantial amount of agricultural biomass waste which present a great opportunity
for harnessing biomass energy in an eco-friendly and commercially-viable manner.
Peninsular Malaysia generates large amounts of wood and agricultural residues, the
bulk of which are not being currently utilised for any further downstream operations.
The major agricultural crops grown in Malaysia are rubber (39.67%), oil palm
(34.56%), cocoa (6.75%), rice (12.68%) and coconut (6.34%). Out of the total
quantity of residues generated, only 27.0% is used either as fuel for the kiln drying of
timber, for the manufacture of bricks, the curing of tobacco leaves, the drying
rubber-sheets and for the manufacture of products such as particleboard and
fibreboard. The rest has to be disposed of by burning.

2.2.1 Rice Husk

Rice husk is the outermost layer of protection encasing a rice grain. It is a

yellowish colour and has a convex shape. It is slightly larger than a grain of rice, thus
lengths up to 7mm are possible. Typical dimensions are 4mm by 6mm. It is
lightweight, having a ground bulk density of 340kg/m3 to 400kg/m3. Rice husk is the
most prolific agricultural residue in rice producing countries around the world. It is
one of the major by-products from the rice milling process and constitutes about 20%
of paddy by weight. Rice husk, which consists mainly of lingo-cellulose and silica, is
not utilized to any significant extent and has great potential as an energy source. Rice
husk can be used for power generation through either the steam or gasification route.
For small scale power generation, the gasification route has attracted more attention

9
as a small steam power plant is very inefficient and is very difficult to maintain due
to the presence of a boiler. In addition for rice mills with diesel engines, the gas
produced from rice husk can be used in the existing engine in a dual fuel operation.

2.2.2 Oil Palm Fiber

Oil palm is the most important product from Malaysia that has helped to
change the scenario of it’s agriculture and economy. Lignocellulosic biomass which
is produced from the oil palm industries include oil palm trunks (OPT), empty fruit
bunches (EFB), oil palm fiber (OPF) and palm pressed fibers (PPF), palm shells and
palm oil mill effluent palm (POME) (N.Abdullah and F.Sulaiman, 2013). Oil palm
fiber (OPF) that used in this research are from fruitlet of palm oil where the fibre are
the wastes. Oil palm waste is a reliable resource because of its availability, continuity
and capacity for renewable energy solution. There is abundance of raw materials
available of the palm tree consisting of around 90% of biomass wastes and only
around 10% of oil. About 90 million tonnes of oil palm fuit production was recorded
in 1998: however, 43045% of this was mill residues in the form of EFB, shell and
fibre. Palm fronds and stems are currently underutilised and the presence of these oil
palm wastes has created a maor disposal problem. Therefore, maximising energy
recovery from the wastes is desirable for both the environmental and economic
reasons. Direct combustion, gasification, pyrolysis, liquefaction, fermentation and
anaerobic digestion are alternate conversion technologies available to maximise
energy recovery.

Besides, converting dried oil palm wastes into various value added products,
it also have potential as a source of renewable nergy. Utilization of oil palm wastes
as a source energy will bring other environmental benefit like reduction in CO2
emissions. The greenhouse gases that are present in the atmosphere include water
vapor, CO2, methane and ozone, and the increase of greenhouse gases primarily CO2
is the major cause global warming. Oil palm wastes such as fiber, shell and EFB can
be used to produce steam for processing activities and for generating electricity.
Hence, the emission of CO2 in Malaysia can be decreased significantly if all
industries in Malaysia can replace or partially replace fossil fuel with oil palm wastes
to generate energy without degrading the environment (N.Abdullah and F.Sulaiman,
2013).

10
 2.2.3 Sugarcane Bagasse

Sugarcane bagasse (SB) is the biomass that is studied in this project. Bagasse
is the crushed remnants of sugarcane after syrup extraction (Devnarain et al., 2002).
Sugarcane is a type of grass with peripheral fibres enclosing a soft central pith
(Nassar et al., 1996). Sugarcane utilises solar energy by means of photosynthesis, to
grow and therefore produce biomass. During photosynthesis CO2 is extracted from
the air and this CO2 is released back into the atmosphere during combustion
rendering the whole process CO2 neutral. This enrgy is then released either by means
of natural decay, or it can be harvested by means of controlled combustion or
chemical reactions. Sugarcane is the crop that produces the highest yield of biomass
over an average year. Up to 8 tons/acre of carbohydrate (sugar and bagasse) can be
produced annually (Calvin, 1974). Sugarcane is a fibrous plant which causes the
crushed remnants to be this long particles that are interwoven with each other.
Therefore bagasse has very poor flow characteristics and it tends to bunche together
(Rasul et al., 1999). Additional size reduction before pyrolysis will enhance the flow
ability of bagasse.

Bagasse consists mainly of fibre particles, with a large lenth to width ratio
and small spongy dust-like particles (Rasul et al., 1999). The dust-like particles have
a much lower density of 220 kg/m3, compared to the fibrous particles density of 550
kg/m3 (Garcia-Perez et al., 2002). Bagasse ia a lignocellulosic compound which
implies that it contains varying amounts of cellulose, hemicellulose and lignin. the
study of lignocellulosic compounds is relevant to pyrolysis because decomposition
these components occurs at different temperatures. Hemicellulose typically
decomposes in the range of 160-360oC, while cellulose degrades at the higher
temperature range of 240-390oC. The loss of lignin typically occurs at a slower rate
over a much wide temperature range of 180-900oC. Cellulose and hemicellulose are
both polymeric carbohydrate structures, termed polysaccharides. Cellulose is a
polymer, consisting of linear chains of, 4-D-glucopyranose units. Hemicellulose a
complex polysaccharide found mostly in cell walls which is a branched sturcture
composed almost entirely of sugars such as glucose, mannose, xylose, arabinose,
methlyglucoronic and galaturonic acids. Cellulose is crystalline and strong whereas
hemicellulose has an amorphous structure with little strength. The main difference
between cellulose and hemicellulose is that cellulose is glucose derived and

11
hemicellulose is derived from a variety of sugars (Mohan et al., 2006). Lignins are
highly branched, substituted, mononuclear aromatic polymers in the cell walls of
certain biomass, especially woody species. Lignin is an amorphous cross linked are
believed to be a three-carbon chain attached to rings of six carbon atoms, called
phenyl-propanes (Mohan et al.,2006). Bagasse contains 35-59 wt% cellulose, 20-30
wt% hemicellulose, 20-27 wt% of lignin and 8-12 wt% extractives and ash (Garica-
Perez et al., 2001). Bagasse is mainly used for onsite combustion (Asadullah et al.,
2007). The remainder is typically used to produce paper pulp, chemical reactants, or
animal feed additives (Devnarain et al., 2002). Implementing thermo-chemical
processing of bagasse will extend its uses to high-density energy products (char and
bio-oil) as well as activated carbon and high quality fertilizer (from char).

2.3 Pyrolysis

Pyrolysis is the heating of biomass feedstock under controlled conditions to

produce combustible synthesis gas (‘syngas’) and oil (‘bio-oil’) that can be burnt to
produce heat, power or combined heat and power. Pyrolysis is a decomposition
process of biomass at high temperature in the absence of oxygen (Anchan & Kunio,
2012). The yields and compositions of end products of pyrolysis are highly
dependent on types of biomass and structural compositions of biomass and other
physical parameter such as temperature, heating rates, reactors, particle size, co-
reactant and other (Nasrin, 2011). Babu (2008) claimed the pyrolysis mechanism
started by the heat transfer to the solid particle surface of biomass by radiation and/or
convection and then to the inside of the particle when the biomass is heated in an
inert atmosphere. Next, the moisture removal in the biomass occurs due to the
temperature increment within the biomass particle. The rise of temperature then
initiated the pyrolysis process. The volatile and gaseous products flow through the
pores of the particles during heat transfer process. The pyrolysis process proceeds
with a rate depending on the local temperature. As the biomass converts into gases
during the reaction, the pores of the solid particle become more porous. Thus, the
enlarged pores provide many reaction sites to the volatile and gaseous products of
pyrolysis and favor their interaction with the hot solid particle of biomass.

12
 Biochar, the third combustible product produced in pyrolysis, is the solid
charred and carbon-rich residue. Pyrolysis has a requirement for intial energy, in the
same way as in straight combustion. Some heat in the flame is used to initiate
combustion of new feedstock. The potential advantage of pyrolysis-derived
bioenergy over other bioenergy strategies in terms of greenhouse gas emissions
results not only solely from the retention of up to 50% of the feedstock carbon in
stable biochar but from indirect savings that may result from the use of biochar in
agriculture, specifically the soil (Gaunt and Lehmann, 2008). The pyrolysis process
greatly affects the qualities of biochar and its potential value to agriculture in terms
of agronomic performance or in carbon sequestration.

The process and process-parameters, mainly temperature and furnace

residence time, are important in the quality of the product. The process and process
conditions, however, also interact with feedstock type in determining the nature of
the product. These variables together influence the chemical, biological and physical
properties, which limit the potential use for biochar products. Each category of
pyrolysis process is characterized by a contrasting balance among biochar, bio-oil
and syngas as shown in Table 2.6.1. The precise ratio in these products may vary
between plants and may be optimized at a particular installation (Demirbas, 2004).

It is critical that maximising the production of biochar relative to mass of

initial feedstock (Demirbas, 2006), is always at the expense of usable energy in the
liquid or gaseous form. Although a greenhouse gas migitation strategy may favour
maximising the biochar product (Gaunt and Lehmann, 2008), the balance that is
realised is a function of market and engineering constraint.

13
 Process Process Liquid Solid Gas
(bio-oil) (biochar) (syngas)
FAST PYROLYSIS
Moderate
temperature (~500 75% 12% 13%
°C) (25% water)
Short hot vapour
residence time (<2s)
INTERMEDIATE
PYROLYSIS
Low-moderate 50% 25% 25%
temperature, (50% water)
Moderate hot vapour
residence time
SLOW
PYROLYSIS 30% 35% 35%
Low-moderate (70% water)
temperature,
Long residence time
GASIFICATION
high temperature 5% tar
(>800 °C) 5% water 10% 85%
Long vapour
residence time

Table 1.2.1 : Fate of initial feedstock mass between products of pyrolysis

processes Source: (IEA, 2007).

14
 2.3.1 Slow Pyrolysis

Slow pyrolysis can be divided into tradisional charcoal making and more
modern processes. It is characterized by slower heating rates, relatively long solid
and vapour residence times and usually a lower temperature than fast pyrolysis,
typically 400oC (Bridgwater et al., 1999). The target product is often the char but this
will always be accompanied by liquid and gas product although these are not always
recovered. Slow pyrolysis can alse be defined as the thermal conversion of biomass
by slow heating at low medium temperatures (450 to 650oC) in the absence of
oxygen with the simultaneous capture of syngas (David et al., 2006).

There are two industrial char production technologies, namely: kiln

technologies which produce charcoal as sole product and slow pyrolysis retorts
which produce charcoal along with by-products (bio-oil and bio-gas). Carbonization
in a retort allows for integrated utilization of the energy contained in the raw mineral.
The by-products are usually re-used for heating. The charcoal quality is of higher
grade in retort processes than kiln processes. Industrial char production by means of
slow pyrolysis has a relatively short history, dating back only about 150 years
(Honsbein et al., 2007).

2.3.2 Fast Pyrolysis

Fast pyrolysis is characterized by high heating rates and short vapour

residence times. This generally requires a feedstock prepared as small particle sizes
and a design that removes the vapours quickly from the presence of the hot solids.
There are a number of different reator configurations that can achieve this including
ablative systme, fluidizes beds,, stirred or moving bed and vacuum pyrolysis
systems. A moderate temperature of around 500oC is usually used (Ensyn, 2009).
Very rapid feedstock heating leads to a much greater proportion of bio-oil and less
biochar.

15
 Various technologies have been used and proposed or tested including : fixed
beds, augers, ablative methods, rotating cones, fluidized beds and circulating
fluidized beds. Surface charring must be continuously removed during reaction to
prevent pyrolysis of particle interiors being inhibited by its insulating effect. The bio-
oil is a low grade product, it is unsuitable as a mainstream liquid transport fuel even
after refining and is most suitable as a fuel-oil substitute (BEST Energies, 2009).

16
 CHAPTER 3

MATERIALS AND METHODOLOGY

3.1 List and Materials

Materials Descriptions

Rice Husk Taken from Pendang, Kedah.

Sugarcane Bagasse Taken from Sura Gate, Dungun,

Terengganu.

Oil Palm Fiber Taken from Rasau, Kerteh, Terengganu.

17
 3.2 List of Apparatus and Equipments.

Equipment Model Descriptions

Sieve Endecotts Test Used for get precise particle size

Sieve analysis

Drying Oven ULM 500 Used to dry the sample for

remove moisture content.

Muffle Furnace ELF 11/14B Used in pyrolysis process to get

biochar

Electronic Weight Mettler TOLEDO, To weight the mass of samples.

Balanced B2002-S

Sealed Crucible - Used in pyrolysis process when

heat in muffle furnace.

Dessicator DURAN To stored biochar for prevent

moisture outside.

Blender Panasonic MX- To grind the sample before sieve.

GM1011 H(Grey)

pH Meter Mettler TOLEDO To measure the pH of sample

320 pH Water water after 1 day.

Beaker Boeco Germany Used to weight the sample and

analysis.

Fourier Transform Infra- Thermo Science Used for analysis characterization

Red (FTIR) Analysis Nicolet iS10 biochar to determine the
Thermo Science functional groups.

Particle Size Analyser Malvern Used for analysis characterization

MS2000/HYDRO to determine the particle surface
2000MU area of biochar.

18
 3.3 Sample Preparation

The raw materials of agriculture waste namely RH, OPF and SB were
washing for 1 day and the colour, pH and turbidity were determine. Then, these raw
materials were dried for about 24 hours in drying oven at 55oC for removing the
moisture in raw materials and the moisture content was calculated using equation (2).

After drying, the raw materials were grinded and sieved to the size range of
2.5mm – 1mm to get the precise particle size of biochar. Then, RH, SB and OPF
were stored in tight container before pyrolysis process.

3.4 Preparation Of Char

100 g of dried 2.5mm – 1mm sized RH, OPF and SB were pyrolysed in a
muffle furnace at 400oC, 600oC and 800oC for 2 hours to produce a solid char. The
char were removed from the furnace, allowed to cool down and stored in a
dessicator. It is refered to as the biochar (B-PAS) and was used directly for next
analysis. The char yields % using equation (1) and burn of contents % using equation
(3) were calculated.

3.5 Characterization Of Char

3.5.1 Particle Size Analyser

The biochar was analysis using Particle Size Analyser (PAS) Model Malvern
MS200/HYDRO 2000MU to determine the particle specific surface area for each of
types biochar. Deionized water was prepared in th beaker and set ultrasonic bath for
5 minutes. Mastersizer and dispersion unit controller was switch on. The motor speed
was set at 2000 RPM and tab water was used to flash the dispersion unit. The
program was started at desktop using mastersizer 2000 program. Then, clicked
Measure for start/stop and biochar.sop was choosed as standard operating procedure.
Every sample was named and waited for a few second for the next instructions in the
yellow field of the analysis window. The sample of biochar was added using 4 scoop
of small spatula in the dispersion unit and wait for 5 minutes. Then, button start was
clicked and all data was collected and saved. This analysis was repeated again to
analysis another samples. From the graph, the specific surface area for each biochar
were determined.
19
 3.5.2 Fourier Transform Infra-red (FTIR) Analysis

The biochar were analysis using FTIR model Thermo Science Nicolet iS10
using OMNIC Software. OMNIC Software was launched from desktop and solid
sample of biochar was placed on sample compartment which was crytal using a
spatula. After that, the OMNIC Software proceed recorded the spectrum of each
biochar to determine functional groups. After finish, the collected sample was
renamed and saved, then the sample compartment was clean using ethanol and
wiped the crystal gently using tissue. The data was print out and repeated for another
sample of biochar.

20
 CHAPTER 4

RESULTS AND DISCUSSIONS

4.1 Washing Process

Table 4.1.1 : Mass of Raw Materials in Washing Process.

Mass (g)
Raw Materials Before After
Rice Husk 1281.94 g 3806 g
Sugarcane Bagasse 632.71 g 3320 g
Oil Palm Fiber 529.76 g 1384 g

RH, OPF and SB samples with different types of agriculture waste were
obtained via washing, as listed in Table 4.1.1. The mass for each raw materials after
washing were increased because of the moisture content after been soaking for 1 day.
From the Table 4.1.1, the mass of SB from before was 632.71 g and increased to
3320 g, this showed SB fibre absorbed more water because bagasse consists mainly
of fibre particles, with large length to width ratio and small spongy-like particle
(Rasul et al., 1999). For RH the mass before was 1281.94 g and increased to 3806 g,
from this showed that RH has slightly different from SB, where the water absorbed
in RH was less than SB, even the mass before for RH was more than SB. The OPF
mass before was 529.76 g and increased to 1384 g, the water absorbed in OPF was
less than SB and RH. This was because the OPF fiber was not have spongy-like
particles like SB, so the water in OPF was less.

21
 4.2 Colour of Raw Materials

Table 4.2.1 : Colour and Odour of Raw Materials After 1 Day.

Colour
Raw Materials Before After Description
A. D.
The colour of
rice husk after 1
Rice Husk day was dark
brown. The
odour was have
strong smell.

B. E.
The colour of
sugarcane
Sugarcane bagasse after 1
Bagasse day was yellow
brown. The
odour was smell
sour and not
very strong.
C. F.
The colour of oil
palm fiber after
1 day was brown
Oil Palm Fiber oily. The odour
was smell palm
oily and have
small solid
precipitate at the
bottom.

22
 4.3 Turbidity and pH

Table 4.3.1 : Turbidity

Raw Materials Reading of Turbidity

Rice Husk 158 NTU
Sugarcane Bagasse 151 NTU
Oil Palm Fiber 562 NTU

Table 4.3.2 : pH

Raw Materials Reading of pH

Rice Husk 6.40
Sugarcane Bagasse 4.70
Oil Palm Fiber 5.31

4.4 Moisture Content

Table 4.4.1 : Drying 24 Hours (Moisture)

Mass (g)
Raw Materials Before After
Rice Husk 150.0022 g 81.44 g
Sugarcane Bagasse 150.0521 g 30.47 g
Oil Palm Fiber 150.656 96.11

Table 4.4.2 : Moisture Content %

Raw Materials Moisture Content %

Rice Husk 45.71 %
Sugarcane Bagasse 76.69 %
Oil Palm Fiber 35.93

23
 4.5 Raw Data
4.5.1 Pyrolysis Process ( 2 Hours)

Table 4.5.1.1 : Rice Husk

Mass (g)
Temperature °C Before After
400 °C 100 g 41.71 g
600 °C 100 g 32.64 g
800 °C 100 g 29.34

Table 4.5.1.2 : Sugarcane Bagasse

Mass (g)
Temperature °C Before After
400 °C 100 g 28.37 g
600 °C 100 g 14.10 g
800 °C 100 g 9.82

Table 4.5.1.3 : Oil Palm Fiber

Mass (g)
Temperature °C Before After
400 °C 100 g 39.93 g
600 °C 100 g 27.77 g
800 °C 100 g 18.62 g

24
 4.6 Char Yield %

Table 4.6.1 : Percentage of Char Yield % for each Biochar.

Temperature °C
Raw Materials 400 °C 600 °C 800 °C
Rice Husk 41.71 % 32.64 % 29.34 %
Sugarcane Bagasse 28.37 % 14.10 % 9.82 %
Oil Palm Fiber 39.93 % 27.77 % 18.62 %

4.7 Burn Off Content %

Table 4.7.1 : Percentage of Burn Off Content % for each Biochar.

Temperature °C
Raw Materials 400 °C 600 °C 800 °C
Rice Husk 58.29 % 67.36 % 70.66 %
Sugarcane Bagasse 71.63 % 85.90 % 90.18 %
Oil Palm Fiber 60.07 % 72.23 % 81.38 %

25
 4.8 Characterization of Analysis
4.8.1 Partical Surface Area

Table 4.8.1.1: Specific Surface Area of Biochar.

Samples Temperature oC and Specific Surface Area (m2/g)

400oC 600oC 800oC

Rice Husk 0.256 m2/g 0.26 m2/g 0.228 m2/g

Oil Palm Fiber 0.238 m2/g 0.0354 m2/g 0.198 m2/g

Sugarcane Bagasse 0.199 m2/g 0.24 m2/g 0.2552/g

Figure 4.8.1.2 : Graph Specific Surface Area of Rice Husk for each
Temperature.

26
Figure 4.8.1.3 : Graph Specific Surface Area of Oil Palm Fiber for each
Temperature.

Figure 4.8.1.4 : Graph Specific Surface Area of Sugarcane Bagassse for each
Temperature.

27
 4.8.2 Functional Group of FTIR

Table 4.8.1.1 : FTIR Functional Groups of Biochar

Samples Temperature oC and Types of Functional Groups /

Wanumber (cm-1)

400oC 600oC 800oC

Rice Husk Kaolin Clays / Kaolin Clays / Kaolin Clays /

Alumino Silicates Alumino Silicates Alumino Silicates

3800 – 3300 cm-1 / 3800 – 3300 cm-1 / 3800 – 3300 cm-1 /

1200 – 900 cm-1 1200 – 900 cm-1 1200 – 900 cm-1

Aliphatic Aliphatic
Hydrocarbons Hydrocarbons

3000 – 2800 cm-1 3000 – 2800 cm-1

1500 – 1300 cm-1 1500 – 1300 cm-1

Oil Palm Fiber Aliphatic Primary Kaolin Clays / Inorganic

Amines Alumino Silicates Phosphates

3400 – 3200 cm-1 3800 – 3300 cm-1 / 3500 – 2600 cm-1

1200 – 900 cm-1
1700 – 1500 cm-1 1500 – 1400 cm-1

1100 – 1000 cm -1 1100 – 1000 cm-1

900 – 700 cm-1

Sugarcane Bagasse Aliphatic Primary Primary Aliphatic n/a

Amines Alcohols

3400 – 3200 cm-1 3600 – 3200 cm-1

1700 – 1500 cm-1 1100 – 1000 cm-1

1100 – 1000 cm-1 Alipahtic Ethers

900 – 700 cm-1 1200 – 1000 cm-1

*n/a : not available.

28
 Appendix

Using equation 1 :

𝑚1
Char Yield (%) = x 100 %
𝑚2
m1 = Is the mass, in grams, of the char.
m2 = Is the mass, in grams, of the raw material.

Temperature °C
Raw Materials 400 °C 600 °C 800 °C
Rice Husk

41.71 𝑔 32.64 𝑔 29.34 𝑔

x 100 % x 100% x 100 %
100 𝑔 100 𝑔 100 𝑔
= 41.71 % = 32.64 % = 29.34 %

Sugarcane
Bagasse 28.37 𝑔 14.10 𝑔 9.82 𝑔
x 100 % x 100 % x 100 %
100 𝑔 100 𝑔 100 𝑔
= 28.37 % = 14.10 % = 9.82 %
Oil Palm Fiber

39.93 𝑔 27.77 𝑔 18.62 𝑔

x 100 % x 100 % x 100 %
100 𝑔 100 𝑔 100 𝑔
= 39.93 % = 27.77 % = 18.62 %

29
Using equation 2 :

(Ww−Wd)
Moisture content (%), Mn = ( Ww
) x 100 %

in which:
Mn = Moisture content (%) of material n.
WW = Wet weight of the sample, in grams.
Wd = Weight of the sample after drying, in grams.

Raw Materials Moisture Content %

Rice Husk (150 𝑔 − 81.44 𝑔 )
x 100 % = 45.71 %
150 𝑔
Sugarcane Bagasse (150𝑔 − 30.47 𝑔 )
x 100 % = 79.69 %
150 𝑔
Oil Palm Fiber (150 𝑔 − 96.11𝑔 )
x 100 % = 35.93 %
150 𝑔

30
Using equation 3 :

(𝑥1−𝑥2)
Burn Off Content (%) = x 100 %
𝑥1

x1 = Weight of the sample before burn, in grams.

x2 = Weight of the sample after burn, in grams.

Temperature °C
Raw 400 °C 600 °C 800 °C
Materials
Rice Husk

(100 𝑔−41.71 𝑔) (100 𝑔−32.64 𝑔) (100 𝑔−29.34 𝑔)

x x x
100 𝑔 100 𝑔 100 𝑔
100 % 100 % 100 %
= 58.29 % = 67.36 % = 70.66 %
Sugarcane
Bagasse (100 𝑔−28.37 𝑔) (100 𝑔−14.10 𝑔) (100 𝑔−9.82 𝑔)
x x x
100 𝑔 100 𝑔 100 𝑔
100 % 100 % 100 %
= 71.63 % = 85.9 % = 90.18 %
Oil Palm
Fiber (100 𝑔−39.93 𝑔) (100 𝑔−27.77 𝑔) (100 𝑔−18.62 𝑔)
x x x
100 𝑔 100 𝑔 100 𝑔
100 % 100 % 100 %
= 60.07 % = 72.23 % = 81.38 %

31