OPTIMIZATION OF BIODIESEL PRODUCTION FROM USED FRYING OIL

WITH MODIFIED BIOCHAR AS CATALYST

MUHAMMAD SHAFIQ BIN NAZAR

55220114206

Report Submitted to Fulfill the Partial Requirements for the Bachelor of

Engineering with Honours (Chemical)
Universiti Kuala Lumpur

MAY 2018

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 APPROVAL PAGE

We have supervised and examined this report and verify that it meetds the
program and university‘s requirement for the Bachelor of Engineering with
Honours (Chemical)

Date: 28/05/2018 Signature:…………………………………

Supervisor : Dr. Yuhanees Binti
Mohamed Yusof
Official stamp:

ii
 ACKNOWLEDGEMENT

I am thankful to Allah Almighty who gave me the chance to finish this research
and also to my parents for giving me all support that I need in order to complete
this task.

I wish to express my sincere gratitude to my supervisors, Dr. Yuhanees

Binti Mohamed for her overall guidance throughout my research and spending
countless hours discussing and reviewing the content of this research.

I also thank the department of Chemical Engineering, University Kuala

Lumpur (MICET) for the laboratory permissions and not to forget to all laboratory
technicians and friends with the guide and encouragement provided.

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 CONTENT

APPROVAL PAGE .............................................................................................. ii

ACKNOWLEDGEMENT ..................................................................................... iii

CONTENT .......................................................................................................... iv

LIST OF FIGURES ............................................................................................ vii

LIST OF TABLES ............................................................................................... ix

LIST OF ABRIVIATION........................................................................................ x

ABSTRACT ........................................................................................................ xii

ABSTRAK ......................................................................................................... xiii

CHAPTER 1: INTRODUCTION ...........................................................................1

1.1 Background of study ...................................................................................1

1.2 Problem statement .....................................................................................4

1.3 Objective of study .......................................................................................6

1.4 Significance of study ..................................................................................6

1.5 Scope of study............................................................................................7

CHAPTER 2: LITERATURE REVIEW .................................................................9

2.1 Biodiesel .....................................................................................................9

2.1.1 Biodiesel feedstock ............................................................................11

2.1.2 Used frying oil (UFO) .........................................................................13

2.2 Biodiesel production method ....................................................................16

2.2.1 Transesterification reaction for biodiesel production ..........................18

2.3 Energy application in biodiesel production ...............................................20

2.4 Catalyst ....................................................................................................21

2.4.1 Homogeneous catalyst ......................................................................22

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 2.4.2 Heterogeneous catalyst .....................................................................23

2.4.3 Biochar as Heterogeneous Acid Catalyst ..........................................25

2.5 Glycerol ....................................................................................................27

2.6 Respose surface methodology as a tool for optimization .........................27

CHAPTER 3: METHODOLOGY ........................................................................28

3.1 Introduction ..............................................................................................28

3.2 Preparation and pretreatment of used frying oil .......................................29

3.3 Analysis of used frying oil .........................................................................30

3.3.1 Acid Value and FFA content ..............................................................30

3.3.2 Saponification value (SV) ..................................................................31

3.3.3 Average molecular weight of used frying oil and biodiesel ................32

3.3.4 Density of used frying oil ....................................................................32

3.4 Modification of catalyst .............................................................................33

3.4.1 Impregnated of Zn – loaded biochar ..................................................33

3.4.2 Characterization of Zn – loaded biochar ............................................34

3.5 Biodiesel production by using Zn - loaded biochar as catalyst .................35

3.6 Analysis of biodiesel .................................................................................39

3.7 Design of experiment ...............................................................................39

3.8 Project management ................................................................................40

3.8 Financial ...................................................................................................42

CHAPTER 4: RESULT AND DISCUSSION .......................................................43

4.1 Analysis of UFO sample ...........................................................................43

4.2 Characterization of Zn – loaded biochar catalyst .....................................45

4.2.1 TGA analysis .....................................................................................45

4.2.2 FTIR analysis .....................................................................................47

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 4.3 Optimization of biodiesel production.........................................................48

4.3.1 Regression model equation ...............................................................48

4.3.2 Anova ................................................................................................52

4.4 Effect of variables on the yield of biodiesel ..............................................54

4.4.1 Effect of molar ratio and catalyst loading on biodiesel yield ...............54

4.4.2 Effect of molar ratio and reaction time on biodiesel yield ...................57

4.4.3 Effect of catalyst loading and reaction time on biodiesel yield ...........59

4.4.4 Optimization values for transesterification process ............................61

4.5 Effects of modified and unmodified catalyst on biodiesel production at

optimum values of parameter .........................................................................65

4.6 Analysis of biodiesel .................................................................................66

CHAPTER 5: CONCLUSION AND RECOMMENDATION.................................68

5.1 Conclusion ...............................................................................................68

5.2 Recommendation .....................................................................................69

REFERENCE .....................................................................................................70

APPENDIX A: Analysis of UFO .........................................................................76

APPENDIX B: Optimization Experimental Data .................................................78

APPENDIX C: TGA Analysis .............................................................................79

APPENDIX D: GC Analysis ...............................................................................81

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 LIST OF FIGURES

Figure 1. 1 World palm oil productions (Thomas, 2017) ......................................3

Figure 2. 1 World oil production from major oil crop source from (Woiciechowski
et al., 2016) ........................................................................................................12
Figure 2. 2 Statistic Production of cooking oil in Malaysia (Statista, 2017) ........14
Figure 2. 3 Conversion of Triglyceride into Diglyceride (K. Ramachandran et al.,
2013)..................................................................................................................19
Figure 2. 4 Conversion of Diglyceride into Monoglyceride (K. Ramachandran et
al., 2013) ............................................................................................................19
Figure 2. 5 Conversion of Monoglyceride into Glycerol (K. Ramachandran,
Suganya, Nagendra Gandhi, & Renganathan, 2013) ........................................20
Figure 2. 6 Figure 2. 5 Conversion of Monoglyceride into Glycerol (K.
Ramachandran, Suganya, Nagendra Gandhi, & Renganathan, 2013) ..............21
Figure 3. 1 Process block diagram of biodiesel production ................................28
Figure 3. 2 Used frying oil collected ...................................................................29
Figure 3. 3 Saponification test ...........................................................................31
Figure 3. 4 Filtration of modified biochar catalyst ...............................................34
Figure 3. 5 Experimental set up for transesterification of biodiesel ....................35
Figure 3. 6 Product of transesterification process ..............................................38
Figure 3. 7 Washing process .............................................................................38
Figure 4. 1 TGA analysis for unmodified biochar ...............................................46
Figure 4. 2 TGA analysis for modified biochar with Zn(NO3)2.6H2O ..................46
Figure 4. 3 FT-IR analysis for modified biochar with Zn(NO3)2.6H2O .................47
Figure 4. 4 Actual against predicted plot ............................................................49
Figure 4. 5 Effect of methanol to oil molar ratio and catalyst loading on biodiesel
yield at 270 minutes ............................................. Error! Bookmark not defined.

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Figure 4. 6 Effect of methanol to oil molar ratio and reaction time on biodiesel
yield at catalyst loading of 1% .............................. Error! Bookmark not defined.
Figure 4. 7 Effect of catalyst loading and reaction time on biodiesel yield at
molar ratio of 10.5 ................................................ Error! Bookmark not defined.
Figure 4. 8 Ramp function graph of desirability for optimization of biodiesel
production ..........................................................................................................62
Figure 4. 9 Contour plot for optimum values of variables when reaction time at
354 minutes ......................................................... Error! Bookmark not defined.
Figure 4. 10 Dimensional plot for optimum values of variables when reaction
time at 354 minutes ............................................. Error! Bookmark not defined.
Figure 4. 11 Pertubation plot for optimum values of variables at optimum value
...........................................................................................................................64
Figure 4. 12 GC-FID chromatograms of optimized biodiesel production ...........67

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 LIST OF TABLES

Table 2. 2 Quantity of generated UFO in selected country (Panadare & Rathod,

2015)..................................................................................................................14
Table 2. 3 Properties of Used Frying Oil (Ezzah-Mahmudah, Lokman, Saiman, &
Taufiq-Yap, 2016) ..............................................................................................16
Table 2. 4 Major lignocellulosic components in EFB fibre (Hassan & Badri, 2016)
...........................................................................................................................25
Table 3. 1 Independent variables and level used for experimental design ….40

Table 3. 2 Gantt chart for EFYP2 .......................................................................41

Table 3. 3 Financial budget................................................................................42
Table 4. 1 Charatristic of used frying oil…………………………………. ….43

Table 4. 2 Full factorial central composite design matrix for biodiesel production
...........................................................................................................................50
Table 4. 3 Analysis of variance (ANOVA) for the quadratic polynomial model ...52
Table 4. 4 Fit statistics .......................................................................................52
Table 4. 5 Optimum value for transesterification of ufo using Zn-loaded biochar
as catalyst ..........................................................................................................61
Table 4. 6 Biodiesel production by using modified and unmodified biochar as
catalyst...............................................................................................................66
Table 4. 7 Composition of methyl ester present in biodiesel ..............................66

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 LIST OF ABRIVIATION

Al2O3 - Aluminium (II) Trioxide

AV - Acid value

BET - Brunauer-Emmett-Teller

CaO - Calcium Oxide

CCD - Central composit design

CO - Carbon Monoxide

CO2 - Carbon Dioxide

CCD - Central Composite Design

EFYP2 - Engineering Final Year Project 2

EFB - Empty fruit bunch

FAME - Fatty Acid Methyl Ester

FAAE - Tatty Acid Alkyl Ester

FFA - Free Fatty Acid

FT-IR - Fourier transform infrared spectrometer

GC - Gas Chromatography

GC-FID - Gas Chromatography – Flame Ionization Detector

H2SO4 - Sulfuric Acid

H+ - Hydrogen ion

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KOH - Potassium Hydroxide

K3PO4 - Potassium Phosphate Tri-basic

min - Minutes

MgO - Magnesium Oxide

MeOH - Methanol

MeOH/oil - Methanol to oil molar ratio

MT - Million tons

NaOH - Sodium Hydroxide

OH- - Hydroxide group

OH- - Hydroxide ion

RSM - Response Surface Method

SiO2 - Silicon Dioxide

SrO - Strontium Oxide

SO3 - Sulfur Trioxide

SV - Saponification value

TGA - Thermal gravimetry analysis

UFO - Used frying oil

Zn(NO3)2.6H2O - Zinc nitrate hexahydtare

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 ABSTRACT

Problem of improper disposable of UFO nowadays keep increasing with the

increasing production of the cooking oil itself. The recycling of UFO into
biodiesel is a reliable solution to overcome the environmental problems caused
by UFO. The development of cheaper heterogeneous catalyst from biochar also
enhances the production of biodiesel in current industry. This report focused on
the optimization production of biodiesel from used frying oil and heterogeneous
catalyst from modified biochar with impregnated zinc nitrate hexahydrate as a
surface area modifying method. Response surface methodology was utilized as
optimization tool in which central composite design (CCD) model was employed.
Three variables were put into consideration in optimization process which are
methanol to oil molar ratio, catalyst loading (wt%), and reaction time (minutes). It
was found that the highest conversion of triglycerides into methyl ester (89.93%)
was found at parameters of 14.6 methanol to oil molar ratio, 1.04% catalyst
loading and 354 minutes reaction time. Analysis was done on used frying oil to
study for its acid value, saponification value, density and average molecular
weight. As for modified biochar catalyst, functional group analysis was done
using the Fourier Transform Infrared Spectrometer (FT-IR) and the thermal
decomposition was investigated using thermal gravimetric analysis (TGA-DTG).
The produced biodiesel was subjected to methyl ester determination by using
gas chromatography (GC-FID) analysis and it is found there were methyl
myristate, methyl palmitate, methyl oleate, methyl stereate and methyl linoleate
with different composition were found in the content of biodiesel.

xii
 ABSTRAK

Masalah pembuangan minyak masak terpakai kini semakin meningkat dan kitar
semula minyak masak terpakai ke biodiesel adalah penyelesaian yang boleh
dipercayai untuk mengatasi masalah alam sekitar yang disebabkan oleh minyak
masak terpakai. Perkembangan pemangkin heterogen yang lebih murah dari
biochar juga meningkatkan pengeluaran biodiesel dalam industri semasa.
Laporan ini memberi tumpuan kepada pengoptimuman penghasilan biodiesel
daripada minyak masak terpakai dan pemangkin heterogen berasaskan biochar
yang diubahsuai dengan zink nitrate hexahydrate sebagai kaedah
pengubahsuaian terhadap keluasan permukaan pemangkin. Metodologi
response surface methodology (RSM) telah digunakan sebagai alat
pengoptimuman di mana model central composite design (CCD) telah
digunakan. Tiga pembolehubah telah dipertimbangkan dalam proses
pengoptimuman iaitu nisbah molar metanol kepada minyak, berat pemangkin
(wt%), dan masa tindak balas (minit). Telah didapati bahawa penukaran
trigliserida tertinggi ke dalam metil ester (89.93%) didapati pada parameter 14.6
nisbah molar metanol kepada minyak, 1.04% berat pemangkin dan masa tindak
balas 354 minit. Analisis dilakukan pada minyak masak terpakai yang digunakan
untuk mengkaji nilai asid, nilai saponifikasi, ketumpatan dan purata berat
molekul. Bagi pemangkin biochar yang telah diubah suai, analisis kumpulan
fungsional telah dilakukan dengan menggunakan Fourier Transform Infrared
Spectrometer (FT-IR) dan penguraian termal telah dilakukan menggunakan
thermal gravimetric analysis (TGA-DTG). Biodiesel yang dihasilkan telah dikaji
untuk menentukan jenis metil ester yang terkandung di dalam biodiesel dengan
menggunakan analisis gas kromatografi (GC-FID) dan didapati terdapat metil
myristate, metil palmitat, metil oleate, metil stereate dan metil linoleate dengan
komposisi yang berbeza didapati di dalam kandungan biodiesel.

xiii
 CHAPTER 1: INTRODUCTION

1.1 Background of study

Originally, biodiesel was invented by Rudolph Diesel in 1890 where diesel from
petroleum was not available. He used the pure vegetable oils to power up the
diesel engines to do agricultural activities. Later on in 1834, S. Casey introduced
the first US pattern for alcohol to be used as a lamp fuel. The development of
biofuel growing very fast where in1850, thousands of distilleries of
―Camphene‖(biofuel blend from turpentine and ethanol) was produced around
90 million gallons per year (Köpke, Noack, & Dürre, 2011).

In 1930, a research was done at Belgium where researchers found a new

modern way to produce biofuel by synthesizing vegetable oils into compounds of
Fatty Acid Methyl Ester (FAME) and this process called transesterification
process and since then biodiesel has becoming the trade name of FAME
(Bulletin, 2001). Due to the concern of global warming and environment safety,
biodiesel product is further developed and being used worldwide now.

1
 Nowadays, the world is facing the most critical energy and environment
crisis in its entire history. This is because most of the country still highly
dependent on petroleum crude and natural gas as the main energy sources for
transportation and electrical energy and contribute to increasing of high price of
petroleum fuels every other day. Thus, sustainable energy also known as
renewable energy is the only possible way to overcome energy crisis and
environmental friendly at the same time. There are many types of alternative
energy that are sustainable such as wind, solar, geothermal, hydropower and
biomass that currently under development but still most of this energy is
expensive and not economically feasible (Lam, Tan, Lee, & Mohamed, 2009).
However, there are also modern countries such as Germany that currently
developing their renewable energy source aggressively in order to convert their
main source of energy from coal into sustainable energy and they already
surpassed their 2020‘s energy generation target which is 35% where they
succeeded to generate 37.6% energy in 2017 (Craig Morris, 2017).

The best option that might fulfill both economic feasibility and sustainable
energy is biomass and due to its readily availability makes it the quickest
solution to the crisis. On top of that, biomass also has the potential of net zero
carbon emission which give impact in controlling global warming problem and
solves the dwindling reserve of conventional fuel (Agustian, 2012).

Indonesia and Malaysia are among the countries which actively produce
oil due to abundance crops of palm fruits resources for the purpose of
commercial and biodiesel production. Figure 1.1 shows that Malaysia is the
second largest palm oil producer with world share of 28% and Indonesia hold
the largest percent of world share of palm oil production which is 32%(MBA,
2017b). To date, Malaysia is embarking on more progressive crude palm oil
(CPO) production to achieve 900 000 tonnes of biodiesel production by the end

2
of 2017 and soon Malaysia is on its way to upgrade from B5 biodiesel program
into B10 biodiesel program meanwhile Indonesia already implemented B20
biodiesel program and providing subsidies to encourage its adoption . Besides,
biodiesel production will not gain interest without subsidy and tax exemption
support from government (Lam et al., 2009). This is because the cost of
production itself is higher compared to conventional diesel. On top of that, the
usage of refined vegetable oils as feedstock of biodiesel in most of the biodiesel
plants will cause super expensive cost which is 80% from the overall production
cost. With all these proves that economic feasibility has become the major
concern in biodiesel production (MBA, 2017a).

Figure 1. 1 World palm oil productions (Thomas, 2017)

This limitation can be overcome by focusing on the development of low

cost biodiesel either low cost feedstock, catalyst, newly found method or
process and so on. Thus, the usage of waste cooking oil as substitute of

3
vegetable refined oil can be one of the effective solutions due to the cheap
feedstock price compared to refined oil and utilization of this waste can solve
improper disposable of used frying oil (UFO) in the water ways at the same time.
In fact, with the increasing demand of cooking oil leads to more waste oil will be
generated. Due to concern of the environmental impact of UFO, several
programs were launched by government to spread awareness of the importance
to recycle UFO into biodiesel and provide solution to this problem by collecting
waste cooking oil program in residential area.

1.2 Problem statement

Problem of improper disposable of UFO nowadays keep increasing with the

increasing production of the cooking oil itself. Other than causing environmental
problems, it also leads to deceases and non Halal issues for Muslims consumer.
Thus by recycling oil cooking waste into biodiesel is found to be the best
promising way to reduce problems related to waste cooking oil while generates
renewable energy at the same time.

Economic feasibility is the major concern in biodiesel production industry

where the cost is very expensive if compared to petroleum diesel. Thus, the
selection of raw materials for production is a very important issue needs to be
considered. Conventional biodiesel production uses refined biodiesel oil which
cause 80% from total production cost(Lam et al., 2009). Same goes to the type
of catalyst that will be used in biodiesel production process. The recent
discoveries on the use of biological enzyme as catalyst promising a high yield of
biodiesel and almost zero glycerol byproduct generation but require longer time
reaction and very expensive. Thus, waste cooking oil and biochar from waste
palm oil industry which is empty fruit bunch (EFB) can be fully utilized to produce

4
biodiesel and perfect combination to produce high yield and also green
innovation.

Used frying oil is known to be not totally miscible with alcohol and the rate
of mass transfer in the transesterification reaction causes a very slow reaction
and took longer time to obtain highest yield of biodiesel. Emulsion from this
mixing process can be obtained by providing vigorous mechanical energy to the
mixture. Thus with the aid of heating and mechanical stirring mechanism will
ensure the conversion happened in more efficient way.

In previous study, researchers used conventional ‗one-variable-at-a-time‘

approach in order to optimize parameters in biodiesel production. This approach
keeps certain variables as constant and optimizes one factor at a time. This
approach benefits in selection of particular parameters affecting biodiesel yield
and simples to implement. However, this approach is less efficient due to the
time restrictive, consumes large amount of raw materials and chemicals, less
economic plus combined interactions among parameters will be ignored. Thus,
response surface method (RSM) can be useful method to optimize parameters
while simultaneously investigate several factors‘ effects in biodiesel production
(S. K. Singh, Singh, Tripathi, Khare, & Garg, 2011).

5
1.3 Objective of study

The objectives of this research are as followed:

1. To synthesize biodiesel by transesterification of used frying oil with

modified biochar with zinc nitrate hexahydrate Zn(NO3)2.6H2O as catalyst.
2. To optimize parameters (reaction time, methanol to oil molar ratio and
catalyst loading) for transesterfication process by using response surface
method (RSM).
3. To study the composition of Fatty Acid Methyl Ester (FAME) in the
produced biodiesel by using gas chromatography (GC)

1.4 Significance of study

The achievement of the objectives of this research will enhance the commercial
production of biodiesel from UFO. The study of the optimal conditions of the
process will contribute valuable information to the development of low cost, low
energy and fast reaction time with high yield of biodiesel and may also develop
the application of this research method into the large scale of biodiesel
production. Besides, application of RSM in this research will simplify the
experiment by reducing the number of experimental trials in order to evaluate
multiple parameters along with their interactions. RSM also benefits in economic
analysis for this research where it saves time and cost due to the less
experiment trials and less chemical and energy consumptions.

In the other hand, this research also will widen the application of biochar
generated from waste of EFB from palm oil industry as a reliable and low cost

6
heterogeneous catalyst. This study also shows that every waste from palm oil
industry can be utilized to the maximum level as possible and increased the
products that can be commercialized in palm oil industry itself. This research
may also contribute to the improvement and modification of biochar for future
development and further implementation in various science applications.

In term of safety and sustainable environment, this research may

contribute to the reduction of UFO to be disposed into the drainage system and
waterways. Awareness can be instilled within readers to paramount the recycle
of UFO into the biodiesel as it can reduce environmental problems, produce
green and renewable energy and support governmental program to collect UFO
from residential areas at the same time.

1.5 Scope of study

In order to achieve the objectives of the research, several research scopes have
been identified. Analyze of UFO can be done by using analysis standard method
for each properties such as: acid value (ASTM D974), density (ASTM D4052),
saponification value (ASTM D464) and FFA composition (AOCS CD 3D-63).

Transesterification of UFO and optimization of biodiesel production will be

conducted using ultrasonic bath with varying parameter (methanol to oil molar
ratio, catalyst loading and reaction time). Design of experiment will utilize the
used of response surface method as an important optimization tool for biodiesel
production. Biodiesel and glycerol byproduct produced from this reaction will be
separated by using conventional settlement process.

7
 Lastly, the results of biodiesel were subjected to be analyzed by using gas
chromatography-flame ionization detector (GC-FID) to determine the yield of
FAME present in the sample oil.

8
 CHAPTER 2: LITERATURE REVIEW

2.1 Biodiesel

Biodiesel can be defined as all kinds of fuels synthesized from any types of
vegetable oils or fats of animal. Biodiesel can also be referred as an alternative,
renewable, environmental friendly and biological nature diesel fuel where it is
nontoxic, free from aromatics and sulphur and produce cleaner burning fuel in
contrast of conventional diesel fuel that made of petroleum. Biodiesel also found
to be superior to the conventional diesel due to its high flash point, good
lubrication for engine, better cetane number and specific gravity
(Ramachandran, K., 2013).

Biodiesel has the same functions and properties of conventional diesel

which can be used as fuel for cars, trucks and can be blended and mixed with
conventional refined oil. Mixed diesel can be designated as BXX where XX is
the percentage of biodiesel in the blend. For example, B20 diesel containing
20% biodiesel and another 80% is conventional diesel. In addition, no necessary
modification is required for vehicles engines to use biodiesel (Carlos, A. 2011).

9
 A resent research was done by Bharathi et.al., (2016) to determine
emission yield by diesel and biodiesel run engine test using KIRLOSKER TV-I
engine and the biodiesel was made from UFO that had been collected at the
regular cafeteria. The results show positive interaction for both carbon monoxide
(CO) and carbon dioxide emissions (CO2). As for CO emission, B100 was
reported to emit 40% less CO compared to conventional diesel. Meanwhile for
CO2 emission test result shows that CO2 emission is decreased with the
increased in biodiesel blends and at B100 there was 15% less CO 2 emission
was recorded. This experiment has proved that biodiesel is able to perform a
more excellent job in completing the combustion process within the engine
compared to conventional biodiesel.

Other advantage of biodiesel is it has more favorable combustion profile.

Biodiesel has relatively high flash point compared to petroleum diesel, which
make it less volatile and better condition in term of safety and easy to handle
and transport. In addition, it also acts as lubricating agent that maintains engine
performance, reduces wear and longer engine life. Thus with all these prove that
biodiesel make a good alternative to conventional petroleum diesel (Encinar,
Gonzalez, & Rodriguez-Reinares, 2005).

10
 2.1.1 Biodiesel feedstock

Biofuels can be classified into three generations which are first

generation, second generation and third generation. First generation biodiesel
such as biofuel, biogas and bioethanol is made from the main crop of
commodities such as palm oil, starch, sugar and animal fat (Naik, Goud, Rout, &
Dalai, 2010). However first generation biofuels have several disadvantages
related to food-versus-fuel which cause price of foods to arise, disrupting the
carbon balance, consume large amount of land use and water management.

Second generation biofuels made from plant biomass which is

lignocellulosic materials, majority of abundant non-food material or can be
referred as agricultural waste or forestry residue (Köpke et al., 2011).

Third generation biofuel is made of algae which can produce more

diverse products such as biodiesel, butanol, ethanol, gasoline and jet fuel. It also
able to produce a higher yield of biodiesel at lower resource input (K.
Ramachandran, Suganya, Nagendra Gandhi, & Renganathan, 2013).

Feedstock of biodiesel is selected depending on content of the oil and

harvest of the seed that lead to the oil volumes produced per hectare is different
according to the crop.

11
Figure 2. 1 World oil production from major oil crop source from (Woiciechowski
et al., 2016)

Soybean is an important crop that supplies high quality of protean and the
demand of this crop is very high to feed meat animals and vegetable oils. 25%
from total global consumption of soybean is to produce biodiesel while 65% is
for food crop (Araújo, Mahajan, Kerr, & Silva, 2017).

Palm oil can be considered as the prime feedstock for biodiesel but it is
also majorly used for nutritional segments (industrial frying, chocolate,
margarine, pasta, vegetable cream and ice cream) and cosmetic production
(shampoo, skincare products, detergents and soaps). Compared to soybean,
palm produces higher yield of oil per hectare where 10 hectares of oil produced
from soybean crop equal to one hectare oil produced by palm (Araújo et al.,
2017).

Presently, canola or also known as rapeseed also contain high amount of

oil around 38 to 45% and high protein contain. The volume of rapeseed oil
produced worldwide is said to surpass the volume of oil produced by palm and

12
soybean oil. However, biodiesel production from rapeseed oil is costly due to the
high price of the canola oil itself (Araújo et al., 2017).

As for sunflower, it is a highly potential crop for biodiesel production and

also as important as rapeseed. The oil contains within the seeds is very high
about 45% and it is suitable to consume as edible oil due to its excellence
quality. It also contains high amount of protein in range of 28 to 32% (Araújo et
al., 2017).

2.1.2 Used frying oil (UFO)

Used frying oil (UFO) also known as waste cooking oil usually made of
palm oil. UFO if used repeatedly contain high amount of free fatty acid which is
not safe and no longer fit to consume. Figure 2.5 shows that Malaysia itself as
second largest palm oil producer recorded an increasing production of cooking
oil from 586.23 Metric ton in 2015 to 669.89 Metric ton in 2016. Due to the
increasing demand of cooking oil around the world will produce large amount of
waste cooking oil and disposal issues has become a major concern. Table 2.1
shows the quantity of UFO generated in selected country.

13
 Production of cooking oil in Malaysia

Production of Thousand Metric

800
700 669.89
609.67 586.23
Tonnes 600
500
409.5
400
300
200
100
0
2013 2014 2015 2016
Year

Figure 2. 2 Statistic Production of cooking oil in Malaysia (Statista, 2017)

Table 2. 1 Quantity of generated UFO in selected country (Panadare & Rathod,

2015)

Country Quantity (MT/year)

Canada 0.135
European country 0.700-1.000
United Kingdom 0.200
China 4.500
India 0.167
Japan 0.450-0.570
Ireland 0.153

Disposal of UFO from daily consumption without any pretreatment will

lead to various health and environmental problems. It is said that a liter of oil can
pollute up to 500000 liters of water. Oil layers will alter the ecosystem and kill
aquatics life by preventing oxygen change. Besides, disposable of UFO in the
drainage system generates bad odors, congealing of waste and block the sewer
14
pipes which later give rise to health problems due to infection of parasite and
viruses (Carlos ., ndr s, Fabio E., 2011).

Thus, recycle is one of the most effective ways to reduce problems

regarding UFO by converting into biodiesel rather than disposing it into the
drainage and polluting the environment. Other than biodiesel, UFO also can be
used as raw material for many other products such as soaps, additive for bio
lubricant, production of hydrogen gas, generation of electric and raw material for
value added product such as polyurethane (Panadare & Rathod, 2015).

Physical and chemical properties of UFO are usually changed depending

on the frying conditions such as the amount of the reusability of UFO,
temperature and cooking time. During cooking process, Triglyceride tends to
undergo breakdown into Diglyceride, Monoglyceride and FFAs. The amount of
FFA also depends on the amount of water and heat supply during the process
which can enhance the hydrolysis process of Triglyceride. The FFA content in
the UFO will determine the quantity of biodiesel where a very low content of FFA
(less than 0.2) could result in 100% yield of biodiesel (S. Singh, Sumeet, Kundu,
Mohapatra, & Patiala, 2012). Moreover, the matter and heat transfer between
the food and frying oil also cause higher water content. Other than that,
saponification number and viscosity also increased due to the oxidation and
polymerization reactions. Both hydrolysis and saponification process could lead
to the lower yield of biodiesel in the transesterification process and consumed
large amount of catalyst. Thus information on the properties of various sources
of biodiesel becomes basis to decide on investment in biodiesel industry(Zhang,
Dubé, McLean, & Kates, 2003).

15
Table 2. 2 Properties of Used Frying Oil (Ezzah-Mahmudah, Lokman, Saiman, &
Taufiq-Yap, 2016)

Properties of UFO Method Value

Acid Value (AV) ASTM D974 36.8 ± 2.53 mg KOH/g
Density ASTM D4052 900 kg/m3
Saponification Value (SV) ASTM D464 175.93 ± 3.72 mg KOH/g
Mean molecular mass - 956.6 ± 4.5 g/mol
Free fatty acid (FFA)
AOAC 969.33 18.4 ± 1.45
composition
Fatty Acids Formula Composition, wt%
Palmitic acid C16H32O2 43.07
Oleic acid C18H34O2 43.16
Stearic acid C18H36O2 2.70
Linoleic acid C18H32O2 9.54
Myristic acid C14H28O2 1.53

2.2 Biodiesel production method

There are several methods can be used in production of biodiesel that has been
developed by researchers such as direct use and blending, micro emulsion
process, pyrolysis and transesterification process.

16
 Vegetable oil can be directly use without any treatment or process but it is
not favorable as processed biodiesel due to the high viscosity and lower volatility
which later on will cause problems in the long run and some engines need to be
modified before use this type of biofuel (Vivek & Gupta, 2004). At early
application was run by Rudolf Diesel himself using soybean oil to run the engine.
Among the advantages of direct vegetable oil usage are it behaves as liquid in
nature and portability, and has good heating value (80% of diesel fuel). After
long term of used, it is discovered that several problems have occurred such as
trumpet and coking is produced at the injector resulting in difficulties of fuel
atomization, formation of carbon deposits, oil ring sticking and thickening, and
gelling of the vegetable oil after certain period (Vivek & Gupta, 2004).

The definition of micro emulsion is thermodynamically stable, colloidal

equilibrium dispersion of isotropic liquid mixture of oil, surfactant and water. This
method can solve the problem of high viscosity of oil. Alcohols such as methanol
and ethanol are used as additives in lowering the viscosity and as surfactants
and alkyl nitrates is added as cetane improver. However, there are several
disadvantages from using this method such as carbon deposits formation,
injector needle sticking and incomplete combustion process (Gashaw,
Getachew, & Teshita, 2015).

Pyrolysis can be defined as conversion of a substance to another with the

application of heat and can also be known as thermal cracking. This reaction
requires the presence of oxygen or air in relatively high temperature around
450oC (or sometimes catalyst such as silicon oxide SiO2 and aluminium oxide
Al2O3 is used) and cleavage of chemical bond to produce smaller molecules with
properties similar to petrol diesel such as alkanes, alkenes, alkadienes,
carboxylic acid and aromatics in various proportion depending on different path
of reaction (S. Singh et al., 2012). Thus this process has make parolytic

17
chemistry difficult to characterize due to variety reaction paths and products that
might be obtained. In addition, product from pyrolysis need to be further
processed in distillation equipment for separation of various fractions which
requires expensive equipment to complete the process. Besides, it is reported
that fuel from this process contains sulphur which is less environmental friendly
and the removal of oxygen has eliminated the benefit of using oxygenated fuel
(Gashaw et al., 2015).

Transesterification or can be known as alcoholysis is the most common

process to produce biodiesel nowadays. This reaction requires vegetable oil to
react with alcohol to produce fatty acid alkyl ester (FAAE) which is biodiesel and
by product of glycerol with the aid of catalyst to speed up the reaction (Gashaw
et al., 2015).

2.2.1 Transesterification reaction for biodiesel production

Transesterification process is selected to be applied in this research due

to several advantages such as operates at low temperature and pressure,
produces high yield of biodiesel, requires short reaction times, direct conversion
process, simplicity of operation, economic and environmental benign (S. Singh
et al., 2012).

Transesterification reaction process consists of three consecutive

reactions, one molecule of triglyceride will react with three molecules of alcohol
(usually methanol) in the presence of catalyst to produce a mixture of FAAE and
glycerol and the reaction is a reversible reaction thus; higher yields of FAAE can
be achieved by the excess amount of alcohol. The mechanism of the reaction is
shown in Figure 2.2, 2.3 and 2.4. First, Triglycerides will be converted into

18
Diglyceride (DG), Monoglyceride (MG) and lastly glycerol and in each step will
liberate one mole of FAAE (K. Ramachandran et al., 2013).

Figure 2. 3 Conversion of Triglyceride into Diglyceride (K. Ramachandran et al.,

2013)

Figure 2. 4 Conversion of Diglyceride into Monoglyceride (K. Ramachandran et

al., 2013)

19
Figure 2. 5 Conversion of Monoglyceride into Glycerol (K. Ramachandran et al.,
2013)

There are several parameters that have been used by researchers to

study the mechanism and yield efficiency of transesterification reaction process
such as temperature and pressure, reaction time, type of alcohol, molar ratio of
alcohol to oil, type and concentration of catalyst, concentration of moisture and
free fatty acid (FFA) content in oil, mechanical processing method (mechanical
stirrer, microwave, ultrasonic water bath) (Vivek & Gupta, 2004).

To study the optimal conditions of parameters in this research, ultrasonic

catalytic transesterification with parameters of molar ratio of alcohol to oil,
catalyst loading and reaction time have been choose to be evaluated.

2.3 Energy application in biodiesel production

It is not easy to form emulsion from mixing of vegetable oil and methanol
because of their properties that not totally immiscible with each other and poor
mass transfer between these two immiscible phases mixture resulting in
relatively long time of reaction. Thus, it is crucial to provide external energy to

20
initiate and enhance the area contact between these two substances (K.
Ramachandran et al., 2013).

Agitation by mechanical stirring method is a conventional method in

production of biodiesel and quite common in most of the biodiesel process
industry. Homogeneous catalyst such as sodium hydroxide or sodium methylate
is often used to achieve high conversion of biodiesel either in batch or
continuous system and sodium is recovered back after the reaction in form of
sodium methylate, sodium soaps and sodium glycerate (Agustian, 2012).

2.4 Catalyst

Catalyst

Homogeneous Biocatalyst Heterogeneous

Acid Catalyst Base Catalyst Enzyme Based Catalyst

Acid Heterogeneous Base Heterogeneous

Ion Exchange Resin Metal Oxide Based Catalyst

Metal Based Catalyst Carbon Based Group Catalyst

Carbon Based Catalyst Boron Group Based Catalyst

Waste Material Based Catalyst

Figure 2. 6 Figure 2. 7 Conversion of Monoglyceride into Glycerol (K.

Ramachandran et al., 2013)

21
 2.4.1 Homogeneous catalyst

Homogeneous catalyst commonly cause several drawbacks such as

produce high soap formation, difficult to separate and not economic (K.
Ramachandran et al., 2013). Currently, homogeneous base catalyst is
commonly used in most of the biodiesel production industry, such as sodium
hydroxide (NaOH) or potassium hydroxide (KOH). These catalysts have several
advantages such as ability to catalyze transesterification reaction at low
temperature and pressure atmosphere, high conversion rate in short time (4000
times quicker compared to acid catalyst), economical and supply widely
available. However this catalyst is limited for oil with low FFA content (less than
2 wt%) where catalyst has high tendency to produce undesired formation of
soap when react to high amount of FFA (Lam, Lee, & Mohamed, 2010).

Acid catalyzed system is not commonly used in commercial application

due to several drawbacks. Jacobson et al. reported that the used of this type of
catalysts require longer time reaction, high temperature reaction, high alcohol to
oil molar ratio, cause corrosion to equipment and not eco-friendly. (Lam et al.,
2010).

Enzyme application has drawn researchers‘ interest for past several

years to catalyze transesterification. Enzyme such as Lipase is found to be able
to overcome problems caused by chemical catalyst which are high generation of
waste water and difficult to remove glycerol which leads to high cost and not
environmental friendly. In contrast, enzymatic catalyzed transesterification has
the ability to produce no glycerol as by product, simplicity of recovery of
biodiesel, reusable of catalyst and insensitive to FFA content. However there are
still several drawbacks such as expensive price of enzyme, deactivation of
enzyme and long reaction time (Agustian, 2012). A research was done by Chen

22
et al. to produce biodiesel with the application of immobilize R. Oryzae lipase by
a three step batch reactors were used. Stepwise process also was applied to
reduce the effect of poisoning on enzyme by methanol. It is reported that the
optimal conditions for this process are operation temperature of 40oC and
atmospheric pressure, 4:1 molar ratio of methanol to oil and 30 hours reaction
time (Chen, 2006).

2.4.2 Heterogeneous catalyst

To date, many heterogeneous catalysts have been developed in

production of biodiesel due to their ability to catalyze fast reaction, easy
separation from the product and some of the catalyst can be reused and
regenerated. The effectiveness of the process depends on the activity of the
solid catalyst itself and the reaction time and temperature are reduced to a
minimal range (Lam et al., 2010). Heterogeneous catalyst is divided into two
types of catalyst which are heterogeneous acid catalyst and heterogeneous
base catalyst. Heterogeneous base catalyst is found to be more active if
compared to acid catalyst.

Heterogeneous base catalyst, metal oxide group such as calcium oxide,

barium oxide, strontium oxide, magnesium oxide, titanium oxide, zinc oxide,
mixed oxide, zeolites and hydrotalcites are widely studied to enhance
transesterification reaction. On top of that, alkaline metal oxides like MgO, CaO
and SrO are having good characteristics of heterogeneous in nature (K.
Ramachandran et al., 2013). Calcium oxide is the most attractive where it has
high basic strength, mostly available, low solubility in methanol, cost effective
where it can be obtained from cheap source like eggshell, limestone and
calcium hydroxide (Lam et al., 2010). From a research done by Mootabadi, et.
al., (2010) reported that the catalytic activity between CaO, SrO and BrO related

23
to their basic strength and BrO is the most active catalyst followed by SrO and
CaO.

Currently, heterogeneous acid catalyst also found to be a strong potential

to be further developed and replaced liquid acid catalyst. This is because solid
acid catalyst has several advantages such as insensitive to FFA content,
simultaneous occurrence of both esterification and transesterification reactions,
no washing step is needed, catalyst can be separated from reaction zone easily
and highly reusable. There are also several drawbacks of using solid acid
catalyst such as slow reaction rate and produced undesirable side reaction.
Ideal solid acid catalyst is said to have characteristics such as moderate to high
concentration of strong acid cites, interconnected system with large surface of
pores and a hydrophobic surface (Lam et al., 2010).

Ramachandran et al. in his research using Al(HSO4)3 as solid acid

catalyst to synthesize methyl ester from the waste vegetable oil. The result
yields 81 wt% conversion of triglyceride with 50 minutes reaction time at high
temperature of 220oC. The molar ratio of methanol to oil is 16:1 and loading
catalyst of 0.5 wt%. He also stated that the high activity of catalyst was caused
by the strong and high acid site density, hydrophobic site that prevent hydration
of –OH group and hydrophilic functional groups that provide accessibility of
methanol to the triglyceride (Kasirajan Ramachandran, Sivakumar, Suganya, &
Renganathan, 2011).

24
 2.4.3 Biochar as Heterogeneous Acid Catalyst

Biochar can be defined as porous solid and carbon-rich content obtained

from thermal decomposition or pyrolysis of biomass with a little or zero available
air at high temperature in range of 350 to 700oC. This process always mirrors
the charcoal production and biochar also is a type of biocarbon. Biocarbon
usually can be derived by various feedstocks with wide range of carbon
materials such as plant, animal and microbial. Other than pyrolysis, it also can
be produced by other processes such as carbonization, hydrothermal treatment
and gasification (Liu, Jiang, & Yu, 2015).

In past few years, the great potential of biochar in providing versatile and
efficient platform for synthesis of biodiesel as catalyst where biochar has the
advantages to produce high yield of biodiesel, high stability in acidic and basic
conditions, high surface area, low cost and environmental friendly if compared to
other heterogeneous catalyst (Kastner et al., 2012). In this research, biochar
source is utilized from waste of palm oil industry which is empty fruit bunch
(EFB). EFB typically contain 30.5 wt% of lignocellulosic, 2.5 wt% of oil and 67
wt% of water. Table 2.2 shows the major lignocellulosic components in EFB
fibre (Kong, Loh, Bachmann, Rahim, & Salimon, 2014).

Table 2. 3 Major lignocellulosic components in EFB fibre (Hassan & Badri, 2016)

Lignocellulosic components Composition (wt%)

Cellulose 45.0

Hemicellulose 32.8

Lignin 20.5

25
 To date, many researchers actively study the modification of biochar to
bring out full potential of biochar in producing high yield of biodiesel. Recently, a
research done by Ahmad Farid et al., (2017) using biochar from EFB as solid
acid catalyst was calcined with potassium phosphate tri-basic (K3PO4) with
surface area of 680 m2/g and basicity amount of 11.21 mmol/g had produced
high yield of biodiesel, 98% F ME‘s yield. The minimum conditions of parameter
of the research are 12:1 methanol to oil molar ratio, 5 wt% of catalyst loading at
temperature of 60oC and 4 hours reaction time using conventional magnetic
stirring method.

Generally the researchers focused on the modification of biochar catalyst

based on various parameters that might give significant catalyzing effect on the
reaction such as the surface area, volume of porosity, ash value, functional
group that attached to the surface of catalyst, thermal degradation, bulk density,
pH value, and reusability of the catalyst. With the aid of proper reliable
instruments, various biochar modifications have been widely studied such as
acid and base treatment, surfactant modification, steam activation, impregnation
of mineral sorbent, amination and magnetic modification (Rajapaksha et al.,
2016). The focus of this study is to enhance the production of biodiesel yield by
introducing heterogeneous metal catalyst which is zinc nitrate hexahydrate into
the transesterification reaction system-which could possibly become an acid or
basic catalyst. According to Vinh (2014) stated that impregnation of biochar with
zinc nitrate had significantly improve the pore structure by 42.8% of increment in
surface area and adsorption capacity of the biochar from 5.7 to 7.0 µg g-1.

26
2.5 Glycerol

Glycerol is the main byproduct of transesterification of biodiesel. It is a sugar

alcohol; contain three carbon atoms that bonded together with three hydroxyl
groups. It is also hygroscopic, which is absorb and soluble in water. The melting
point is at 17.8oC and the boiling point is at 290oC, and is viscous. During late in
19th century, before biodiesel production was produced at large scale, glycerol
was produced at large scale as byproduct of soap, fatty acid and fatty alcohol
which cause the price of glycerol to drop and overly supply in 2010 (Shattuck &
Jacobsen, 2014). Thus, it is important to study more on glycerol and develop it
into more valuable side product that can be sold as profit.

2.6 Respose surface methodology as a tool for optimization

Response Surface Methodology (RSM) is a method that applies the combination

of experimental design and statistical techniques in order to optimize problem.
RSM offers multiple techniques to map responses with multidimensional
patterns in order to verify control factors and govern physical processes. With
the application of regression analysis on experiment‘s data, which later can be
used to determine minimum and maximum in response patterns with the
optimum are within the design space of the regressed point (Nagendra, n.d.).

In this project, RSM was applied to optimize the heterogeneous-catalyzed

transesterification with highest yield of biodiesel as a function of three factors
which are catalyst loading, methanol to oil molar ratio and reaction time.

27
 CHAPTER 3: METHODOLOGY

3.1 Introduction
In this chapter, the methodology of the transesterification process of biodiesel
production will be discussed in detail including the procedure, all the equipments
and chemicals involved.

Used frying oil collection

Heterogeneous biochar
solid base catalyst
preparation Used frying oil analysis

Heterogeneous biochar
solid base catalyst and FFA content <3% No Pretreatment
methanol mixing process

Yes

Transesterification process

Optimization of biodiesel
production by using RSM

Obtaining biodiesel and

glycerol

Separation and
Glycerol as byproduct
centrifugation

Biodiesel as product

Analysis of biodiesel

Figure 3. 1 Process block diagram of biodiesel production

28
3.2 Preparation and pretreatment of used frying oil

Used frying oil as raw material for this research was collected at the cafeteria of
UniKL MICET as in Figure 3.2. The type of cooking oil is palm oil which is
common among Malaysian. The UFO that has been collected was used to cook
fried chicken where the oil was used one times only to ensure low FFA value of
the oil. The collected oil was placed within the recycled plastic bottle with tightly
enclosed closure to prevent moisture content to increase.

Filtration process was done to remove flour waste, solid particle, organic
material and contaminants in UFO. The UFO first was heated up to 110oC in
order to remove water content, homogenize and lower the viscosity of UFO and
enhanced filtration process. By using filter paper as filtering medium, UFO
sample was poured on it and purified UFO was collected and placed in a clean
reagent bottle.

Figure 3. 2 Used frying oil collected

29
3.3 Analysis of used frying oil

After filtration process is done, the filtered UFO underwent analysis process to
determine its properties. In this study, several characteristics and properties
were determined experimentally.

3.3.1 Acid Value and FFA content

To determine acid value in UFO, 10 g sample of oil was weighted using

analytical balance and placed in clean conical flask. Then the oil sample was
dissolved and refluxed with 50 mL of ethanol for about 5 minutes in hot water
bath in order for hydrolysis process to occur. Then 1 mL of phenolphthalein was
added into the solution before being titrated with 0.1 N of ethanolic KOH. The
volume of alcoholic KOH used for the titration was recorded and acid value of
the UFO was calculated using equation 3.1. Then by using equation 3.2, FFA
value was calculated.

Acid Value (AV) = (3.1)

Where, T = titration volume (mL)

N = Normality of KOH solution (g/mol)

W = Weight of oil sample (g)

( )
( ) (3.2)

30
 3.3.2 Saponification value (SV)

Saponification process is a process of conversion of triglicerols into

glycerols and potassium salt of fatty acid which also can be known as soap.
Saponification value (SV) can be determined with titration method. 1 g of oil
sample was weighted and placed in a conical flask. 25 mL of 0.1M of alcoholic
was added into the sample and a blank sample also was prepared without
contain oil sample. Both of the flasks were refluxed in boiling water bath for
about 30 minutes. The refluxed solutions were left to be cooled at room
temperature. 1 mL of phenolphthalein indicator was added in each of the
solutions before being titrated with 0.5M of hydrochloric acid until the pink color
of indicator disappeared. The volumes of HCl used to titrate for both blank and
sample solution were recorded and SV value was calculated using equation 3.3
as follows.

( )
Saponification Value (SV) (mgKOH/g) = (3.3)

Where, B = Blank titration volume (mL)

T = Oil sample titration volume, (mL)

W = Weight of oil sample, (g)

Figure 3. 3 Saponification test

31
 3.3.3 Average molecular weight of used frying oil and biodiesel
Average molecular weight of UFO can be obtained from Equation 3.4

Average molecular weight,

M = 56.1 ×1000 × 3 / ( SV – AV ) (3.4)

Where,

SV: Saponification value (mg KOH/g)

AV: Acid Value (mg KOH/g), (Huaping et al., 2006)

After the average molecular weight of UFO was obtained, average

molecular weight of biodiesel from UFO also can be calculated by using
equation 3.5

( )
(3.5)

3.3.4 Density of used frying oil

Mass of empty 25 mL volumetric flask was measure by using analytical

balance. Then filtered UFO was placed in the flask until reach the indicated
mark and the mass of flask and the oil was weighted again and the value was
recorded. The mass of the 25 mL oil is then can be calculated using Equation
3.6 and 3.7.

Msample = M1 – M0 (3.6)

Where, Msample = mass of 25 mL UFO

M1 = mass of volumetric flask and UFO

M0 = mass of empty volumetric flask

32
 Density of oil is then can be calculated straightly by dividing the
mass of sample with volume of the oil as in Equation 3.5

(3.7)

Where, = Density of oil (g/mL)

M sample = mass of 25 mL UFO (g)

V oil = Volume of oil, 25mL

3.4 Modification of catalyst

3.4.1 Impregnated of Zn – loaded biochar

1 M of zinc nitrate hexahydrate Zn(NO3)2.6H2O was prepared by diluting

59.5 g of the Zn(NO3)2.6H2O crystalline powder into 200 ml of distilled water.
Solution was stirred by using magnetic stirrer to dissolve the solid particle of
Zn(NO3)2.6H2O completely.

Modification of biochar impregnated with zinc nitrate hexahydrate

Zn(NO3)2.6H2O was prepared by placing 10 g of biochar into a flask and mixed
together with the solution. The mixture was stirred by using magnetic stirrer for
about 24 h at room temperature (25oC) to provide more surfaces in contact
between biochar surface and the solution. Then the Zn–loaded biochar was
subjected to filtration proses by using filter paper as in Figure 3.4 and was dried
in an oven overnight at temperature of 110 oC to remove moisture content. Then
the Zn–loaded biochar was stored within tight end closed container to ensure
there is no contamination and moisture content preservation.
33
 Figure 3. 4 Filtration of modified biochar catalyst

3.4.2 Characterization of Zn – loaded biochar

Zn–loaded biochar underwent characterization process to study the effect

of impregnated on the biochar. Thermo-gravimetric (TG/DTA) analyzer was
used to observe the thermal stability of the modified biochar in which the
biochar‘s samples weight lost were recorded to be evaluated. Then the modified
biochar was subjected to the functional group analysis which was conducted by
using a Fourier transform infrared spectrometer (FTIR)over 600 – 4000 cm-1
using the KBr pallet technique.

34
3.5 Biodiesel production by using Zn - loaded biochar as catalyst

After the catalyst is ready to be used, experimental setup for biodiesel

production was prepared where several essential equipments such as hot plate,
magnetic stirrer and condenser. The experiment was setup as in Figure 3.5.

Figure 3. 5 Experimental set up for transesterification of biodiesel

By referring to the designed experiment constructed using response

surface methodology, optimization experiments were carried out in batch
condition within the 100 mL conical flask mounted with condenser on the top of
the flask supported by the retort stand. The condenser functions to reduce the
evaporating rate of methanol as lowest as possible. The temperature of every
run of experiments is controlled within range of 50 to 60oC below the boiling
point of methanol which is 65oC where thermometer was used to observe the
35
temperature changes within the reaction system. There were also several
parameters other than temperature, that have been kept constant during
running the experiment such as the volume of UFO sample used and the speed
rotation of magnetic stirrer to provide mechanical force.

The designed experiments composed of three different controlling

parameters that need to be studied which are reaction time, methanol to oil
molar ratio and amount of catalyst used. As for methanol to oil molar ratio, the
amount of methanol that will be used for each run was calculated because the
volume of oil sample remain unchanged. The molecular weight of UFO obtained
from equation 3.4 was used to determine the molarity of UFO and from that the
volume of methanol needed for the experiment was calculated
stoichiometrically. Meanwhile, the weight of Zn–loaded biochar catalyst for each
run was calculated based on the weight of the ufo sample used.

The experiment started with heating of 10 mL of UFO within the conical

flask until the temperature is within range of 50 to 60 oC. Then the catalyst and
methanol with the desired value were mixed together before being placed in the
reactor for the main reaction to happen with the desired reaction time. The
magnetic stirrer was put in the reactor the stirring process started right after all
the solutions are mixed together.

After the reaction finished, the mixture product was centrifuged for 10
minutes at 4000 rpm in order to separate the catalyst from biodiesel solution.
Then, the product is placed in the separation funnel for at least 8 hours to form
two separated layers of product and by-product. Biodiesel accumulated at the
bottom of the separation funnel was placed in a beaker and the excess
methanol and glycerol by product were placed in other beaker. Then 10 to 20

36
mL of distilled water was added for washing purpose to purify the biodiesel and
the beaker was swirled several times before being placed again within the
separation funnel to let the water settle. After several hours, the layer of water
was removed and the purified biodiesel was collected and heated to remove the
water residual within temperature range from 100 to 110oC for 6 hours.

Before excess methanol and glycerol are removed, the beaker was
weighted first using analytical balance. Then excess methanol and glycerol were
placed within the beaker and the solution was heated within the water bath at
65oC in order to evaporate the excess alcohol. The process was done after 30 to
one hour when the entire excess of methanol was removed completely and
viscous brownish liquid that remain which is glycerol. Then the beaker with the
glycerol was weighted again and the mass of glycerol was calculated and
recorded.

The yield of biodiesel was calculated based on the amount of glycerol

that can be extracted. With the stoichiometry relation, the amount of biodiesel
produced was estimated in which if there is 1 mole of glycerol produced, there
will be 3 mole of biodiesel produced.

1 mole of glycerol produced Ξ 3 mole of biodiesel

Then the mass of biodiesel was calculated by multiplying the mole

of biodiesel with the biodiesel molar mass obtained from equation 3.5, the yield
of FAME is then calculated using the Equation 3.8:

%yield of FAME = (3.8)

37
Where,

MFAME = mass of FAME

M UFO = mass of used frying oil

Glycerol and
access methanol

Biodiesel

Figure 3. 6 Product of transesterification process

Figure 3. 7 Washing process

38
3.6 Analysis of biodiesel

Gas chromatography-flame ionization detector (GC-FID) equipped with Quadrex

007-FFAP GC Column is used to analyze the FAME composition of the purified
biodiesel. Helium gas is used as carrier gas move at flow rate of 1 mL/min. The
GC column is then maintained at 180oC for duration of 1 minute. Then it will be
heated up to 240oC at rate of 10oC/min. The temperature of detector and injector
will be set at 250oC.

Then, the sample of biodiesel product from experiment can be prepared

to be injected into the GC. 0.5 g of the biodiesel sample is diluted into 5 ml of n-
hexane solvent. Then, 1 µL of this mixture solution is injected into the GC and
the composition of FAME can be obtained.

3.7 Design of experiment

In this study, Design Expert Software (version 11.0.4.0) was used in order to
design the experiment and to optimize the reaction variables. A central
Composite Design (CCD) is the experimental design applied in this work with a
two-level-three-factor which including 20 experiments. Three independent
variables ware selected for optimization study which were methanol to oil molar
ratio as A, catalyst loading as B, and reaction time as C where the experimental
range and levels of each independent variables can be seen in Table 1. The
response was the percentage yield of FAME from transesterification of used
frying oil. The response function was analyzed using regression analysis as a
second order polynomial.

39
 ∑ ∑ ∑ ∑

From the equation, Y is the predicted response, ẞo is the offset term, ẞi

represent the linear coefficient, ẞii represent quadratic coefficient and ẞij is the
interaction coefficient meanwhile Xi and Xj are the independent variable.

Table 3. 1 Independent variables and level used for experimental design

Independent Range of response

variables -1 0 +1
Methanol to oil
6.0:1 10.5:1 15:1
molar ratio
Catalyst loading,
0.5 1.0 1.5
w/w%
Reaction time,
180 270 360
min

3.8 Project management

In EFYP2, all the experiments to optimize biodiesel production were done and
the findings were discussed in chapter 4. Table 3.2 is the Gantt chart of time
duration to complete the research

40
Table 3. 2 Gantt chart for EFYP2

FINAL YEAR PROJECT 2

Month January February March April May

Item/Week 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17
Submission and approval
of JSA form
Analysis of UFO
Literature Review
Exp 1: Controlled
parameters
Exp2: Optimization of
experiment by RSM (36
trials)
Exp5: Optimized
parameters
Analysis of result and
Discussion
Report Writing
Submission of 1st report's
draft
Submission of final report
Presentation
Correction and submission
of final report

41
3.8 Financial

All the expanses that were spent to carry out the research were summarized in
Table 3.3. All chemicals such as methanol, hydrochloric acid, potassium
hydroxide, phenolphthalein, n-hexane and etc that have been used throughout
the research were already available from the university‘s inventory and all the
technologies and utility available in the university were fully utilized after
obtained permissions from technicians and lecturers. Zinc nitrate hexahydrate
was supplied from Sigma-Aldrich and the appliances such as dropper and test
tubes were obtained from Lazada.com.

Table 3. 3 Financial budget

Cost Price
Item Cost per Unit RM Quantity OUM
RM
Variable cost
Zinc Nitrate Hexahydrate 397.50 500 g 500 g 397.50
Test tubes 30 pcs 20.50 30 pcs 20.50 20.50
Dropper 100 pcs 10.00 100 pcs 10.00 10.00
Total cost .428.00

42
 CHAPTER 4: RESULT AND DISCUSSION

4.1 Analysis of UFO sample

Based on the analyses that have been done on the UFO sample, the
characteristic can be seen in table 3.1.

Table 4. 1 Characteristics of used frying oil

Type of analyses Value Unit

Acid value 1.009 mg KOH/g
Saponification value 171 mg KOH/g
FFA content 0.5 %
Density 0.878 g/ml
Average molecular
990 g/mol
weight of used frying oil
Averahe molecular
270 g/mol
weight of biodiesel

43
 Acid number can be defined as the quantity of base, expressed in term of
mass milligrams of potassium hydroxide per gram of sample that is needed to
neutralize or titrate a sample to a specified end point(Chamber, 2005). Based on
the result obtained, the value of acid within the UFO is 1.009 mg KOH/g which is
low that indicates that there is small amount of carboxylic acid group in within
the sample such as free fatty acid (FFA). Low FFA value which is 0.5% is good
enough for the UFO sample to straightly to be converted into biodiesel through
transesterification reaction without going through pretreatment process. This is
because high FFA value will hinder the conversion process by generating
moisture thus lower the biodiesel production.

The saponification value can be defined as the milligrams of potassium

hydroxide (KOH) required to saponify 1g of fat. It also indicates the amount of
saponifiable compound (acyl groups) in the UFO. The SV value obtained from
the titration method is considered as low which is 171 mg KOH/g closely related
If compared with the SV obtained by Ezzah et all (2016) which is 175 mg
KOH/g. The low SV is due to the predominantly high proportion of longer carbon
chain lengths of fatty acid which indicates that UFO sample contain less
glycerides molecules per gram of fat and this will resulting in higher molecular
weight of desirable triacylglycerol in oil sample (Odoom & Edusei, 2015).

44
4.2 Characterization of Zn – loaded biochar catalyst

4.2.1 TGA analysis

The modified biochar with zinc nitrate hexahydrate and unmodified

biochar were analyzed with thermal gravimetric analysis (TGA-DTG) to identify
the thermal stability of the catalysts.

The difference of thermal degradation steps between these two catalysts

can be observed on Figure 4.1 and 4.2. The pattern for decomposition in figure
4.1 shows three stages same goes to figure 4.2. At the early stage of
decomposition, unmodified catalyst showed relatively small changes in weight
loss at temperature range of 50oC to 116oC meanwhile modified catalyst
showed a significant weight lost at temperature range of 50oC to 200oC. This is
due to the removal of water content that present on the surface of the catalysts.

At temperature range of 250oC until 506oC, modified catalyst showed a

major weight loss (11.39 wt%) with the peak around 307oC which correspond to
the present of zinc nitrate which significantly affects the main degradation
mechanism of the biochar and also means that unmodified biochar has lower
degradation rate if compared to modified biochar (Mayer, Apfelbacher, &
Hornung, n.d.). From 500oC onwards, both modified and unmodified biochar
showed a steady gradual loss of weight loss which indicates that decomposition
of carbon structure. From the decomposition analysis, modified biochar lost
about 24.27% of total weight loss meanwhile unmodified biochar loss 14.62% of
its overall weight. This indicates that modified biochar contains more surface
area that in contact with the flame to undergo complete combustion compared to
unmodified biochar.

45
 Figure 4. 1 TGA analysis of unmodified biochar

Figure 4. 2 TGA analysis of modified biochar with Zn(NO3)2.6H2O

46
 4.2.2 FTIR analysis

Information on the structural of the modified and unmodified biochar were

obtained from FT-IR analysis by using KBr pallet techniques due to the solid
powder form of the samples. From the result obtained in figure 4.3, the first
broad band was identified between 3700 cm -1 and 3000 cm-1 with maximum
peak of 3421.35 cm-1which corresponds to the stretching vibration of O-H
carboxylic functional groups (Mayer et al., n.d.). Medium peak was observed at
2364.79 cm-1 which indicates the presence of alkyne functional group. Strong
stretching band was observed between 1600 cm-1 and 1500 cm-1 with the
maximum peak of 1559.38 cm-1 which represent the aromatic functional group.
The stretching band of C-N and the N-H can be observed at peak between 1350
cm-1 and 1000 cm-1 and finally the peak of C-Hn bond ban be identiat at the peak
between 900 cm-1 and 800 cm-1 (Vinh, Zafar, & Behera, 2014).

Figure 4. 3 FT-IR analysis for modified biochar with Zn(NO3)2.6H2O

47
4.3 Optimization of biodiesel production

4.3.1 Regression model equation

The relation between the independents variables and the response which
is percentage yield of Fame was evaluated using the CCD technique. The
independent variables are methanol to oil molar ratio denoted as A, catalyst
loading as B, and reaction time as C and the predicted model for percentage
yield of FAME (Y) in terms of the coded factors can be seen in equation 4.1

( )

(4.1)

The equation in terms of coded factors can be used to make predictions

about the response for given levels of each factor. By default, the high levels of
the factors are coded as +1 and the low levels are coded as -1. The coded
equation is useful for identifying the relative impact of the factors by comparing
the factor coefficients.

20 experiments were performed to get the experimental values of FAMEs

yield. Experimental and predicted values for FAMEs yield responses at the
design points was tabulated on Table 4.2. Experimentally, maximum FAMEs
yield which is 86.89% was recorded. A variation of 1.5% was observed between
experimental maximum and predicted maximum yield which is within the
acceptable variation between experimental and theoretical value.

48
Figure 4. 4 Actual against predicted plot

49
Table 4. 2 Full factorial central composite design matrix for biodiesel production

Catalyst Reaction time FAME Yield %

Run X1 X2 X3 MeOH/Oil ratio
loading (w/w%) (min) Experimental Predicted
1 0 0 0 10.5 1 270 65.2 65.22
2 0 0 +1.68 10.5 1 421 86.89 85.59
3 -1 +1 -1 6 1.5 180 31.9 31.50
4 -1 -1 +1 6 0.5 360 38.48 41.88
5 +1 +1 +1 15 1.5 360 66.93 100.00
6 0 0 0 10.5 1 270 60.85 65.22
7 0 0 0 10.5 1 270 57.00 65.22
8 -1 +1 +1 6 1.5 360 41.45 40.18
9 +1.68 0 0 18.1 1 270 56.47 60.00
10 +1 -1 +1 15 0.5 360 70.10 68.66
11 +1 +1 -1 15 1.5 180 39.21 33.96
12 0 0 0 10.5 1 270 63.00 65.22
13 0 +1.68 0 10.5 1.84 270 45.76 48.99
14 +1 -1 -1 15 0.5 180 28.80 28.22
15 -1 -1 -1 6 0.5 180 69.37 67.52

50
16 0 0 -1.68 10.5 1 118 40.32 44.33
17 -1.68 0 0 2.9 1 270 36.04 35.44
18 0 0 0 10.5 1 270 73.54 65.22
19 0 -1.68 0 10.5 0.16 270 46.24 45.60
20 0 0 0 10.5 1 270 72.12 65.22

51
 4.3.2 Anova

Table 4. 3 Analysis of variance (ANOVA) for the quadratic polynomial model

Sum of Mean
Source DF F-value p-value
squares square
Model 4638.27 9 515.36 15.70 0.0002 significant
A-MeOH/Oil ratio 599.22 1 599.22 18.26 0.0021
B-Catalyst loading 11.29 1 11.29 0.3441 0.5719
C-Reaction time 1686.39 1 1686.39 51.39 < 0.0001
AB 632.68 1 632.68 19.28 0.0017
AC 1583.57 1 1583.57 48.25 < 0.0001
BC 427.34 1 427.34 13.02 0.0057
A² 544.48 1 544.48 16.59 0.0028
B² 561.29 1 561.29 17.10 0.0025
C² 0.1218 1 0.1218 0.0037 0.9528
Residual 295.37 9 32.82
not
Lack of Fit 86.96 4 21.74 0.5216 0.7260 significant
Pure Error 208.40 5 41.68
Cor Total 4933.64 18

Table 4. 4 Fit statistics

Standard deviation 5.73

Mean 53.83
Coefficient of variation (CV%) 10.64
R2 0.9401
Adjusted R2 0.8803
2
Predicted R 0.7417
Adequate precision 13.7973

52
 The ANOVA for the regression model presented in Table 4.3 shows that
the model fit in evaluating the relationship between the response (biodiesel
yield) and the variables. This model employed a high f-value and low p-value.
The Model f-value of 15.70 implies the model is significant. This also implies that
most of the variations in the responses can be evaluated by the model‘s
equation and there is only a 0.02% chance that an f-value this large could occur
due to noise. p-values less than 0.0500 indicate model terms are significant. In
this case A, C, AB, AC, BC, A², B² are significant model terms. The lack of it f-
value of 0.52 implies the lack of fit is not significant relative to the pure error.
There is a 72.60% chance that a lack of fit f-value this large could occur due to
noise and non-significant lack of fit is good. Result experimental of run number 5
was ignored during the determination of p-value of the model due to the large
difference in term of standard error with the predicted value. Meanwhile, from
Table 4.4, it can be seen that the value of regression coefficient R 2 is 0.9401
which means that 94% of the experimental data are compatible with the model‘s
predicted data which also indicates that the model is good in term of fitness. The
Predicted R² of 0.7417 is in reasonable agreement with the Adjusted R² of
0.8803.

Besides, coefficient of variation is also low which is desirable and

indicates that the fitted model is reliable. Adequate precision measures the
signal to noise ratio. A ratio greater than 4 is desirable. The ratio of 13.797
obtained in the table indicates an adequate signal. This model can be used to
navigate the design space.

53
4.4 Effect of variables on the yield of biodiesel

The combine effects of the parameters on the biodiesel yield were studied by
plotting 3D surface curves. The curve will show the interactive effects of any two
independent variables while the other variable is kept at their zero/central level.

4.4.1 Effect of molar ratio and catalyst loading on biodiesel yield

Based on figure 4.5, it can be seen that reaction time 270 minutes, the
highest biodiesel yield can be obtained is 72% at highest methanol to oil molar
ratio (15:1) and highest catalyst loading (1.5%). This indicates that as the
methanol to oil molar ratio and catalyst loading increase will cause the biodiesel
yield also increases. This can conclude that the biodiesel yield is significantly
affected by the mass transfer between catalyst and reactant. When the amount
of methanol is excess will balance the viscosity of the reaction mixture with high
amount of catalyst loading. It also can enhance the transesterification process
and promote the forward reaction of the process and able to extract the methyl
ester and glycerin from the surface of catalyst and renew it for next molecules to
react(Yan, Lu, & Liang, 2008). In addition, Ezzah Mahmudah (2016) stated that
the increasing of catalyst will cause the number of sites for the reaction to take
place.

Meanwhile the lowest yield of biodiesel can be observed when the

catalyst loading is at the highest value (1.5%) and ratio is at the lowest value
(6:1). This is because of the influence of the mass transfer resistance that the
catalyst caused on the boundary between the methanol and oil phases (El-
gendy, Deriase, Hamdy, & Abdallah, 2015). This is also because when the
catalyst amount is too high, will cause the reaction solution to be more viscous.

54
According to El-gendy et al. (2015), the viscous condition also is a factor that
can affect reaction rate to be decrease and consequently cause decrease in
biodiesel yield. This statement also supported by Ezzah Mahmudah (2016) in
which other than causing the reaction solution to be more viscous, access
catalyst also cause the agglomeration effect on the system which can be
observed by naked eyes.

55
Figure 4. 5 Effect of methanol to oil molar ratio and catalyst loading at reaction time 270 minutes

56
 4.4.2 Effect of molar ratio and reaction time on biodiesel yield

Figure 4.6 shows the biodiesel yield as a function of methanol to oil ratio
and reaction time at constant catalyst loading (1%). Under such condition, it can
be seen that as increasing in both factor would increase the biodiesel yield in
which the highest yield (94%) is observe at the highest molar ratio (15:1) and
reaction time (360). And it is also possible to observe that the yield can be
increase further at higher methanol to oil molar ratio and reaction time. The
lowest yield can be observed at the highest methanol to oil molar ratio and
lowest reaction time 180 minute.

As the time reaction and molar ratio increase, biodiesel yield also
increase to a certain limit. This is due to the variation of reaction order that might
exist during the reaction progressed. At early stage, the reaction only happens
at the boundary between methanol and oil where the reaction rate might be zero
order reaction with respect to oil concentration. Then increasing in reaction time
and molar ratio caused the miscibility in the reaction mixture to increase and
also cause the reaction shifts its rate into first order kinetic (El-gendy et al.,
2015).

In addition, there was almost no interaction between molar ratio and

reaction time if molar ratio is set at lowest value (6:1). Meanwhile if reaction time
is set at lowest period (180 minutes), the response shows decrease in biodiesel
yield as the molar ratio increase. According to Nour et al. (2015) stated that the
decreasing in biodiesel yield might be caused by the dilution effect of catalyst
and reactant.

57
Figure 4. 6 Effect of methanol to oil molar ratio and reaction time at catalyst loading 1

58
 4.4.3 Effect of catalyst loading and reaction time on biodiesel yield

Figure 4.7 shows biodiesel yield respond on interactive factors of reaction

time and catalyst loading at constant methanol to oil molar ratio (10.5). The yield
of biodiesel that has been observed is increasing as reaction time and catalyst
loading increase and the highest yield of biodiesel (80%) is predicted at highest
reaction time (360min) and catalyst loading (1.5). this can conclude that the
combination of these two factors give significance effect to the response in
which can be seen at the contour figure where more than 80% yield could be
generated at high levels.

From the contour figure, it can be seen that when reaction time is set at
the lowest value (180 minutes), the biodiesel yield is improved as the amount of
catalyst increase of 0.5% to 1% and from that moment it then reduced from
1.1% to 1.5%. The yield is maximum at 1% catalyst loading which shows that
even if excess catalyst loading might enhance the yield of biodiesel but a further
increase in catalyst absorption will deter the transesterification process. This is
due to the multiple phase system where the high of catalyst amount will become
resistance to the process (Lee, Yunus, Juan, & Tau, 2011). This effect also was
explained briefly in section 4.4.2 where the effect of access catalyst caused the
reaction solution to be more viscous and agglomeration effect within the system.

59
Figure 4. 7 Effect of catalyst loading and reaction time at methanol to oil molar ratio of 10.5

60
 4.4.4 Optimization values for transesterification process

For this study, the optimum conditions for transesterification process was
determined from the response surface plot in which the coordinate of stationary
central point is located at the highest contour levels in each plots of variables
which corresponds to its optimum values. From this study, the optimum
condition of each variables are presented tn table 4.5. Based on the optimum
value, the highest biodiesel yield can be obtained is 93.42%. From Figure 4.10
shows the peturbation plot for all variables which explains how the yield of
biodiesel changes at optimum values as reference point.

In order to confirm the optimum value, experiments were conducted by

using the optimum values of parameters and the result from the experimental
vaue obtained was 89.93% with standard error of 3.74%. This can conclude that
the model is reliable and correctly describes the effect of process variable on the
biodiesel production from ufo.

Table 4. 5 Optimum value for transesterification of ufo using Zn-loaded biochar

as catalyst

Variables Optimum value

Methanol to oil molar ratio 14.6
Catalyst loading (%) 1.04
Reaction time (min) 354
Biodiesel yield % 93.42%

61
Figure 4. 8 Ramp function graph of desirability for optimization of biodiesel
production

62
Figure 4. 9 Dimentional and contour plot for optimum values for transesterification reaction

63
Figure 4. 10 Pertubation plot for optimum values of variables at optimum value

64
4.5 Effects of modified and unmodified catalyst on biodiesel production at
optimum values of parameter

In order to describe the effect of modification of catalyst on biodiesel production,

experiments were done by using both modified Zn-loaded biochar and raw
unmodified biochar as catalyst. From the experiment, the result was presented
on table 4.6 where the yield of biodiesel produced from unmodified biochar is
84.54% which is lower than modified biochar (89.93%). This revealed that
modified biochar with Zn(NO3)2.6H2O shows significant effect on biodiesel
production where the production yield of biodiesel recorded yield increment of
6%.

According to a research (Vinh, Zafar, & Behera, 2014), the modification of

biochar impregnated by zinc nitrate hexahydrate will cause the alteration of the
surface area of the biochar. The comparisons of modified and unmodified
biochar like stated from the research are modified biochar has higher in term of
bulk density, ash value (wt%), fixed carbon, surface area and micropore volume
and has a lesser value in term of moisture content and volatile matter. Lokman
I.M. (2014) in his research stated that in term of biodiesel application, the
improvement of the catalyst with increment in surface area and larger pores
catalyst will increase the rate of reaction due to increasing in number of active
sites and easy access of the reactant to attach to the active sites of the catalyst.

65
Table 4. 6 Biodiesel production by using modified and unmodified biochar as
catalyst

Catalyst Methanol to Catalyst Reaction Yield of

oil ratio loading time (min) FAME
(w/w%) (%)
Unmodified biochar 14.6 1.04 354 84.54
Modified biochar with
14.6 1.04 354 89.93
Zn(NO3)2.6H2O

4.6 Analysis of biodiesel

The optimum condition (MeOH/oil:14.6, 1.04% catalyst loading & 354 minutes
reaction time) of biodiesel production was analyzed using gas chromatography
with flame ionization detector (GC-FID) to determine the methyl esters that
present in the biodiesel. From the result obtained, there were five types of FAME
components were identified which is methyl myristate, methyl palmitate, methy
stearate, methyl oleate and methyl linoleate which can be seen in table 4.7.

Table 4. 7 Composition of methyl ester present in biodiesel

Composition Retention time

Methyl Ester Formula
(wt%) (min)
Methyl Myristate C15H30O2 9.05 1.928
Methyl Palmitate C17H34O2 3.88 2.771
Methyl Stearate C19H38O2 81.90 4.168
Methyl Oleate C19H36O2 4.31 4.391
Methyl linoleate C19H34O2 0.86 5.929

66
Figure 4. 11 GC-FID chromatograms of optimized biodiesel production

67
 CHAPTER 5: CONCLUSION AND RECOMMENDATION

5.1 Conclusion

In conclusion, the production of biodiesel was conducted and optimized using

modified biochar impregnated with zinc nitrate hexahydrate (Zn(NO 3)2.6H2O)
and response surface methodology (RSM) as optimization tool. The optimum
values of variable for the production of biodiesel were found to be 14.6:1
methanol to oil molar ratio, 1.04 wt% catalyst loading and 354 minutes reaction
time with the highest yield of biodiesel which is 89.93%. There were five types of
methyl ester that can be found in the analysis of biodiesel content using GC-FID
and the composition of methyl stereate is found to be the highest (81.9%),
methyl myristate (9.05%), methyl oleate (4.31%), methyl palmitate (3.88%) and
methyl linoleate (0.86%). It can be conclude that impregnated of Zn(NO3)2.6H2O
on biochar as catalyst of transesterification process gives significant enhance in
biodiesel production yield.

68
5.2 Recommendation

As for future work, improvement on the study of the topic should should be
extended and include more analytical test on UFO and biodiesel such as iodine
value, cetane number, cloud and pour point, flash point and sulfur content so
that the quality of the biodiesel produced can be compared to the conventional
diesel and the standard biodiesel guideline in Malaysia.

The properties of the modified biochar also should be further investigate

such as the surface area, pores volume, structure, morphological study by
utilizing respected technology such as Brunauer-Emmett-Teller (BET) analysis
and scanning electron microscopy (SEM).

69
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 APPENDIX A: Analysis of UFO

Acid Value and FFA% content

( )

( )

( )
( )

( )

Saponification value

( )
( )( )

Based on experiment,

Titration of ufo volume = 17.30 ml

Blank volume = 23.40 ml

( )
( )( )

Average molecular weight of ufo

76
Average molecular weight of biodiesel

( )

( )

Density of oil

77
 APPENDIX B: Optimization Experimental Data

Tabulated experimental data for optimization of biodiesel production

Run Mass of
Mass Mass
glycerol Mass of Mass of Yield of
of Mole of Mole of of ufo
and glycerol biodiesel biodiesel
beaker glycerol biodiesel sample
beaker (g) (g) (%)
(g) (g)
(g)
1 15.195 15.8458 0.6508 0.0071 0.0212 5.725 8.780 65.20
2 15.189 16.0563 0.8673 0.0094 0.0283 7.629 8.780 86.89
3 15.198 15.5164 0.3184 0.0035 0.0104 2.801 8.780 31.90
4 15.195 15.5791 0.3841 0.0042 0.0125 3.379 8.780 38.48
5 15.200 15.8681 0.6681 0.0073 0.0218 5.876 8.780 66.93
6 15.194 15.8014 0.6074 0.0066 0.0198 5.343 8.780 60.85
7 15.189 15.7580 0.5690 0.0062 0.0185 5.005 8.780 57.00
8 15.186 15.5998 0.4138 0.0045 0.0135 3.639 8.780 41.45
9 15.200 15.7637 0.5637 0.0061 0.0184 4.958 8.780 56.47
10 15.192 15.8917 0.6997 0.0076 0.0228 6.155 8.780 70.10
11 15.190 15.5814 0.3914 0.0043 0.0128 3.443 8.780 39.21
12 15.192 15.8209 0.6289 0.0068 0.0205 5.531 8.780 63.00
13 15.194 15.6508 0.4568 0.0050 0.0149 4.018 8.780 45.76
14 15.200 15.4875 0.2875 0.0031 0.0094 2.529 8.780 28.80
15 15.195 15.8875 0.6925 0.0075 0.0226 6.091 8.780 69.37
16 15.187 15.5895 0.4025 0.0044 0.0131 3.540 8.780 40.32
17 15.198 15.5578 0.3598 0.0039 0.0117 3.164 8.780 36.04
18 15.190 15.9241 0.7341 0.0080 0.0239 6.457 8.780 73.54
19 15.200 15.6616 0.4616 0.0050 0.0150 4.060 8.780 46.24
20 15.198 15.9179 0.7199 0.0078 0.0235 6.332 8.780 72.12

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APPENDIX C: TGA Analysis

Unmodified biochar data sheet

79
Modified biochar with zinc nitrate hexahydrate

80
APPENDIX D: GC Analysis

81
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