CHAPTER 1

INTRODUCTION

1.1 Research Background

Fuel is one of the basic needed in human life. Fuel can be define as materials that
store potential energy that can practicably release and use as heat energy. Demand of the
fuel in make human make research about it more struggle. One of the solution found is to
make some bio-fuel. Diesel fuel is one type of fuel that can be make some biological, to
increasing its sustainability.

Biodiesel is one of the bio-fuel, biodiesel also receive increasing attention as an

alternative, non-toxic, biodegradable and renewable diesel fuel (J. Zhang, 2010).
Biodiesel is product of transesterication process from triglycerides, the main
constituents of vegetable oils or animal fats with an alcohol such as methanol in the
presence of a suitable catalyst such as alkali metal. It also strong by Hameed in 2009,
Biodiesel is an alternative biodegradable and nontoxic fuel. This fuel is made up by
biomass conversion. Biomass can be referred to recently living organisms or plantderived materials. This biomass can be convert in 3 ways to become bio-fuel, that are

2
thermal conversion, chemical conversion, and biochemical conversion. From this
conversion, there are 3 state that can produce, such as solid, liquid and gas state. In
addition, this high demand of usage of oil for biodiesel production could lead many
negative impacts such as deforestation and desertification (A. Mazubert, 2013). Biodiesel
also can be done in our country.

Every biodiesel production need their own catalyst, there are 2 type of catalyst,
either homogenous or heterogeneous catalyst. Heterogeneous catalyst are catalyst that
different phase to feed substance. It can make from activated carbon that impregnate with
chemical, such as alkali metal. Activated carbons are the most versatile and commonly
used adsorbents because of their extremely high surface areas micropore volumes, large
adsorption capacities, fast adsorption kinetics, and relative ease of regeneration. The most
precursors used for the production of activated carbons are organic materials that are rich
in carbon From Hayyan in 2011, Malaysia being one of the largest world palm oil
producers and exporters, so Malaysia has a big potential of leading the palm oil biodiesel
production sector.

1.2 Problem Statement

Renewable sources such as bio product can change the world attention due to
increasing demand of the non-renewable product. It support by J. Kasendo in 2009, the
production of biodiesel lately gain attention to the world due to increasing demand for a
cleaner, safer and renewable energy. From the statement, biodiesel is one of the
renewable sources that can't give the negative effect to the surrounding. Bio product also
known as bio-based product, it referred to material, chemical or energy that derived from
renewable biological resources.

World standard biodiesel are made by using homogenous catalyst. This type of
catalyst not easy to separate from the final product, if can it must to use complex liquidliquid separation process (J.Kansedo 2008). For the solution, use the heterogeneous
catalyst can easily separate the catalyst from the final product. Sell price for biodiesel are

3
cheaper than diesel fuel, but it still high, this problem come from high production cost,
the most cost actually come from liquid-liquid extraction of the homogenous catalyst
from the product.

Another than that, use of waste cocking oil in production of biodiesel are hard,
because there are too many impurities. low-cost materials usually contain significant
amounts of free fatty acids (FFA), which give rise to a depletion of the catalysts,
increased purification costs, and lower yield in alkali-catalyzed transesterification (J.
Zhang, 2010). For the solution, refined palm oil used in this experiment.

1.3 Objective

The objective of study of this experiment are:

1. To determine the best effective of mass of catalyst in the FAME production for
the ratio catalyst.
2. To determine the effect of the biodiesel as the temperature increase during
transesterification.

1.4 Scope Of Study

This experiment is the production of biodiesel from refined palm oil based on two
parameter. The first parameter is to determine the best effective of mass of the catalyst in
the FAME production and to determine the effect of the biodiesel as the temperature
increase during transesterification process.

First step is making the catalyst, it can be done by activated carbon method. Then,
it continue to impregnation process an calcination process to produce the catalyst. Then
the experiment continue to transesterification process. There are several parameter of
process transesterification to study effect of each Fatty Acid Methyl Ester(FAME)
produced. The first parameter for this experiment is about ratio of catalyst of catalyst to
oil (0.5wt%, 1wt%, 2wt%, 3wt%). For the second of parameter is temperature use in the

4
transesterification process (30C, 40C, 50C, 60C). FAME produced from
transesterification

process

analyzed

using

Gas

Chromatography

Mass

Spectrometry(GCMS).

This experiment is to determined effect of FAME in each parameter study, to

make the best effectively biodiesel.

CHAPTER 2

LITERATURE REVIEW

2.1 Introduction

Biodiesel is one of the sources of energy that can be renewable. Lately,

consuming of energies are from non-renewable resources such as fossil fuel and coal.
This non-renewable resources come from died plants and animals that buried under soil
for thousands years with specific temperature and pressure. This called as non-renewable
because, it need a very long time to recreate the resources. Heavy consumption of fossil
resources, effect on global warming and concerns of energy security are main drivers for
growth of biofuels (S. Semwal, 2011). From further studies, world now can create
renewable energy from renewable resources. The example or renewable resources are,
biodiesel, wind, sunlight and water. Renewable resources actually come when demand of
energy become very high, and at the same time, there are energy crisis. This is because
non-renewable resources become decrease from day to day. Withought any further
research, our future maybe have no more energy that can be consuming. Renewable
energy named because, even it been used and finished, it can easily remake again and

6
again using renewable resources. This resources is actually, can't finish even we used it
for a thousand times, or it can easily remake again. As the world is clamouring to prevent
the effects of greenhouse gases from further damaging the environment, biodiesel is the
fast gaining momentum for expansion in terms of production and usage and it is mainly
because of the closed carbon cycle of biodiesel with clean tail pipe emissions that reduce
hydrocarbons, carbon monoxides, particulate matter and sulphur dioxide emissions when
blended with fossil fuel (P. L. Boey, 2012)

Table 2.1.1 List of advantages and disadvantages of fossil fuel

Advantages

Disadvantages

Can generate high amounts of

Hazardous to living things

energy only in a single location.

Rising prices from days to days

Produce high of carbon dioxide that

Easy to find by digging

can reduce the thickness of ozon

Less transportation cost by using

layer

pipe line

Power plants that utilize gas are

very efficient.

Non-renewable

Large amount of reserves oil

needed

Bio products are one of the renewable resources that can be a renewable energy.
The simple example of bio products are biofuel. Biofuel is a fuel that contains energy
from geologically recent of carbon fixation. Carbon fixation is the conversion of
inorganic carbon or known as carbon dioxide to organic compounds. One of the example
of biofuel is biodiesel.

7
2.2 Biodiesel

In chemical terms, biodiesel is made up of methyl or ethyl esters of fatty acids

that can be produced from different lipid sources, through transesterification, reaction
with alcohol in the presence of a base, acid, enzyme or solid catalyst. Nowadays
esterification and transesterification reactions are the most commonly used to produce
biodiesel. Any type of feed stock containing free fatty acids and/or triglycerides, such as
vegetable oil and animal fat, can be converted into biodiesel (C. D. Mandolesi, 2013).
Use of biodiesel as alternative fuel has been extensively evaluated in many countries
especially in modern countries which are very sensitive about the environment and
pollution(Choo, 2000). Biodiesel feedstock can be sourced from edible oils, non-edible
oils, waste oils or animal fats. The food-for-fuel controversy plaguing the biodiesel
industry has shifted the interest of stakeholders and scientists alike to non-edible, waste
oils and animal fats for use as biodiesel feedstock (P. L. Boey, 2012). Biodiesel also
known as x alternative diesel fuel. It also one of the Bio-fuels. It build for transportation,
such as cars, lorries and heavy vehicle. Biodiesel can be easily use in diesel engine with
little or no modification(L. Guangrui, 2013). In few years from now biodiesel can be the
most important fuel for heavy vehicle, because of demand of diesel fuel from petroleum
is too high and can't full fill easily. Biodiesel also friendly energy resources. Finding an
alternative fuel has attracted considerable attraction in recent years due to limitation of
traditional fossil resources and increasing of crude oil prices as well as concern over
greenhouse gas emissions (M. Zabeti, 2009).

8
Table 2.2.1 List of Fatty acid that have in biodiesel

Common Name of Acid

Formal Name of Acid

Lauric Acid

Dodecanoic Acid

Myristic Acid

Tetradecanoic Acid

Myristoleic Acid

Cis-9-Tetradecanoic Acid

Palmitic Acid

Hexadecanoic Acid

Palmitoleic Acid

Cis-9-Hexadecanoic Acid

Stearic Acid

Octadecanoic Acid

Oleic Acid

Cis-9-Octadecanoic Acid

Linoleic Acid

Cis-9,12-Octadecanoic Acid

Linolenic Acid

Cis-9,12,15-Octadecanoic Acid

Arachidic Acid

Eicosenoic Acid

Gondoic Acid

Cis-11-Eicosenoic Acid

Behenic Acid

Docosanoic Acid

Brucic Acid

Cis-13-Docosanoic Acid

9
Table 2.2.2 Advantages and disadvantages of biodiesel

Advantages

Renewable source

Less polluting than petroleum diesel

Has no sulfur

Can use in car withought any engine

modification

The lubricating property of the

Expensive

due

to

need

of

methanol

Requires energy to produce

biodiesel

Can harm rubber hoses in some

engines

Can be used in existing oil heating

system

Disadvantages

Shortage

of

food,

sources

extracted from vegetable oil

biodiesel may lengthen the lifetime

of engines

2.2.1 Transesterification

Transesterification is the reaction of a fat or oil with and alcohol to form esters
and glycerol as shown in picture 2.2.1.1. The reaction may be facilitated by catalyst using
primary or secondary monohydric aliphatic alcohols having 1e8 carbon atoms. It should
be noted that this equilibrium reaction needs greater amounts of alcohol to shift the
reaction equilibrium forward to produce more methyl esters as the desired product.
Although methanol and ethanol are most frequently used, ethanol is the preferred alcohol
as it can be derived from agricultural products and is renewable and biologically less
objectionable within the environment. However, methanol is mainly employed because of
its low cost and its physical and chemical advantages (E. F. Aransiola, 2014).

10

Figure 2.2.1.1 Transesterification process

2.3 Catalyst

The increase in the rate of a chemical reaction of two or more reactants due to the
participation of an additional substance called a catalyst. There are two type of catalyst
that can be use in the transesterification process. The transesterification reaction can be
catalyzed by both homogeneous and heterogeneous catalysts (S. Sinha, 2008). The type
of catalyst are homogenous and heterogeneous catalyst. The example of catalyst are, acid
catalyst, enzymatic catalyst and alkaline catalyst.

2.3.1 Homogenous Catalyst

Homogenous catalyst is one of the types of the catalyst. This type of catalyst is
same phase to the feedstock phase. This type of catalyst have the advantages and
disadvantages on their own.

Separation of methyl esters becomes a major problem and the conventional

homogeneous base catalysts will be consumed in the reaction (P. L. Boey, 2012).

11
Production costs were rather high as the process involved number of washing and
purification steps in order to meet the stipulated quality and it was quite difficult to
remove the traces the catalyst remaining in the product and separation of glycerin also
posed technical challenges (S. Semwal, 2011). The homogeneous alkali-catalyzed
transesterification has been the commonest method used at laboratory, pilot and industrial
scale levels. This process is catalyzed by alkaline metal hydroxides and alkoxides as well
as sodium or potassium carbonates. The production cost of these catalysts is low and they
show a very high performance when feedstocks (vegetable oils) with low free fatty acid
are used. Also, this reaction leads to high conversion of triglycerides to their
corresponding methyl esters in short reaction times (E. F. Aransiola, 2014).

2.3.2 Heterogeneous Catalyst

Another type of catalyst is Heterogeneous catalyst, this type of catalyst is phase of

catalyst that not same to the phase of feedstock.

The high production cost of biodiesel is due to both the cost of raw materials and
processing costs. The application of heterogeneous catalysts in biodiesel production
alternative the problems associated with homogeneous catalysis. Heterogeneous catalysts
can be recycled and re-used several times with better separation of the final product.
According to Aransiola in 2014, heterogeneous catalysis in biodiesel production, unlike
homogeneous catalysis, removes the costly and time-consuming water washing and
neutralization steps to separate and recover the spent catalyst. Also, contaminated water
from homogeneous catalysis process is greatly reduced and the need for waste water
treatment minimized. One of the disadvantages with use of solid catalyst is the formation
of three phases together with oil and alcohol, which leads to diffusion limitations thus
decreasing the rate of the reaction (S. Semwal, 2011). This is type of catalyst chosen for
this experiment.

12
2.3.3 Support Of The Catalyst

Every heterogeneous catalyst need their own support that also known as carrier.
This support is to bring and hold the catalyst from react with the FAME. Support chose
must be a good absorbent of alkaline catalyst, because the catalyst that need to use is
sodium(Na). Sodium is a alkali metal. To make it good absorbent of alkali, the support
must be an activated carbon. In this experiment, Oil Palm Kernel Shell(OPKS) had been
chosen as a support. OPKS chosen because it is less of fiber, so during burning in the
furnace, there are less combustion and become ash. hardness of OPKS also can make it
easily separate between catalyst and final product.

Activated Carbon(AC) is porous materials that have a high surface area and high
adsorption capacity, which can remove a wide variety of pollutants such as dyes, heavy
metals, pesticides and gases. Due to its adsorptive properties, the ACs are used to purify,
detoxify, deodorize, filter, discolor or alter the concentration of many liquid and gaseous
materials (A. M. M. Vargas, 2011). Reaction of refined palm oil and methanol can be
biodiesel, but to make the reaction faster and to increase the percentage of the product,
catalyst needed. If we need to avoid complex liquid-liquid extraction between biodiesel
and homogenous catalyst, heterogeneous catalyst use in this experiment. The problem
that occur is the carrier of the catalyst. The solution is using Oil palm kernel shell. This
carrier must be in good absorbent of catalyst, catalyst type that been use is heavy metal
type, so the carrier must be good metal absorbent. Activated carbon is the best absorbent
of heavy metal. AC prepared by burn in the furnace in 3h at 600C.

13

CHAPTER 3

METHODOLOGY

3.1 Introduction

This chapter will discuss more about the methodology for catalyst making,
production of FAME by transesterification and preparation of solution to analysis in Gas
Chromatography Mass Spectrometry (GCMS).
3.2 Chemical And Material

In this experiment, Oil Palm Kernel Shell(OPKS) used as a raw material, to make
activated carbon. For the catalyst, distilled water and sodium hydroxide(NAOH) mix
with it. Methanol and refined cocking oil use together during transesterification, as shown
in the table 3.2.1.

14
Table 3.2.1 list of chemicals and materials use in this experiments
Name Of Chemical and Material

Purpose

0.5M sodium hydroxide solution (NaOH)

Alkali metal that make catalyst

Methanol

For transesterification process

n-Hexane

Dilute FAME before analysis in GCMS

Oil Palm Kernel Shell(OPKS)

Carrier of the heterogeneous catalyst

Refined palm oil

Vegetable oil that make biodiesel

3.3 Apparatus

The list of apparatus that used in the experiment for preparation of heterogeneous
catalyst, FAME production by esterification and preparation of FAME to analysis are
shown on the table 3.3.1.

Table 3.3.1 list of the apparatus

Equipment
Hot plate

Purpose

Diagram

Heat solution in the beaker

until

dry

during

impregnation

Balancing

Measure weight of NAOH

pallets, activated carbon,
catalyst and OPKS

Centrifuge

Separate solution in the

centrifugal bottle

15
Gas Chromatography Mass Analysis solution in the
Spectrometry (GCMS)

GCMS bottle

Furnace

Calcinate
impregnated

OPKS

and

activated

carbon
Oven

Dry OPKS before burn in

the furnace

Grinder

Grind OPKS into smaller

size

Reflux

Use in transesterification
process

Siever

Sieve activated carbon

16
3.4 Methodology

3 basics things that needed to making biodiesel in this experiment are palm oil,
methanol and catalyst, as shown in figure 3.4.1.

CATALYST
METHANOL

PALM
OIL

BIODIESEL
Figure 3.4.1 Flow chart of overall for biodiesel production

3.4.1 Catalyst

Oil Palm Kernel Shell(OPKS) that had been broke into pieces taken from the
factory washed using tap water to remove dirt. Then it taken to the library for drying
process before the OPKS ic carbonized, this process is to remove all water that stick to
OPKS during washing process. OPKS must be sure dry before place in the furnace for
carbonization process, this can avoid the furnace from broken because of a drop of water.
So, OPKS dried about 5 hours by 110C in the oven. This will make OPKS totally dried.
To make it as activated carbon, OPKS will burn in the furnace about 600C in 3 hours.
This process call carbonized. The carbonized OPKS call activated carbon.

17
Then, the activated carbon grinded using grinder to turn it into smaller size. The
size of OPKS needed are in between 1mm to 2mm. This can easily measure by next step
that is siever. Actually, size of OPKS under 1mm have too much ash. this ash will
contaminate the catalyst during impregnation process.

Impregnation process is actually the main process to produce the catalyst, this
including the type of metal chosen, molarity and the perfect ratio of metal to carrier.
Before impregnation, sodium pallets weighted using balancing about 1.826g, this is based
on ratio to activated carbon weighted about 9.45g. This sodium need to diluted in the
0.046L of distilled water to produce 0.5mol of sodium hydroxide. Then, the dilution is
impregnated to activated carbon and dry on the hot plate until there are no more liquid.
Then impregnated activated carbon burn again using furnace. This process called
calcination process. At this time the temperature used only 500C in 4 hours.

18

OPKS wash using tap water to remove dirt

OPKS dry in oven for 5h at 110

Carbonized OPKS by burn it using furnace for 3h at 600

Activated Carbon(AC) sieve to get range between 1-2mm using siever

AC, NaOH and water impregnated

Mixture of impregnated heated together on hot plate until dry

Calcinate dry mixture using furnace for 4h at 500

Figure 3.4.1.1 Process flow of making catalyst

19
3.4.2 Transesterification

Transesterification process is the process that the most important and the final
process of FAME production. This also called heart of the biodiesel, it is because when
these process is failed, so the FAME production also failed. Process start with heating oil
until parameter temperature. Then, mass of parameter catalyst mix in the same reflux also
with methanol. Time taken for transesterification start. Switch stopped after 4 hours of
reaction. The parameter are shown in the table 3.4.2.1 and 3.4.2.2. After finished
transesterification process, all of product collected and placed in centrifugal bottle. The
product centrifuged about 4000rpm in jus 10 minutes. Function of this centrifuge is to
split between FAME, glycerol and catalyst into layers that can easily remove.

Table 3.4.2.1 Ratio of catalyst to oil

Ratio methanol to oil (10:1)
Manipulated Variable

Reaction time (4 hours)

Temperature process (60C)

Responding Variables
(ratio catalyst to oil)

0.5 wt%

1 wt%

2 wt%

3 wt%

Table 3.4.2.2 Temperature of transesterification process

Ratio methanol to oil (10:1)
Manipulated Variable

Ratio catalyst to oil (1 wt%)

Reaction time (4 hours)

Responding Variables
(temperature process)

30C

40C

50C

60C

20

Catalyst and methanol mixed together

Oil measured and heated until temperature needed using reflux

Mixture and oil mixed together in sam reflux

Product of transesterification place in centrifugal bottle

Product centrifuged at 4000rpm in 10min

Figure 3.4.2.1 Process flow of transesterification

21
3.4.3 Gcms Analysis

GCMS in machine that can analysis the methyl ester by calculating the percent
area on the graph. 1ml of FAME and 5ml of n-Hexane mixed together into one beaker.
Then, it placed in the GCMS bottle before it can be placed on the GCMS pore to analysis.
The result collected and the percent area of every sample calculated manually.

1ml FAME and 5ml n-Hexane diluted in beaker

1ml of mixture placed in the GCMS bottle

GCMS bottle placed in the GCMS

Percent area of FAME calculated

Figure 3.4.3.1 Process flow of GCMS analysis

22

CHAPTER 4

RESULT AND DISCUSSION

4.1 Introduction

This chapter will discuss about result and discussion from GCMS result to
analysis it and the best parameter for biodiesel production.

4.2 Result

After finished transesterification process, sample that had been mix with nHexane placed in the GCMS to analysis the percent area of FAME that contained in
every sample in every parameter study. As a result in the table 4.2.1 and table 4.2.2 show
the percent area in every type of fatty acid that had been detected by GCMS.

23
Table 4.2.1 Percent area of FAME by GCMS for parameter ratio of catalyst
Percent In Sample (Ratio Catalyst To Oil) (%)
Name Of Acid
0.5wt%

1wt%

2wt%

3wt%

Lauric

Myristic

0.87

1.7

3.98

Myristoleic

21.14

19

21.22

22.66

Stearic

8.35

5.36

4.96

5.38

Oleic

13.33

13.36

24.54

7.33

Linoleic

3.16

27.65

Linolenic

Arachidic

Gondoic

0.91

Behenic

Brucic

Other

9.41

10.44

24.9

2.78

Non-methyl ester

44.61

47.29

22.68

22.1

100

100

100

100

Palmitic
Palmitoleic

Total

24
Table 4.2.2 Percent area of FAME by GCMS for parameter temperature of process
Percent In Sample (Temperature of Process) (C)
Name Of Acid
30C

40C

50C

60C

Lauric

0.28

Myristic

1.04

3.98

Myristoleic

2.71

19.72

12.11

25.75

22.66

19.60

Stearic

4.19

4.21

5.38

Oleic

15.33

15.36

24.66

7.33

Linoleic

1.84

6.4

27.65

Linolenic

Arachidic

Gondoic

0.91

Behenic

Brucic

Other

15.02

30.4

7.21

2.78

Non-methyl ester

44.61

47.97

10.01

22.1

100

100

100

100

Palmitic
Palmitoleic

Total

25
4.3 Discussion

Based on the graph 4.3.1, 0.5wt% of loading catalyst is 55.39% of Fatty Acid
Methyl Ester(FAME), for 1.0wt% loading catalyst is 52.03% of FAME. From this result,
the FAME producing is slightly decrease, but the decreasing of FAME is not too much,
so we can simplify it as a unchanged or constant FAME production. For 2.0wt% loading
catalyst is producing 77.32% of FAME. The percent different of FAME production for
1.0wt% between 2.0wt% loading catalyst are too high, thus we can simplify that, higher
percent of loading catalyst, producing higher percent of FAME. 3.0wt% loading catalyst
give 77.9% of FAME production, even the percent only slightly increase, it still a
increasing graph, thus higher wt% of loading catalyst, higher the percentage of FAME
production.

26

90
80

77.32

77.9

2wt%

3wt%

70
60

55.39

52.03
50
40
30
20
10
0
0.5wt%

1wt%

Graph 4.3.1 Yield percent for first parameter

From graph 4.3.2, fatty Acid Methyl Ester(FAME) production for 30C
temperature during transesterification is 54.26%, for the 40C can produce 67.54% of
FAME. This mean, FAME production is increase as the temperature increase. 50C
temperature can produce 89.99% of FAME. This temperature also is the best temperature
during transesterification for production of FAME. For 60C of process temperature, only

27
cam produce 52.03% of FAME. This can be said that, higher production temperature, can
produce higher yield of FAME, but over temperature can effected to the yield of FAME
during the process. This is because higher the temperature of the process, can make close
to the boiling point of the methanol. The methanol can be easily evaporate during the
process of transesterification at 60C.

100
89.99
90
80
67.54

70
60

54.26

52.03

50
40
30
20
10
0

30C

40C

Graph 4.3.2 Yield percent for second parameter

50C

60C

28

CHAPTER 5

CONCLUTION AND RECOMMENDATION

5.1 Conclution

From this Experiment, I can conclude that biodiesel making are possible in the
laboratory. Biodiesel also one of the renewable resources that can save from finishing
fossil fuel. Another than that, biodiesel can be commercialist due to cost of its production
is not too high. This is because, using refined palm oil is the fastest way for making
biodiesel. In other word, refined palm oil doesn't need another purification then waste
cocking oil. Another than that, heterogeneous catalyst is best solution to avoid complex
liquid-liquid separation process between biodiesel and homogenous catalyst.

From the result, increasing the mass of catalyst can make FAME production also
increase. This is because it has back to the function of the catalyst that reduce the reaction
time. From this experiment also, the best temperature for production of biodiesel is 50C.

29
5.2 Recommendation

From this experiment, the recommendation that can made for the further research are:
1. Use the smaller size of catalyst.
2. Use 3wt% of loading catalyst into the temperature experiment.
3. Use different type of alcohol, so that temperature of experiment can be higher.
4. Use another alkali metal as a catalyst.