PRODUCTI ON OF BIODIESEL FROM CRUDE PALM OIL

(CPO) AND WASTE COOKING OIL (WCO) THROUGH

TRANSESTERI FICATION METHOD

BY:
SITI KARTINA BINTI ABDUL KARIM

NOVEM BER 2010

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Tarikh

: 1 November 2010

No. Fail Projek

: 600-RMI/ST/5/3/Rst (30/2009)

Penolong Naib Canselor (Penyelidikan)

Institut Pengurusan Penyelidikan
Universiti teknologi MARA
40450 Shah Alam

Y. Bhg. Prof.,
LAPORAN AKHIR PENYELIDIKAN PRODUCTION OF BIODIESEL
FROM CRUDE PALM OIL (CPO) AND WASTE COOKING OIL (WCO)
THROUGH TRANESTER IFICATION METHOD

Merujuk kepada perkara di atas, bersama-sama ini disertakan 2 (dua) naskhah

Laporan Akhir Penyelidikan bertajuk Production of Biodiesel from Crude Palm Oil
(CPO) and Waste Cooking Oil (WCO) through Transesterification Method.

Sekian, terima kasih.

Yang benar,

SITI KARTINA BINTI ABDUL KARIM

Ketua Projek Penyelidikan

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PROJECT TEAM MEMBER

SITI KARTINA BINTI ABDUL KARIM

Team Leader

......................................................................
Signature

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Acknowledgements

The team is indebted to the following groups and individuals who have made this
research project successful. My heartfelt thanks go to:

Prof. Dr. Saifollah Abdullah

Dean, Fac. of Applied Sciences

Dr. Siti Halimah Sarijo

Head of Program (AS 225)

Dr. H.N.M. Ekramul Mahmud

Fac. of Chemical Engineering

and

Academic and non academic staffs of the faculty, who have lent their hands in
helping to complete the research project.

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Table of Contents
List of Tables ..................................................................................................................... vii
List of Abbreviations......................................................................................................... viii
Abstract .............................................................................................................................. ix
Chapter 1 ............................................................................................................................ 1
1.1

Problem Statement ............................................................................................... 1

1.2

Significance of Study ........................................................................................... 2

1.3

Objectives of Study.............................................................................................. 3

Chapter 2 ............................................................................................................................ 4
2.1

Palm Oil .............................................................................................................. 4

2.1.1

Chemical Composition of Palm Oil .............................................................. 4

2.1.2

Physical Properties of Palm Oil .................................................................... 6

2.1.3

Palm Oil as Fuel Substitute .......................................................................... 7

2.2

Transesterification Process ................................................................................... 9

2.2.1

Acid-Catalysed Process ...............................................................................10

2.2.2

Base-Catalysed Process ...............................................................................11

2.2.3

Enzyme-Catalysed Process ..........................................................................14

2.3

Biodiesel.............................................................................................................14

2.3.1

Properties of Biodiesel ................................................................................15

2.3.2

Engine Performance Tests ...........................................................................18

Chapter 3 ...........................................................................................................................19
3.1

Materials.............................................................................................................19

3.1.1

Chemicals Used ..........................................................................................19

3.1.2

Palm Oil Samples ........................................................................................19

3.2

Experimental Methods ........................................................................................20

3.2.1

Preparation of Palm Oil Samples .................................................................20

3.2.2

Transesterification Process ..........................................................................20

3.4

Product Analysis .................................................................................................21

Chapter 4 ...........................................................................................................................23
4.1

Yield of Biodiesel ...............................................................................................23

4.2

Methyl Ester Composition in Biodiesel ...............................................................25

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Chapter 5 ...........................................................................................................................28
5.1

Conclusion..........................................................................................................28

5.2

Recommendations...............................................................................................29

Bibliography ......................................................................................................................30

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List of Tables
Table No.

Title

Page

2.1
2.2
2.3

Major Fatty Acids Composition in Palm Oil

Physical Properties of Palm Oil
Standard Specifications for Biodiesel Fuels
(B100) Blend Stock for Distillate Fuels (ASTM
D6751)
European Standard for Biodiesel (EN 14214)
Chemicals Used in Transesterification
Conditions for GC
Yield of Biodiesel from CPO and WCO
Compositions of Major Components in Biodiesel

5
6
16

2.4
3.1
3.2
4.1
4.2

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17
19
22
23
26

List of Abbreviations
CPO
FAME
FFA
HHV
RBD
WCO

Crude palm oil

Fatty acid methyl ester
Free fatty acid
Higher heating value
Refined, bleached, deodourised
Waste cooking oil

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Abstract

Conversion of palm oil to fuel is one way to add value to waste and also resources of
palm oil. Palm oil can be changed to biofuel through several ways, the simplest and
most widely used is transesterification. Crude palm oil (CPO) and waste cooking oil
(WCO) is chosen to be the feedstock in order to reduce the cost of feedstock used.
The yield and composition of biodiesel produced from these sources are compared to
identify which one is the better source. Three different sources of WCO and one
sample of CPO are used for transesterification. The sources of WCO are Cafe
KKUiTM, McDonalds (Section 2) and a fried banana stall (Section 2). The results
showed that the yield of CPO (97 wt%) is very similar with the yield of all WCO
samples, which is in the range of 93-98 wt%. However, the methyl ester composition
of biodiesel from CPO has a higher value of C16 and C18 compared to the WCO
samples. Further researches on the physical properties of biodiesel produced, cost
implication of the feedstock and alternative feedstocks are needed in order for these
researches to be viable for industry purposes.

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Chapter 1

Introduction

1.1

Problem Statement
Global concern on environmental pollution and diminishing supply of fossil
fuels are the key factors in initiating research for alternative sources of
energy. In 2008, 34.7% of fossil fuel consumption was coming from liquid
fossil fuels (BP Corporation, 2009). Even though liquid fossil fuels are
expected to stay as the major contributor for energy sources, the world oil
prices will lead the global energy users to change to other types of energy
sources. The projections made by Energy Information Administration (EIA)
show a steady decline of liquid fossil fuel use at 0.3 percent a year on a
worldwide basis (Energy Information Administration, 2009). As a result,
more research on alternative energy fuels are done in order to partially
replace the declining energy sources that is left by fossil fuels.

Plant oils, consisting of long chain triglycerides, have the potential to

substitute for liquid fuels in the near future, due to their environmental
benefits and renewability. Nonetheless, several setbacks hinder the possible
use of plant oil as a replacement for fossil fuels. The current cost of plant-oil
based fuels is higher than petroleum fuels and in European Union countries,
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the new standard for carbon emission from plant-oil based fuels is 35% less
than fossil fuels (Palm Oil HQ Pty Ltd., 2009). Thus, considerable effort still
needs to be done in order to find a suitable feedstock for the conversion of
palm oil to biodiesel which can meet the cost and environmental criteria for
its possible worldwide usage.

1.2

Significance of Study
Biodiesel produced from plant oil can be used as an alternative to fossil fuels
due to its similar characteristics to fossil fuels. The testing done by Malaysian
Palm Oil Board (MPOB) shows that Malaysian palm oil biodiesel had
achieved the standards set by the European Standards for Biodiesel (EN
14214) and American Standards Specifications for Biodiesel Fuel (ASTM
D6751) (Cheng, Choo, Yung, Ma, & Basiron, 2004). Therefore, the potential
use of plant oil-based fuels can reduce the dependency on fossil fuels.

Aside from similar physical properties, plant oil-based fuels do not contribute
to the net increase of carbon dioxide emission in the atmosphere. This is
because if the palm oil trees are replanted after being harvested for production
of fuel, the carbon dioxide is returned back to the cycle of growth. The net
carbon dioxide emission would be equal to zero. Other benefits for the
environment include the reduction in smoke emission and exhaust odour. It

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can also be used as blend to decrease sulfur emission and aromatics (El
Bassam, 1998).

The cost factor that hinders the commercial use of plant oil-based fuels can be
lowered by careful selection of feedstock that has the lowest price and is
available readily. Thus, crude palm oil (CPO) and waste cooking oil (WCO)
is chosen in order to determine their suitability as a cheap feedstock to
produce biodiesel.

1.3

Objectives of Study
The objectives of this research are:
a) To compare the yield of biodiesel produced from crude palm oil (CPO)
and waste cooking oil (WCO)
b) To analyse the methyl esters produced from transesterification of crude
palm oil (CPO) and waste cooking oil (WCO)

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Chapter 2

Literature Review

2.1

Palm Oil
Palm oil is obtained from the mesocarp of the palm fruit. It contains
approximately 50% saturated fat and 50% unsaturated fat. Due to such a
unique charateristic, palm oil may be separated under controlled thermal
conditions into two components, a solid form (palm stearin) and a liquid form
(palm olein). It is this chemical composition that defines the chemical and
physical characteristics of palm oil.

2.1.1 Chemical Composition of Palm Oil

Triglycerides form the major component present in palm oil. The remainder is
composed of less than 0.5% diglycerides, 0.1% free fatty acids (FFA), 0.3%
sterols, 0.1% tocopherols and phospholipids and pigments at ppm level.

Fatty acid is long chain monocarboxylic acid that constitutes of 2 to 30

carbon atoms but C16 and C18 are the most commonly found (Hart, 1987).
Fatty acid can be classified into saturated and unsaturated fatty acid.
Saturated fatty acid is usually straight-chained with even number carbon
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atoms. Unsaturated fatty acid is limited to C16 and C18 with 1, 2 or 3 double
bonds.

Fatty acids can be present in free form as free fatty acids (FFA) or combined
with other molecules to form ester. Mostly the esters formed are from
glycerols with all the hydrogen in the hydroxyl groups in the glycerol
molecules replaced by fatty acid chain via the acid carboxylic ends (Chong,
1993).

For Malaysian palm oil, the chain lengths of the major fatty acids present in
the triglycerides fall within a very narrow range from 14 to 18 carbons as
shown in Table 2.1.

Table 2.1: Major Fatty Acids Composition in Palm Oil (Basiron, 1996)
Fatty Acid

% of Total

(Carbon:Double-Bond)
Mean

Range Observed

Myristic Acid (14:0)

1.09

0.9-1.5

Palmitic Acid (16:0)

44.02

41.8-46.8

Stearic Acid (18:0)

4.54

4.2-5.1

Oleic Acid (18:1)

39.15

37.3-40.8

Linoleic Acid (18:2)

10.12

9.1-11.0

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Apart from triglycerides, other cmponents in palm oil are sterols, tocopherols,
phospholipids and pigments. All these components constituted less than 1%
of oil; nevertheless they play a significant role in the stability and refinability
of the oil. Crude palm oil (CPO) contains tocopherols and tocotrienols, which
are antioxidants and provide some natural oxidative protection to the oil.

2.1.2 Physical Properties of Palm Oil

The physical properties of fatty acid depend on the chain lengths and the
degrees of unsaturation. For saturated fatty acid, melting point increases with
the number of carbon atoms. However, for unsaturated fatty acid the melting
point decreases with the increase of double bonds. Some of the physical
properties for fatty acids are summarised in Table 2.2.

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Table 2.2: Physical Properties of Palm Oil (Perry, Green, & Maloney, 1998;
Weast & Astle, 1985)
Fatty Acid

Molecular Weight

Melting Point (C) Boiling Point (C)

Myristic

228.38

53.9

250100

Palmitic

256.43

63

350, 267100

Stearic

284.48

71-2

360, 23215

Oleic

282.47

16.3

286100, 228-915

Linoleic

280.45

-5

229-3016

2.1.3 Palm Oil as Fuel Substitute

A number of researches have been done to convert palm oil to liquid fuel.
These researches are mostly centered in Malaysia, which produces the largest
amount of palm oil from the last three decades.

PORIM has done intensive research to convert palm oil to diesel. Ma and his
colleagues (1996) converted palm oil to methyl esters as an alternative to
diesel and tested it in large vehicles. They found that the performance of this
fuel, which is called palm diesel, is very good and the fuel is compatible with
diesel engine.

Comparative studies of palm oil methyl ester using compression ignition

engine have been jointly done by UTM, PORIM and Petronas (Azhar &
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Anuar, 1998). This study also showed that palm diesel could be used directly
in diesel engine and its performance is very similar with diesel fuel.

Production of biodiesel using crude palm oil (CPO) was shown to have
similar properties and more environmentally friendly than petroleum based
diesel. The fuel properties of biodiesel fermented with acetone, butanol and
ethanol are found to be very much like No. 2 Diesel, with higher cetane
numbers and boiling points (Crabbe, Cirilo, Genta, Kenji, & Ayaaki, 2001).
Another work by de Almeida and co-workers (2002) presented several
problems associated with direct use of palm oil as fuel, such as poor
atomisation, carbon deposits, clogging of fuel lines and starting difficulties in
low temperatures. However, they also reported better combustion when using
palm oil at temperature of 100C.

Extensive research using CPO as biodiesel by MPOB showed that the use of
CPO as feedstock to produce biodiesel does not affect engine performance
and no modifications of the engine is needed (Basiron & Choo, 2004). The
conversion of CPO to biodiesel can also be taken as a measure to stabilize the
price of palm oil. Nonetheless, the production of palm oil to fuel uses is still
under consideration due its major uses as edible oil.

Thus, another alternative to convert palm oil to biodiesel is by using palm

fatty acid distillate (PFAD) and waste cooking oil (WCO). PFAD is a by8

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product from production of refined, bleached and deodourised (RBD) palm

oil used as cooking oils, thus will utilize fully products from palm oil. The
main drawback with using both PFAD and WCO is the high content of FFA
in both oils, increasing the production steps because usually two-step process
is needed in order to convert these oils to biodiesel (Chongkong, Tongurai, &
Chetpattananondh, 2009; Yujaroen, Goto, Sasaki, & Shotipruk, 2009). High
FFA content also means that most of the conversion will be done in acidic
environment, which is more corrosive, has no reusable catalyst and high cost
of equipment (Wang, Ou, Liu, Xue, & Tang, 2006).

2.2

Transesterification Process
Transesterification is a chemical reaction involving vegetable oil and alcohol
to yield fatty acid alkyl esters and glycerol. Factors that can affect the yield of
fatty acids in transesterification include the original fatty acid composition,
free fatty acid content of the oil, type of catalyst, type of alcohol and water
content in the oil (Kusdiana & Saka, 2004; Lapuerta, Herreros, Lyons,
Garcia-Contreras, & Briceno, 2008; Banerjee & Chakraborty, 2009;
Freedman, Pryde, & Mounts, 1984). Depending on the fatty acid content and
water content in vegetable oil, the transesterification process can be
performed by using acid-catalysed, base-catalysed or enzyme-catalysed
process.

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2.2.1 Acid-Catalysed Process

The transesterification process is catalysed by Brnsted acids, preferably by
sulfonic or sulfuric acids. This process is necessary for vegetable oils
containing high free fatty acids and water content (Freedman, Pryde, &
Mounts, 1984). However, it is not preferable in industrial setting due to the
very corrosive nature of acid catalysts compared to alkali catalysts and longer
period of reaction (Wang, Ou, Liu, Xue, & Tang, 2006). The acid catalysts
give high yield of ethyl esters, but the reactions are slow and usually
accompanied by medium to high temperature to reach completion. A
comparison of transesterification with methanol, ethanol and butanol using
concentrated sulfuric acid. The reaction time needed to achieve high
conversions to alkyl esters are from 3 hours to 69 hours (Freedman, Pryde, &
Mounts, 1984). It was concluded that reaction time affected the process more
than the type of alcohol. When the reactions were done at similar temperature
(65C), similar conversions were achieved after 69 hours. This result is
supported by another work done on palm oil (Crabbe, Cirilo, Genta, Kenji, &
Ayaaki, 2001). A high yield to ester (99.7%) was found after 9 hours at 95C
while a similar yield was achieved after 24 hours at 80C. The optimised
variables for acid-catalysed transesterification of CPO were 5% (vol/wt)
sulfuric acid, temperature of 95C and 9 hours of reaction time.

The alcohol/vegetable ratio is also one of the main factors affecting acidcatalysed process. The stoichiometric ratio of alcohol to triglyceride is 3 to 1.
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An excess of alcohol favours the product formation, but it also makes the
recovery of glycerol difficult. Therefore, an ideal alcohol to vegetable oil
molar ratio needs to be established to get the optimum product (Demirbas,
2005). Molar ratio of 6 to 1 is the most commonly reported, but ratio as high
as 40 to 1 under different experimental conditions can also yield esters
(Ramadhas, Jayaraj, & Muraleedharan, 2004; Sahoo, Das, Babu, & Naik,
2007; Crabbe, Cirilo, Genta, Kenji, & Ayaaki, 2001).

2.2.2 Base-Catalysed Process

In a base-catalysed process, the alkaline catalyst, such as KOH or NaOH is
dissolved into a short-chained alcohol. The oil is transferred into a vessel,
then the alcohol/catalyst mixture is added in. The final mixture is usually
stirred for several hours at ambient temperature (Demirbas, 2009a; Demirbas,
2009b; Ghadge & Raheman, 2005). A good transesterification process
produces two separate liquid phases, which are the ester and glycerol.

Base-catalysed transesterification proceeds at a faster rate than the acidcatalysed process. The methanolysis of four refined vegetable oils were
investigated with 6 to 1 alcohol to glyceride molar ratios, and it was reported
that after 1 hour, all vegetable oils produced conversion between 93 to 98%.
Lower conversions were found at a lower molar ratio (Freedman, Pryde, &
Mounts, 1984). In a base-catalysed transesterification of used frying oil, it
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was found that after 1 hour, with a methanol to oil molar ratio of 4.8 to 1, the
highest yield of methyl ester was obtained (Felizardo, Corriea, Raposo,
Mendes, Berkemeier, & Bordado, 2006).

There are several factors affecting the yield of biodiesel using alkaline
catalyst, namely the molar ratios of alcohol to glyceride and temperature (Ma
& Hanna, 1999). The molar ratio of alcohol to glyceride for base-catalysed
process was usually set at 6 to 1 to achieve optimum ester yield (Freedman,
Pryde, & Mounts, 1984). Higher molar ratios resulted in higher ester
conversion in shorter time (Demirbas, 2009a). Transesterification of waste
cooking oil with methanol and sodium hydroxide with a methanol to oil ratio
of 6 to 1 was reported to yield about 90% conversion (Meng, Chen, & Wang,
2008). A high yield of 98% was obtained from similar molar ratio, to produce
biodiesel from mahua oil (Ghadge & Raheman, 2006).

Transesterification can occur at several different temperatures. Temperature

affected the reaction rate and also the yield of biodiesel (Demirbas, 2002).
Increasing the temperature, notably supercritical temperature has a favourable
effect on biodiesel yield. In transesterification of used frying oil using sodium
methoxide, the reaction temperature is maintained at 65C (Cvengros &
Cvengrosova, 2004). Leung and Guo (2006) studied the effect of reaction
temperature towards yield and reaction time. They found that the optimum
temperature is 60C, with a yield of about 88%. Other study on the effect of
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temperature in transesterification was conducted at 6 to 1 alcohol to oil molar

ratio, 1 wt% sodium hydroxide and a reaction time of 60 minutes. The yield
of biodiesel was found to be at optimum value at 50C (Meng, Chen, &
Wang, 2008). It can be inferred that transesterification can be performed at
various temperatures, from ambient temperature to the boiling point of the
alcohol used or even higher. Temperatures can give positive impact on the
yield of biodiesel and also the reaction rate (Banerjee & Chakraborty, 2009).

To some extent, the type of alkaline catalyst used plays a role in

transesterification. The effect of three different basic catalysts towards
transesterification of used frying oilsnhas been investigated by Leung and
Guo (2006). NaOH, NaOCH3 and KOH were used and compared in terms of
the ester content in biodiesel. Although all three catalysts showed similar
trends on the conversion of oil, but sodium hydroxide produced the best
result.

Another

comparison

between

NaOH

and

NaOCH3

for

transesterification of beef tallow showed that these catalysts reached

maximum activity at 0.3% and 0.5% w/w respectively (Ma, Clements, &
Hanna, 1998). Ester conversions for the two catalysts at 6 to 1 molar ratio
were reported to be almost the same after 60 minutes (Freedman, Pryde, &
Mounts, 1984). However, sodium hydroxide was chosen widely in industry
because it is cheaper.

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2.2.3 Enzyme-Catalysed Process

Biodiesel can also be produced from enzyme-catalysed transesterification.
Transesterification of jatropha oil in solvent-free system using three different
lipases (Chromobacterium viscosum, Candida rugosa and Porcine pancreas)
illustrated that only C. Viscosum produced appreciable yield of biodiesel
(Shah, Sharma, & Gupta, 2004). The immobilisation of C. Viscosum
enhances the biodiesel yield to 71% with a process time of 8 hours at 113K.

Although this ttype of process has yet to be commercially developed, more

results on this process has been reported (Dizge, Aydiner, Imer, Bayramoglu,
Tanriseven, & Keskinler, 2009; Li, Du, Liu, Wang, & Li, 2006; Fukuda,
Kondo, & Noda, 2001). Several parameters were usually chosen to be
optimised, such as solvent, temperature, pH and type of microorganism to
determine the suitability to withstand industrial applications. Nonetheless, the
reaction yield and reaction time are still not favourable compared to basecatalysed process.

2.3

Biodiesel
Biodiesel comes from a Greek word bio, which means life and Diesel,
courtesy of Rudolf Diesel, who tested the first diesel engine. It is defined as a
diesel-equivalent fuel derived from biological sources, such as plant oils

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(Demirbas, 2008). It also refers to a mixture of monoalkyl esters of long

chain fatty acids from renewable lipid feedstock, such as animal fat or
vegetable oil. Biodiesel usually consists of alkyl fatty acids of short chain
alcohol, with chain length of fatty acids between 14 to 22 carbons. The higher
heating values of biodiesels are comparatively high compared to other fuel.
The heating values of biodiesel are in the range of 39 to 41 MJ/kg, slightly
lower than gasoline (46 MJ/kg), petroleum (42 MJ/kg/) but higher than coal
(32-37 MJ/kg) (Demirbas, 1998).

2.3.1 Properties of Biodiesel

Biodiesels can be characterised according to several physical and chemical
properties, such as viscosity, cetane number, distillation range, ash content,
sulfur content, carbon residue, acid value and higher heating value (HHV).
The parameters are all specified through the biodiesel standard, ASTM
D6751 and EN 14214. ASTM D6751 identifies the parameters that a pure
biodiesel must meet before being used as pure fuel or blended with
petroleum-based fuels. EN 14214 is an international standard for minimum
requirements that must be met for biodiesel produced from rapeseed oil.

Tables 2.3 and 2.4 show the properties and specifications of biodiesel as
required by the standards.

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