1

CHAPTER 1

INTRODUCTION

1.0

Introduction

Yanmar Co., Ltd. is a Japanese-based diesel engine and related products

manufacturer that is founded by Tadao Yamaoka at March, 1912 with a history
of more than 100 years. The main office of Yanmar Co., Ltd. is situated at
Osaka, Japan. However, its primary mission of creating a sustainable lifestyle
for humanity marks its branch offices all over the globe including Brazil, India,
China, Malaysia, and more.
Its founder, Mr. Tadao Yamaoka, invented the first horizontal small
diesel engine, which was greatly welcomed by the community especially
agricultural industries where the dependency on animal and labor workforce
was high. By then, the company was named as YANMAR. Subsequently, the
small diesel engine was made commercially viable at 1933 and the name
Yanmar Diesel Co., Ltd. was adopted at 1952, where the worlds smallest 4cycle horizontal water-cooled diesel engine was produced. It was awarded
Diesel Gold Medal by the German Inventors Association at 1955. Following
that, it was awarded the German Merit Cross and a Japan stone garden
commemorating Dr. Rudolph Diesel was donated to the city of Augsburg,
Germany at 1957. Along the years, Yanmar Diesel Co., Ltd opened several
branches around the world, including Brazil (1957), Indonesia (1972),
Thailand (1978), Netherlands (1988), Singapore (1989), Italy (1995), China
(1999), United States of America (2004), India (2005), Malaysia (2007), Russia
(2007), and United Kingdom (2009). At year 2002, the name Yanmar Co.,
Ltd was adopted and is used until now.

At 2007, Yanmar Kota Kinabalu R&D Center Sdn. Bhd. is opened as the
first oversea research and development center other than Research &
Development Center, Maibara, Japan. It is located inside the biomass-rich
Asia, where R&D activities focusing on "next generation fuel technologies",
such as biofuels and alternative energies that are both greener and cleaner
for the environment. In addition, researches on the biofuels are also matched
up with development of engine that can perform well with biodiesel.
1.1

Logo

Yanmar Co., Ltd. has a logo (Fig 1) that is a combination of three curved lines
and a capital Y letter.

Figure 1.1 Logo of Yanmar Co., Ltd.

The capital Y signifies Yanmar Co., Ltd. while the three curved lines signify
the research and development of Yanmar in the field of land, sea, and cities.
As the companys main production is diesel engine, therefore, it eventually
develops

into

researching

technology

for

optimizing

diesel

engine

performance and also development of diesel engine application such

agricultural machinery (land), maritime machinery (sea), and construction
machinery (city).
1.2

Mission and Vision

The corporate principles of Yanmar Co., Ltd. has the mission statement as
We strive to provide sustainable solutions for needs which are essential to
human life. We focus on the challenges our customers face in food

production and harnessing power, thereby enriching people's lives for all our
tomorrows. A sustainable solution is focused to seek the balance between
humanity developments and environment quality, such as development of
biodiesel-friendly engines so that dependency on diesel, a non-renewable
resource, could be lowered and leads to a greener environment. Moreover,
diesel engine application such as maritime rotary engines are used on fast
boat and public sea transports that shortens the time consumed on
travelling for the passengers. On the other hand, small diesel engines that
are integrated into harvesters also decrease the labor work of farmers and
brings higher yield for the agricultural industries. In addition, development
of geothermal heat pump (GHP) for air-conditioning unit also marks the
mission of harnessing power.

All of these applications are in-lined with the mission statement that
is aimed to solve the challenges of food production and power efficiency, so
that humans life could be optimized without jeopardizing the environment.
These also match the vision statement of Yanmar Co., Ltd. that is Grateful
to serve for a better world. To conserve fuel is to serve mankind.

1.3

Corporate Organization Chart

Managing
Managing
Director
Director
(1)
(1)
Directors
Directors
Finance
Finance &
&
Adminstrative
Adminstrative
Group
Group

Engine
Engine
Group

Fuel
Group
Fuel Group

Manager
Manager
(1)
(1)

Manager
Manager
(1)
(1)

Manager
Manager
(1)
(1)

Assistant
Assistant
Manager
Manager
(1)
(1)

Assitant
Assitant
Manager
Manager
(1)
(1)

Engine
Engine
Specialist
Specialist
(1)

Research
Officer
(0)
Officer (0)

Adminstrat
Adminstrat
ive
ive
Assistant
Assistant
(1)
(1)
Accounting
Accounting
Assistant
Assistant
(1)
Maintainen
Maintainen
ce
Supervisor
(1)
Cleaner/Cl
erk
(1)
erk (1)

Engine
T
Technician
echnician
s (9)

Research
Assitant
Assitant
(4)
Laboratory
Laboratory
Assitant
(1)

Sustainability
Sustainability
Research Group
Group
Research
Researcher
Researcher
(2)
(2)

CHAPTER 2

WEEKLY ACTIVITIES SCHEDULE

2.0

Weekly Activities Schedule

Wee

Date

k
1

Span
1 - 5th July
st

Activities

Briefing of the history and corporate info of Yanmar

Kota Kinabalu R&D Center Sdn. Bhd. along with the
signing of confidentiality letter and touring of the

company building.
Supervised by Ms. Michelle Ni Fong Fong with her
research on transesterification of low quality oil

feedstock.
Learn the basic analyses done in fuel and oil
analysis.

Example:

Induction

Period

Oxidation

(OSI

IP),

Stability

iodine

value

Index
(IV),

viscosity test and water content Test.

Learned FTIR spectrometer, Metrohms Titrino, Karl
Fisher Titrator, Viscometer bath and Rancimeter,
with reference to the standard operating procedure

8th 12th
July

(SOP).
Learned and practiced glassware and laboratory

apparatus washing according to SOP.

Introduction and Planning of Yanmar Way of Kaizen

(YWK).
Personal

Laboratory Safety Briefing.

Field trip to companys Jatropha farm
Sample Analyses (viscosity, water

Protective

induction period)

Equipments

(PPE)

and

content,

15th 19th

Learned basicity test for catalysts and Hammetts

acidity function.
Photography of samples
Sample Analyses (viscosity,

induction period)
Biodiesel production (Basicity test)
Calorific value briefing and analysis
Ester content briefing and analysis
Initiation of mini-project analysis on Petronas, Shell

and Esso diesel samples.

Fuel deterioration briefing and analysis by using

Metrohm Rancimeter
Fuel dilution test briefing and analysis by using gas

chromatography
Biodiesel production

content)
Sample Analyses

induction period)
Biodiesel
production

July

22nd 26th
July

29th July
2nd August

5th 9th

heterogeneous

August

12th 16th
August

19th 23rd

(basicity
(viscosity,

water

test
water

content,

and

content,

(homogeneous

transesterification,

ester

and

basicity

test

and ester content)

Company Internship Experience Presentation
Biodiesel
production
(homogeneous

and

heterogeneous

test

transesterification,

basicity

and ester content)

Briefing and practice on Ion-exchange of catalyst
Briefing and practice on sulfated ash
Biodiesel production (biodiesel washing and ester

content)
Sample analyses

induction period, density, FTIR)

Briefing and practice on Thermoprep water content

analysis
Briefing and practice on Total Glycerol Content

analysis
Briefing and practice on Methanol Content analysis

August

CHAPTER 3

(viscosity,

water

content,

SPECIFICATION OF WORKS

3.0

Specification of Works

In YKRC, the job scope is differentiated into two areas i.e. research and
analysis.
3.1

Research

One of the ongoing researches in YKRC is the transesterification of low quality

feedstock into biodiesel. Conventionally, low quality feedstock such as used
cooking oils is hard to be converted as biodiesel. However, by using YKRC
catalyst, the transesterification processes are made possible. I was assigned
in research on transesterification of different types of feedstock by using both
homogeneous and heterogeneous methods. After formation of fatty acid
methyl ester (FAME), ester content is determined to identify the value of FAME
in the biodiesel produced. Heterogeneous method used in YKRC is solid
catalyzed transesterification. Therefore, I also helped in ion-exchanged of
catalyst and basicity test of catalyst.
3.1.1 Tranesterification
Transesterification is the process of exchanging the organic group (R) of an
ester with the organic group (R) of an alcohol (Eq 3.1).

R' OH + R OCORR OH + R ' OCOR

(Equation 3.1)

This reaction often produces fatty acid alkyl ester. For example, if methanol is
used to react with a given ester, then the products formed are known as fatty
acid methyl ester (FAME), which is the main composition of biodiesel.
Therefore, transesterification is often regarded as biodiesel production.
Generally, transesterification are catalyzed by either a base or an acid
catalyst. In YKRC, biodiesel production focuses more on

base catalyzed

transesterification.

base-catalyzed

transesterification

However,
are

used

two
i.e.

distinct

types

homogeneous

of

transesterification

and

heterogeneous transesterification.
In homogeneous transesterification, conventional method is applied,
where sodium hydroxide is used as the base catalyst. Briefly, a required
amount of feedstock is measured by measuring cylinder and poured into a
three-necked flask (Fig 3.1). The flask is then mounted with a thermometer
and a stopper on two of the necks respectively. The feedstock in the flask is
then heated up to more than 50oC but less than 70oC. Depending on the
required weight percentage of the catalyst compared to the feedstock weight,
a certain amount of sodium hydroxide is weighed and dissolved in methanol
by using a stirrer. Then, along with the stirrer, the mixture is quickly poured
into the flask and a condenser is swiftly mounted on the top neck. The
temperature is then maintained between 60 oC to 70oC and continuously
stirred for 2 hours.

Figure 3.1 Transesterification set up.

For heterogeneous transesterification, instead of using base such as
sodium hydroxide, solid catalyst is used instead. These catalysts are natural
zeolites and synthetic zeolites that have been calcinated and ion-exchanged
as base solid catalyst. The method of heterogeneous transesterification is
similar (including steps, conditions and time usage) to homogeneous
transesterfication. However, instead of dissolving the sodium hydroxide in
methanol, the weighed solid catalyst is dissolved in methanol and poured into
the feedstock.
Heterogeneous transesterification has an advantage of easier recovery
of the catalyst used while also being able to recycle, regenerate and reuse.
On the other hand, homogeneous transesterification can never recycle the
base catalyst used, such as sodium hydroxide. Any excessive catalysts will be
treated as waste. Therefore, heterogeneous transesterification generates less
waste as compared to homogeneous transesterification as sodium hydroxide
is not used.

10

In general, feedstock with high free fatty acids (FFA) percentage has
lower yield of biodiesel; sometimes, even unsuccessful. This is because FFA
hinders the process of transesterification by reacting with the base catalysts
used such as sodium hydroxide. This results in soap formation instead as
there is not enough catalysts to trigger transesterification process. In
industry, feedstock with high FFA, such as waste cooking oil, is first treated
with acid-catalyzed transesterification, where acids, such as sulfuric acid,
catalyze the formation of esters from the FFA and the alcohol introduced.
Then, it is followed by base-catalyzed transesterification. However, by using
two-steps process, this greatly increases the cost and budget of a company. In
addition, greater amount of waste is also be generated. Hence, YKRC aims to
solve the problem by introducing YKRC-zeolites that can process high FFA
feedstock to become FAME with just one step. Often in YKRC, feedstock
samples are mixed with a certain volume of FFA purposely so as to determine
which catalysts and what conditions are suitable to process the feedstock into
biodiesel. In YKRC, feedstock such as nut oil, crude Jatropha oil, refined
bleached

deodorized

(RBD)

palm

oil

and

many

more

are

used

in

transesterification.

3.1.2 Ester Content

Before biodiesel could be marketed, the purity of the biodiesel has to be
determined. According to EN14103, the minimum content of FAME in the
biodiesel has to be 96.5% (% m/m).
I practiced on determination of the ester content of several feedstock
include ground nut oil, palm oil and Jatropha oil. In brief, the FAME obtained
from the transesterification process is first washed with hot water. Next, the
washed FAME is stirred and heated at 105 oC to remove the water molecules
within. When the FAME turns clear in color, some soap will form due to
hydrolysis. Then, the FAME is filtered by using simple filtration. The filtrate,
which is the washed FAME, is then weighed 250.0 mg into a 10 mL vial. After

11

that, 1 mL of internal standard methyl heptadecanoate (C17:0) is mixed with

the FAME and shakes vigorously. The mixture is then transferred into a 2 mL
GC vial and GC analysis is run. Agilent 7890A GC System (Fig 3.2) is used to
determine the ester content with split/splitless injector, flame ionization
detector and hydrogen as carrier gas.

Figure 3.2 Agilent 7890A GC System

Four samples were transesterified and their ester content determined.
Results (Fig 3.3) shows that ground nut oil, Jatropha oil and palm oil can be
successfully transesterified into biodiesel with high fatty acid methyl ester
content. Castor oil, on the other hand, shows an unexpected low ester
content. It could be due to improper handling of the transesterification
process.

Ester Content (%)

Fig 3.3

Ester content of four samples transesterified during internship.

12

3.1.3 Calcination and Ion-Exchange of Catalyst

Calcination is a treatment process for thermal decompositions, phase
transition or removal of volatile fractions in the sample. General functions of
calcinations are i) decomposition of carbonate minerals, hydrated minerals
and volatile matter; 2) inducing phase transitions within the samples through
high temperature; and, 3) removal of ammonium ions in synthesis of zeolites.
In YKRC, calcination is used to unclog the pores of natural and synthetic
zeolites. Often these zeolites contain impurities within the pores, or some
other compounds clog the pores, for example, calcium carbonate. By high
temperature treatment, calcium carbonate is decomposed to calcium oxide
with the release of carbon dioxide. This increases the pores diameters and
eventually led to increase in total surface area of the samples. A higher total
surface area of the zeolites is desired as more ions exchangeable sites are
freed up.
Briefly, the zeolites are put into clean crucible after washing. Then, the
zeolites are calcinated at 700oC for 5 hours. After that, the calcinated zeolites
will be ion-exchanged.
Ion-exchange process is used to substitute the ions between two
electrolytes or between an electrolyte solution and a complex. This process is
a reversible process as the samples can be regenerated or load with desirable
ions through excess washing of a particular ion. It is widely used in multiple
industries such as food and beverage, chemicals and petrochemicals,
pharmaceuticals, ground and portable water treatment, softening of industrial
water and more. In YKRC, ion-exchange process is approached to remove
undesired ions within the zeolites, and also load the zeolites with basic
anions.

13

In general, ion-exchange process is approached by first putting the

desired solid sample into a 100mL centrifuge tube (Fig 3.4). The sample
should be added until the calibrated line of 30mL. Then, a base solution is
added into the centrifuge tube until the calibrated line of 80mL. After that, the
centrifuge tube with the mixture is immersed in a water bath heated at 4045oC and stirred for 1 hour. After the heating and stirring process, the mixture
is centrifuged for 5 minutes. The clear solution is disposed and the solid is
approached with two more times the ion-exchange process. After all three
times are completed, the mixture is then put into a crucible and heated at
150oC for 3 hours. After heating, the mixture would become dried. The solid
catalysts are then transferred into a plastic petri dish. The solid catalysts are
then readied for both basicity test and transesterification.

14

Figure 3.4 Diagrams of ion-exchange process

3.1.4 Basicity Test
The solid catalysts that undergone the ion-exchange process become basic in
nature. Hence, it is required to determine the basic strength of the solid
catalysts in order to determine whether the solid catalysts are basic enough
for transesterification process. Basic strength is defined as the ability of the
surface sites to convert adsorbed electrically neutral acids into its conjugate
basic form, which is based on the Hammetts acid equation (Eq 3.2).
H_ = pKa + log([A-]/[HA])

(Equation 3.2)

In YKRC, basic strength is determined by running titration on the solid

catalyst. First, the solid catalysts are mixed with 10mL of four different types
of hammetts indicators (Table 3.1 and Fig 3.5) in separate beakers
respectively.

Indicators

Color at neutral
pH

Color at basic
pH

pH
value

Methyl Orange

Red

Yellow

3.7

Phenolphthalei
n

Colorless

Purple

9.8

2,4dinitroaniline

Yellow

Slight red

15.0

4-nitrophenol

Pink/yellow

Slight red

18.4

Table 3.1

Color changes and pH value of selected Hammets indicators

15

a)

b)

c)

d)

Figure 3.5 Color changes of Hammetts indicator with YKRC catalyst; a) in

phenolphthalein; b) in 4-nitrophenol; c) in 2,4-dinitroaniline; and d) in methyl
orange.
If the catalysts are very basic in nature, it will instantly turn color. For
example, a catalyst that turns colorless phenolphthalein into purple color is
quite basic in nature. On another hand, if a catalyst that does not turn the
colorless phenolphthalein to purple instantly; instead, it occurs by over a
period, and then this catalyst is weak in nature. After that, the solid catalysts
and Hammetts indicators are stirred for 10mins. Following that, 0.02mol of
benzoic acid dissolved in ethanol is titrated into the mixture. The volume
required to change the color of Hammetts indicator (for e.g. purple
phenolphthalein) into its original color (for e.g. colorless phenolphthalein) is
noted as the end point. Then, the basic strength is calculated (Eq 3.3).

Basic strengt h ( mmol ) =

V benzoic acid used 0.02 mol

mass of sample gram

(Equation

3.3)
Then, the basic strength of the solid sample with respect to each indicator is
calculated. After that, the total basic strength is calculated by summarizing
the basic strength in each indicator.
Assuming that the color observed when the Hammetts indicators are
added into the catalysts is equal to 50% conversion of the benzoic acid with

16

the indicator, the basic strength of the catalyst will be equal to the pK a of the
benzoic acid. Therefore, by using a variety of indicators, the basic strength of
solid catalysts could be determined quickly.
3.2

Sample Analyses

The samples analyzed in YKRC are mainly grouped as biodiesel and

lubricants. Biodiesels, such as palm oil biodiesel, Jatropha biodiesels and
more, are highly regarded as the next fuel source after non-renewable fuel i.e.
petroleum based fuel. It is both renewable and bioenvironmental friendly.
However, the downside of such biodiesels is the lack of stability due to their
readiness to be oxidized. As a R&D company that focuses on developing new
technologies regarding biodiesels, several analyses are required to monitor
the parameters of such biodiesels according to the European Nation (EN)
standards and/or American Society for Testing and Materials (ASTM)
International.

These

parameters

include

viscosity,

oxidation

stability

(induction period), water content, total acid number, peroxide value, iodine
value, CHN value, sulfur value, density, carbon residue, flash point, calorific
value, and boiling point distribution.
As there are two of us begun our internships in YKRC for these three
months, each of us were assigned different analyses. I am assigned with
viscosity, oxidation stability (induction period), water content, density,
calorific value, and boiling point distribution. On the other hand, the analyses
carried out by the fuel research group at times are related to the engine
research group. Hence, I was also assigned fuel dilution analysis.

3.2.1 Viscosity
Viscosity, also known as thickness of liquid, is the measure of resistance
towards gradual deformation due to shear stress on liquid. It determines how

17

likely a liquid will flow under given circumstances. There are two types of
viscosity that could be determined for a liquid sample i.e. kinematic viscosity
and dynamic viscosity. Kinematic viscosity is the ratio of dynamic viscosity to
the density of the liquid sample while dynamic viscosity is the measure of
resistance to flow when an external force is applied on the liquid sample.

Figure 3.6 Seta KV-5 Viscometer Bath

In YKRC, the kinematic viscosity of fuel and oil are determined by using
a Seta KV-5 Viscometer Bath (Fig 3.6) according to EN ISO 3104. According to
this standard, the kinematic viscosity is determined by measuring the time
taken for the liquid sample to flow under gravity through a calibrated glass
capillary viscometer (Eq 3.4).

v =C t

(Equation

3.4)

where

= kinematic viscosity,

= kinematic constant of liquid sample,

= time taken.

Then, the dynamic viscosity of the liquid sample could be determined by

relating the density of liquid sample (Eq 3.5).

18

v=

(Equation 3.5)

where

= kinematic viscosity,

= dynamic viscosity,

= density.

However, the standard used in YKRC only specifies the monitor of kinematic
viscosity; thus, dynamic viscosity is not carried out in YKRC.
Generally, when temperature increases, the resistance to flow of a
liquid decreases, hence, kinematic viscosity of a liquid sample decreases and
become more fluid. The kinematic viscosity of liquid sample is determined
under two temperatures i.e. 40 oC and 100oC. Normally, kinematic viscosity at
40oC is the basis of monitoring a liquid sample such as fuel according to the
standard. However, when viscosity index is needed, especially for oil samples,
determination of kinematic viscosity at 100oC is carried out and the
relationship of the kinematic viscosity at 40oC and 100oC is determined.
Viscosity index is the measurement for the change of viscosity of a
liquid sample under variations of temperature (Eq 3.6). It is normally used to
characterize the quality of lubricating oils. As mentioned, viscosity decreases
when temperature increases. If an oil sample has a lower viscosity at high
temperature, the machinery surfaces will come into contact and increases
friction. On the other hand, if the oil is very thick even at high temperature,
the machinery will require a large amount of energy to move. Hence, an oil
will a satisfying viscosity at both low temperature (40 oC) and high
temperature (100oC) is highly emphasized. Therefore, viscosity index is used
to determine how likely the oil sample will have an unsatisfying viscosity
when temperature changes.

v . i.=100 (
3.6)

LU
)
LH

(Equation

19

where

v . i.

= viscosity index,

= kinematic viscosity,

LH

= values

based on kinematic viscosity at 100oC.

As mentioned, capillary glass viscometers are used to determine the
liquid sample. Based on different types of samples, different types of
viscometers are used (Fig 3.7). For fuel (diesel and biodiesel) samples, a Utube is used as the liquid is clear and will not obscure the analyst when
determining the movement of liquid passing through the calibrated mark. On
the other hand, oil samples (lubricants) are dark colored; thus, an opaque
tube is used as it allows easy determination of the samples. Other than that,
different viscosities of liquids require different types of tubes i.e. 100, 200,
300 and 400 tubes, where more viscous liquids will require a higher number
of the tube.

Figure 3.7 U tube (left) and opaque tube (right). U tube is used for fuel
samples which are clear and transparent, allowing determination of the
flowing of liquid passing through the calibrated mark easily through
gravitational pull. For opaque tube, the oil sample is first vacuum sucked into
the reservoir bulb, and the flowing of sample is easily determined as it moves
upward of the tube by filling the tube.

20

I practiced viscosity test on samples (i.e. Jatropha oil and palm oil)
stored on open-bottle condition and closed-cap condition. The results (Fig 3.8)
show that over the time of storage, viscosity of samples increases. This could
be caused by air oxidation as oxidation process causes the samples to
thicken. Comparing both open-bottle and closed-cap condition, it could be
seen that closed-cap condition resists the change in viscosity in a higher
efficiency than open-bottle condition. This is due to the lesser interaction of
air with the oil sample.

50
40
30
Viscosity (mm2/s)

20
10
0

Time of storage

Closed-cap Jatropha Oil

Closed-cap Palm Oil
Open-bottle Jatropha Oil
Open-bottle Palm Oil

21

Figure 3.8 Viscosity of samples stored in different condition over ten

months.
3.2.2 Oxidation Stability (Induction Period)
Fuel and oil samples are organic compounds. Biodiesels, especially, are series
of

unsaturated

hydrocarbons.

These

hydrocarbons

are

susceptible

to

oxidation process, where oxidized fuel and oil samples are termed as
deteriorated. A series of oxidized products will form such as acids and
polymers due to free radical reactions. These oxidized products will cause
clogging on plugs and filters of machinery, eventually reduces the efficiency
of the concerned machines. Therefore, it is required for fuel and oil analysis to
determine the stability of a sample toward oxidation.
According to EN 15751, oxidation stability is the period when 50% of
the sample is oxidized. On the other hand, induction period is the period from
the start of measurement to the first rapid formation of oxidized products. In
YKRC, induction period is determined by using Metrohm Rancimeter (Fig 3.9).

Figure 3.9 Metrohm Rancimeter.

Based on the standard, 10L/hr of dry air is purged through the liquid
sample at a temperature of 110oC. The oxidized products are volatile and will
move from the measuring vessel into the reaction vessel where the
conductivity is recorded. There are two types of measuring vessels i.e. a short
measuring vessel and long measuring vessel (Fig 3.10). Depend on different
types of measuring vessels, the conditions, such as weight of sample used

22

and volume of deionized water used on the reaction vessels, vary. For short
measuring vessel, 3.0 g of sample and 50.0 mL of deionized water are used.
On the other hand, 7.5 g of sample and 60.0 mL of deionized water are used
for long measuring vessel.

Figure 3.10 Short (left) and long (right) measuring vessel. A short measuring
vessel is intended for biodiesel samples, while long measuring vessel is
intended for diesel samples.
I practiced induction period on Jatropha oil and palm oil samples. The
results (Fig 3.11) show that induction period of the samples decreases over
time of storage. This implies that the samples could not resist oxidation
efficiently over time and hence the time taken to induce first oxidation
products shortens over time. Similar to viscosity test, closed-cap condition
shows a better efficiency in resisting the oxidation process as it has limited air
molecules to interact with since the cap is closed.

23

25
20
15
Induction Period (hr)

10
5
0

Closed-cap Jatropha Oil

Closed-cap Palm Oil
Open-bottle Jatropha Oil
Open-bottle Palm Oil

Time of Storage

Figure 3.11 Induction period of samples stored in different condition over ten
months.
3.2.3 Water Content
Biodiesel has high hydrophilicity; it attracts water easily. Presence of water
within biodiesel is a troublesome situation as water content promotes the
growth of microbes as biodiesel is a very ideal nutrient base. Growth of
microbes will result in clogging of fuel pump, filter and more. Other than that,
water content also reduces the heat of combustion of the fuel, resulting in
more exhaustion smoke, less power and harder starting of the engine.
According to EN 14214, water content in fuel/oil sample is determined
by using coulometric Karl Fischer titration method (Figure 3.12).

24

Figure 3.12 Coulometric Karl Fischer titrator (left); schematic diagram of KF

titrator (right). The titrator has two chambers i.e. the cathode and the anode
chambers. The sample is directly injected into the anode solution and iodine
is generated at the generated electrode. Generated iodine will react with
water molecules in sample to produce iodide ions. During equivalent point,
excess iodine molecules are present as there is no more water molecules to
react with the iodine molecules. The measuring electrode will then measure
the current needed to achieve such amount of iodine molecules, and is
marked as end-point.
A small weighted sample is injected into the Karl Fisher titrator, which
contains chloroform and Hydranal mixture. Chloroform is used to dissolve the
fuel/oil sample while Hydranal contains the reagents (an alcohol, a base,
sulfur dioxide and iodine) that will react with the water molecules. During the
chemical reactions, one molecule of iodine will be liberated at the anode as
iodide ion with one molecule of water consumed (Eq 3.7 & Eq 3.8) when
current passed through.

+ BSO 3
+ I
B I 2+ B SO 2 + H 2 O+ B 2 BH

+ ROSO3
BSO 3 + ROH BH
3.8)

(Equation 3.7)

(Equation

25

The

end

point

of

the

chemical

reaction

is

detected

by

bipotentiometric method, where a second electrode is immersed in the anode

solution and both have a constant current maintained between the two
electrodes. Before equivalence point, the water molecules in the sample
actively engaged iodine molecules, causing the solution to contain iodide
ion but little iodine molecules. However, at equivalence point, excess iodine
molecules appear resulting in an abrupt voltage drop, which marks the end
point. Therefore, the amount of current needed to generate the required
amount of iodine molecules to reach the end point is then used to calculate
the amount of water in the injected sample.
Similar to the tests before, Jatropha oil and palm oil samples are tested
on water content analysis. The results (Fig 3.13) show that water content of
the samples increase over time. This shows that over time of storage, the fuel
absorbs more water molecules into the liquid. This could be due to the
formation of peroxide molecules and acid molecules during oxidation process
as they are highly hygroscopic. Comparison between open-bottle condition
and closed-cap condition, similar to viscosity test and induction period test,
show that closed-cap condition has a lesser increment in terms of water
content as the sealed condition limited the amount of water molecules to be
interacting with the samples.

Closedcap
Jatropha
Oil

Closedcap Palm
Oil

Openbottle
Jatropha
Oil

Openbottle
Palm Oil

Figure 3.13 Water content of samples stored in different condition over ten
months.

26

3.2.4 Density test

Density is a specific physical characteristic of matter. By checking the density
of a substance, the purity of the substance could be safely assumed. In fuel
and oil analysis, ASTM D4052 is used as a standard test method for density
and relative density of liquid by using a digital density meter. According to the
standard, the density or relative density of petroleum distillates and viscous
oils is determined at test temperatures range from 15 oC to 35C. The
standard also only restricted to the density determination of liquids with
vapor pressures less than 600 mm Hg (or equivalent to 80 kPa) and
viscosities lower than 15 000 mm2/s.
In YKRC, Anton Paar DMA 535N Density Meter (Fig 3.14) is used to
determine the density of fuel and oil samples.

Pump
ON key
Display
Sample cell

Tube

Figure 3.14 Anton Paar DMA 535N Density Meter

Briefly, the density meter is on before analysis is done. Next, the pump is
pressed fully and the tube connected to the density meter is immersed in
washing agent such as toluene as toluene is a suitable solvent to dissolve fuel
and oil sample. Then, the pump is released slowly and the solvent should be
sucked into the sample cell. It is to be noted that the sample cell should be

27

completely filled with the solvent without air bubbles. Then, the liquid is
pumped out and washing is repeated for twice or until no indication of
samples within. After that, washing is continued with acetone as traces of
toluene within the sample cell have to be washed away. Acetone is also a
highly volatile liquid that it will vaporize very quickly afterward. Then, the
tube is immersed in a sample to be determined. Repeating the pumping and
releasing, the sample is sucked into the sample cell and it must be confirmed
that there are no air bubbles within the sample cell as air bubbles significantly
affect the determination of density. Following that, a reading of density and
temperature of the liquid is displayed. When the temperature stopped
blinking, then the density value is recorded. After analysis is completed, the
density meter tube is washed in the same fashion as above.
The density values displayed in the density meter are with respect to
the temperature of the liquid. However, ASTM D4052 requires a value of
density at 15oC as the standard guidance. Hence, calculation has to be done
for the density value to be converted to density value at 15 oC (Eq 3.9)

15=T + 0.723(T 15)

(Equation

3.9)

Where

= temperature the reading is taken.

Jatropha oil and palm oil samples are tested on density test (Table 3.2).
Sample
Denisty (kg m-3)
Jatropha Oil
921
Palm Oil
920
Table 3.2 Density of samples tested in YKRC.
Both test results are confirmed with Zhou et al. (2006), who states that the
density of Jatropha oil is 900 kg m -3 at 25oC, and Sultanar Yasser (2012), who
states palm oil as having 907 kg m-3 at 25oC.

28

3.2.5 Carbon Residue Test

Carbon residue of a fuel is the tendency of carbon deposits to form under high
temperature of combustion in an inert atmosphere, such as in nitrogen
atmosphere. It is shown that there is a negative impact when carbon residue
exists in diesel engine. Therefore, a carbon residue test is used to indicate the
carbonaceous deposit-forming tendencies of the fuel.
ASTM D4530, Standard Test Method for Determination of Carbon
Residue (Micro Method), is used to determine the amount of carbon residue
formed after evaporation and pyrolysis under inert atmosphere. It is used to
provide indication of the relative coke forming tendency. Carbon residue test
serves as an approximation of the tendency of the material to form
carbonaceous type deposits under degradation conditions. In YKRC, SETA
Micro Carbon Residue Tester (Fig 3.15) is used to determine the carbon
residue of sample.

Figure 3.15 SETA Micro Carbon Residue Tester

29

In brief, the vials are pre-heated in an oven at 80 oC for 1 hour to

remove contaminants and moisture content. A hook (Fig 3.16) must be used
to hook and unhook the vials container to ensure no contaminants transferred
on the vials as it might affect the reading during weighing.

Vials
Hook

Figure 3.16 Hook and vials used for carbon residue test.
After pre-heating, the vials are cooled to room temperature in a dessicator.
After that, the vails are weighed in the beam balance. The weights of vials are
recorded and 5.0 g samples are weighed into the vials. Then, the vials, along
with the container, are put into the micro carbon residue tester to be
combusted in nitrogen atmosphere in 553 oC for 20 minutes. Cares have to be
taken that the lid of the tester has to be fully closed else explosion might
occur. After the temperature has cooled down below 100 oC, the vials are
transferred to a dessicator to be cooled down. Finally, the vials are weighed
again and the values are recorded. The carbon residue is then calculated in
mass percentage (m/m %) (Eq 3.8).

Carbonresidue ( m/m )=

mass of residue
100
mass of sample

(Equation

3.9)
The carbon residue value of three commercial diesels sold in Malaysia
is determined (Fig 3.17). The results show that commercial diesel 2 has a
higher carbon residue value, while the rest of the two are around 0.0040.005%. The difference in residue value might arise due to differences in
production methods.

30

0.02

0.02
0.01
0.01
0.01
0.01
0.01
Carbon Reisdue (% m/m)

0.01

0
0

Figure 3.17 Carbon residue value of three different commercial diesels sold
in Malaysia.
3.2.6 Calorific Value
Fuel is combusted in engine and the energy released is used to drive the
pistons within engine, which in turn drive the mechanical energy required by
the vehicle to move. Therefore, calorific value of fuel samples has to be
monitored as less calorific value fuels tend to burn inefficiently and thus
produces higher amount of exhaust which leads to air pollution.
Calorific value is determined by using ASTM D4809, which is the
Standard Test Method for Heat of Combustion of Liquid Hydrocarbon Fuels by
Bomb Calorimeter. According to this standard, a weighed sample is burned in
an oxygen-bomb calorimeter, where the energy released during the
combustion is absorbed by the water bath surrounding the bomb. As the
water molecules absorbed the energy, temperature increases and the heat
change is determined. In YKRC, IKA Calorimeter C2000 (Fig 3.18) is used. This
instrument is a type of isoperibol calorimeter, where a static water jacket is

31

used to insulate the water bath, which contains the bomb. The water jacket is
kept under a constant temperature by using IKA KV 600 Digital water cooler.

IKA Calorimeter
C2000

KV 600 Digital
water cooler

Figure 3.18 IKA Calorimeter C2000 and KV 600 Digital water cooler.
In brief, 1.00 g of sample is weighed in the sample sup (Fig 3.19). Next,
a cotton thread is connected to the sample sup and serves as an ignition
point. Then, the bomb is assembled by putting the sample sup within the
bomb and sealed tight. After that, the bomb is inserted to the calorimeter.
After the sample weighed has been keyed into the calorimeter, START
button is clicked and the bomb will be immersed into the water bath and the
calorimeter will be sealed. Analysis normally takes 30 minutes to complete.
After completion, the display will show the calorific value of the sample
analyzed. The bomb will be ejected out of water bath. At this stage, the bomb
is highly pressurized; hence, a depressurizer is used to release the pressure of
the bomb. Then, the bomb is dismantled and wiped clean before next
Seal cap
analysis.

Depressurizer

Bomb
canister

Sample Soup
Thread

32

Figure 3.19 Schematic diagram and actual diagram of bomb canister for
bomb calorimeter.
Calorific values of several samples are tested. Results (Fig 3.20)
showed that diesel samples generally have higher calorific value than the
biodiesel. However, as the current economy employs usage of blended
biodiesel, which are either B5 or B20, the effect of less calorific value of the
biodiesel is not significant.

Jatropha
Oil

Palm Oil

Commer
cial
Diesel
#2

Commer
cial
Diesel
#3

Commer
cial
Diesel
#1

Figure 3.20 Calorific values of different samples.

3.2.7 Methanol Content Analysis
Methanol is a by-product of biodiesel production, which occurs as excessive
reagent that could not be washed off completely during biodiesel washing.
According to EN14110, maximum amount of methanol within a biodiesel is
0.20 % (m/m). This is because methanol is highly volatile and results in higher
vapor pressure of the fuel. This causes the fuel to be highly flammable and
hard to be stored. Agilent 7890A GC System (Fig 3.21) is used to determine

33

the methanol content. As methanol is highly volatile, headspace sampling

method is used.

Figure 3.21 Agilent 7890A GC System and 7694E Headspace Sampler

I practiced the calibration procedure of methanol content analysis.
Briefly, a QC-graded palm oil sample is transferred to the calibrated mark in a
10 mL volumetric flask. Next, 112 g of methanol is added into the volumetric
flask. The volumetric flask is shook vigorously to homogenize the mixture.
Then, 5 mL of the mixture is transferred into another 10 mL volumetric flask
and the QC-graded palm oil sample is added to the calibration mark. The
mixture is, again, shook vigorously. Lastly, 1 mL of the mixture in the 2 nd
volumetric flask is transferred to a 3 rd 10 mL volumetric flask and calibrated
with QC-graded palm oil sample. Three mixtures with concentration
percentage of 5.0%, 1.0 % and 0.1% are produced. Then, each mixture is
transferred to a 20 mL headspace vial respectively. After that, the headspace

34

vials are inserted into a headspace sampler, which is set to vaporize the
sample at 80oC during injection so that methanol will be liberated. GC system
is using a split/splitless injector with hydrogen as carrier gas.
The detector of GC is flame ionizing detector. The 7694 headspace
sampler and GC system are computationally fixed to communicate between
injections so that the injector will not sample the methanol when there is a
run ongoing in the GC system. Finally, a calibration chromatogram (Fig 3.22)
is obtained and the calibration curve graph is calculated. The graph shows a
very good correlation factor at 0.99989 and hence could be used for actual
sample determination.

Figure 3.22 Chromatogram of methanol content calibration (left) with the

calibration curve graph (right).
3.2.8 Fuel Dilution Analysis
Fuel is directly injected to the diesel engine. Then, compression from piston
leads to combustion. Overtime, some fuels are not combusted completely and
will stick on the wall of the engine. These fuel droplets will eventually drop
down to the lubricating oil of engine by being pulled by piston. These fuels
then dilute the lubricating oil of engine and leads to poor performance of
lubricants as dilution causes less viscous lubricants. ASTM D3524 is used to
determine how dilute is the engine lubricating oil so as to monitor a constant
inner environment of the engine.

35

Agilent 7890A GC System (Fig 3.23) is the main instrument used to

identify the fuel dilution in diesel engine. Cool-on column injector is used with
helium as the carrier gas. Automated liquid sampler is used as sampling
method and flame ionizing detector is used as the detector. In brief, 1.0 g of
n-decane is transferred to a short measuring tube of Metrohm Rancimat,
which acts as the internal standard to compare to the fuel within the sample.
Next, 10.0 g of fuel diluted lubricating oil is transferred into the tube
containing n-decane and homogenized on a vortex machine for 30 second.
Then, 0.5 g of the mixture is transferred to a 10 mL volumetric flask and top
up with the solvent, carbon disulfide, to the calibrated mark. After that, the
mixture is shook vigorously and transferred into a 2 mL GC vial.

Figure 3.23 Agilent 7890A GC System

A chromatogram (Fig 3.24) is obtained after the analysis is completed.
The peak area of diesel component is then compared to the peak area of ndecane. The ratio (Eq 3.10) is then calculated to give the percentage of fuel
dilution.

36

Figure 3.24 A typical fuel dilution chromatogram.

Ratio=

peak area of diesel

peak area of ndecane

(Equation 3.10)
In YKRC, fuel dilution percentage is used to monitor how diluted is the
lubricating oil in engine, which the project aims to identify at what dilution
percentage that the engine performance will decrease. As the current aim is
to determine the performance of engine in fuel dilution percentage at 20%,
the engine lubricating oil is monitored to remain in 20% range. If the dilution
percentage is low, then fuel is added into the lubricating oil to ensure it stays
at 20% value. Then, the dilution value will rise and over the time of running,
will decrease again. After that, the top-up of fuel is repeated (Fig 3.25).

30
25
20
15
Fuel Dilution (%)

10
5
0

37

Fig 3.25

A typical fuel dilution graph plotted over a run of twenty times.

3.2.9 Total Glycerol Content

During production of biodiesel, transesterification occurs. Triglycerides react
with methanol to form fatty acid methyl ester (FAME). When the 1 st glycerin
reacts with methanol, diglyceride is formed and 1 molecule of FAME is
released. When the 2nd glycerin reacts, monoglyceride is formed and another
1 molecule of FAME released. When the monoglyceride reacts with methanol,
glycerol is produced and releases last molecule of FAME. In biodiesel
production, sometimes the triglycerides do not react completely. According to
EN14105, monoglyceride, diglyceride, triglyceride, and free glycerol content
are kept maximum in 0.80 % (m/m), 0.20 % (m/m), 0.20 % (m/m) and 0.02 %
(m/m) respectively. Therefore, determination of the total glycerides content
and glycerol content helps to understand how well the conversion of
transesterification process is.
I practiced the calibration procedure for total glycerol content in YKRC.
Agilent 6890N GC System (Fig 3.26) is used to determine total glycerol
content, with cool on column as the injector, flame ionizing detector as
detector and hydrogen as carrier gas.

Figure 3.26 Agilent 6890N GC System

38

For

calibration

mixture

preparation,

standards

graded

monoglyceride,

diglyceride, triglyceride, 2,4-butanediol, tricaprin, and glycerol are used. Four

different concentration mixtures are prepared with respective ratio of mixture
(Table 3.3) and mixed in four different 10 mL volumetric flasks respectively.
Next, 100 L of N-methyl-N-(trimethylsilyl)trifluoroacetamide is mixed into
each of the volumetric flask and shake vigorously. Then, the flasks are sit still
in room temperature for 15 minutes. After that, 8 mL of solvent (n-heptane) is
mixed into each of the flask. The mixture in each flask is then transferred into
2 mL GC vials and set to run for GC analysis.
Standard (L)
1
Glycerol
10
Monoglyceride
50
Diglyceride
10
Triglyceride
10
Butanediol (STD #1
80
Tricaprin (STD #2)
100
Table 3.3 Mixing ratio of each standard.

2
40
120
40
30
80
100

3
70
190
70
60
80
100

4
100
250
100
80
80
100

A calibration chromatogram (Fig 3.27) is then obtained which showed

unsatisfying curves due to noisy peaks. Hence, the calibration is re-run again
by another operator and the graphs are compared. The in-house calibration
graph is clearer and with minimal noise. Then, a series of calibration graphs
(Fig 3.26)is plotted and the correlation factors all show satisfying values;
hence, it could be used in actual sample determination.

1
5
4
23

7
6

Figure 3.27 Comparison of in-house calibration chromatogram (above) with

the calibration chromatogram that I produced (below).

39

Figure 3.27 Calibration

curve

calibration chromatogram.

graphs

for

in-house

methanol

content

40

References:
Zhou, H., Lu, H.F. & Liang, B. 2006. Solubility of Multicomponent Systems in
the

Biodiesel Production by Transesterification of Jatropha curcas L. Oil with

Methanol. J. Chem. Eng. Data, 51(3):1130 1135.

Sultana Yasser. 2012. Density Table for Palm Oil Products.

Retrieved on, 11th September 2013
From, http://sultanayasser.blogspot.com

41

CHAPTER 4

CONCLUSION

In conclusion, I learned a great deal of laboratory skills and techniques

especially

involved

in

chemicals

and

apparatus

handling.

learned

instrumental techniques of gas chromatography and also transesterification

processes. In addition, I also learned various analyses such as viscosity test,
water content test, induction period test, density test, calorific value test, and
carbon residue test. Other than that, I learned of proper procedures in
scheduled waste disposal. Three months of experiences in Yanmar Kota
Kinabalu R&D Center S/B is very fulfilling and challenging. I will definitely
suggest YKRC as one of the companies that fit for internship learning.