1

CHAPTER 1

INTRODUCTION
1.1

Yanmar

Yanmar Co., Ltd. ( Yanm Kabushiki-Gaisha?) is a Japanese

company involved in the manufacture and sales of engines, agricultural machinery and
light ships. Yanmar's headquarters are at 1-32 Chayamachi in the Kita ward of the
Japanese city of Osaka. Yanmar is the patron of the J. League soccer team Cerezo
Osaka and for the Yanbo Marbo weather forecast programme on Japanese television.
Originally, the company planned to trade under the name "Tonbo", meaning
"dragonfly", as dragonflies are a symbol of agriculture in Japan. However, this
trademark was already registered to a Shizuoka soy sauce maker. Therefore, the name
was changed to "Oniyanma" (Anotogaster sieboldii), the largest of all dragonflies in
Japan. It is said that in the end, the name was also selected because it sounded similar
to the surname of the company's founder, Yamaoka Magokichi. It is likely that the
"oni" was dropped because it means "devil" or "demon" in Japanese.
Yanmar is for the most part a corporation specializing in diesel engines, and
also makes light fishing boats. In recent years Yanmar has started sales of hulls for
ships. Manufacturing tractors, combine harvesters, rice-planting machines, and Heavy
Utility Machinery. Yanmar ranks along with Kubota and Iseki & Co. as one of the top
brands of agricultural machinery in Japan. Yanmar was the first to put a diesel engine
in a rice planting machine with a passenger seat. Yanmar's flagship product in the
construction machinery business is light hydraulic shovels.
In recent years, Yanmar has also manufactured industrial power generators and
small to medium sized snow removal machines. In typical Yanmar fashion, some of
the smaller snow removal machines feature light, air-cooled diesel engines. Yanmar
also supplies engines to Thermo King Corporation used in refrigerated trucks and

trailers. In 2007, the Yanmar Model HB horizontal diesel engine (made in 1933) was
added to the Mechanical Engineering Heritage of Japan.
1.1.1

Company Profile

Trade name

Yanmar Co., Ltd.

Head office

1-32 Chayamachi, Kita-ku,Osaka, Japan

Founded

March, 1912

Capital

6.2 billion yen

Chairman

Tadao Yamaoka

President

Takehito Yamaoka

1.1.2

Founders Spirit

Yanmar's fouder, Mr. Magokichi Yamaoka, believed that, "there are so many serious
things around us, like Mother Earth and life itself, but if we simply work with hearts
of sincerity and gratefulness, then surely everything will open up before us, people
everywhere

will

thank

each

other

and

better

world

will

unfold."

Thus he came up with the founding spirit, "Grateful to serve for a better world".
1.1.3

Mission

We, the YANMAR group, will strive to create new and meaningful value together in
partnership with our worldwide customers. We will be innovators and leaders in
harnessing energy, while contributing to an environmentally sustainable society,
through the delivery of unrivaled products and services.
1.1.4

Brand mark

The new Yanmar brand logo mark represents the intangible value intrinsic to Yanmar.
The center of the brand mark combines the upper-case "Y" and lower-case "r" of
Yanmar. The three lines at the bottom represent the arena for our activities; the sea, the
land, and urban. In other words, the Earth.The image represents all of us at Yanmar
boldly advancing into the future firmly committed to fulfilling our valuable mission
on this precious Earth.

1.1.5

Targetmark

The Yanmar trademark is a rich symbol. The inner circle represents Japan, the outer
circle the world, and Yanmar is the bridge connecting the two. The Yanmar name rises
gradually to the right symbolizing Yanmar's commitment to growth and progress.

1.1.6

Company History

Table 1.1 showed the history of Yanmar group.

Table 1.1
Year
2007

Company history

YMU.
Production of compact utility tractors at YAMA starts
Yanmar Celebrates 5 Millionth Engine.

India sales office established.

Yanmar develops woods based biomass power generation for

2006

History
Restructuring of North America Companies New YA, YAMA and

Higashi-ohmi city.
2005

2004

2003

New Yanmar brand mark and mission statement established.

Yanmar Noki Korea established.
Capital Participation of Yanmar in India Tractor Manufacturer, ITL
Yanmar Construction Equipment Co.,Ltd. established.
Yanmar Construction Equipment Sales Co.,Ltd. established.
Yanmar Agricultural Machinery(Thailand) Co.,Ltd. established.

Yanmar Energy System Co.,Ltd. established

Yanmar Engine(Shanghai) Co.,Ltd. established.
Shandong Shefeng Yanmar Engine Co.,Ltd
established.

2002

2001
2000

1999
1998

1997

Yanmar's 90th anniversary since foundation

Company name changed to Yanmar Co., Ltd.
Yanmar Marine International BV, Yanmar Marine System Co., Ltd.

Yanmar Logistics Service Co.,Ltd. established.

Joint venture company for production of parts launched in Indonesia
New R&D Institute opened in Maibara
Trade and Industry Ministry's energy-saving prize for micro-gas-

turbine generation and mirror-cycle gas cogeneration

Yanmar Energy System Mfg. Co., Ltd. established
Domestic operations reorganized into seven sales companies
Environment Minister's prize for cool containers

Tadao Yamaoka decorated by the nation

Takehito Yamaoka assumed the presidency and Tadao Yamaoka the

chairmanship
ISO14001 certification for all plants

1995

Ultra-modern Biwa Plant opened

Joint venture company launched with Cagiva in Italy
Representative office opened in Shanghai
FIE pump unit injector wins national invention prize
ISO9001 certification for all business operations
Ten millionth diesel engine produced
Full-scale entry into environmental business with development of

raw garbage processing and water purification equipment

Subsidiary established in the Netherlands
Subsidiary established in Singapore
Joint venture company launched with Ammann in France
Production of gas engine heat pump launched
Marine farm established
World's first diesel outboard engine developed
World's smallest air-cooled diesel engine developed
Production of gas turbines launched
Subsidiary established in the United States
Subsidiary established in Thailand
Amagasaki Plant's production facilities certified by AB and LR

Amagasaki Plant first factory in Japan to receive mass production

facility certification from NK (Japan Maritime Association)

Service base established in the Netherlands
Yanmar Shipbuilding & Engineering Co., Ltd. established
Yanmar Sangyo Co., Ltd. established
Subsidiary established in Indonesia
Deming Prize (first in this industrial sector)
Subsidiary established in Malaysia
Service base opened in Thailand
Production of compact construction equipment launched

Yasuhito Yamaoka passes away. Succeeded as president by Tadao

1962

Yamaoka (current chairman)

Test operation of rotary engine
Service base opened in Singapore
Magokichi Yamaoka passes away. Succeeded as president by

1961
1957

Yasuhito Yamaoka
Yanmar Agricultural Equipment Co., Ltd. established
Subsidiary established in Brazil
Awarded German Merit Cross

1955

Awarded Diesel Gold Medal by German Inventors' Association

1952
1947

Company name changed to Yanmar Diesel Engine Co., Ltd.

Entered the market for small-sized diesel engines in fishing boats

1993
1992
1990
1989

1988
1987
1983
1982
1981
1978
1977
1976
1972

1968
1967
1966

1963

1942
1936
1933
1921

1.2

Nagahama Plant opened

Amagasaki Plant opened
World's first practical small diesel engine developed
Yanmar brand name adopted

Yanmar Kota Kinabalu R&D Center (YKRC)

In January 2008, Yanmar opened the Yanmar Kota Kinabalu R&D Center (YKRC)
research and development base in Malaysia. This is Yanmar's first overseas research
and development base, and the base has been established as part of the company's
efforts to strengthen its environmental technologies. The initial roles of YKRC are
twofold: (1) To develop technologies for engines capable of "B100" operation
(operation using 100% biodiesel fuel) and endurance testing of these engines, and (2)
To analyze and evaluate fuels and lubricating oils for biodiesel engines. Biodiesel fuel
is made from raw materials, plant matter, which can rot over time. Therefore,
important research themes in this area include the analysis of fuel processing quality
and storage conditions, and the effects of fuel changes on the engine.
YKRC is located in the Kota Kinabalu Industrial Park in Sabah where it would
be possible to obtain a stable supply of large quantities of biodiesel fuels. A large
amount of fuel is required for the endurance testing of engines that use biodiesel fuel.
Many types of fuels can be used, including waste cooking oil, rape seed oil, palm oil,
and even Jatropha oil, which have recently been receiving attention as a nonconsumable type of oil. At YKRC, it is actually possible to perform research with
various types of biodiesel fuels.
YKRC currently has a staff of 13. Two of them are Japanese and the rest are
locals. YKRC consist of multiracial staff such as Kadazan, Dusun, Rungus, Bajau,
Chinese, Indian and Bugis. In the future, YKRC will not only help to expand the
development of biotechnologies involving biogas and wooden gas to facilities
overseas, the organization also plans to begin working in the development of
technologies for protecting marine environments, such as land-based circulating
aquaculture, and to have YKRC become a technology hub for the Asian region.

1.2.1

YKRC Organization Chart

Figure 1.1 showed the organization chart of YKRC

Managing Director

Finance &
Administrative

Manager

Assistant

Assistant

Engine R&D

Fuel R&D

Manager
(Director)

Manager
(Director)

Assistant
Manager

Assistant
Manager

Research
Assistant

Research
Officer

Research
Assistant

Figure 1.1

Lab
Assistant

Organization chart of YKRC.

CHAPTER 2

TRAINING SCHEDULE

The table below showed the activities and projects done during practical training.

Table 2.1

Training schedule
Activities/Projects

Glasswares Cleaning
Stock checking
Manual titration (AOCS)
Chemicals categorization
Total Acid Number (TAN) test on blended biodiesel
Viscosity test on blended biodiesel
Biodiesel making-1 step base catalyzed transesterification process
Jatropha seed project

Oil press (sample preparation) by using hydraulic press machine

Sample analysis by using 785 DMP Titrino for the total acid

Week
1

2
3
3-4
4
5-7

number (TAN) ;and 831 KF Coulometer for water content

Protein content determination by using CHNS/O analyzer

CHAPTER 3

ACTIVITIES/ PROJECT SPECIFICATION

3.1

Standard Method for Biodiesel Analysis

Biodiesel is defined as the mono alkyl esters of long chain fatty acids derived from
vegetable oils or animal fats, for use in compression-ignition (diesel) engines. The
most common biodiesel fuel is made by the transesterfication of soy or rapeseed
triacyglycerides with methanol in the presence of a strong base catalyst such as
sodium hydroxide, potassium hydroxide, or sodium methoxide.
In YKRC, two standard methods are currently being used in biodiesel analyses
which include ASTM D6751 and EN 14214. In the US, the ASTM (American Society
for Testing and Materials) recently adopted D 6751, which specifies properties for
neat biodiesel intended for blending with diesel fuel containing up to 500-ppm sulfur.
European standards organization, CEN (Comit Europen de Normalisation) has
released specifications for biodiesel, EN 14214, which specifies properties and the test

10

methods needed to determine compliance. This standard allows any feedstock to be

used, but its specifications are most easily met by rapeseed methyl esters.
3.1.1

ASTM D 6751

ASTM fuel standards are the minimum accepted values for properties of the fuel to
provide adequate customer satisfaction and/or protection. ASTM D6751-08 details
specifications for biodiesels blended with middle distillate fuels. This specification
standard specifies various test methods to be used in the determination of certain
properties for biodiesel blends.
For diesel fuel, the ASTM standard is ASTM D 975. All engine and fuel
injection manufacturers design their engines around ASTM D 975. In cooperative
discussions with the engine community early in the biodiesel industry's development,
engine manufacturers strongly encouraged the biodiesel industry to develop an ASTM
standard for biodiesel fuel which would allow them to provide their customers with a
more definitive judgment on how the fuel would affect engine and fuel system
operations compared to ASTM D 975 fuel for which an engine was designed.
An ASTM standard is not easily achieved. Some standards can take over 10
years to gain agreement and be issued by ASTM. This rigorous, time-consuming
process is why ASTM standards are recognized and adopted by others worldwide. The
approval of this biodiesel standard, and the technical reviews necessary to secure its
approval, has provided both the engine community and customers with the
information needed to assure trouble free operation with biodiesel blends.
3.1.2

EN 14214

EN 14214 is an international standard that describes the minimum requirements for

biodiesel.

11

Table 3.1

Specification for Biodiesel (B100) ASTM D6751-08

Property

Limits

Units

Flash Point

ASTM
Method
D93

130 min

Degrees C

Water & Sediment

D2709.

0.050 max

% vol

Kinematic Viscosity, 40 C

D445

1.9 - 6.0

mm2/sec.

Sulfated Ash

D874

0.020 max.

% mass

Sulfur
S 15 Grade
S 500 Grade

D5453

Copper Strip Corrosion

D130.

No. 3 max

Cetane

D613

47 min.

Cloud Point

D2500

Report

Degrees C

Carbon Residue
100% sample

D4530*

0.050 max.

% mass

Acid Number

D664

0.50 max.

mg KOH/gm

Free Glycerin

D6584

0.020 max.

% mass

ppm
15 max.
500 max.

12

Total Glycerin

D6584

0.240 max.

% mass

Phosphorus Content

D 4951

0.001 max.

% mass

Distillation Temp,Atmospheric
Equivalent Temperature, 90%
Recovered
Sodium/Potassium

D 1160

360 max.

Degrees C

UOP 391

5 max,
combined

ppm

Table 3.2

EN 14214

Property

Test method

Ester content
Density at 16 C

prEN 14103
EN ISO 3678
EN ISO 12186
EN ISO 3104
ISO/DIS 3679
prEN ISO 20846
prEN ISO 20884

Viscosity at 40 C
Flash point
Sulfur content

Limits
Minimum Maximum
96.5
860
900

Units
% (m/m)
kg/m3

3.50
120
-

5.00
10.0

mm2/sec.
C
mg/kg

Carbon residue (on 10

% distillation residue)
Cetane number
Sulfated ash content

EN ISO 10370

0.30

% (m/m)

EN ISO 5165
ISO 3987

51.0
-

0.02

% (m/m)

Water content
Total contamination

EN ISO 12937
EN 12662

-.
-

500
24

mg/kg
mg/kg

Copper strip corrosion

(3 h at 60C)

EN ISO 2160

Oxidation stability,
110C
Acid value
Iodine value
Linolenic acid methyl

prEN 14112

Rating
Class 1

prEN 14104
prEN 14111
prEN 14103

6.0

Hours

0.50
120
12.0

mg KOH/gm
% mass
% (m/m)

13

ester
Polyunsaturated
methyl esters (>= 4
double bonds)
Methanol content
Monoglyceride
content
Diglyceride content
Triglyceride content
Free glycerol

% (m/m)

prEN 14110
prEN 14105

0.20
0.80

% (m/m)
% (m/m)

prEN 14106

0.20

% (m/m)

prEN 14106
prEN 14105

0.20
0.02

% (m/m)
% (m/m)

0.25
5.0

% (m/m)
mg/kg

5.0

mg/kg

10.0

mg/kg

prEN 14106
prEN 14105
prEN 14108
prEN 14109
prEN 14538

Total glycerol
Group I metals
(Na + K)
Group II metals
(Ca + Mg)
Phosphorus
prEN 14107
content
3.2 Analysis of crude Jatropha curcas oil
Jatropha curcas seed

Hydraulic mechanical
expression of jatropha oil seed

Analysis

Water content

Figure 3.1

Total acid number (TAN),

Free fatty acid (FFA)

Total protein
content

Overall methodologies.

Jatropha curcas L. (Euphorbiaceae) has attained significant economic importance due

to its industrial uses and as a very promising source of non-edible oil that can be used
as feedstock for production of bio-diesel. Currently, soybean, sunflower, rapeseed and

14

cotton seed oils are being used for production of bio-diesel. However, J. curcas are
preferred in tropical countries over other feedstock since these are hardy species and
can be cultivated on non-agricultural land and do not compete with land for the
production of food.
Augustus et al. (2002) have reported that J. curcas seeds contain around 20
40% oil. Mechanical expression using hydraulic presses is one of the ways by which
oil is removed from oilseeds by the use of presses. This method is generally preferred
because of its lower initial and operational costs. It produces relatively
uncontaminated oil as compared to the solvent extraction process and it allows the use
of the cake residue.
It is important to notice the distinction that is made between the characteristic
(fixed) and variable properties. Characteristic properties are relatively constant for a
given kind of oilseed. Variable properties are strongly influenced by processing and
seasons, e.g. climatic and geographic influences during growth of the seeds, the
storage of the seeds, pressing conditions and further processing of the oil. Hence, it is
necessary to determine what quality can be obtained from the crude jatropha oil
extracted from different batches of jatropha fruit. The variable properties such as acid
value and water content of the jatropha oil were determined. Kinematic viscosity
which is one of the characteristic properties was also determined.
Water is naturally present in the oil in small amounts. Its amount should be
kept as low as possible, because it can cause cavitation, erosion and corrosion in the
injection system. Furthermore a boundary between water and oil in the tank (possible
above some 0.1 %) may provoke the development of bacteria and fungi that block the
fuel filter. In colder climates, the water freezes and lead to obstruction of the fuel
system.
Fatty acids can be bound or attached to other molecules, such as in
triglycerides or phospholipids. When they are not attached to other molecules, they are
known as free fatty acids. FFA, represented by the acid number, can cause corrosion
and lubrication oil problems, and finally complete engine breakdowns. The acid value

15

or neutralisation number expresses the amount of free fatty acids in the oil and its
influenced (positively) by refining of the oil and (negatively) by aging. Hence, the
acid value and FFA must be kept as low as possible because these acids may attack
metal components in the injection system and because they may harm the engine oil,
endangering the engines lubrication. This must be taken very seriously because the
potential damage is very costly. Potential damage is failure of the injection equipment,
or the entire engine. Aging of the pure plant oil can be slowed down by storing the
seeds and the oil at dark, cold and in closed cans (excluding air exchange).
The viscosity of the crude oil is more or less constant for a given kind of oil,
but may increase with aging of the oil. The viscosity is dependent on the temperature
of the oil. The viscosity of the crude oil has an enormous influence on the atomisation
of the fuel upon injection. The high viscosity of the crude oil may possibly causing
incomplete combustion with excess noise, smell and emissions and cause engine
damage in the longer run. Some kinds of injection equipment may take permanent
damage from running with too high fuel viscosity.

Objectives

To clarify optimum condition of jatropha seed extraction under different

conditions.

To determine the effect of different batches of jatropha seed sample on the oil
content and quality.

To study feasibility of fruit kernel as high protein source for other commercial
purpose.

Procedure
Approximately 50.0 g of the jatropha seeds were weighted and the shells were then
removed to facilitate the mechanical expression using hydraulic presses. The fresh
crude jatropha oil was then used to test for its water content, TAN and viscosity.

3.2.1

Water Content Determination

16

Objective
To determine the water content present in the jatropha oil by using 831 Karl Fischer
Coulometer.
Procedure
Approximately 1 ml (~1 g) of the jatropha oil was filled into a syringe and then
injected into the 831 Karl Fischer Coulometer. 3 replicates were done.
Discussion
Karl method for quantifying water content in a biodiesel. The fundamental principle
Fischer titration is a widely used analytical behind it is based on the Bunsen reaction
between iodine and sulfur dioxide in an aqueous medium. Karl Fischer discovered that
this reaction could be modified to be used for the determination of water in a nonaqueous system containing an excess of sulfur dioxide. Primary alcohol (methanol) is
used as the solvent, and a base (pyridine) as the buffering agent.
ROH+SO2 + RN

[RNH]SO3R + H2O + I2 + 2RN

2[RNH]I +[RNH]SO4R

[alcohol] [base] [alkylsulfite salt] [water] [iodine] [hydroiodic acid salt] [alkylsulfate
salt]
The alcohol reacts with sulfur dioxide (SO 2) and base to form an intermediate
alkylsulfite salt, which is then oxidized by iodine to an alkylsulfate salt. This oxidation
reaction consumes water. Water and iodine are consumed in a 1:1 ratio in the above
reaction. Once all of the water present is consumed, the presence of excess iodine is
detected voltametrically by the titrators indicator electrode. That signals the end-point
of the titration. The amount of water present in the sample is calculated based on the
concentration of iodine in the Karl Fisher titrating reagent (i.e., titer) and the amount
of Karl Fisher Reagent consumed in the titration.
Corrective action
Karl Fischer Coulometer is very sensitive to sample size. Hence, we have to make
sure approximately 1 ml of sample had been injected for every each of the 3
replicates.

17

3.2.2

Total acid number (TAN) determination

Objective
To determine the total acid number (TAN) and free fatty acid (FFA) present in the
jatropha oil by using 785 DMP Titrino.
Introduction
The Total Acid Number (TAN) is the amount of potassium hydroxide (KOH) in
milligrams that is needed to neutralize the acids in one gram of oil. It is an important
quality measurement of crude oil. There are two types of methods used to determine
the TAN value which include potentiometric titration or by color indicator titration,
AOCS method.
Potentiometric titration is the titration method used in 785 DMP titrino for
determination of the oils TAN. The sample is normally dissolved in toluene and
propanol with a little water and titrated with alcoholic potassium hydroxide (if sample
is acidic). A glass electrode and reference electrode is immersed in the sample and
connected to a voltmeter/potentiometer. The meter reading (in millivolts) is plotted
against the volume of titrant. The end point is taken at the distinct inflection of the
resulting titration curve corresponding to the basic buffer solution. The total acid
number was calculated by using the following equation:
Acid number in mg KOH / g sample = (EPn C31) * C01 * C02 * C03 / C00
EPn = Titrant consumption in mL to reach the nth (last) equivalence point.
C00 = Sample weight in g
C01 = 0.1 (concentration of the titrant in mol/L)
C02 = Titre of the titrant
C03 = 56.106 [M(KOH) in g/mol]
C31 = Blank value consumption for the used quantity of solvent
FFA value can be calculated by using the formula below:
FFA = TAN/1.99
Color indicating titration is the type of titration method in which an appropriate
pH color indicator eg phenolphthalein, is used. Titrant is added to the sample by

18

means of a burette. The volume of titrant used to cause a permanent color change in
the sample is recorded and used to calculate the TAN value. This is the standard
AOCS method used for TAN determination.
Procedures
The reagents below were prepared which include:

Standard: 1.220 g of benzoic acid in 100 mL ethanol

Titrant/blank: 0.1 mol of KOH in IPA
Solvent mixture: 500 mL toluene + 495 mL IPA + 5 mL H2O

The standard, blank and solvent mixtures reagents were then analyzed and done in 3
replicates. Once the TAN analysis for the standard, blank and solvent mixtures had
been completed, the oil sample was then weighed and the solvent mixture was then
poured into the sample prior to determination. The sample size depends on the
expected acid value.
Upon completion of the titration, the electrodes were rinsed first with toluene
or IPA, then with ethanol and finally with distilled water. The surface of the electrode
was then dapped with tissue because the electrode has a membrane layer which needs
to be protected. In sample changer operation, the electrodes were immersed, while
stirring, for 10 s each in toluene/IPA, then ethanol, and finally rinse well in a separate
beaker with distilled water. When not in use, the Solvotrode and the reference
electrode were stored in the respective electrolyte solutions. The Pt Titrode should be
stored in distilled water.
Discussion
Acid value (or "neutralization number" or "acid number" or "acidity") is the mass of
potassium hydroxide (KOH) in milligrams that is required to neutralize one gram of
chemical substance. The acid number is a measure of the amount of carboxylic acid
groups in a chemical compound, such as a fatty acid, or in a mixture of compounds.
The acid number is used to quantify the amount of acid present, for example in a
sample of biodiesel. It is the quantity of base, expressed in milligrams of potassium
hydroxide that is required to neutralize the acidic constituents in 1 g of sample.

19

High TAN crude oils contain naphthenic acids, a broad group of organic acids
that are usually composed of carboxylic acid compounds. These acids corrode the
distillation unit in the refinery and form sludge and gum which can block pipelines
and pumps entering the refinery. Hence, crude oil with lower TAN has better quality.
Corrective action
The solvent mixture must be poured into the sample and not vice-versa to prevent lost
of the oil sample. The mixture was then stirred for a few minutes to ensure the mixture
was homogenized.

3.2.3

Viscosity Test

Objective
To determine the viscosity of the crude jatropha oil at 40, 50, 60, 70 and 80 C
Introduction
Kinematic viscosity is defined as the resistance to flow of a fluid under gravity. The
result of kinematic viscosity was calculated at different temperatures for the measured
flow time and the viscometer constant, by using the following equation:
V= C x t
Where,
V= kinematic viscosity, mm2/s
C= calibration constant, mm2/s2
t = measured flow time, s
The Seta KV-8 has a 40 litre temperature controlled oil bath that can
accommodate up to eight standard viscometer tubes. Digital temperature control and
an inbuilt cold water cooling coil provide accurate and stable test temperatures from
ambient to 150 C (0.01 C below 100 C and 0.03 C at 150 C). The bath is
protected by low liquid level and over temperature cut-outs. Equipped with a

20

toughened glass front window, easily accessible drain valve, levelling feet, and with
provision for fitting diffused back lighting, top plate, and attachments.
Procedures
The viscosity of the jatropha oil was tested by using KV-5 Viscometer Bath. The oil
samples were filled into the viscometer U tubes and tested at 40, 50, 60, 70 and 80 C.
Three types of viscometer U tubes are available which included tube 100, 200 and 300
and each with different calibration constants. Selection of types of U tubes was
according to the expected viscosity value. Tube 200 was used for crude jatropha oil.
The time required for the meniscus to flow from the first and second timing mark was
recorded. 3 replicates were done.
Discussion
Viscosity refers to how thick or thin the oil is. Oil is rated for viscosity by heating it to
a specified temperature, and then allowing it to flow out of a specifically sized hole.
Its viscosity rating is determined by the length of time it takes to flow out of the hole.
If it flows quickly, it gets a low rating. If it flows slowly, it gets a high rating. The
absolute viscosity of a fluid is strongly influenced by temperature. As temperature
increases, the viscosity of the oil sample decreases. It is customary to express this
relationship as a plot of viscosity versus temperature. Engines need oil that is thin
enough for cold starts and thick enough when the engine is hot. Since oil gets thinner
when heated, and thicker when cooled, most of us use what are called multi-grade, or
multi-viscosity oils. These oils meet SAE specifications for the low temperature
requirements of light oil and the high temperature requirements of heavy oil.
Kinematic viscosity also influenced by the compound structures of the oil.
Kinematic viscosity increases with chain length of either the fatty acid or alcohol
moiety in a fatty ester or in an aliphatic hydrocarbon. The increase in kinematic
viscosity over a certain number of carbons is smaller in aliphatic hydrocarbons than in
fatty compounds. The kinematic viscosity of unsaturated fatty compounds strongly
depends on the nature and number of double bonds with double bond position
affecting viscosity less. Terminal double bonds in aliphatic hydrocarbons have a
comparatively small viscosity-reducing effect. Branching in the alcohol moiety does

21

not significantly affect viscosity compared to straight-chain analogues. Free fatty acids
or compounds with hydroxy groups possess significantly higher viscosity. The
viscosity range of fatty compounds is greater than that of various hydrocarbons
comprising petrodiesel. The effect of dibenzothiophene, a sulfur-containing compound
found in petrodiesel fuel, on viscosity of toluene is less than that of fatty esters or
long-chain aliphatic hydrocarbons. Overall, the sequence of influence on kinematic
viscosity of oxygenated moieties is COOH is approximately equal to C-OH >
COOCH3 which is approximatly equal to C=O > C-O-C > no oxygen. Further research
needed to be done.
Corrective action
Random error or human error may affect the results of viscosity test since the time
needed for the oil to flow from the initial to the final mark happens in a split second.
Hence, to avoid those errors, we have to observe the meniscus level very carefully and
response quickly. In the future, the kinematic viscosity of numerous fatty compounds
present in the crude jatropha oil can be determined at 40 C (ASTM D445) as this is
the temperature defined in biodiesel and petrodiesel standards in order to obtain a
database on kinematic viscosity under identical conditions that can be used to define
the influence of compound structure on kinematic viscosity

3.2.4

Total protein content analysis

Objective
To determine the total protein content present in the jatropha seed cake by using
PerkinElmer 2400 Series II CHNS/O Elemental Analyzer.
Introduction
By determining the % of nitrogen present in the seed cake, the total protein content of
the seed cake can be calculated by using the following equation:
Total protein content (%) = % of nitrogen x 5.3
Procedures

22

2.0 0.1 mg of k-factor, Cystine and 1.0 0.1 mg of the jatropha seed cake were
measured in tin capsules using micro analytical balance. The empty aluminum vials
was run as blank. Cystine was run as standard k-factor. Once the blank and cystine
had met the standard value, then only proceed to the sample.
Discussion
A schematic diagram of the PerkinElmer 2400 Series II CHNS/O Elemental Analyzer
is shown in Figure 3.2. The CHN and CHNS modes are based on the classical PreglDumas method where samples are combusted in a pure oxygen environment, with the
resultant combustion gases measured in an automated fashion. The 2400 Series II
system is comprised of four major zones:
Combustion Zone
Gas Control Zone
Separation Zone
Detection Zone
In the Combustion Zone, samples encapsulated in tin or aluminum vials are
inserted automatically from the integral 60-position autosampler or manually using a
single-sample auto injector.

Figure 3.2

Schematic diagram of the PerkinElmer 2400 Series II CHNS/O

Elemental Analyzer.

23

In the presence of excess oxygen and combustion reagents, samples are

combusted completely and reduced to the elemental gases CO 2, H2O, N2 and SO2. The
combustion products are then passed to the Gas Control Zone. Gases are captured in
the mixing chamber of the Gas Control Zone. Here, gases are rapidly mixed and
precisely maintained at controlled conditions of pressure, temperature and volume.
The result is the thorough homogenization of product gases. After homogenization of
product gases, the mixing chamber is depressurized through a column in the
Separation Zone of the instrument. The separation approach used is a technique
known as Frontal Chromatography. As the gases elute, as illustrated in Figure 2, they
are measured by a thermal conductivity detector in the Detection Zone of the analyzer.
Since measurements in this design are made as stepwise changes from the carrier gas
baseline, the variations associated with the quantification of peak signals in other
CHNS/O analyzers is eliminated.
Corrective action
Sample preparation was very difficult because very small amount of sample (~1 mg)
was used. The tin capsule was very tiny hence we need to handle it with care.
3.3

Biodiesel making

Introduction
Bio-diesel is defined as the mono alkyl esters of long chain fatty acids derived from
renewable feed stock, such as vegetable oil or animal fats, for use in compression
ignition engine. Biodiesel produced by transesterification reaction can be catalyzed
with alkali, acid or enzyme. Chemical catalyst processes, including alkali and acid
ones are more practical compared with the enzymatic method. Alkali process can
achieve high purity and yield of biodiesel product in a short time (Dorado et al., 2004;
Meher et al., 2006a; Tiwari et al., 2007). Methyl or ethyl esters are the product of
transesterification of vegetable oils with alcohol (methanol / ethanol) using an alkaline
catalyst. In addition, the process yields glycerol which has great applications in the
pharmaceutical, food and plastics industries (Meher et al., 2006b). Thus, almost all
biodiesel is produced by using base catalysed transesterification process, as it is a
simple process and requiring only low temperature.

24

Objectives
The plant oils usually contain free fatty acids, phospholipids, sterols, water, odorants
and other impurities and thus the oil cannot be used as fuel directly. To overcome
these problem the oil requires slight chemical modification mainly transesterification.
The transesterfication is an important process used to reduce the viscosity of the
triglycerides.

Procedures
Preheating of oil
(100 C, 10 min)
minutes
Oil + Sodium
methoxide

Sodium
methoxide

MeOH +
1 % (w/v) NaOH

Stirring (550 rpm) and

heating at (60 C 70 C)
for 2 hours

Settling of the
mixture (24 hrs)
Gravity separation

Biodiesel

Pure biodiesel

Glycerin

25

Washing and drying

Figure 3.4

Process

flow

chart

for

biodiesel

production

(base-catalyzed

transesterification).
1. 200 g of the feedstock was filled into a three-necked round-bottomed flask. A
water-cooled condenser and a thermometer with cork were connected to the side
openings on either side of the round-bottomed flask. The set up for biodiesel
production was shown in Appendix.
2. 2 g of catalyst, 1 % NaOH (w/v) was weighed and dissolved completely in the
required amount of methanol by using a stirrer to form sodium methoxide
solution. Meanwhile, the oil was pre-heated at about 100 C for 10 minutes by
placing the round-bottomed flask in the water bath.
3. The sodium methoxide solution was then added into the oil for vigorous mixing by
means of a mechanical stirrer fixed into the flask.
4. The mixture was stirred at 550 rpm and maintained at 65 C for 2 hours.
5. The reacted mixture was poured into the separating funnel. The mixture was
allowed to separate and settle overnight by gravity settling for into a clear, golden
liquid biodiesel on the top with the light brown glycerol at the bottom as shown in
Appendix.
6. The next day, the glycerol was drained off from the separating funnel, leaving the
biodiesel at the top.
7. The raw biodiesel was collected and water-washed to bring down the pH of
biodiesel to 7.
8. Drying is ascertained by heating the washed fuel approximately to 110 C in an
open container on a hot plate with magnetic stirrer inside until there is no more
steam from in the fuel, which should be a clear, amber- colored liquid. Then it is
allowed to cool to room temperatures and transferred into a storage container.
Discussion

26

Transesterification also called alcoholysis is the displacement of alcohol from an ester

by another alcohol in a process similar to hydrolysis except that an alcohol is used
instead of water. (Meher et al., 2006b; Srivastava and Prasad, 2000). The
transesterification is represented as:
RCOOR + ROH

RCOOR +ROH

Methanol was used in this process then and thus it is called methanolysis.
Methanolysis of triglycerides represented in the equation below:

Transesterification is one of the reversible reactions and proceeds essentially by

mixing the reactants. However, the presence of a catalyst (a strong acid or base)
accelerates the conversion.
The important factor that affects the transesterification reaction is the amount
of methanol and sodium hydroxide, reaction temperature and reaction time (Demirbas,
2003). In YKRC, a molar ratio of 6:1 was used to produce biodiesel. A molar ratio of
6:1 is normally used in industrial processes to obtain methyl ester yields higher than
98% by weight, because lower molar ratio required more reaction time. With higher
molar ratios conversion increased but recovery decreased due to poor separation of
glycerol. (Srivastava et al., 2000).
The maximum ester yield of 97.8 % was obtained using 1.0 % NaOH
concentration. If the NaOH concentration was decreased below or increased above the
optimum, there was no significant increase in the biodiesel production, but there was
increased formation of glycerol and emulsion. For YKRC biodiesel production, 1 % of
NaOH was used. For the preparation of sodium methoxide solution, sodium hydroxide
(NaOH) pellets were completely dissolved in methanol and added into the oil, since
NaOH pellets would react with CO2 and water present in the atmosphere and yield

27

sodium carbonate, which would affect the performance of the catalyst during the
transesterification reaction. The oil was preheated at about 100 C for 10 minutes in
order to remove water contents. The reaction temperature influences the reaction rate
and yield of ester. Therefore, the reaction is conducted close to the boiling point of
methanol, 60 to 70 C at atmospheric pressure (Freedman et al., 1984; Van Gerpen,
2004). Further increase in temperature is reported to have a negative effect on the
conversion (Srivastava et al., 2000). Speed of stirrer less than 550 rpm would affect
the transesterification process. In this case the mixture will not be mixed together and
mixing will be improper.
Sodium methoxide settles at the bottom of the funnel because of higher density
compare with biodiesel whereas small amount of catalyst, methanol and glycerol are
in the upper bio-diesel layer. Washing is a process to remove impurities such as
entrained glycerol, catalyst, soap and excess methanol. The excess methanol in
biodiesel corrodes the fuel injection system and hence it should be separated from the
bio-diesel. Drying is ascertained by heating the washed fuel approximately to 110 C
in an open container on a hot plate with magnetic stirrer inside until there is no more
steam from in the fuel, which should be a clear, amber- colored liquid. This heating
process will also drive off any traces of remaining alcohol as well.

28

CHAPTER 4

CONCLUSION

From this industrial training, I had learned a lot of things that I never learned it before
during the lectures.
In Yanmar Kota Kinabalu Research Center Sdn. Bhd (YKRC)s laboratory, I
had learned biodiesel making from various types of feedstocks by transesterification
process, blended biodiesel preparation, biodiesel sample analysis and how the quality
of the biodiesel would affect the engines performance. Various analytical methods
were developed for analyzing mixtures containing fatty acids esters and mono-, di-,
and triglycerides obtained by the transesterification of vegetable oils.
It is inappropriate to implement a full complement of GLP policies for a
student laboratory as the experimental studies are not related to a commercial product.
However, it is useful to incorporate those GLP policies which are fundamental to any
sound laboratory work, and to provide an introduction to GLP policies that are a part

29

of any contemporary commercial laboratory. The laboratory of YKRC provided me an

opportunity to practice GLP. The following GLP policies are implemented which
include:

The analyst certification, based on satisfactory performance of basic set of

analytical procedures

Waste disposal management

Performance of laboratory studies utilizing Standard Operation Procedures

(SOP's)

Instrument verification and validation

Reagent/materials certification is an obvious element of quality assurance.

However, GLP guidelines emphasize that certification must follow accepted
procedures, and must be adequately documented.

Laboratory notebook maintenance to contemporary standards

Maintenance of laboratory records based on instrument and reagent
certifications

Accountability for instrument and reagent certification

Besides that, I was also exposed to Japanese culture. It is very important for

Japanese to greet people. All the staffs of YKRC are sharing the same office space
regardless of their position is. I was surprised when I first saw them but this shows
that the staffs here have good working relationship. They are very kind, generous and
treat us very well. Whenever they go to Japan for work, they will buy us souvenirs.
Honestly, YKRC has a very nice working environment.
10 weeks of industrial training seems too short for us to be able to learn all
the things in this industry. In the future, I would like to find a job related to fuel
industry since I am very interested in this field and had the basic knowledge of it.
Hopefully, the industrial training period will be extended to 6 months in order for
industrial chemistrys student to learn more. I hope that in the coming year, YKRC
will take more UMS students for industrial training.

30

REFERENCES
A.Murugesan, T.R.Chinnusamy, M.Krishnan, V.Chandraprabu, C.Umarani,
R.Subramanian, N.Nedunchezhian. Department of Mechanical Engineering,
K.S.Rangasamy Collage of Technology, Tiruchengode-637 215. Preparation of
methyl ester (bio-diesel) from low cost transesterification
Augustus, G.D.P.S., Jayabalan, M., Seiler, G.J., 2002. Evaluation and bioinduction of
energy components of Jatropha curcas. Biomass Bioenergy 23, 161164.
Demirbas, A. 2003. Bio diesel fuels from vegetable oils via catalytic andnon-catalytic
supercritical alcohol transesterification and other methods; a survey. Energy
conservation and management. 44: 2093-2109.
Dorado, M. P.; Ballesteros, E.; Lopez, F. J.; Mittelbach, M., (2004). Optimization of

31

alkali-catalyzed transesterification of brassica oil for biodiesel production.

Energ. Fuel, 18 (1), 77-83
Fischer, K.; Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes
von Flssigkeiten und festen Krpern, Angew. Chemie, 48, 394, 1935
Freedman, B., Pryde, E.H. and Mounts, T.L. "Variables Affection the Yields of Fatty
Esters from Transesterified Vegetable Oils." Journal of American Oil Chemists
Society, 1984, 61 (10): 1638-1643.
Ma F, Clements LD, Hanna MA. The effect of catalyst, free fatty acids, and water on
Transesterification of beef fallow. Trans ASAE 1998;41(5):12614
Meher, L. C.; Dharmagadda, S. S. V.; Naik, S. N., (2006a). Optimization of alkalicatalyzed transesterification of Pongamia pinnata oil for production of
biodiesel. Bioresour. Tech., 97 (12), 1392-1397.

Shay EG. Diesel fuel from vegetable oil; Status and opportunities. Biomass Bioenergy
1993;4(4):22742.
Srivastava A, Prasad R. Triglycerides based diesel fuels. Renew Sustain Energy Rev
2000;4:11133.
Tiwari, A. K.; Kumar, A.; Raheman, H., (2007). Biodiesel production from jatropha
oil (Jatropha curcas) with high free fatty acid: An optimized process. Biomass
Bioenerg., 31 (8) 569 -575.
Van Gerpen, J., (2005). Biodiesel processing and production. Fuel Proc. Tech., 86
(10), 1097-110.

32

APPENDIX

33

831 KF Coulometer

Seta KV-5 Viscometer Bath

785 DMP Titrino

PerkinElmer 2400 Series CHNS/O

Elemental Analyzer

34

Reflux condenser

Thermometer

3 neck round bottom flask

Hot plate stirrer

Set up for base-catalyzed transesterification process

Biodiesel

Glycerol

Separation of glycerol from biodiesel.

35

Industrial visit by UMS lecturer, Dr. Noumie Surugau.