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 world’s smallest 4-cycle 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
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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 world’s smallest 4-
cycle 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.
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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 company’s 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
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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 human’s 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
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Managing Director (1)
Finance & Adminstrative Group
Manager (1)
Adminstrative Assistant (1)
Accounting Assistant (1)
Maintainence Supervisor (1)
Cleaner/Clerk (1)
Engine Group
Manager (1)
Assistant Manager (1)
Engine Specialist (1)
Engine Technicians
(9)
Fuel Group
Manager (1)
Assitant Manager (1)
Research Officer (0)
Research Assitant (4)
Laboratory Assitant (1)
Sustainability Research Group
Researcher (2)
Directors
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CHAPTER 2
WEEKLY ACTIVITIES SCHEDULE
2.0 Weekly Activities Schedule
Wee
k
Date
Span
Activities
1 1st - 5th July 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: Oxidation Stability Index
Induction Period (OSI IP), iodine value (IV),
viscosity test and water content Test.
Learned FTIR spectrometer, Metrohm’s Titrino, Karl
Fisher Titrator, Viscometer bath and Rancimeter,
with reference to the standard operating
procedure (SOP).
Learned and practiced glassware and laboratory
apparatus washing according to SOP.
Introduction and Planning of Yanmar Way of Kaizen
(YWK).
Personal Protective Equipments (PPE) and
Laboratory Safety Briefing.
2 8th – 12th Field trip to company’s Jatropha farm
6
July Sample Analyses (viscosity, water content,
induction period)
Learned basicity test for catalysts and Hammett’s
acidity function.
Photography of samples
3 15th – 19th
July
Sample Analyses (viscosity, water content,
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.
4 22nd – 26th
July
Fuel deterioration briefing and analysis by using
Metrohm Rancimeter
Fuel dilution test briefing and analysis by using gas
chromatography
Biodiesel production (basicity test and ester
content)
Sample Analyses (viscosity, water content,
induction period)
5 29th July –
2nd August
Biodiesel production (homogeneous and
heterogeneous transesterification, basicity test
and ester content)
Company Internship Experience Presentation
6 5th – 9th
August
Biodiesel production (homogeneous and
heterogeneous transesterification, basicity test
and ester content)
Briefing and practice on Ion-exchange of catalyst
7 12th – 16th
August
Briefing and practice on sulfated ash
Biodiesel production (biodiesel washing and ester
content)
Sample analyses (viscosity, water content,
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induction period, density, FTIR)
8 19th – 23rd
August
Briefing and practice on Thermoprep water content
analysis
Briefing and practice on Total Glycerol Content
analysis
Briefing and practice on Methanol Content analysis
CHAPTER 3
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
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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 +ROCOR→ROH+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. However, two distinct types of base-catalyzed
transesterification are used i.e. homogeneous 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 60oC to 70oC and continuously
stirred for 2 hours.
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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.
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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 105oC 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
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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.
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Ground Nut Jatropha Oil Palm Oil Castor Oil0
20
40
60
80
100
120
91.5897.88 99.5
79.76Es
ter C
onte
nt (%
)
Fig 3.3 Ester content of four samples transesterified during internship.
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.
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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.
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
40-45oC 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.
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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 Hammett’s 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 hammett’s indicators (Table 3.1 and Fig 3.5) in separate beakers
respectively.
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Indicators Color at neutral pH
Color at basic pH
pH value
Methyl Orange Red Yellow 3.7
Phenolphthalein
Colorless Purple 9.8
2,4-dinitroaniline
Yellow Slight red 15.0
4-nitrophenol Pink/yellow Slight red 18.4
Table 3.1 Color changes and pH value of selected Hammet’s indicators
Figure 3.5 Color changes of Hammett’s 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 Hammett’s 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 Hammett’s 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).
a) b)
c) d)
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Basic strengt h (mmol )=V benzoic acid used×0.02mol
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 Hammett’s indicators are
added into the catalysts is equal to 50% conversion of the benzoic acid with
the indicator, the basic strength of the catalyst will be equal to the pKa 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