30

CHAPTER 1

INTRODUCTION1.1YanmarYanmar 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.1.1.1Company Profile

Trade nameYanmar Co., Ltd.

Head office1-32 Chayamachi, Kita-ku,Osaka, Japan

FoundedMarch, 1912

Capital6.2 billion yen

ChairmanTadao Yamaoka

PresidentTakehito Yamaoka

1.1.2Founders 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 a better world will unfold."Thus he came up with the founding spirit, "Grateful to serve for a better world".

1.1.3Mission

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.1.1.4Brand 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.

1.1.5Targetmark

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. 1.1.6Company HistoryTable 1.1 showed the history of Yanmar group.

Table 1.1 Company historyYearHistory

2007 Restructuring of North America Companies New YA, YAMA and YMU.

Production of compact utility tractors at YAMA starts

2006

Yanmar Celebrates 5 Millionth Engine.

India sales office established.

Yanmar develops woods based biomass power generation for Higashi-ohmi city.

2005

New Yanmar brand mark and mission statement established.

Yanmar Noki Korea established.

Capital Participation of Yanmar in India Tractor Manufacturer, ITL

2004

Yanmar Construction Equipment Co.,Ltd. established.

Yanmar Construction Equipment Sales Co.,Ltd. established.

Yanmar Agricultural Machinery(Thailand) Co.,Ltd. established.

2003 Yanmar Energy System Co.,Ltd. established

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

Shandong Shefeng Yanmar Engine Co.,Ltd established.

2002

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.

2001 Joint venture company for production of parts launched in Indonesia

2000

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

1999

Domestic operations reorganized into seven sales companies

Environment Minister's prize for cool containers

1998 Tadao Yamaoka decorated by the nation

Takehito Yamaoka assumed the presidency and Tadao Yamaoka the chairmanship

1997 ISO14001 certification for all plants

1995 Ultra-modern Biwa Plant opened

Joint venture company launched with Cagiva in Italy

1993 Representative office opened in Shanghai

FIE pump unit injector wins national invention prize

1992 ISO9001 certification for all business operations

Ten millionth diesel engine produced

1990 Full-scale entry into environmental business with development of raw garbage processing and water purification equipment

1989 Subsidiary established in the Netherlands

Subsidiary established in Singapore

Joint venture company launched with Ammann in France

1988 Production of gas engine heat pump launched

Marine farm established

1987 World's first diesel outboard engine developed

1983 World's smallest air-cooled diesel engine developed

1982 Production of gas turbines launched

1981 Subsidiary established in the United States

1978 Subsidiary established in Thailand

Amagasaki Plant's production facilities certified by AB and LR

1977 Amagasaki Plant first factory in Japan to receive mass production facility certification from NK (Japan Maritime Association)

1976 Service base established in the Netherlands

1972 Yanmar Shipbuilding & Engineering Co., Ltd. established

Yanmar Sangyo Co., Ltd. established

Subsidiary established in Indonesia

1968 Deming Prize (first in this industrial sector)

1967 Subsidiary established in Malaysia

1966 Service base opened in Thailand

Production of compact construction equipment launched

1963 Yasuhito Yamaoka passes away. Succeeded as president by Tadao Yamaoka (current chairman)

1962 Test operation of rotary engine

Service base opened in Singapore

Magokichi Yamaoka passes away. Succeeded as president by Yasuhito Yamaoka

1961 Yanmar Agricultural Equipment Co., Ltd. established

1957 Subsidiary established in Brazil

Awarded German Merit Cross

1955 Awarded Diesel Gold Medal by German Inventors' Association

1952 Company name changed to Yanmar Diesel Engine Co., Ltd.

1947 Entered the market for small-sized diesel engines in fishing boats

1942 Nagahama Plant opened

1936 Amagasaki Plant opened

1933 World's first practical small diesel engine developed

1921 Yanmar brand name adopted

1.2Yanmar 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 non-consumable 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.1.2.1YKRC Organization ChartFigure 1.1 showed the organization chart of YKRC

Figure 1.1Organization chart of YKRC.CHAPTER 2TRAINING SCHEDULEThe table below showed the activities and projects done during practical training.Table 2.1Training schedule

Activities/ProjectsWeek

Glasswares Cleaning Stock checking Manual titration (AOCS)1

Chemicals categorization2

Total Acid Number (TAN) test on blended biodiesel 3

Viscosity test on blended biodiesel3-4

Biodiesel making-1 step base catalyzed transesterification process4

Jatropha seed project

Oil press (sample preparation) by using hydraulic press machine

Sample analysis by using 785 DMP Titrino for the total acid number (TAN) ;and 831 KF Coulometer for water content Protein content determination by using CHNS/O analyzer5-7

CHAPTER 3 ACTIVITIES/ PROJECT SPECIFICATION3.1Standard Method for Biodiesel AnalysisBiodiesel 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 methods needed to determine compliance. This standard allows any feedstock to be used, but its specifications are most easily met by rapeseed methyl esters.

3.1.1ASTM 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.3.1.2EN 14214EN 14214 is an international standard that describes the minimum requirements for biodiesel.Table 3.1Specification for Biodiesel (B100) ASTM D6751-08PropertyASTM MethodLimitsUnits

Flash PointD93130 minDegrees C

Water & SedimentD2709.

0.050 max% vol

Kinematic Viscosity, 40 CD445

1.9 - 6.0mm2/sec.

Sulfated Ash

D8740.020 max.

% mass

Sulfur

S 15 Grade

S 500 Grade

D5453

15 max.

500 max.

ppm

Copper Strip CorrosionD130.

No. 3 max

CetaneD613

47 min.

Cloud PointD2500Report

Degrees C

Carbon Residue

100% sample

D4530*0.050 max.% mass

Acid NumberD6640.50 max.mg KOH/gm

Free GlycerinD65840.020 max.

% mass

Total GlycerinD65840.240 max.

% mass

Phosphorus ContentD 49510.001 max.% mass

Distillation Temp,Atmospheric Equivalent Temperature, 90% RecoveredD 1160

360 max.Degrees C

Sodium/PotassiumUOP 3915 max,

combinedppm

Table 3.2EN 14214PropertyTest methodLimitsUnits

MinimumMaximum

Ester contentprEN 1410396.5% (m/m)

Density at 16 CEN ISO 3678

EN ISO 12186860900kg/m3

Viscosity at 40 CEN ISO 31043.505.00mm2/sec.

Flash pointISO/DIS 3679120C

Sulfur contentprEN ISO 20846

prEN ISO 20884-10.0mg/kg

Carbon residue (on 10 % distillation residue)EN ISO 10370-0.30% (m/m)

Cetane numberEN ISO 516551.0

Sulfated ash contentISO 3987-

0.02% (m/m)

Water contentEN ISO 12937-.500mg/kg

Total contaminationEN 12662-24mg/kg

Copper strip corrosion (3 h at 60C)EN ISO 2160Class 1

Rating

Oxidation stability, 110CprEN 141126.0

-Hours

Acid valueprEN 141040.50mg KOH/gm

Iodine valueprEN 14111120% mass

Linolenic acid methyl esterprEN 1410312.0% (m/m)

Polyunsaturated methyl esters (>= 4 double bonds)1% (m/m)

Methanol contentprEN 141100.20% (m/m)

Monoglyceride contentprEN 141050.80% (m/m)

Diglyceride contentprEN 141060.20% (m/m)

Triglyceride contentprEN 141060.20% (m/m)

Free glycerolprEN 14105

prEN 141060.02% (m/m)

Total glycerolprEN 141050.25% (m/m)

Group I metals

(Na + K)

Group II metals

(Ca + Mg)prEN 14108

prEN 14109

prEN 145385.0

5.0mg/kg

mg/kg

Phosphorus

contentprEN 1410710.0mg/kg

3.2 Analysis of crude Jatropha curcas oil

Figure 3.1Overall 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 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 2040% 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 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.ProcedureApproximately 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.3.2.1Water Content Determination

ObjectiveTo determine the water content present in the jatropha oil by using 831 Karl Fischer Coulometer. ProcedureApproximately 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 non-aqueous 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 (SO2) 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. 3.2.2Total 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.

IntroductionThe 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/1.99Color 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 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 H2OThe 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 thenpoured 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.DiscussionAcid 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.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 actionThe 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.3.2.3Viscosity Test

ObjectiveTo determine the viscosity of the crude jatropha oil at 40, 50, 60, 70 and 80 C

IntroductionKinematic 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/s2t = 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 toughened glass front window, easily accessible drain valve, levelling feet, and with provision for fitting diffused back lighting, top plate, and attachments.ProceduresThe 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. DiscussionViscosity 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 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 actionRandom 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 viscosity3.2.4Total protein content analysis

ObjectiveTo determine the total protein content present in the jatropha seed cake by using PerkinElmer 2400 Series II CHNS/O Elemental Analyzer.

IntroductionBy 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

Procedures2.0 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 Pregl-Dumas 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 3.2Schematic diagram of the PerkinElmer 2400 Series II CHNS/O Elemental Analyzer.In the presence of excess oxygen and combustion reagents, samples are combusted completely and reduced to the elemental gases CO2, 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 actionSample 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. 3.3Biodiesel makingIntroductionBio-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. ObjectivesThe 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

Figure 3.4Process 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

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 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.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 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.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

alkali-catalyzed transesterification of brassica oil for biodiesel production. Energ. Fuel, 18 (1), 77-83Fischer, K.; Neues Verfahren zur massanalytischen Bestimmung des Wassergehaltes

von Flssigkeiten und festen Krpern, Angew. Chemie, 48, 394, 1935Freedman, 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 alkali-

catalyzed 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.APPENDIX

831 KF Coulometer 785 DMP Titrino Seta KV-5 Viscometer Bath PerkinElmer 2400 Series CHNS/O

Elemental Analyzer

Set up for base-catalyzed transesterification process

Separation of glycerol from biodiesel.

Industrial visit by UMS lecturer, Dr. Noumie Surugau.Managing Director

Finance & Administrative

Fuel R&D

Engine R&D

Manager (Director)

Manager (Director)

Manager

AssistantManager

AssistantManager

Assistant

ResearchAssistant

ResearchOfficer

Lab Assistant

Jatropha curcas seed

Hydraulic mechanical expression of jatropha oil seed

Analysis

Total protein content

Water content

Total acid number (TAN), Free fatty acid (FFA)

Assistant

MeOH +

1 % (w/v) NaOH

Pure biodiesel

Washing and drying

Biodiesel

Glycerin

Gravity separation

Settling of the mixture (24 hrs)

Stirring (550 rpm) and heating at (60 C 70 C) for 2 hours

Sodium methoxide

Oil + Sodium methoxide

Preheating of oil (100 C, 10 min) minutes

Hot plate stirrer

3 neck round bottom flask

Reflux condenser

Thermometer

Glycerol

Biodiesel

ResearchAssistant