Waste Management 30 (2010) 26312635

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Waste Management
journal homepage: www.elsevier.com/locate/wasman

Transesterication reaction of the fat originated from solid waste of the leather industry
_ Asl Isler *, Serap Sundu, Melek Tter, Filiz Karaosmanoglu
Istanbul Technical University, Chemical Engineering Department, 34469, Maslak, Istanbul, Turkey

a r t i c l e

i n f o

a b s t r a c t
The leather industry is an industry which generates a large amount of solid and liquid wastes. Most of the solid wastes originate from the pre-tanning processes while half of it comes from the eshing step. Raw eshing wastes which mainly consist of protein and fat have almost no recovery option and the disposal is costly. This study outlines the possibility of using the eshing waste as an oil source for transesterication reaction. The effect of oil/alcohol molar ratio, the amount of catalyst and temperature on ester production was individually investigated and optimum reaction conditions were determined. The fuel properties of the ester product were also studied according to the EN 14214 standard. Cold lter plugging point and oxidation stability have to be improved in order to use the ester product as an alternative fuel candidate. Besides, this product can be used as a feedstock in lubricant production or cosmetic industry. 2010 Elsevier Ltd. All rights reserved.

Article history: Received 24 January 2010 Accepted 3 June 2010 Available online 9 July 2010

1. Introduction Energy drives our daily lives while the energy demand is increasing day by day. The rst reason for that is the population of the world which is growing at an ever-increasing rate. Second reason is the industrialization of societies. The two reasons are also the reasons for high waste production rates. In short words, energy consumption and waste production always exist hand in hand, which must be properly organized and managed. In the near future, biobased products are expected to play crucial role in the energy sector. These biobased products are the outputs of bioreneries, which look like oil reneries, but they use biomass as a feedstock instead of oil. A biorenery consists of different biomass conversion processes and equipments to produce a exible product mixture of biochemicals, biomaterials, biofuels, heat and electricity. Biomass, which includes wood, oil seed plants, carbohydrate plants, ber plants, vegetal wastes, animal wastes, biodegradable part of municipal and industrial wastes, can be utilized through thermochemical and biochemical conversion processes (Isler and Karaosmanoglu, 2009). Fatty acid alkyl esters are one of the valuable oleochemicals having a widespread application in the industry. They can be converted into a great number of useful chemicals as a feedstock for various syntheses. One of the commonly used fatty acid alkyl esters are methyl esters. Fig. 1 shows production methods and application areas of methyl esters. Alkanolamides can be used either as an emulsier or surfactant; fatty alcohols used as a lubricant can also be used as an additive in the pharmaceutics and cosmetic
* Corresponding author. Tel.: +90 212 285 68 37; fax: +90 212 285 29 25. _ E-mail address: isleras@itu.edu.tr (A. Isler). 0956-053X/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.wasman.2010.06.005

industry. In brief, direct use of methyl esters is limited: they are generally used for valuable oleochemical synthesis as intermediate products (Otera, 2003; Shahidi and Bailey, 2005). Fatty acid methyl esters can be used as an alternative diesel fuel as pure biodiesel or biodiesel blend. Based on the production type and feedstock choice, the biofuels are classied as rst-, second-, third-, or fourth-generation. Biodiesel (fatty acid methyl ester) is one of the rst generation biofuels. Biodiesel is usually produced by transesterifying triglycerides such as animal fats or vegetable oils with alcohol in the presence of a homogeneous or heterogeneous catalyst. Generally, methanol and ethanol are the most common alcohol types used in transesterication reaction and the process can be conducted with basic catalysts (potassium hydroxide, sodium hydroxide, and sodium methoxide or sodium ethoxide), acidic catalysts (sulfuric acid), or enzymatic catalysts (lipase). There are several options for fat or oil choice in transesterication process. Usually, vegetable oils such as soybean oil, canola oil, sunower oil, corn oil, palm oil, cottonseed oil, mustard oil, etc.; animal fats such as pork lard or beef tallow; waste oils; trap and oat grease; edible oil technology by-products are the most common types used in transesterication reaction (Knothe et al. 2004; Mittelbach et al., 2004). The leather industry generates considerable amount of fat-originated solid and liquid wastes while processing hides and skins. These wastes, which can create major environmental problems, must be managed regularly. Pre-eshing, eshing, shaving and trimming are the pre-tanning stages of the leather production processes where most of the solid waste is originated. Pre-eshing process is performed in order to remove esh and to ease the penetration of the chemicals. Wastes of pre-eshing process contain large amounts of fat and protein. Despite their fat content there

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Hydrolysis

_ A. Isler et al. / Waste Management 30 (2010) 26312635

Fatty Acids
Hydrogenation

Oils and Fats

Esterification Alcoholysis Amidation

Fatty Alcohol Alkanolamide Soap -Sulfate Methyl Ester Sucrose Esters

Fatty Acid Methyl Ester

Saponification Sulfurization Sucrolysis Alcoholysis

Other Fatty Acid Methyl Esters

Other Application Areas

Alternative Diesel Fuel

Fig. 1. Production methods of methyl esters.

is almost any application method to recover those wastes. The waste which is rich in fat and protein content can be used in the production of fatty acid methyl ester as an alternative raw material or diesel fuel by transterication (Colak et al., 2005; Dikmen et al., 2004; Yucesu et al., 2001). There are a limited number of studies on the utilization of waste eshing oil, but studies about tallow and waste cooking oil transesterication reaction can be used as good examples for the transesterication reaction of raw eshing oil. zgnay et al. (2007) studied the possible use of biodiesel obtained from preeshing wastes, and investigated its engine performance and emission values. The same study also compared the performance of waste based biodiesel with commercial diesel fuel. The results indicated that the pre-eshing oil can be used in diesel engines with lower emissions for hydrocarbons and particulate matter. In the study, the need for further studies on the usage of pre-eshing oil based biodiesel in diesel engines was stated and its use was recommended as an additive because of the high pour point. Chung et al. (2009) investigated duck tallow as an alternative feedstock for the transesterication reaction using various alkali catalysts. In the study, composition and chemical properties of fatty acid methyl ester in the raw duck tallow and the biodiesel were compared. The fatty acid methyl ester content of the product was 97% (reaction temperature: 65 C, catalyst: KOH) and the major constituent in the ester product was oleic acid. Fatty acid methyl ester content, acid value, density and kinematic viscosity were found to be in the limits of European biodiesel qualities. ner and Altun (2009) investigated inedible animal tallow as a substitute fuel for diesel engines. Fuel properties of tallow methyl ester which was prepared by base-catalyzed (0.5% NaOH w/w) transesterication reaction (reaction temperature: 60 C, oil/alcohol molar ratio: 6/1, reaction period: 3 h) were determined. Those fuel properties were compared with diesel fuels (B5, B20 and B50). It was observed that tallow methyl ester and its blends can be used without any engine modications in a direct injection diesel engine. The engine performance run by tallow methyl ester and its blends were comparable with the performance run by diesel fuel and the exhaust emissions were lower than those of diesel fuel. Lower exhaust emissions made tallow methyl ester and its blends more environmentally friendly fuels. Bhatti et al. (2008) investigated acid catalyzed transesterication reaction by using chicken and mutton tallow. The physical and fuel properties of both fats were found generally comparable to the recommended biodiesel properties.

Demirbas (2009) studied biodiesel production from waste cooking oil via supercritical methanol and base-catalyzed transesterication reaction. Water and free acid contents were determined as important factors in the catalytic transesterication of waste oil, which produced negative effects on the yield of methyl ester. It was observed that high oil/alcohol molar ratio and high reaction temperature resulted in an increase in ester production in a shorter time. Besides, the reaction yield increased and reached an optimum where catalyst was 56% of the weight of the oil. Supercritical reaction was found to be not sensitive to both water and free acid content, and free fatty acids in the waste cooking oil were transesteried simultaneously. Phan and Phan (2008) investigated the effect of oil/alcohol molar ratio, catalyst concentration and temperature on the transesterication reaction of waste cooking oils, collected within Ho Chi Minh City. Although being collected from different sources, waste cooking oils had similar chemical and physical properties. The yield of ester production was found as 88% (temperature: 30 C, oil/alcohol molar ratio: 7/1, 0.75% (w/w) KOH) and 90% (temperature: 50 C, oil/alcohol molar ratio: 8/1, 0.75% (w/w) KOH). Most of the physical properties were within the EN 14214 standard except the carbon residues, which was 4.0 wt.% for the biodiesel but only 0.05 wt.% for diesel. The results indicated that B20 (20% biodiesel and 80% diesel, v/v) could be used in engines without any modication. In this study, raw eshing oil which is a fat-originated solid waste of the leather industry is chosen as a raw material for transesterication reaction. Effect of oil/alcohol molar ratio, the amount of catalyst and the temperature on the yield of transesterication reaction was investigated. In the second part of the study, fuel properties of the product were determined according to the standard EN 14214. As a result, nal product is offered to the industry as an alternative raw material candidate. 2. Experimental section 2.1. Materials and methods Properties of raw eshing oil were determined according to the AOCS standard test methods for oil and fat. Fatty acid composition of the raw eshing oil was analyzed by capillary gasliquid chromatography (GLC) equipped with the Hewlett Packard 5890 series II apparatus. Fatty acid methyl esters were prepared according to AOCS Ofcial Method Ce 266 for GLC analysis using BF3methanol reagent. Set values for the analysis are given in Table 1. Fat composition of raw eshing oil was investigated with Thin Layer Chromatography/Flame Ionization Detector (TLC/FID) Iatroscan TH-10 MK IV analyzer with SIII rods (Iatron Lab, Tokyo). Set values for TLC/FID analyzer are given in Table 2.

Table 1 Set values for the GLC analyzer. Flame ionization detector temperature Injection temperature Gas ow Carrier gas, N2 Hydrogen Air Oven temperature program 280 C 250 C 4.5 mL/min 30 mL/min 400 mL/min 170 C (5 min) 170275 C (10 C/min) 275 C (10 min) Ultra 1(25 m 0,32 mm, 0,52 lm lm thickness of 100% dimethyl polysilanoxane)

Column

_ A. Isler et al. / Waste Management 30 (2010) 26312635 Table 2 Set values for TLC/FID analyzer. Developing System Sample Volume Sample Composition Developing Solvent Mixtures Developing Time Drying System Flame Ionization Detector Air Flow Rate Hydrogen Flow Rate Scan Speed Recorder Calculation Method 1 lL 0.1 g Sample/ 10 mL Chloroform Benzene:Chloroform:Acetic Acid (50:20:0.7) Hexane:Benzene (35:35) 23 and 30 min, respectively 5 min in air temperature and 5 min in air oven at 80 oC (after each solvent baths) Table 3 Properties of raw eshing oil. Property Density, 15 C, g/cm 50 C, g/cm3 Acid Value, mg KOH/g Iodine Value, g I/100 g Saponication Value, mg KOH/g Unsaponication Matter, wt.% Sediment, wt.% Water Content, ppm Refractive Index, 20 C Fatty Acid Composition, wt.% Miristic Acid C14:0 Miristoleic Acid C14:1 Palmitic Acid C16:0 Palmitoleic Acid C16:1 Stearic Acid C18:0 Oleic Acid C18:1 Linoleic Acid C18:2 Arasitic Acid C20:0 Calculated Mean Molecular Weight, kg/kg-mol
3

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Raw Fleshing Oil 0.92 0.89 0.28 57 193 0.79 1.17 6617.1 1.47 4.2 2.16 28.4 8.1 10.67 43.83 1.8 0.84 848.9

160 mL/min 2000 mL/min 30 s/s Iatrocorder TC-11 Absolute calculation

Transesterication reactions of raw eshing oil were performed using methanol as the alcohol. Since the alkali catalyst was reported to be preferred in the case of low acid value, sodium hydroxide was used as a catalyst in the reaction. For the transesterication reaction, the results of the studies of zgnay et.al (2007), Bhatti et al. (2008), Phan et al. (2008), Chung et al. (2009), ner et al. (2009), Demirbas (2009) were considered. Methanol and sodium hydroxide were obtained from Merck and raw eshing oil was obtained from Sepiciler ayrbas Leather Com pany. A 250 ml, three-necked ask equipped with condenser and a thermometer were used for reactions. Raw eshing oil was heated and kept at constant temperature (50 oC). Sodium hydroxide, which was dissolved in methanol, was added to the reaction at the reaction temperature 50 oC (1 oC). 1 ml samples for TLC/ FID analysis were taken from the reaction mixture at certain time intervals to the test tubes containing 1 ml cold distilled water. The upper phase was analyzed for its mono-, di-, tri-glyceride, free fatty acid and methyl ester content by TLC/FID. An appropriate portion of the reaction mixture was dissolved in chloroform to have a nal concentration of 0.1 g/mL. These solutions (1 lL) were applied to the rods. The rods were developed in glass tanks using a developing system described in Table 2. They were then kept at room temperature for 5 min and dried at 110 oC in a drying oven for another 5 min. Rods were placed in the Iatroscan Analyzer, and the results were obtained by Iatrocorder TC-11. Throughout the experiments, the mixing speed (1000 rpm/min) and the reaction period (1 h) were kept constant. The effect of different amount of catalyst (0.25%, 0.50%, 0.75% and 1%), different temperatures (40, 45, 50, 55 and 60 C) and different oil/alcohol molar ratios (1/3, 1/4, 1/5 and 1/6) on transesterication reaction were investigated. For the renement, the method mentioned in Karaosmanoglu et al. (1996) was applied. After the completion of the reaction, mixture was quenched in cold distilled water and cooled down to room temperature. The product mixture was transferred to a separatory funnel in order to separate ester and glycerin phases. The ester phase was washed with hot distilled water (the ratio of ester phase and water: 1/1) with stirring at 50 C. The samples were kept over the heated Na2SO4 (25% of the amount of the ester product) at 130 C overnight and then ltered. Fuel properties were determined at Vitsan Laboratory according to the EN 14214 standard. The results were compared to the specied limits of the EN 14214 standard. 3. Results and discussion Properties of raw eshing oil are presented in Table 3. Fatty acid composition measurements show that the oil is highly composed of oleic and palmitic acids where the weight percentages are

43.8 and 28.4, respectively. Raw eshing oil has a viscosity of 0.92 g/cm3 at 15 C and 0.89 g/cm3 at 50 C. According to the fatty acid composition of raw eshing oil, calculated mean molecular weight is 848.9 kg/kg-mol.
100 90 80 70

Ester Content, %

60 50 40 30 20 10 0 2 4 8 10 15 20 30 45 60 0.25% 0.50% 0.75% 1.00%

Time, min
Fig. 2. The effect of catalyst amount on ester content.

100 90 80 70

Ester Content, %

60 50 40 40C 30 20 10 0 2 4 8 10 15 20 30 45 60 45C 50C 55C 60C

Time, min
Fig. 3. The effect of temperature on ester content.

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100 90 80

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Ester Content, %

70 60 50 40 30 20 10 0 2 4 8 10 15 20 30 45 60 1:3 1:4 1:5 1:6

Time, min
Fig. 4. The effect of oil/alcohol molar ratio on ester content.

The results of the experiments are depicted in Figs. 24. The stochiometry of transesterication reaction requires 1 mol triglyceride and 3 mol alcohol to produce 3 mol of fatty ester and 1 mol of glycerin. At the beginning, experimental conditions were set as follows: oil/alcohol molar ratio, 1/6; reaction temperature, 60 C 1 C; catalyst weight percentage, 0.25% NaOH; reaction period, 1 h. Fig. 2 shows the effect of catalyst weight percentage on ester content as a function of time. As it can be seen on the graph, the ester content reached only 55.02% in 1 h. To observe the effect of the catalyst weight percentage, 0.50% NaOH of the weight of oil was chosen to be the new reaction parameter, while the other parameters were kept constant. With those set values, 87.03% of ester content was obtained. The catalyst weight percentage was increased to 0.75% while the other reaction parameters were again kept constant. The ester content increased from 68.03 to 85.59% between 2nd and 4th minutes. Ester content reached 100% after 20 min, where it was constant in the rest of the period of 1 h. Finally, the catalyst weight percentage was set as 1% while the other parameters were kept constant. The ester content rose from 74.85 to 86.23 between 2nd and 4th minutes and reached 100% after 20 min. As seen in Fig. 2, the ester content obtained by using 0.75% NaOH and 1% NaOH are almost identical. Therefore, catalyst weight percentage was set as 0.75% for the rest of the experiments where the effect of temperature and molar ratio was investigated. The effect of temperature on ester content was observed at constant oil/ alcohol molar ratio (1/6), and catalyst weight percentage (0.75% NaOH). Fig. 3 shows the effect of temperature as a function of time. As it can be seen on the graph, the reaction was completed after 20 min at 50, 55 and 60 C. A temperature of 40 C resulted in an ester content almost equal to 100% after 1 h, and a temperature of 45 C after 30 min. As the ester content after 20 min was almost equal to the ester content in the case of 50, 55 and 60 C, optimum temperature was chosen as 50 C. Fig. 4 shows the effect of oil/alcohol molar ratio on ester content as a function of time. The conditions which were kept constant are as follows: temperature: 50 C 1 C; catalyst weight percentage: 0.75% NaOH; reaction period: 1 h. Oil/alcohol molar ratios of 1:3; 1:4; 1:5 and 1:6 were experimented and ester contents were measured with time. In 1 h, the ester content reached 68.83% and 84.51% for oil/alcohol molar ratios 1/3 and 1/4, respectively. As it can be seen in Fig. 4, the reaction was completed after 20 min for 1/5 oil/alcohol molar ratio and 15 min for 1/6 oil/alcohol molar ratio. Therefore optimum oil/alcohol molar ratio was chosen as 1/6. As a result, the appropriate reaction conditions were determined as follows: reaction temperature: 50 1 C; catalyst weight percentage: 0.75%; oil/alcohol molar ratio: 1/6 and reaction period: 15 min.

As shown in Table 4, fuel properties of raw eshing oil methyl ester, which was produced under the appropriate reaction conditions, are listed and compared with the EN 14214 standard limits. Free glycerin, total glycerin, triglyceride, diglyceride and monoglyceride contents are 0.019, 0.16, 0.194, 0.045 and 0.31, respectively, which are in accordance with EN 14214 standard limits. After the transesterication reaction, the methyl ester content was determined to be 97.23 wt.%. This composition is acceptable, given that ester requirement of the EN 14214 standard is 96.5 wt.%. Linolenic acid methyl ester content was determined with GLC analyzer as 0 wt.%, which was in accordance with maximum 12 wt.% of linolenic acid methyl ester content requirement of EN 14214. Maximum biodiesel water requirement is 500 ppm according to EN 14214 and water content of eshing oil methyl ester was measured as 180 ppm. Density of eshing oil methyl ester was measured as 876 kg/m3. The ash point was determined to be 175 C. This high value of ash point brings an advantage for transport and storage. Also, the acid value, iodine value and sulfur content were determined to be 0.21 mg KOH/g, 56 g I/100 g and 1 mg/ kg respectively, which are in accordance with the limits of the EN 14214 standard. Sulfur content is the most important advantage of biodiesel over No. 2 Diesel fuel, because environmental concerns put certain limitations to sulfur content and EN 14214 sulfur content requirement is 10 ppm. The other properties such as kinematic viscosity, residue carbon, sulphated ash, total pollution, copper corrosion tests, group I metals, group II metals, phosphorus content, polyunsaturated methyl ester content and methanol content are all in accordance with the limits of the EN 14214 standard. Cold lter plugging point and oxidation stability do not match the required limits given in the biodiesel standard. In order to use raw eshing oil methyl ester as an alternative fuel candidate, cold ow properties and oxidation stability have to be improved with cold ow improvers and appropriate additives. Utilizing the raw esh-

Table 4 Fuel properties of raw eshing oil methyl ester. Properties EN 14214 Fleshing Oil Methyl Ester 876 4.2 175 9

Density, 15 C, kg/m3 Kinematic Viscosity, 40 C, cSt Flash Point, C, min. Cold Filter Plugging Point, C Summer: March 1-April 14, April 15-September 30 Winter: October 1-November 15, November 16February 28 Residue Carbon, wt.%, max. Copper Corrosion Test, min. Oxidation Stability, 110 C, h, min. Acid Value, mg KOH/g, max. Iodine Value, g I/100 g, max. Ester Content, wt.%, min. Sulfur Content, mg/kg, max. Water Content, mg/kg, max. Total Pollution, mg/kg, max. Sulphated Ash, wt.%, max. Free Glycerin Content, wt.%, max. Total Glycerin Content, wt.%, max. Phosphorus Content, mg/kg, max. Methanol Content, wt.%, max. Triglyceride Content, wt.%, max. Diglyceride Content, wt.%, max. Monoglyceride Content, wt.%, max. Group I Metals (Na + K), mg/kg Group II Metals (Ca + Mg), mg/kg Linoleic Acid Methyl Ester Content, wt.%, max. Polyunsaturated Methyl Ester Content, wt.%, max.

860 900 3.55.0 120 10; 0 10; 20 0.3 No:1 6 0.5 120 96.5 10 500 24 0.02 0.02 0.25 10 0.2 0.2 0.2 0.8 5 5 12 1

0.01 1A 2.4 0.21 56 97.23 1 180 4.6 0.001 0.019 0.16 0.1823 0.194 0.045 0.31 0.1216 0.1004

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ing oil methyl ester as an intermediate product in industries is more reasonable. 4. Conclusion Since prehistoric times, leather has played an important role in the industry. With the increase of the human population and production rates, leather processing and its wastes have increased. Leather processing produces solid and liquid wastes, which is difcult and expensive to dispose of it. Using these wastes as biobased industrial products and intermediate feedstock in the industry will ensure solid waste management of leather processing. In this study, base-catalyzed transesterication reaction of raw eshing oil was investigated. The effect of catalyst weight percentage, temperature and molar ratio of oil/alcohol were investigated and the optimum reaction conditions were determined as follows: molar ratio of oil/alcohol: 1/6; reaction temperature: 50 1 C; catalyst weight percentage: 0.75% and reaction period: 15 min. The fuel properties of raw eshing oil methyl ester were also studied. Fuel properties of raw eshing oil methyl ester were in accordance with the required limits of EN 14214 except for cold lter plugging point and oxidation stability. These properties have to be improved for further use as an alternative fuel candidate. Alternatively, this ester product can be used as a feedstock in cosmetic industry and in lubricant production. Acknowledgement The authors would like to thank Sepiciler ayrbas Leather Company and Vitsan Laboratory.

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