Research Journal of Chemical Sciences ______ ______________________________ ______ ____ ISSN 2231 - 606X Vol. 2 ( 5 ), 66 - 71 , May (201 2 ) Res.J.Chem.Sci. International Science Congress Association 66 Production of Bio - diesel (Methyl Ester) from Simarouba Glauca Oil Mishra S.R.* 1 , Mohanty M.K. 2 , Das S.P. 3 and Pattanaik A.K. 4 1 Department of Chemistry, C. V. Raman College of Engineering, Bhubaneswar, Odisha, INDIA 2 Department of Farm Implement Design Unit, College of Agricultural Engineering and Technology, Bhubaneswar, Odisha, INDIA 3 P.G. Dept. of Chemistry, Ravenshaw University , Cuttack, Odisha, INDIA 4 P.G. Dept. of Chemistry, Khallikote (A) College, Berhampur, Odisha, INDIA Available online at: www.isca.in (Received 8 th March 201 2 , revised 16 th March 201 2 , accepted 22 nd March 201 2 ) Abstract In developed countries, most of biodiesel is produced from the refined oil like soybean and canola etc. produced from farmers ’ field using methanol and alkaline catalyst. But a large amount of tree borne oils and fats are available for biodiesel produc tion in developing and under develop countries. Simarouba glauca oil is one of these oils. This paper deals with the transesterification of Simarouba glauca oil by means of methanol in presence of Potassium hydroxide catalyst at less than 65 0 C. The viscosity o f biodiesel is nearer to that of the diesel. The biodiesel is characterized by TLC and the important properties of biodiesel such as density, flash point, cloud point, pour point, carbon residue and ash content are found out and compared wi th that of diese l. The studies encourage the production of biodiesel from unrefined Simarouba glauca oil as viable alternative to the diesel fuel. Keywords: Simarouba glauca oil, b iodiesel, t ransesterification, s imarouba o il m ethyl e ster Introduction Simarouba belongs to the family Simaroubaceae Quasia. It had also been known as paradise tree, Laxmi taru, Acetuno, a multipurpose tree that can grow well under a wide range of hostile ecological condition. Its origin is native to North America, now found in different regions of India. It was a medium sized tree generally attains a height about 20 m and trunk diameter approximately 50 – 80 cm and life about 70 years. It could grow under a wide range of agro climatic conditions l ike warm, humid and tropical regions. Its cultivation depends upon rainfall distribution (around 400 mm), water holding capacity of the soil and sub - soil moisture. It was suited for temperature range 10 – 40 0 C, pH of the soil should be 5.5 – 8. It produce s bright green leaves 20 - 50cm length, yellow flowers and oval elongated purple colored fleshy fruits 1 . Its seeds contain about 40 % kernel and kernels content 55 - 65% oil. The amount of oil would be 1000 – 2000 kg/ha/year for a plant spacing of 5m x5m. I t was used for industrial purposes in the manufacture of s oaps, d etergents and l ubricants etc. The oil cake being rich in nitrogen (7.7 to 8.1%), phosphorus (1.07%) and potash (1.24%) could be used as valuable organic manure 2 . Simarouba was a rich source of fat having melting point of about 29 0 C. The major g reen e nergy components and their sources from Simarouba were biodiesel from seeds, ethanol from fruit pulps, biogas from fruit pulp, oil cake, leaf litter and thermal power from leaf litters, shell, unwanted branches etc. Unlike fossil fuels, biodiesel is a renewable source of energy, because it comes from biological sources like plants and animals which can be replenished by farming. On the other hand, fossil fuels come from underground deposits of hydrocarbons which cannot be renewed. Biofuels have become a matter of global importance because of the need for an alternative energy at a cheaper price and with less pollution 3 . Biodiesel was a domestic, renewable fuel for d iesel engine comprised of mono - alkyl esters of long chain fatty acids derived from natural oils/ vegetable oils/animal fats designated as B100 and which meets the specification of ASTM D6751 or BIS IS15607:05 . It was obtained by the transesterification of renewable materials composed of C 14 – C 20 fatty acids triglycerides with short chain alcohol such as methanol or ethanol under the presence of catalyst, usually a base like NaOH or KOH. Instead of using alcohol and catalyst separately, alkoxides such as CH 3 ONa or CH 3 OK were used to reduce tendency to from water. Biodiesel was often referred to as f atty a cid m ethyl e sters (FAME) when methanol was used. The Glycerol was produced as a by - product which has commercial value 4 . The transesterification reaction formally requires a molar ratio of alcohol to oil of 3:1 but in practice a molar ratio of 6:1 needs to be applied for the reaction to proceed properly to high yield. The transesterification usually requires about 1hour at normal pressure with the reaction temperature 60 – 65 0 C (for m ethanol) 5 . Research Journal of Chemical Sciences ______ _ _ _______________________________ ______________ _ ____ ISSN 2231 - 606X Vol. 2 ( 5 ), 66 - 71 , May (201 2 ) Res.J.Chem.Sci International Science Congress Association 67 Biodiesel Transesterification Reactions: Transesterification process consists of a sequence of three consecutive reversible reactions i.e. conversion of triglycerides to diglycerides followed by diglycerides to monoglycerides. The glycerides were converted into glycerol and one ester molecule at each step. The mechanism was represented in equations as follows 6 . Pre - step OH - + ROH RO - + H 2 O Or KOR RO - + K + O - Step.1. O | R' – C + RO - R' – C – OR | | OR" OR" Step.2. O - O - | | R’ – C – OR + ROH R’ – C – OR + RO - | | OR" R"OH + step.3. O - | R' – C – OR R'COOR + R"OH | R"OH + Where R" = CH 2 – | CH – OCOR' | CH 2 – OCOR' R' = Carbon chain of fatty acid , R = Alkyl group of alcohol The methanolysis transesterification reaction is represented in equation 1. CH 2 - OCOR' CH 2 OH R'COOCH 3 ׀ Catalyst ׀ CH - OCOR" + 3CH 3 OH CHOH + R"COOCH 3 ׀ | CH 2 - OCOR"' CH 2 OH R'"COOCH 3 Triglycerides Methanol Glycerol Methyl Esters If the oil contains more than 5% free fatty acids (FFA), then a two step transesterification is applicable to convert the high FFA oils to its mono esters 7 . The first step, the acid catalyzed esterification reduces the free fatty acid content of the oil. The second step, alkaline transesterification process converts the products of the first step to its mono - e sters and glycerol. Material and Methods Experimental Procedure for production of Biodiesel : The objective of this study was to develop a process for producing b iodiesel from Simarouba glauca oil. The process consists of mainly transesterification i.e . after removing the impurities; the oil was transesterified into its mono esters using alkaline catalyst. Simarouba seeds were collected from different part of Odisha, India and decorticated manually. The extraction of oil from Simarouba kernel was done by using mechanical expeller and solvent extraction by soxhlet apparatus using n - hexane as solvent. The yields were given in t able - 1. Calculation of acid value : It was the amount of KOH required in milligrams to neutralize the free fatt y acid present in one gram of oil expressed as acid value. Volume of N/10 KOH in ml runs down Acid value = x 5.6 Weight of the oil sample in gram = 5.34 Generally free fatty acid value in the half of the acid value. Hence percentage of FFA of Simarouba glauca oil is 2.67. Potassium h ydroxide flakes (Merck), m ethanol (99.8% pure, HIMEDIA) were used for the transesterification experiment. Gas c hromatographic method was used to determine the fatty acid composition of the oil. Process of Alkaline Transesterification : The apparatus was a 1Liter glass reactor ( shown in f igure - 1) equipped with a digital rpm controller with mechanical stirrer, a water condenser a nd funnel, and surrounded by a heating mantle controlled by a temperature controller device. A digital temperature indicator had been used to measure the reaction temperature. Reaction process : 750ml Simarouba oil was taken in the reactor. The anhydrous KOH and CH 3 OH solution or p ottasium methoxide (prepared recently) were added to the closed reaction vessel. The important parameter is stirring speeds and temperature which play a vital role in transestrification process 8 . The mixture was heated to the required reaction temperature of 60 - 65 0 C by the temperature controller for about 2 hours with stirring speed of 600 rpm. Samples of 10 ml were taken from the reaction mixture at regular intervals, typically 10 min, neutralized, and analyzed by gas chroma tography. When the conversion of the oil was quantitative, as determined by the GC, the heating mantle was switched off. The mixture was then allowed to cool in the reactor and was neutralized with the stoichiometric amount of concentrated hydrochloric aci d , appearing as two distinct phases after switching off the stirrer. These two phases were decanted using the bottom outlet of the reactor. The excess methanol in Research Journal of Chemical Sciences ______ _ _ _______________________________ ______________ _ ____ ISSN 2231 - 606X Vol. 2 ( 5 ), 66 - 71 , May (201 2 ) Res.J.Chem.Sci International Science Congress Association 68 both phases was evaporated at vacuum. Biodiesel without further purification was a clear, lig ht green liquid. The final Biodiesel layer required washing with tap water in order to remove the excess catalyst and the methanol. The final product after washing was heated to remove the moisture. It had been observed that the best yield was obtained wi th a catalytic condition of 1% KOH. For higher value of catalytic concentration the value was lower. It had been found that when the oil contains large amount of free fatty acid the addition of KOH compensates the acidity and avoids catalytic deactivation. Whereas for refined oil with FFA less than 1 % the addition of excess alkaline catalyst results in the formation of an emulsion which increases the viscosity and leads to the formation of gels 10 . Analyses : The transesterification reaction was monitored by using t hin l ayer c hromatography shown in f igure - 2 to check the completion of the reaction. Results and Discussions The percentage composition of fatty acids present in Simarouba oil was determined by gas c hromatographic analysis (Chemito CERES 800 plus G.C) and is represented in t able - 2. Simarouba glauca oil consists of 96.11% pure triglyceride esters. The physicochemical properties of Simarouba glauca oil were determined and compared with other oils and the results are presented in t able - 3. The fuel pr operties of Simarouba Oil Methyl Esters (SOME) are determined as per BIS, shown in t able - 4 and also compared with Karanja Oil Methyl Ester (KOME), Corn Oil Methyl Ester (COME) and Rapeseed Oil Methyl Ester (ROME). Viscosity : Among the general parameters for b iodiesel the viscosity controls the characteristics of the injection from the diesel injector because high viscosity leads to unfavorable pumping; inefficient mixing of fuel with air contributes to incomplete combustion which results in increased carb on deposit formation 15 . The kinematic viscosity of crude Simarouba oil was found to be 34 centistokes and it is reduced to 4.68 centistokes after transesterification. A graph is plotted between k inematic v iscosity vs t emperature and is given in f igure - 3. The kinematic viscosity decreases with increase in temperature. Density : The comparison of densities of crude oil, SOME and diesel were given in f igure - 4. The higher densities of Simarouba oil and SOME as compared to diesel may be attributed to the highe r molecular weights and triglyceride molecules present. Flash Point : It was the lowest temperature at which the oil gives off enough vapors that ignite for a moment, when a tiny flame is brought near it. Flash point of crude Simarouba oil and SOME were d etermined 225 0 C, 165 0 C respectively and is compared with diesel in f igure - 5. The flash point of b io diesel was higher than the diesel, which was safe for transport. The above listed properties from the experimental results indicate that SOME was the best suited as per BIS norms for using as b io diesel. Table – 1 Percentage yield of oil from Simarouba Kernel Extraction Method Yield in % Mechanical Expeller 15 Soxhlet Apparatus 55 – 60 Table – 2 The Fatty acid composition of Simarouba oil determined by Gas Chromatography in which the total number of Carbon and number of double bond is mentioned by first and second subscripts Fatty acid Percentage (%) Stearic Acid (C 18:0 ) 27.3 Oleic Acid (C 18:1 ) 54.6 Palmitic Acid (C 16:0 ) 12.3 Linoleic Acid (C 18:2 ) 2.3 Arachidic Acid (C 20:2 ) 1.2 Erucic Acid (C 22:2 ) 0.4 Linolenic Acid (C 24:0 ) 0.2 Heptadecanoic Acid (C 17:2 ) 0.1 Research Journal of Chemical Sciences ______ _ _ _______________________________ ______________ _ ____ ISSN 2231 - 606X Vol. 2 ( 5 ), 66 - 71 , May (201 2 ) Res.J.Chem.Sci International Science Congress Association 69 Table – 3 The physicochemical properties of Simarouba glauca oil (As per BIS method) with the comparisons of other oils Chemical properties Value Simarouba Oil Karanja Oil 9 Corn Oil 12 Beef Tallow Oil 6 NeemOil 13 Acid Value (mg KOH/gm) 5.34 5.06 0.23 - - Saponification value (mg KOH/gm) 176 187 - 193.202 189 Iodine value (gm/100gm) 83.4 86.5 125.4 35 – 48 99 Table – 4 The fuel properties of Simarouba Oil Methyl Esters (SOME) as determined as per BIS method with the comparisons of other oils of methyl esters Property Experimental Values Test Method BIS specification SOME KOME 9 COME 12 ROME 14 Kinematic Viscosity at 40 0 C in CSt 4.68 5.431 4.14 4.76 IS 1448 P: 25 2.5 – 6.0 Density at 15 0 C Kg/m 3 865 889 865 885 IS 1448 P: 16 860 - 900 Flash Point 0 C 165 116 - 156 IS 1448 P: 20 ≤ 120 Cloud Point 0 C 19 22 - 5 - 2 IS 1448 P: 10 - Pour Point 0 C 14.2 15.8 - 6 - 7 IS 1448 P: 10 - Carbon Residue % w/w 0.10 0.08 - - IS 1448 P: 8 ≤ 0.05 Ash content % w/w 0.005 0.003 - 0.015 IS 1448 P: 4 ≤ 0.02 Figure - 1 Transestrifeactor (Schematic diagram) Research Journal of Chemical Sciences ______ _ _ _______________________________ ______________ _ ____ ISSN 2231 - 606X Vol. 2 ( 5 ), 66 - 71 , May (201 2 ) Res.J.Chem.Sci International Science Congress Association 70 0 5 10 15 20 25 30 35 40 20 30 40 50 60 70 Temperature Viscosity in Centistokes Crude Oil Biodiesel Diesel 910 865 822 760 780 800 820 840 860 880 900 920 Crude Oil Biodiesel Diesel Density in Kg/m3 225 165 55 0 50 100 150 200 250 Crude Oil Biodiesel Diesel Flash Point (0C) (0C) Figure - 2 Figure - 3 Thin Layer Chromatographic analysis. Kinematic Viscosity verses Temperature Triglycerides (Simarouba glauca oil) and Methyl Esters of Simarouba glauca Figure - 4 Figure - 5 Comparison of densities of Crude Oil, SOME and Diesel Flash point of crude Simarouba glauca oil, SOME and Diesel Conclusion Biodiesel has become more attractive to replace the petroleum fuels. As per reputed literature, most of the transestrification studies have been done on edible oils like r apeseed, s oybean, and s unflower etc by using NaOH or KOH catalyst. The tree borne oil like Simarouba glauca is the most potential species to produce biodiesel in India which could offer opportunity the generation of rural employment. The process is based on the alkaline catalyzed transesterification and can be further improved to get high yield and good fuel quality Biodiesel. Acknowledgements The authors are grateful to Department of Science and Technology, Government of India and Science and Technology Department, Government of Odisha for funding diffe rent projects on Bio - fuel for production and testing. One of the author SRM is thankful to Head, Department of Chemistry, Utkal University, Bhubaneswar for providing necessary laboratory facilities. References 1. Gilman E.F. and Watson D.G., Simarouba glauca: Paradise - Tree, Institute of Food and Agricultural Sciences, University of Florida, Gainesville FL 32611. Fact Sheet ST - 590 , http://hort.ufl.edu/database/docume nts/ pdf/tree_fact_sheets/simglaa.pdf 2. 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