International Journal of Emerging Technologies and Engineering (IJETE) Volume 1 Issue 1 January 2014

Comparison of Palm Oil and JatrophacurcasSeed Oil for Biodiesel production in Nigeria Using Bulk CaO Catalyst
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Haruna Ibrahim*, 1Chika Ezeanyanso, 1AminuHayatudeen , 1Deborah C.U. Nwakuba,1Olabode Olabimtan . 2 Aminu A. 3Amina M. Ibrahim
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Petrochemical Division, National Research Institute for Chemical Technology, Zaria, Nigeria. 2 Chemical Engineering Department.Ahmadu Bello University, Zaria, Nigeria. 3 Turkish-Nigerian University, Abuja, Nigeria..

ABSTRACT Biodiesel is a renewable, biodegradable and environmental benign liquid fuel capable of replacing fossil diesel. A study on comparison of biodiesel processing raw materials was carried out with palm oil and Jatrophacurcasoilusing calcium oxide catalyst to determine which should be relied upon for biodiesel production. At 600C and 90 minutes of reaction time, the yields of 86.41% and 99.08% for palm oil and Jatrophacurcas oil were obtained respectively. The results obtained at650C and 75 minutes were 89.41% and 96.93% for palm oil and Jatrophacarcass oil respectively.For all the reactions the mole ratio of methanol to oil was 5.5:1 and the quantity of catalyst used was 1.5% w/w of oil. The methyl ester contents were analyzed with GC-MS.Jatrophacurcasseed oil gave higher yield but it highly acidic which require more energy, time and materials to refine. Keywords: palm oil, jatropha oil, calcium oxide, catalyst, biodiesel, production cost I. Introduction Biodiesel is a renewable, biodegradable and environmental benign liquid fuel capable of replacing fossil diesel for use in diesel engines. Biodiesel has a lot of advantages over fossil diesel such as; lubricating, low sulphur emission [1], low greenhouse gas emission [2], absence of aromatic compounds and its renewability. However, the cost of production of biodiesel is expensive, hence the diesel users do not ask for it which makes the business of producing it in Nigeria especially unattractive. As a prospective fuel it has to compete economically with petro-dieseltherefore, the only way of reducing the biodiesel cost is to use less

expensive process and raw materials such as nonedible oil and cheap catalysts. Biodiesel is prepared from natural triacylglycerols (TAG) of vegetable oils and animal fats [3] by the process known as transesterification.Lengyelet al [3] produced biodiesel from rapeseed oil and methanol using calcium oxide catalyst and got a yield of 98.8%. With canola oil and methanol using nano calcium oxide catalyst at 650C a yield of 100% was obtained [4]. Transesterification was carried with Jatophacurcasseed oil and methanol using zinc oxide as catalyst by Highinaet al [5] resulted 96.46% methyl esters.If Nigeria joins the League of Nations producing biofuels for transport sector it will go along to benefit from the targeted interventions that would reduce the local air pollution and help the country to tackle greenhouse gas emissions [6]. In this work, bulk calcium oxide catalyst was synthesized locally and it was used to produce biodiesel with Palm Oil (PO) and Jatrophacurcasseed Oil (JCO) at the same reaction conditions of time and temperature and their yields were compared. Palm oil is in abundant in Nigeria but the used of it for biodiesel production will definitively affect its price and will result in food crisis. JatrophacurcasOil is not edible whichcan be grown in non-arable land for biodiesel production without causing any food crisis. Calcium carbonate is also found in abundance in Nigeria hence; calcium oxide catalyst can easily and cheaply be synthesized for biodiesel production. II. Materials and Method The materials used in this investigation include; an oven for drying the catalyst sample, a furnace for firing the catalyst and ceramic crucibles. A top 28

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International Journal of Emerging Technologies and Engineering (IJETE) Volume 1 Issue 1 January 2014

loading balance, conical flasks, magnetic stirrer, hot plate, thermometer and separating funnel for separating biodiesel from glycerol were among the apparatus used in this research work. The reagents used include, analytical grade methanol for transesterification. propan-2-ol, 0.1M potassium hydroxide for determination of FFA of the oils and GC-MS for biodiesel yield analysis. 2.1 Preparation of Calcium oxide Catalyst A bag weight of 50kg hydrated lime was collected from Pilot plant division of National Research Institute for Chemical Technology, Zaria. 200g of the hydrated lime was dried in an ovento constant weight. The calcium oxide obtained was calcined in a furnace at 9000C for 90 minutes at 50% power rate.

oil. A magnetic stirrer was dropped into the reaction mixture to stir the reactants. The reaction temperature was maintained at 600C throughout the reaction period. In the second reaction same quantity of palm oil, methanol and catalyst were used at 650C for 75 minutes. The same procedure was repeated for Jatrophacurcasseed oil. The reactions were carriedout in a conical flask covered with aluminium foil and was mounted on a magnetic stirrer. 2.4 Separation At the end of each reaction time the products werefiltered and the filtrated weretransferred into separating funnel and left for an hour or more to allow separation of biodiesel and glycerol by gravity. The residue was the solid catalyst (CaO). Glycerol which is denser than biodiesel was collected out at bottom of the funnel leaving biodiesel on top. These products were collected separately for analysis. 2.5 Ester Test A quick test which is also known as ester test was performed on each of the biodiesel samplesproduced by dissolving 10 ml of biodiesel in 40 ml of methanol. The mixture was shaked thoroughly, left for some minute and then observed to see if there is complete dissolution. 2.6 GC-MS Analysis Biodiesel samples from each batch were taken to GC-MS analysis in the instrumentation Division of National Research Institute for Chemical Technology, Zaria to determine the yield or rather ester content III. Results and Discussions

Ca (OH ) 2 CaO H 2 O

2.2 Determination of FFA and Esterification The acid values of the two oil were first determined by dissolving I.0 g of oil sample in 25 ml of propan2-ol, two drops of phenolphthalein indicator was added and the solution formed was titrated against 0.1 M potassium hydroxide to pink colour. A blank titration was also performed by titrating 25 ml of propan-2-ol against 0.1 M potassium hydroxide to pink. The difference of the two titre values,v was used for determining the FFA.

FFA

0.1M v 56.1g / mol 1 .0 g

Where, v is the titre value.

%FFA FFA / 2

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3.1 Free Fatty Acid Content (FFA) The FFA of the palm oil was found to be 0.56 hence its %FFA 0.28% and FFA of Jatrophaoil was found to be 10.4 and %FFA was 5.2. The FFA of the Jatrophawas reduced to 0.87% by esterifying with methanol and concentrated sulphuric acid after three rounds of esterification. All the four samples dissolved completely in methanol, confirmed that the reaction was complete. 29
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Esterification was carried out by heating 2.25 x %FFA x mass of the oil to esterified (300 g) as mas of methanol and 0.05 x %FFA x mass of oil as mass of sulphuric acid [7] at 600C for 60 minutes on magnetic stirrer with continuous stirring. 2.3 Transesterification 300g of palm oil was transesterified with 60g methanol (1:5.5 mole mratio) and 4.5g (1.5% mass of the oil) of the synthesized calcium oxide catalyst at 600C for 90 minutes. The palm oil was first heated to 600C in a conical flask and then, the calcium oxide and methanol mixture was poured into the hot

International Journal of Emerging Technologies and Engineering (IJETE) Volume 1 Issue 1 January 2014

Table1: Percentage Composition of Methyl Esters in the Products Methyl ester composition Methyl octanoate Methyl nonanoate Methyl decanoate Methyl 10-undecenoate Methyl undecanoate Methyl dodecanoate (laurate) Methyl tridecanoate Methyl mysristate Methyl pentadecanoate Methyl hexadecanoate Methyl palmitoleate Methyl -11-hexadecenoate Methyl-7-hexadecanoate Methyl 14-methylpentadecanoate Methyl 8-(2-hexylcyclopropyl)ocatanoate Methyl 15-methylhexadecanoate Methyl linoate Methyl-9,12-octadecadienoate Methyl-8,11-octadecadienoate Methyl-10,13-octadecadienoate Methyl -3-octadecenoate Methyl oleate Methyl heptadecanoate Methyl cis-octadec-10-enoate Methyl cis-octadec-11-enoate Methyl trans-9-octadecanoate (elaide) Methyl -9-octadecenoate Methyl 9-octadecenoate Methyl -10-octadecenoate Methyl 7-octadecenoate Methyl 8-octadecenoate Methyl 15-octadecenoate Methyl octadecanoate MF C9H18O2 C10H20O2 C11H22O2 C12H22O2 C12H24O2 C13H24O2 C14H28O2 C15H30O2 C16H32O2 C17H34O2 C17H32O2 C17H32O2 C17H32O2 C17H34O2 C18H34O2 C18H36O2 C19H34O2 C19H34O2 C19H34O2 C19H34O2 C19H36O2 C19H36O2 C18H36O2 C19H36O2 C19H36O2 C19H36O2 C19H36O2 C19H36O2 C19H36O2 C19H36O2 C19H36O2 C19H36O2 C19H38O2 8.542 3.888 10.416 11.392 8.542 4.040 25.880 0.422 12.016 8.542 PO 600C(%) PO 650C(%) 0.054 0.054 0.188 0.054 3.694 0.964 1.640 0.410 11.004 0.972 0.972 7.336 0.588 0.112 9.968 4.984 4.984 4.984 0.102 4.040 8.542 4.040 4.040 4.040 12.940 25.880 24.032 1.874 12.016 JCO 600C (%) JCO 650C (%) 0.160 0.040

0.168 0.504 15.200

0.114 0.362 11.032 1.800 0.900 2.758

0.054 0.162 19.920 0.844

15.200 8.740

5.034 0.422 1.874

12.016 8.542 0.900 0.412

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International Journal of Emerging Technologies and Engineering (IJETE) Volume 1 Issue 1 January 2014

Methyl 16-methylheptadecanoate Methyl hydrosterculate Methyl-10-nonadecenoate Methyl -11-icosenoate Methyl eicosanoate Methyl heneicosanoate Methyl -15-tetracosenoate Total

C19H38O2 C20H38O2 C20H38O2 C21H40O2 C21H42O2 C22H44O2 C25H48O2 86.410

2.604

2.848 0.900

5.622

0.486 0.102 0.336 0.354 1.172 89.134 0.412

0.422

99.078

96.93

At 600C palm oil (PO) yielded 86.4% and Jatrophaoil (JCO) yielded 99.1 % methyl esters and at 650C the yields were 89.1% and 96.9% respectively. At the two temperature conditions, Jatrophacurcasoil yields meet the International biodiesel standard of 96.5% methyl ester content [1] but that of palm oil yield were below. The methyl esters found in the biodiesel products are shown in the Table 1 with their percentage composition. The results show that higher esters of 20 to 25 carbons though at relatively small amount were produced at higher temperature with palm oil and not much of such components were found in Jatrophacurcasoil biodiesel products.Shown in the table are the names of the methyl esters, their molecular formulas (MF) and percentage compositions. These results show that the yield of biodiesel from palm oil increases with temperature as shown in the Table from 60 to 650C but that of Jatrophadecreases, but at the same temperature Jatrophacurcasoil yielded more biodiesel than palm oil. In the case of palm oil, 600C temperature favours middle methyl esters of C17C19 while 650C produced all ranges from C10 to C25 methyl esters. The results of Jartophacurcasseed oil do not show much difference, however, methyl esters of C9 and C10 were found in 650C product but not in 600C product. The results also show that using Jatrophacurcasseed oil biodiesel can be produced at low temperature of 600C with just mole ratio of 5.5: 1 of methanol to oil. Temperature higher that 600C may results in lower yield. IV. Conclusion

Calcium oxide catalyst is an excellent catalyst for biodiesel production and it is very simple to synthesize. With calcium oxide, transesterification can now be carried out in 60 minutes as against 150 minutes [8] and 180 minutes [9]. Also, with mole ratio 5.5:1 good yield (99.1%) can be obtained from Jatropha oil using calcium oxide catalyst as against 18:1 [10] and 12:1 [9]. The composition of biodiesel varies with reaction conditions. Jatrophacurcas seed oil can be relied upon among othernon-edible seed oils for biodiesel production. The use of Jatrophacurcasoil and calcium oxide catalyst will make better alternative materialsforbiodiesel production as calcium carbonate is chiefly abundant in the Nigeria. V. Acknowledgement All the reagents and materials used in carryout this research were obtained from the store of National Research Institute for Chemical Technology NARICT, Zaria. References 1. Gerard Hillion, Bruno Delfort, Dominique le Pennec, Laurent Bournay, Jean-Alain Chodorge (2003) Biodiesel Production by a Continuous Process Using a Heterogeneous Catalyst. Prepr. Pap.-Am. Chem. Soc., Div. Fuel Chem., 48(2),638 2. Rubi Romero, Sandra Luz Martnez and Reyna Natividad (2011) Biodiesel Production by Using Heterogeneous Catalysts, Alternative fuel, Centro Conjunto 31

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International Journal of Emerging Technologies and Engineering (IJETE) Volume 1 Issue 1 January 2014

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de Investigacin en QumicaSustentable UAEM-UNAM JozefLengyel, ZuzanaCvengroov, JnCvengro Petroleum & Coal 51(3) 216224, 2009. Transesterification of TriacylglycerolsOver Calcium oxide as Heterogeneous Catalyst Available online at www.vurup.sk/pc Lina Zhao (2010). Novel Solid Base Catalysts for the Production of Biodiesel from Lipids. Chemical and Petroleum Engineering University of Kansas School B. K. Highina, I. M. Bugaje and B. Umar Biodiesel production from Jatropha caucus oil in a batch reactor using zinc oxide as catalyst Journal of Petroleum Technology and Alternative Fuels Vol. 2(9), pp. 146149, September 2011 Available online at http://www.academicjournals.org/JPTAF Sunday OlayinkaOyedepo . Energy and sustainable development in Nigeria: the way forward Energy, Sustainability and Society2012, 2:15. http://www.energsustainsoc.com/content/2/1 /15 Gerpen, J. V., B. Shanks, R. Pruszko, D. Clements and G. Knothe, (2004). Biodiesel Production Technolog, National Renewable

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Energy Laboratory (NREL), 1617 Cole Boulevard, Golden, Colorado Isahsk W.N.R., Ismail, M. J. Jahim, M., Salimon, J. and Yarmo, M.A. (2010). Transesterification of Palm Oil Using NanoCalcium oxide as a Solid Base Catalyst, World Applied Science Journal 9 (Special Issue of Nano Technology): 17-22, 2010 ISSN 1818-4952 Hawash, G.E.l., Diwani, E. and Abdel K. (2011). Optimization of Biodiesel Production from Jatropha Oil By Heterogeneous Base Catalysed Transesterification, International Journal ofEngineering Science and Technology (IJEST) Highina, B. K., Bugaje I. M. and Umar B. (2011). Biodiesel production from Jatropha caucus oil in a batch reactor using zinc oxide as catalyst Journal of Petroleum Technology and Alternative Fuels Vol. 2(9), http://www.academicjournals.org/JPTAF Haruna Ibrahim et al,Economic Evaluation of Continuous Heterogeneous Catalytic Transesterification of Jatropha oil Plant, IJAERT, Volume 1 Issue 1 pp 15-21 December 2013

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