1 © Adama Science & Technology University https://ejssd.astu.edu.et Ethiopian Journal of Science and Sustainable Development (EJSSD) p-ISSN 1998-0531 Volume 5 (1), 2018 Production of Bio-Diesel from Cucumis Sativus Seed oil involving Crystalline Manganese Carbonate – A Green (Nanosized) Catalyst K.S.K. Rao Patnaik1, Melakuu Tesfaye Alemea1, A. Sunil2, Y. Rajeshwer Rao3 1 Adama Science and Technology University, School of Mechanical, Chemical and Materials Engineering, Dept. of Chemical Engineering, P.O.Box.1888, Adama, Ethiopia E.Mail:drkskrao@gmail.com 2 Dept.of Chemical Engineering, Osmania University, Hyderabad, India 3 Department of Chemistry, Rajiv Gandhi University of knowledge Technologies, IIIT Basara-504 107, Telangana State, India Abstract This paper focuses on the production of bio-diesel from low cost feed stock CucumisSativus seed oil using MnCO3 as a Green (Nanosized) catalyst through transesterification process and investigating the effects of process parameters on bio-diesel yield. The optimum parameters for maximum bio-diesel yields were found to be methanol/oil molar ratio of 1:1, catalyst concentration of 1 wt% of oil, at the temperature of 65 ° C and reaction time 3 hours (180 min). The maximum bio-diesel yield at the optimum condition was 86%. Crystalline manganese carbonate was found to be environmentally friendly, easy to handle and non-corrosive green catalyst for the production of biodiesel from cucumber seed oil. The enhancement of the parameters are possible because of the Nano nature of the catalyst used. The results demonstrated high potential of producing economically viable biodiesel from low cost feed stocks with proper optimization of the process parameters. Keywords: Manganese Carbonate, CucumisSativus seed oil, Methanol, Transesterification, Bio-diesel. 1. Introduction Bio-diesel has been a promising alternate fuel during the past decade as a renewable source. It is a Biodegradable from transesterification of vegetables oil with alcohol has been accepted for use in blends with conventional petroleum fuel for transportation applications [1- 4]. Soybean and Rapeseed are common feedstock for biodiesel production in USA and Europe respectively. Likewise, palm is being exploited in South East Asia [5]. In order to explore additional Patnaik et al. Ethiop. J. Sci. Sustain. Dev., 5 (1), 2018 2 © Adama Science & Technology University https://ejssd.astu.edu.et oil resources (Non-Edible oils), the study on potential of Cucumber (Cucumis Sativus) seed oil as bio-diesel resource is reported here. The potentiality of Crystalline Manganese Carbonate as a catalyst has proven worthy for the bio-diesel yield. This was possible because of its Nano nature. Bio-diesel fuel is made from vegetable oils, animal fats, and microbial oil (algae, yeast, bacteria, and fungi).The most common method in the production of bio-diesel is the transesterification reaction, where the triglycerides present in oil react with monohydric alcohol in the presence of a catalyst, such as sodium hydroxide, sodium methoxide, potassium hydroxide, crystalline manganese carbonate and potassium methoxide [1-4, 6]. Bio-diesel synthesis using solid catalysts like Manganese Carbonate, instead of homogeneous catalysts like sodium hydroxide, could potentially lead to cheaper production costs by enabling reuse of the catalyst [7-13]. In the present study, attempt has been made to convert CucumisSativus seed oil to Fatty Acid Methyl Esters (FAME) using crystalline manganese carbonate a low cost, non-corrosive and green catalyst. This brings about 86% conversion of oil to FAME. Transesterification (Fig 1) is the chemical reaction between triglycerides and alcohol in the presence of the catalyst to produce monoesters. The heterogeneous Manganese Carbonate base catalyst is active for high molecular weight alcohol achieving conversion to 90% and produces neither corrosion nor emulsion making it easier to separate the product obtained [2]. In literature, many attempts have been made for search of new effective catalysts and feed stocks using transesterification reaction, for the production of Bio-diesel. M. ArunKumari, et al. (2014) [1], Patnaik et al. Ethiop. J. Sci. Sustain. Dev., 5 (1), 2018 3 © Adama Science & Technology University https://ejssd.astu.edu.et have concluded that Crystalline Manganese Carbonate gave higher yield than Zinc Oxide when producing bio-diesel from PongmiaPinnata and Guizotia Abyssinica feed stocks. Fig.1.Transesterification of triglycerides with alcohol 2. Materials and Methods 2.1. Materials: The Cucumis Sativus seed oil, Crystalline Manganese Carbonate and methanol were purchased directly from the laboratories. Analysis of Cucumber oil: Cucumis sativa seed oil (Cucumber oil) is subjected to Gas chromatography to determine the composition. The samples are analyzed with a Shimadzu GC-2010 gas chromatograph, equipped with a split less injection system. Helium is used as a carrier gas. Instrument conditions are maintained: column oven temperature 75°C, injection temperature 250°C, flow control mode in linear velocity with 92.5 cm/sec, total flow 61.2 ml/min, column flow 5.42 ml/ min, purge flow 1.5 ml/min, pressure 100 kpa, whereas the split ratio 10.0. Samples are prepared for analysis by adding approximately 0.05 gof oil phase to 5 ml of n-Hexane. About 1ml of this mixture is put in to the GC auto sampler vials. Two micro liters of the sample are injected into the column. The obtained results for fatty acid compositions of Cucumis Sativa seed oil (Cucumber oil) are shown in Table 1. Cucumis Sativa seed oil (cucumber oil) has the major fatty acids which are linoleic, stearic, oleic and palmitic acids. 2.2. Experimental Procedure: The CucumisSativus seed oil (cucumber oil) is taken in the reaction flask and heated at 50°C. The mixture of catalyst in methanol with different concentrations is used for the conversion of Patnaik et al. Ethiop. J. Sci. Sustain. Dev., 5 (1), 2018 4 © Adama Science & Technology University https://ejssd.astu.edu.et CucumisSativa seed oil to FAME. Transesterification reactions are performed in a 150 ml round bottom flask with a reflux condenser, stirring is provided by a magnetic stirrer. The stirrer is set at a constant speed throughout the experiments. Initially, the oil was heated at a desired temperature. The methanol and catalyst mixture was added to the round bottom flask containing oil. At that point, the reaction is kept under reflux conditions. The formation of methyl esters from Cucumber oil is monitored by thin layer chromatography. The methyl esters are washed with distilled water and concentrated under vacuum to afford FAME. Fig.2. Schematic Diagram of the Experimental Setup Catalyst analysis: In the present study, XRD and SEM analysis of Manganese Carbonate is Reported (Fig. 3 & 4). Recovery of catalyst: In the present work, the manganese carbonate catalyst is recovered by filtration and washed with 80°C distilled water 4-5 times. Then the catalyst is dried at 50°C for 35 hours in the hot air oven. After the complete drying the catalyst is used in the transestrification reaction. The efficiency of the catalyst is 95%. The catalyst is still Patnaik et al. Ethiop. J. Sci. Sustain. Dev., 5 (1), 2018 5 © Adama Science & Technology University https://ejssd.astu.edu.et efficient even after seven successive runs shown in Table 2. Table 1. Fatty acids CucumisSativa seed oil (Cucumber oil). Fatty acids Cucumber oil % Palmitic(C16/0) 11 Stearic(C18/0) 7 Oleic(C18/1) 14 Linoleic(C18/2) 68 Table 2.The efficiency of the catalyst after seven successive runs Catalyst Quantity 1% Cucumis Sativa methyl esters yield (%) First use Second Third Fourth Fifth Sixth Seventh 95 95 94.5 94.5 94 94 93.5 Figure.3: XRD of Manganese Carbonate. Figure 4:.SEM Image of Manganese Carbonate 3. Results and Discussion Effect of methanol/oil molar ratio: In the present work, transe sterification of CucumisSativus oil with 1% MnCO3 catalyst using alcohol /oil ratio between 1:1 and 5:1 is carried out; it is observed that the ester conversion increases Patnaik et al. Ethiop. J. Sci. Sustain. Dev., 5 (1), 2018 6 © Adama Science & Technology University https://ejssd.astu.edu.et with the decrease in molar ratio up to the value of 1:1. The highest bio-diesel yield achieved at 1:1 molar ratio is 86% in 180 min. The results are depicted in Fig.5. Fig.5. Effect of methanol/oil molar ratio Effect of catalyst quantity: The highest bio-diesel yield 86% is obtained at 1wt% catalyst in 180 min. Further increases of catalyst quantity shows decrease in bio- diesel yield and add extra cost, since the catalyst needs to be removed from the reaction mixture after the reaction. The effects of MnCO3 quantity on transe sterification are presented in Figure 6. At 1% of the catalyst the bio-diesel yield is 86%. Effect of Temperature: The reaction temperature effect on the bio-diesel yield is studied in the range of 28-65°Cat atmospheric pressure. The maximum yield is achieved at 65°C 180 min. The methanol to oil molar ratio was 1:1 and the catalyst concentration is 1% in all the experiments. The temperature dependence of bio- diesel yield is presented on Fig.7. Fig.6. Effect of Catalyst quantity Fig.7. Effect of Reaction Temp. Patnaik et al. Ethiop. J. Sci. Sustain. Dev., 5 (1), 2018 7 © Adama Science & Technology University https://ejssd.astu.edu.et Effect of Reaction time: Experiments are carried out at various speeds between 30-180 min. The experiments showed that conversion of Cucumis Sativa oil to bio-diesel yield of 86% is achieved within 180 min at reflux condition. However, the reaction is carried out at the temperature close to the boiling point of methanol (60-70°C) at atmospheric pressure for a given time. The effect of reaction time on bio-diesel yield is reported in Fig.8. Fig.8. Effect of Reaction time 4. Conclusions The studies on Crystalline Manganese Carbonate as a catalyst for bio-diesel production are cited in the Literature as a potential catalyst. But the reason behind the potentiality may be because of the Nano nature. The results show that at 1:1 ratio of methanol to CucumisSativusoil at 65°C gives the highest yield. The Bio-diesel yield conversion increases directly with decrease in methanol quantity at different catalyst to oil ratios. Using Manganese Carbonate (1% wt.) as the catalyst for Cucumis Sativus oil transesterification with methanol, 86% yield of bio-diesel is achieved. The Crystalline Manganese Carbonate (Nano sized) is found to be an alternative, green and heterogeneous catalyst for the production of Bio-diesel. Acknowledgement The authors would like to thank the Principal, University College of Technology, Osmania University, Hyderabad, India for providing research facilities. The authors are also acknowledge the President, Adama Science and Technology University and Dean, Patnaik et al. Ethiop. J. Sci. Sustain. Dev., 5 (1), 2018 8 © Adama Science & Technology University https://ejssd.astu.edu.et SOMCME, Dept. of Chemical Engineering, Adama, Ethiopia for providing Computer Facilities. References [1] M ArunaKumari, K.S.K.Rao Patnaik, Y Rajeshwer Rao (2014), “Production of Bio- diesel from PongmiaPinnata and GuizotiaAbyssinica seed oil using Crystalline Manganese Carbonate (MnCO3) and Nano Zinc Oxide (ZnO) – A Green Catalyst”, International Scientific Journal of Environmental Science, Vol. 3, pp. 14-20. [2] Rajeshwer Y. Rao, Pudukulathan K. Zubaidha, Dasharath D. Kondhare, Narender J. Reddy, Sushma S. 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