Journal of Advanced Research (2010) 1, 309314

Cairo University

Journal of Advanced Research

ORIGINAL ARTICLE

Production of biodiesel using the microwave technique

Shakinaz A. El Sherbiny, Ahmed A. Refaat, Shakinaz T. El Sheltawy
Department of Chemical Engineering, Faculty of Engineering, Cairo University, Egypt Received 30 October 2009; revised 28 January 2010; accepted 8 March 2010 Available online 15 September 2010

KEYWORDS Microwave; Biodiesel; Transesterication; Non-edible oil

Abstract Biodiesel production is worthy of continued study and optimization of production procedures because of its environmentally benecial attributes and its renewable nature. Non-edible vegetable oils such as Jatropha oil, produced by seed-bearing shrubs, can provide an alternative and do not have competing food uses. However, these oils are characterized by their high free fatty acid contents. Using the conventional transesterication technique for the production of biodiesel is well established. In this study an alternative energy stimulant, microwave irradiation, was used for the production of the alternative energy source, biodiesel. The optimum parametric conditions obtained from the conventional technique were applied using microwave irradiation in order to compare the systems. The study showed that the application of radio frequency microwave energy offers a fast, easy route to this valuable biofuel with the advantages of enhancing the reaction rate (2 min instead of 150 min) and of improving the separation process. The methodology allows for the use of high free fatty acid content feedstock, including Jatropha oil. However, this emerging technology needs to be further investigated for possible scale-up for industrial application.
2010 Cairo University. Production and hosting by Elsevier B.V. All rights reserved.

Introduction Biodiesel has many merits as a renewable energy resource including being derived from a renewable domestic resource, thereby relieving the reliance on petroleum fuel, and being bio* Corresponding author. Tel.: +20 10 6044605. E-mail address: chakinaz@hotmail.com (S.T. El Sheltawy). 2090-1232 2010 Cairo University. Production and hosting by Elsevier B.V. All rights reserved. Peer review under responsibility of Cairo University. doi:10.1016/j.jare.2010.07.003

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degradable and non-toxic. Further, compared to petroleumbased diesel, biodiesel has a more favorable combustion emission prole, such as low emissions of carbon monoxide, particulate matter and unburned hydrocarbons [1]. Fuels derived from vegetable oils, due to their agricultural origin, are able to reduce net CO2 emissions to the atmosphere along with import substitution of petroleum products [2]. They present a very promising alternative to diesel oil since they are renewable and have similar properties [3]. The use of non-edible vegetable oils compared to edible oils is very signicant because of the tremendous demand for edible oils as food. Moreover, edible oils are far too expensive to be used as fuel at present [4]. The interest in using Jatropha curcas as a feedstock for the production of biodiesel is rapidly growing. The properties of the crop and its oil have persuaded investors, policy makers and clean development mechanism (CDM) project developers to consider Jatropha as a substitute for fossil fuels to tackle the

310 challenges of energy supply and GHG emission reduction [5]. The oil produced by this crop can be easily converted to liquid biofuel that meets the American and European standards [6]. Additionally, the press cake can be used as a fertilizer and the organic waste products can be digested to produce biogas (CH4) [5]. The plant itself is believed to prevent and control soil erosion or can be used as a living fence or to reclaim wasteland [7]. Microwave irradiation, an unconventional energy source, has been used for a variety of applications including organic synthesis, wherein chemical reactions are accelerated because of selective absorption of MW energy by polar molecules, non-polar molecules being inert to the MW dielectric loss [8]. Microwaves, representing a non-ionizing radiation, inuence molecular motions such as ion migration or dipole rotations without altering the molecular structure. Because the mixture of vegetable oil, methanol, and potassium hydroxide contains both polar and ionic components, rapid heating is observed upon microwave irradiation, and because the energy interacts with the sample on a molecular level, very efcient heating can be obtained. Microwave heating compares very favourably with conventional methods, where heating can be relatively slow and inefcient because transferring energy into a sample depends upon convection currents and the thermal conductivity of the reaction mixture [9]. To allow for a strict comparison between microwave irradiation and conventional heating under similar conditions (reaction medium, temperature and pressure), a monomode microwave reactor should be used. This ensures wave focusing (reliable homogeneity in the electric eld) and accurate control of the temperature (using an optical bre or infrared detection) throughout the reaction [10]. Reux systems have been developed in an effort to use solvents in microwave assisted organic synthesis without the risk of explosion. Reux systems are at minimal risk of explosion because they are operating at atmospheric pressure and because ammable vapors cannot be released into the microwave cavity. Several examples of microwave irradiated transesterication methods have been reported incorporating adapted domestic ovens for use as ow systems [11] or batch laboratory ovens [12] but only moderate conversions were obtained. A more recent study used homogeneous catalysis, both in a batch and in a ow system [13]. Leadbeater and Stencel reported the use of microwave heating as a fast, simple way to prepare biodiesel in a batch mode [14]. This was followed by a continuous ow approach allowing for the reaction to be run under atmospheric conditions and performed at ow rates of up to 7.2 L/ min using a 4 L reaction vessel [15]. Experimental Materials The main oil treated in this investigation is Jatropha oil. The fatty acid composition of the Jatropha oil used as a feedstock for biodiesel production is given in Table 1 and the oil characteristics are given in Table 2. Determination of the composition of the oil was by gas chromatograph (Auto system XL, PerkinElmer type) using fused silica capillary column 60 m 0.32 mm (ID) at the split ratio 1:5. The oven temperature was planned to remain at 150 C for one min, then heated at 30 C/min up to 240 C.
Table 1
Fatty acid Palmitic (16:0) Stearic (18:0) Oleic (18:1) Linoleic (18:2)

S.A. El Sherbiny et al.

Fatty acid prole of feedstock.
Composition (wt.%) 18.22 5.14 28.46 48.18

Table 2
Parameter

Main characteristics of feedstock.

Unit mm2/s C C C mg KOH g1 mg iodine g1 MJ kg1 Value 46.6 3 2 235 6.2 101 39.54

Viscosity Pour point Cloud point Flash point Acid value Iodine value Caloric value

Helium was used as the carrier gas with a ow rate 1 mL/ min and also as an auxiliary gas for FID. One micrometer of each diluted sample with analytical grade dichloromethane from BDH (England) was injected. The viscosity of the original oil and the produced biodiesel was measured using the Brookeld viscometer model DV-II. As evident from the tables, the fatty acid composition of the oil is dominated by oleic acid (29%) and linoleic acid (48%) i.e., the oil contains about 77% unsaturated fatty acid, which is reected on its pour and cloud points (3 and 2 C, respectively). Methanol (Analytical) El-Nasr Pharmaceutical Chemicals Co. (ADWIC) Mwt. 32.04 Assay 99.8% was used. KOH was used in this study: KOH pellets puried Thann-Fransu. Production methodology Biodiesel production was performed in two-step reaction mechanisms:  Acid-catalyzed esterication.  Base-catalyzed transesterication.

Acid-catalyzed pretreatment The Jatropha oil used had an initial acid value of 6.2 mg KOH/g corresponding to a free fatty acid (FFA) level of 3.1%, which is above the 1% limit for a satisfactory transesterication reaction using an alkaline catalyst [16]. Therefore, FFAs were rst converted to esters in a pretreatment process with methanol (molar ratio methanol/oil = 6.5:1) using H2SO4 as catalyst (0.3%) in 90 min reaction time at 60 C [6]. Base-catalyzed transesterication using the conventional technique The method applied for the production of biodiesel from Jatropha oil in this research is base-catalyzed transesterication in a laboratory-scale setup. The reaction was performed using methanol as alcohol and KOH as catalyst. The transeste-

Microwave biodiesel rication process was studied at two catalyst loadings (1 and 1.5 wt.% KOH) and three alcohol to oil molar ratios (4.5:1, 6:1, and 7.5:1). One of the most important variables affecting the yield of an ester is the molar ratio of alcohol to triglyceride. The stoichiometric ratio for transesterication requires three moles of alcohol and one mole of triglyceride to yield three moles of fatty acid alkyl esters and one mole of glycerol. However, transesterication is an equilibrium reaction in which an excess of alcohol is required to drive the reaction to the right [17]. However, an excessive amount of alcohol makes the recovery of the glycerol difcult, so that the ideal alcohol/oil ratio has to be established empirically [18]. Most of the studies on the base-catalyzed transesterication of WVO reported that maximum conversion to the ester occurred with a molar ratio of 6:1 [1922]. Transesterication of pretreated waste rapeseed oil carried out by Yuan and co-workers showed a maximum conversion at 6.5:1 of methanol to oil ratio [23], whereas an earlier study by Leung and Guo found a maximum conversion at a ratio of 7:1 [24]. Catalyst concentration is closely related to the free acidity of the oil. When there is a large free fatty acid content, the addition of more potassium hydroxide, or any other alkaline catalyst, compensates this acidity and avoids catalyst deactivation [16]. The addition of an excessive amount of catalyst, however, gives rise to the formation of an emulsion, which increases the viscosity and leads to the formation of gels. These hinder the glycerol separation and, hence, reduce the apparent ester yield. The result of these two opposing effects is an optimal catalyst concentration of about 1.01.5%. Reviewing the literature indicated that it was most efcient to x the reaction temperature at 65 C, which is slightly above the boiling point of methanol (64.7 C). When the reaction temperature exceeds the boiling point of methanol, the methanol will vaporize and form a large number of bubbles which may inhibit the reaction [22,25,26]. The agitation rate was kept at 400 rpm. Since this reaction can only occur in the interfacial region between the liquids and also due to the fact that fats and alcohols are not totally miscible, transesterication is a relatively slow process. As a result, vigorous mixing is required to increase the area of contact between the two immiscible phases and co-workers studied the effect of agita[27]. Stamenkovic tion intensity on methanolysis of sunower oil and reported that by using the microphotographic technique, drop size distributions were found to become narrower and shift to smaller sizes with increasing agitation speed as well as with the progress of the methanolysis reaction at a constant agitation speed [28]. Berchmans and Hirata used an agitation intensity of 400 rpm for the two-step methanolysis of Jatropha oil [25]. All the reactions were carried out in the reaction conical asks, which were immersed at 65 C in a thermostatic water bath equipped with a magnetic stirrer at 400 rpm. Potassium methoxide solution was freshly prepared by dissolving the fresh KOH pellets in the predetermined amount of methanol. Mixing was performed by continuous stirring for 5 10 min. Warm oil was then added to the catalyst/alcohol mixture and the reaction mix was kept at 65 C throughout the reaction time. Once the reaction was completed, the reaction mixture was poured into a 200 mL separating funnel and the solution was allowed to settle overnight before the glycerol layer was removed from the bottom of the separating funnel to get the ester layer (biodiesel) to the top. In practice, the separated biodiesel layer should have been water-washed to re-

311 move the excess catalyst, alcohol and other impurities. However, due to the small size of the oil samples used in the glass reaction tubes, the renement stage on this experiment was omitted. The experiments were run in triplicate; each set of operation conditions was conducted three times and the average was recorded. Microwave-assisted technique The optimum parametric conditions that were obtained from the conventional technique were applied using the microwave-assisted technique in order to compare the systems. In order to verify the advantages of microwave irradiation, the technique was applied on the oil without pretreatment. A scientic microwave with advanced vessel technology was used. This allowed fast vessel heating with homogeneous microwave distribution throughout the cavity. The oven used was the Start S (Milestone), manufactured by Milestone Inc., USA. A normal pressure glass reactor is equipped with a 500 mL ask and a reux condenser. The oven is supplied with a colour touch screen controller that enables the creation, storage and use of time vs. temperature or time vs. power reaction proles. The output microwave power is variable up to 1200 watts, controlled via a microprocessor. The optimum parametric conditions obtained from the conventional technique were applied again using microwave irradiation in order to compare the systems. The temperature was adjusted to 65 C, and the oil was preheated to the desired temperature of 65 C using the microwave unit. The alcohol catalyst mixture was then fed into the ask through the condenser, and the mixture was irradiated under reux for different reaction times of 1, 2 and 3 min.

Results and discussion Results obtained by using the mechanical conventional technique The effect of process variables on biodiesel yield The base-catalyzed transesterication result of Jatropha oil was investigated by changing catalyst (KOH) to oil ratios (% w/w) and alcohol to oil ratios (% w/w). The highest conversion was obtained with 1.5% of catalyst (KOH) to oil ratio and 7.5:1 of methanol to oil molar ratio for 60 min, and under these condition, the Jatropha oil methyl ester (JOME) yield was 99.8%. Figs. 1 and 2 show biodiesel yield% with time for KOH 1% and KOH 1.5% at different alcohol/oil molar ratios. One of the most important variables affecting the yield of ester is the molar ratio of alcohol to triglyceride. In this study, a molar ratio of 7.5:1 has given a yield of over 98%. Biodiesel with the best properties was obtained using potassium hydroxide as the catalyst in many studies [2932]. Methanolysis with 1 wt.% KOH catalyst resulted in successful conversion giving the best yields and viscosities of the esters in most of the literature reviewed. However, using a concentration of 1.5% showed better results in this study. Results obtained by using the microwave-assisted technique Applying the microwave technique as previously described in the Experimental section showed that the application of radio

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Fig. 1 Effect of alcohol/oil molar ratios on biodiesel yield using KOH 1% as catalyst.

Fig. 3 Effect of time on biodiesel yields from Jatropha oil using microwave irradiation.

Table 3 Quality assessment of biodiesel production from Jatropha oil.

Property Viscosity (mm2/s) Flash point (C) JOME 5.8 185 ASTM D 6751 1.96.0 P130 EN 14214 3.55.0 P120

Fig. 2 Effect of alcohol/oil molar ratios on biodiesel yield using KOH 1.5% as catalyst.

frequency microwave energy enhances the reaction rate for the conversion of Jatropha oil to biodiesel, and drives the reaction equilibrium toward the production of biodiesel. Highest biodiesel yield (97.4%) was obtained by applying microwave irradiation for two minutes compared to 1 h with the conventional technique. The results are depicted in Fig. 3. It should be pointed out, however, that these results were achieved by using Jatropha oil without pretreatment. It was also evident that exceeding the optimum reaction time will lead to deterioration of biodiesel yield. The interpretation of these results requires further investigation. The most accepted interpretation is that the exceeded time favours the equilibrium in the reverse direction. Attributing the decrease in yield after exceeding the optimum time to cracking followed by oxidizing of the formed fatty acid methyl esters to aldehydes, ketones and lower chained organic fractions could be excluded because the GC results do not show peaks of oxygenated compounds [33]. Quality assessment of produced biodiesel Quality assessment was performed using physical parameters such as viscosity, ash point and caloric value, as shown in Table 3. The viscosity difference forms the basis of an analytical method, viscometry, applied to determine the conversion of vegetable oil to methyl ester. The viscosity difference between

component triacylglycerols of vegetable oils and their corresponding methyl esters resulting from transesterication is approximately one order of magnitude [34]. Kinematic viscosity has been included in biodiesel standards (1.96.0 mm2/s in ASTM D6751 and 3.55.0 mm2/s in EN 14214) [35]. The viscosity of the produced biodiesel was calculated using the Brookeld viscometer Model DV-II and was found to be 5.8 mm2/s. The result obtained is compatible with the reports from other studies on biodiesel from Jatropha oil. Kumar and Sharma reported a value of 5.65 mm2/s [36]. The ash point of the produced biodiesel was estimated to be 185 C. This ash point is quite high compared to diesel. Hence, biodiesel is extremely safe to handle. The high ash point was referred to in many previous literature; Agarwal and Agarwal reported a ash point of 191 C compared to 71 C for mineral diesel [2], and Kumar and Sharma reported a ash point of 170 C for Jatropha oil methyl ester (JOME) [36]. The caloric value (MJ/Kg) for the produced Jatropha biodiesel is 39.632 compared to 45.343 for mineral diesel. Comparing the results with those obtained from neat and waste edible oils The results obtained from this study on Jatropha-based biodiesel are conrming the results obtained in a previous study conducted by Refaat and co-workers on neat and waste edible vegetable oils [33] which also showed that no substantial differences were obtained from different oil origins. Hence, it can be concluded that biodiesel produced from Jatropha oil is at least not inferior to that produced from edible oils. Conclusion From the obtained results, using the conventional technique, the best yield % for the production of biodiesel from Jatropha oil was obtained using a methanol/oil molar ratio of 7.5:1, potassium hydroxide as catalyst (1.5%), and a reaction time

Microwave biodiesel of one hour with the reaction temperature maintained at 65 C. The study also showed that the quality of the produced biodiesel satises the international American and European standards; hence, inedible vegetable oils such as Jatropha oil, produced by seed-bearing shrubs, can provide an alternative, and they do not have competing food uses. The results showed that application of radio frequency microwave energy offers a fast, easy route to this valuable biofuel with advantages of enhancing the reaction rate and improving the separation process. The reaction time was reduced to 2 min instead of 150 minutes (90 min for the pretreatment process and 60 min for transesterication), because, by using the microwave technique, no pretreatment is required. The methodology also allows for the use of high free fatty acid content feedstock, including Jatropha oil. However, this will need time control, otherwise the yield may be affected.

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[12] Mazzocchiaa C, Modica G. Fatty acid methyl esters synthesis from triglycerides over heterogeneous catalysts in the presence of microwaves. CR Chim 2004;7(67):6015. [13] Hernando J, Leton P, Matia MP, Novella JL, Alvarez Builla J. Biodiesel and FAME synthesis assisted by microwaves: homogeneous batch and ow processes. Fuel 2007;86(10-11):16414. [14] Leadbeater NE, Stencel LM. Fast, easy preparation of biodiesel using microwave heating. Energy Fuels 2006;20(5):22813. [15] Barnard TM, Leadbeater NE, Boucher MB, Stencel LM, Wilhite BA. Continuous-ow preparation of biodiesel using microwave heating. Energy Fuels 2007;21(3):177781. [16] Freedman B, Buttereld RO, Pryde EH. Transesterication kinetics of soybean oil 1. J Am Oil Chem Soc (JAOCS) 1986;63(10):137580. [17] Ma F, Hanna MA. Biodiesel production: a review. Bioresour Technol 1999;70(1):115. [18] Schuchardt U, Sercheli R, Vargas RM. Transesterication of vegetable oils: a review. J Braz Chem Soc 1998;9(3):199210. lez JF, Rodriguez Reinares A. Biodiesel from [19] Encinar JM, Gonza used frying oil. Variables affecting the yields and characteristics of the biodiesel. Ind Eng Chem Res 2005;44(15):54919. [20] Gupta A, Sharma SK, Pal Toor A. Production of biodiesel from waste soybean oil. J Petrotech Soc 2007;IV(1):405. [21] Refaat AA, Attia NK, Sibak HA, El Sheltawy ST, El Diwani GI. Production optimization and quality assessment of biodiesel from waste vegetable oil. Int J Environ Sci 2008;5(1):7582. [22] Meng X, Chen G, Wang Y. Biodiesel production from waste cooking oil via alkali catalyst and its engine test. Fuel Process Technol 2008;89(9):8517. [23] Yuan X, Liu J, Zeng G, Shi J, Tong J, Huang G. Optimization of conversion of waste rapeseed oil with high FFA to biodiesel using response surface methodology. Renewable Energy 2008;33(7):167884. [24] Leung DYC, Guo Y. Transesterication of neat and used frying oil: optimization for biodiesel production. Fuel Process Technol 2006;87(10):88390. [25] Berchmans HJ, Hirata S. Biodiesel production from crude Jatropha curcas L. seed oil with a high content of free fatty acids. Bioresour Technol 2008;99(6):171621. [26] Pinto AC, Guarieiro LLN, Rezende MJC, Ribeiro NM, Torres EA, Lopes WA, et al.. Biodiesel: an overview. J Braz Chem Soc 2005;16(6B):131330. [27] Singh AK, Fernando SD. Catalyzed fast-transesterication of soybean oil using ultrasonication. American Society of Agricultural Engineers, ASAE Annual Meeting, July 912, Portland, Oregon, USA: American Society of Agricultural Engineers (ASAE); 2006. OS, Lazic ML, Todorovic ZB, Veljkovic VB, Skala [28] Stamenkovic DU. The effect of agitation intensity on alkali-catalyzed methanolysis of sunower oil. Bioresour Technol 2007;98(14):268899. [29] Ugheoke BI, Patrick DO, Kefas HM, Onche EO. Determination of optimal catalyst concentration for maximum biodiesel yield from tigernut (Cyperus esculentus) oil. Leonardo J Sci (LJS) 2007;6(10):1316. [30] Vicente G, Martinez M, Aracil J. Optimization of Brassica carinata oil methanolysis for biodiesel production. J Am Oil Chem Soc (JAOCS) 2005;82(12):899904. [31] Karmee SK, Chadha A. Preparation of biodiesel from crude oil of Pongamia pinnata. Bioresour Technol 2005;96(13):14259. pez FJ, Mittelbach M. [32] Dorado MP, Ballesteros E, Lo Optimization of alkali-catalyzed transesterication of Brassica carinata oil for biodiesel production. Energy Fuels 2004;18(1):7783. [33] Refaat AA, El Sheltawy ST, Sadek KU. Optimum reaction time, performance and exhaust emissions of biodiesel produced by microwave irradiation. Int J Environ Sci Technol 2008;5(3):31522.

Acknowledgements Sincere thanks are due to both Prof. Dr. Guzine El-Diwani and Dr. Nahed Kamal of the Chemical Engineering Department National Research Center Dokki Egypt, for generously offering the oil and equipment. Thanks are also due to M.A. Refaat, A.M. Hanafy, M.M. Hassen and M.S. Sakr, the undergraduate students in the Department of Chemical Engineering, Cairo University, for their efforts. References
[1] Al Zuhair S. Production of biodiesel: possibilities and challenges. Biofuels Bioprod Bioref 2007;1(1):5766. [2] Agarwal D, Agarwal AK. Performance and emissions characteristics of Jatropha oil (preheated and blends) in a direct injection compression ignition engine. Appl Therm Eng 2007;27(13):231423. [3] Banapurmath NR, Tewari PG, Hosmath RS. Performance and emission characteristics of a DI compression ignition engine operated on Honge, Jatropha and sesame oil methyl esters. Renewable Energy 2008;33(9):19828. [4] Srinivasan S. The food v. Fuel debate: a nuanced view of incentive structures. Renewable Energy 2009;34(4):9504. [5] Achten WMJ, Verchot L, Franken YJ, Mathijs E, Singh VP, Aerts R, et al.. Jatropha bio-diesel production and use. Biomass Bioenergy 2008;32(12):106384. [6] Kumar Tiwari A, Kumar A, Raheman H. Biodiesel production from jatropha oil (Jatropha curcas) with high free fatty acids: an optimized process. Biomass Bioenergy 2007;31(8):56975. [7] Openshaw K. A review of Jatropha curcas: an oil plant of unfullled promise. Biomass Bioenergy 2000;19(1):115. [8] Varma RS. Solvent-free accelerated organic syntheses using microwaves. Pure Appl Chem 2001;73(1):1938. [9] Koopmans C, Iannelli M, Kerep P, Klink M, Schmitz S, Sinnwell S, et al.. Microwave-assisted polymer chemistry: heckreaction, transesterication, Baeyer-Villiger oxidation, oxazoline polymerization, acrylamides and porous materials. Tetrahedron 2006;62(19):470914. [10] Perreux L, Loupy A. A tentative rationalization of microwave effects in organic synthesis according to the reaction medium and mechanistic considerations. Tetrahedron 2001;57(45): 9199223. [11] Saifuddin N, Chua KH. Production of ethyl ester (Biodiesel) from used frying oil: Optimization of transesterication process using microwave irradiation. Malaysian J Chem 2004;6(1): 7782.

314
[34] Knothe G. Analytical methods used in the production and fuel quality assessment of biodiesel. Trans Am Soc Agric Eng 2001;44(2):193200. [35] Knothe G, Steidley KR. Kinematic viscosity of biodiesel fuel components and related compounds. Inuence of compound

S.A. El Sherbiny et al.

structure and comparison to petrodiesel fuel components. Fuel 2005;84(9):105965. [36] Kumar A, Sharma S. An evaluation of multipurpose oil seed crop for industrial uses (Jatropha curcas L): a review. Ind Crop Prod 2008;28(1):110.