Energy & Fuels 2007, 21, 3023-3027

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Biodiesel Production: Reaction and Process Parameters of Alkali-Catalyzed Transesterification of Waste Frying Oils
K. G. Georgogianni, M. G. Kontominas,*, E. Tegou, D. Avlonitis, and V. Gergis|
Section of Industrial and Food Chemistry, Department of Chemistry, UniVersity of Ioannina, 45110-Ioannina, Greece, General Chemical State Laboratory, DChemical SerVices of Pireaus, Akti Kondyli 32, 18510 Pireaus, Greece, Department of Petroleum Technology, Technological Educational Institute of KaVala, 65404-KaVala, Greece, and Department of Food Technology, Technological Educational Institute of Athens, Ag. Spyridonos Str., 12210 Egaleo, Athens, Greece ReceiVed February 26, 2007. ReVised Manuscript ReceiVed May 9, 2007

The transesterification of two different frying oils (soybean oil and a mixture of soybean and cotton seed oil) with methanol, in the presence of an alkali catalyst (NaOH), by means of low-frequency ultrasonication (24 kHz, 200 W) and mechanical stirring (600 rpm) for the production of biodiesel fuel was studied. The two different frying oils gave similar yields of isolated methyl esters both under mechanical stirring and ultrasonication. Also the physical and chemical properties of the two biodiesel fuels produced were investigated. The fuels produced were characterized by determining their density, viscosity, flash point, boiling point, cetane number, sulfur content, cloud point, pour point, cold filter plugging point, acid value, iodine value, and saponification value. From the physical and chemical properties of the two biodiesel fuels, it is concluded that these fuels have very similar properties to those of conventional diesel, except for the cetane number, which is higher, and the sulfur content of the biodiesel, which is negligible. Thus, experimental biodiesel fuels are environmentally friendly and attractive alternatives to conventional diesel.

1. Introduction Alternative fuels for diesel engines are becoming increasingly important because of diminishing petroleum reserves and the environmental consequences of exhaust gases from petroleumfueled engines. Air pollution is one of the most serious environmental problems all over the world. Because diesel engines of vehicles such as buses and trucks exhaust a huge amount of NOx and particulates, a clean alternative fuel is increasingly in demand. Among many possible sources, biodiesel fuel derived from vegetable oil attracts attention as a promising substitute for conventional diesel fuel.1,2 According to the Official Journal of the European Union, biodiesel is composed of methyl or ethyl esters produced from vegetable oil or animal oil, of diesel quality, to be used as biofuel.3 In this context, biodiesel shows the following general advantages: (a) an alternative to petroleum-derived fuel, which implies a lower dependence on crude oil foreign imports; (b) renewable fuel, helping to achieve the European Union (EU) renewable energy target (12% of the total energy output to consist of renewable energy by 2010);4 (c) a favorable energy
* To whom correspondence should be addressed. Telephone: +302651098342. Fax: +302651098795. E-mail: mkontomi@cc.uoi.gr. University of Ioannina. DChemical Services of Pireaus. Technological Educational Institute of Kavala. | Technological Educational Institute of Athens. (1) Laforgia, D.; Ardito, V. Bioresour. Technol. 1995, 51, 53. (2) Schumacher, L. G.; Borgelt, S. C.; Fosseen, D.; Goets, W.; Hires, W. G. Bioresour. Technol. 1996, 57, 31. (3) Directive 2003/30/EC of the European Parliament and of the Council of 8 May 2003 on the promotion of use of biofuels or other renewable fuels for transport OJ L123 17.5.2003, p 42. (4) European Commission. Energy for the future: Renewable sources of energy. White paper for a Community Strategy and Action Plan, COM 1997, 599 final of 26/11/1997.

return on energy invested; (d) a reduction on greenhouse emissions in line with the Kyoto Protocol agreement; (e) lower harmful emissions, which is very advantageous in environmentally sensitive areas such as large cities and mines; (f) biodegradable and nontoxic fuel, being beneficial for reservoirs, lakes, marine life, and other environmentally sensitive areas; and (g) the use of an agricultural surplus, as a raw material for its production in agreement with the European Agricultural Policy regulations, which can also help to improve rural economies. When the above advantages are taken into consideration, there is a growing interest in expanding the biodiesel industry. Along this line, research is focused on improving the biodiesel quality and yield and increasing the number of raw materials available for its production. Fatty acid alkyl esters are products of the transesterification (also called alcoholysis) of vegetable oils and fats with methanol or ethanol in the presence of a suitable catalyst5 (Figure 1). The stoichiometry of the transesterification reaction requires 3 mol of methanol (or ethanol) and 1 mol of triglyceride to give 3 mol of fatty acid methyl (or ethyl) ester and 1 mol of glycerol. After the reaction, the glycerol is separated by settling or centrifuging and purified to be used in its traditional applications (pharmaceutical, cosmetics, and food industries). In addition, glycerol can be used in recently developed applications in the field of animal feed, polymers, surfactants, intermediates, and lubricants.6 The alkyl ester phase is also purified before being used as a diesel fuel. The chemical and physical properties of biodiesel closely resemble those of conventional diesel fuel. This has been
(5) Harrington, K. J.; Arcy-Evans, C. D. J. Am. Oil Chem. Soc. 1985, 62, 1009. (6) Claude, S. Fett/Lipid 1999, 3, 101.

10.1021/ef070102b CCC: $37.00 2007 American Chemical Society Published on Web 08/18/2007

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Table 1. Principal Fatty Acid Composition and Molecular Weight (MW) for Soybean Frying Oil and the Mixture of Soybean and Cotton Seed Oil (1:1) fatty acid molecular weight 256 284 282 280 292 fatty acid content in soybean frying oil (%) 11.5 4.0 24.5 53.0 7.0 fatty acid content in the mixture of frying oil (%) 18.0 3.0 16.0 57.5 5.5

Figure 1. General equation for the transesterification of triglycerides.

documented by many workers.7-9 The cetane number, energy content, viscosity, and phase changes of biodiesel are similar to those of diesel fuel. Moreover, biodiesel is essentially sulfurfree. Engines fueled with biodiesel emit significantly fewer particulates, hydrocarbons, and less carbon monoxide than those operating with conventional diesel fuel.8 Biodiesel has a higher cloud point and a flash point comparable to conventional diesel fuel.10 Although short-term tests using vegetable oils showed promising results, longer tests led to injector coking, more engine deposits, ring sticking, thickening of the engine lubricant, etc.11 Low-frequency ultrasonication is a useful tool for emulsification of immiscible liquids. Ultrasonic processing technology can be used, for example, for the reduction of the particle size in minerals, powders, and emulsions or for water treatment.12 Ultrasonic technology is unique for the activation and acceleration of chemical, petrochemical, and polymerization processes.13 Ultrasonication also has a general accelerating effect on heterogeneous reactions. In the present work, a comparative study on the preparation of biodiesel from two different used cooking oils (a soybean frying oil and a mixture of soybean and cotton seed oil) by two different processes was investigated. The process of conventional alkali-catalyzed transesterification, in which the reacting mixture was stirred using mechanical stirring (600 rpm), was compared to that using ultrasonication. Evaluation of waste cooking-oilbased biodiesels was carried out by the determination of their physical and chemical properties. 2. Experimental Section
2.1. Materials and Reagents. The soybean frying oil was provided from the student cafeteria of the University of Ioannina, and the mixture of frying oils (cotton oil and soybean oil, 1:1) was provided from the student cafeteria of the Technological Educational Institute (TEI) in Kavala, Greece. Sodium hydroxide (>96%) was purchased from Merck (Darmstadt, Germany) and used after milling, to facilitate the dilution in methanol. Methanol of purity >95%, sulfuric acid of purity 9597%, and petroleum ether (pro-analysis) employed were purchased from Fluka (Sigma-Aldrich, Germany). 2.2. Transesterification Reaction. Frying oils (80 g, 0.102 mol) (for molecular weight determination of oils, see section 2.3), methanol (30 mL/0.15 mol), and NaOH in various concentrations [1.0, 1.5, and 2.0% (w/w)] were refluxed in a 500 mL round-bottom flask equipped with a glass anchor-shaped mechanical stirrer, a water condenser, and funnel. Heating was achieved by means of a
(7) Clark, S. J.; Wagner, L.; Schrock, M. D.; Piennaar, P. G. J. Am. Oil Chem. Soc. 1984, 61, 1632. (8) Mittelbach, M.; Tritthart, P. J. Am. Oil Chem. Soc. 1988, 65, 1185. (9) Al-Widnyan, M. I.; Al-Shyoukh, A. O. Bioresour. Technol. 2002, 85, 253. (10) Muniyappa, P. R.; Brammer, S. C.; Noureddini, H. Bioresour. Technol. 1996, 56, 19. (11) Demirbas, A. Energy ConVers. Manage. 2003, 44, 2093. (12) Alcantara, R.; Amores, J.; Canoira, L.; Fidalgo, E.; Franco, M. J.; Navarro, A. Biomass Bioenergy 2000, 18, 515. (13) Telsonic Ultrasonics. www.telsonic.com.

palmitic (16:0) stearic (18:0) oleic (18:1) linoleic (18:2) linolenic (18:3)

Table 2. Yields of Isolated Methyl Esters of Soybean Frying Oil (B1) and the Mixture of Soybean and Cotton Seed Frying Oil (B2) Using Mechanical Stirring (600 rpm) and Ultrasonication (24 kHz) yields (%) 1.0% (w/w) NaOH B1 42 51 57 68 79 82 96 36 45 57 68 82 93 94 B2 42 49 53 64 82 94 95 49 58 63 72 81 83 91 1.5% (w/w) NaOH B1 53 61 68 94 96 94 95 51 77 88 97 96 98 96 B2 55 64 88 94 97 98 95 53 67 71 74 95 97 96 2.0% (w/w) NaOH B1 64 86 97 95 94 96 95 71 88 93 94 94 93 95 B2 58 88 93 95 94 96 95 80 93 95 94 94 93 95

time (min) 5 10 15 20 30 40 60 5 10 15 20 30 40 60

mechanical stirring

ultrasonication

heating mantle controlled by a proportional integral derivative (PID) temperature controller including a type K-thermocouple. The temperature was raised to 60 C, and the mixture was stirred either using the mechanical stirrer (600 rpm) or the low-frequency ultrasonicator (24 kHz, 200 W, UP 200S, IKA, U.K.). Samples (10 mL) were taken from the reaction mixture at predetermined time intervals, neutralized with a 4% methanol solution of citric acid, and analyzed by thin-layer chromatography (TLC). TLC analysis was performed on glass plates coated with Silica Cel G (Merck) and developed in a solvent system of petroleum ether/diethyl ether/hydrochloric acid (8:2:0.1). Spots were determined by an iodine vapor stain.14 After the complete conversion of the vegetable oil, the reaction was stopped and the mixture was allowed to stand for phase separation: the ester mixture formed the upper layer, and glycerin formed the lower layer.15 The residual catalyst and nonreacted alcohol were distributed between the two phases. After phase separation, using a separatory funnel, the ester mixture was dried over anhydrous sodium sulfate and analyzed by gas chromatography. 2.3. Sampling and Analysis. The fatty acid composition of soybean frying oil and the mixture of soybean and cotton seed oils (1:1), shown in Table 1, was determined by the well-established gas chromatographic (GC) procedure of Alcantara et al.:12 A 0.1 mL sample of the mixture of the fatty acid methyl esters (FAMEs) was dissolved in 5 mL of petroleum ether, and 3 L of this solution were injected into a Varian 3700 GC equipped with a flame ionization detector (FID; Varian Associates, Palo Alto, CA). For separation and quantification purposes, a DEGS 15% on Chromosorb, WAW 80/100 mesh, 2 m 1/8 in. packed column was used. The analyses were carried out isothermally under the following conditions: the carrier gas was nitrogen (30 mL/min); the temperature of the detector and injection port was 250 C; and
(14) Kildiran, G. S.; Yucel, O.; Turkay, S. J. Am. Oil Chem. Soc. 1996, 73, 225. (15) Stravarache, C.; Vinatoru, M.; Nishimura, R.; Maeda, Y. Ultrason. Sonochem. 2005, 12, 367.

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Table 3. Physical and Chemical Properties of (a) Conventional Diesel, (b) Biodiesel from Soybean Frying Oil, and (c) Biodiesel from Mixed Soybean and Cotton Seed Frying Oil conventional diesel 825-835 60-70 180-360 51-53 10-40 -15 to -7 -12 to -18 -10 to -15 specifications of diesel 820-845 2-4.5 55 min 51 min 50 max -5 max (October-April) +5 (April-October) biodiesel of soybean frying oil 857 4.76 67 305-355 53.7 0.03 -4 -3 -6 0.80 95 215 biodiesel of mixture frying oil 826 4.45 83 302-354 52.8 0.01 -5 -4 -7 0.50 71 220 standard methoda EN-ISO 3675/98 EN-ISO 3704/96 ISO 2719/02 Pr EN-ISO3405/98 EN-ISO 5165/98 EN-ISO 14596/98 AOCS CD3a-63 EN 116:1997 D 97-87 ISO 3015:1992 AOCS CD1-25 1993 AOCS CD3 1993

fuel property density (kg/m3, 15 C) viscosity (mm2/s, 40 C) flash point (C) boiling point (C) cetane number sulfur content (wt %) CFPP (C) pour point (C) cloud point (C) acid value (mg of KOH/g of oil) iodine value (cg of I/g of oil) saponification value (mg of KOH/g of oil)
a

Methods used to determine physical and chemical properties of oils.

the column temperature was 170 C. The standard mixture of the FAMEs used was purchased from Sigma (stock number 189-3). The analysis of biodiesel by GC was carried out by dissolving 0.050 g of the biodiesel sample in 5 mL of petroleum ether and injecting 3 L of this solution into the GC, under the same conditions as above. The concentration of biodiesel for each sample was quantified by comparing the FID response for each methyl ester of the GC sample of biodiesel with the FID response of the methyl ester standard mixture of FAMEs, respectively. The conversion of oil in each experiment was calculated from the content in methyl esters of biodiesel as analyzed by GC, and the material balance of the reaction weight of biodiesel MW of biodiesel conversion (%) ) biodiesel concentration (%) weight of oil 3 MW of oil (1) MW )

MW

i i

where MW is the mean molecular weight of biodiesel/oil. The mean molecular weight of biodiesel was calculated averaging the individual molecular weights (MWi) of each constituent methyl ester, according to the biodiesel FAME analysis (i). The mean molecular weight of the oil was calculated averaging the individual molecular weights (MWi) of each constituent triglyceride according to the fatty acid oil analysis (i). The factor 3 appears in the formula because each triglyceride molecule yields three methyl ester molecules. 2.4. Physical and Chemical Properties of Biodiesel. Physical and chemical properties of the biodiesel sample produced from the frying oils were determined in the General Chemical State Laboratory, according to the International Organization for Standardization (ISO) norms and standard test methods given in Table 3.

3. Results and Discussion 3.1. Transesterification Reaction: Effect of the Catalyst Concentration and Stirring Method. Yields of methyl esters isolated from both frying oils by conventional transesterification using mechanical stirring and ultrasoncation as a function of the time and NaOH concentration are given in Table 2. 3.1.1. Effect of the Catalyst Concentration. Results in Table 2 show that, for both biodiesels produced, the highest yields were obtained when the catalyst was used at the highest concentration [2.0% (w/w) NaOH]. To be more specific, using

mechanical stirring and 2.0% (w/w) NaOH oil, the transesterification reaction was completed in 15 min (conversion of 97% for soybean frying oil and 93% for mixed soybean and cotton seed frying oil). On the other hand, employing a lower catalyst concentration [1.0 or 1.5% (w/w)] resulted in a 60 and 20 min reaction time, respectively (conversion of 96 and 94% for soybean frying oil, respectively, and 95 and 94% for mixed soybean and cotton seed frying oil, respectively). Similar results were obtained when ultrasonication was employed; i.e., highest yields were obtained when the catalyst was used at the highest concentration. However, a further increase of the catalyst concentration [e.g., 2.5% (w/w) NaOH] led to soap formation and a decrease in the yields of FAMEs (data not shown). In addition, when the amount of alkaline catalyst is increased to 2.0% (w/w) NaOH, the yields of methyl esters also increase using both mechanical stirring and ultrasonication. These results contradict those of Stavarache et al.15 according to which, when the catalyst concentration is increased [to 0.5% (w/w) alcohol solution of NaOH], the yields of isolated methyl esters decrease because of soap formation. According to these authors, when the catalyst concentration is increased, emulsions are formed in the washing step, thus, hindering purification. During washing, the soap present in the ester phase has the tendency to accumulate at the surface of the two liquids. The soap molecules, which are trapped inside esters, form emulsions with the water molecules present in the solution. Thus, the yields of isolated esters are very low. In the present study, this phenomenon did not occur and the increase of the catalyst concentration caused a yield increase of the isolated FAMEs to the threshold of 2.0% (w/w) NaOH for both processes, involving ultrasonication and mechanical stirring. 3.1.2. Effect of Ultrasonication Versus Mechanical Stirring. In comparison to mechanical stirring, the effect of ultrasonication is not clear. Table 2 shows that, for soybean frying oil, the reaction time is the same for catalyst concentrations of 1.5 and 2.0% (w/w), while it decreases for ultrasonication and the catalyst concentration of 1.0% (w/w) as the reaction is completed in 40 min instead of 60 min. Unlike soybean frying oil, for the mixture of soybean and cotton seed frying oil, for 1.0 and 1.5% (w/w) catalyst concentrations, the reaction rate is significantly enhanced when mechanical stirring is employed, i.e., completion of the transesterification reaction in 40 versus 60 min (for 1.0% NaOH) and 20 versus 30 min (for 1.5% NaOH). In the presence of

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2.0% NaOH, the reverse is true; i.e., the reaction is completed in 10 min under ultrasonication versus 15 min under mechanical stirring. Thus, ultrasonication is an efficient, time-saving, and economical process compared to mechanical stirring only in the case of biodiesel produced from mixture frying oils and when the reaction occurs under the most favorable conditions, i.e., appropriate catalyst concentration (2.0% NaOH). Lifka and Ondruscka16 studied the effect of ultrasonication versus mechanical stirring on the alkaline transesterification of rapeseed oil using NaOH at a concentration of 0.5% (w/w) at 45 C. A conversion of 80-85% was obtained for both ultrasonicated and mechanically stirred reactions after 30 min. Ji et al.17 studied the effect of mechanical stirring, ultrasonication, and hydrodynamic cavitation on methyl ester yields in the alkaline (KOH) transesterification of soybean oil using methanol (alcohol/oil molar ratio of 6:1) at a temperature of 45 C and reported that ultrasonication gave the shortest reaction time and highest yield, while mechanical stirring gave the shortest reaction time and the lowest yield. Stavarache et al.18 studied the alkaline (KOH and NaOH) transesterification of a series of vegetable oils using both mechanical stirring and ultrasonication and concluded that yields in both cases were identical but a significantly shorter reaction time was observed in the case of ultrasonication. Finally, Stavarache et al.19 studied the effect of ultrasonication versus mechanical stirring in the transesterification of palm oil and commercial edible oil in a bench-scale continuous process. Additional parameters investigated included the reaction volume and residence time. The highest conversion was achieved when the short residence time was employed. The advantage of an ultrasonic continuous manufacture of biodiesel was a small size reactor (2.6 L) and shorter reaction time (20 min). 3.2. Evaluation of Biodiesel Properties. Physical and chemical quality parameters of the two biodiesel samples were determined. Samples were produced using 2% (w/w) NaOH and ultrasonication as described in section 3.1. Data are presented in Table 3. For comparison purposes, properties of conventional diesel (typical values of commercial diesel fuels for year 2006 based on unpublished data of the General Chemical State Laboratory) are also presented. 3.2.1. Density. The densities of biodiesels produced from soybean oil and the mixture of soybean and cotton seed frying oil were 857 and 826 kg/m3, respectively (Table 3). Alcantara et al.,12 Strivastava et al.,20 and Varese et al.21 reported that the density of soybean oil ranged between 880 and 890 kg/m3. The density of conventional diesel ranges between 825 and 835 kg/m3. The higher density of experimental biodiesels may result in the delivery of a slightly greater mass of fuel in the engine as the fuel injection equipment operates on a volumemetering principle. Of course, there are additional factors to be considered to the volume metering, including the respective calorific values. 3.2.2. Viscosity. Viscosity is the most important property of biodiesel because it affects the fluidity of the fuel. High viscosity leads to poorer atomization of the fuel spray and less accurate operation of the fuel injectors.22 As shown in Table 3, the
(16) Lifka, J.; Ondruschka, B. Chem. Eng. Technol. 2004, 27, 1156. (17) Ji, J.; Wang, J.; Li, Y.; Yu, Y.; Xu, Z. Ultrasonics 2006, 44, e411. (18) Stravarache, C.; Vinatoru, M.; Maeda, Y. Ultrason. Sonochem. 2006, 13, 401. (19) Stravarache, C.; Vinatoru, M.; Maeda, Y.; Bandow, H. Ultrason. Sonochem. 2007, 14, 413. (20) Srivastava, A.; Prassad, R. Renewable Sustainable Energy ReV. 2000, 4, 111. (21) Varese, R.; Varese, M. INFORM 1996, 7, 816. (22) Demirbas, A. Energy ConVers. Manage. 2006, in press.

kinematic viscosities of the soybean frying oil and the mixture of soybean and cotton seed frying oil were 4.76 and 4.45 mm2/s at 40 C, respectively. Meher et al.23 reported that the kinematic viscosity of biodiesel ranges between 3.5 and 6.0 cSt, as measured in Austria, Czech Republic, France, Germany, Italy, and the U.S.A. Moreover, Alcantara et al.,12 Strivastava et al.,20 and Varese et al.21 reported that the viscosity of soybean oil ranges between 4.0 and 4.5 mm2/s. Thus, the viscosities of both biodiesels evaluated in the present study are within these limits. Besides, the kinematic viscosity of the conventional diesel ranges between 2 and 4.5 mm2/s at 40 C. Thus, it can be concluded that the biodiesels, produced from the above frying oils, are within the viscosity range of conventional diesel. 3.2.3. Cetane Number (CN). Cetane is a hydrocarbon molecule that ignites very easily under compression, being assigned a score of 100. All of the hydrocarbons in diesel fuel are compared to cetane as to how well they ignite under compression. The higher the cetane number, the more ignitable the fuel is. Biodiesel generally has a higher cetane number than mineral diesel.11 The cetane number decreases with a decreasing chain length and increasing branching.24 As shown in Table 3, the cetane number of the biodiesel produced from the soybean frying oil was 53.7 and the respective number of the biodiesel produced from the mixture of soybean and cotton seed oil was 52.8. Meher et al.23 mentioned that the cetane number of biodiesel is g48, as measured in Austria, Czech Republic, France, Germany, Italy, and the U.S.A. Alcantara et al.,12 Strivastava et al.,20 and Varese et al.21 reported that the cetane number of soybean oil ranges between 45 and 56. Thus, the cetane numbers of both biodiesels evaluated in the present study are within these limits. In addition, the cetane number of these biodiesels is within the specifications of conventional diesel (cetane number of 51). 3.2.4. Sulfur Content. The purpose for limiting the sulfur content in diesel and other liquid fuels is both to reduce the formation of sulfur oxides and particulates during combustion and to enable the use of add-on control devices for diesel-fueled internal combustion engines. From data in Table 3, it is obvious that, in contrast to conventional diesel fuels (sulfur content of 50 ppm), the biodiesel from soybean frying oil had a negligible sulfur content (0.03 ppm), while that from the mixture of soybean and cotton seed oil had a sulfur content of 0.01 ppm. It is important to mention that, when the biodiesels were neutralized with a 4% methanol solution of sulfuric acid, instead of a 4% methanol solution of citric acid, the sulfur content was 70.5 ppm for the soybean frying oil and 72.8 ppm for the mixture of frying oil. In other words, the sulfur content of biodiesels was greater than that of conventional diesel fuels. Thus, sulfuric acid should not be used in the production of biodiesel at all. 3.2.5. Flash Point. The flash point of a fuel is the temperature at which vapor given off will ignite when an external flame is applied under specified test conditions. Even when fuels are at a temperature below their measured flash point, they are capable of producing light hydrocarbons in the tank headspace, such that the vapor composition may be close to or within the flammable range. Hence, all fuel oil headspaces should be considered to be potentially flammable.23
(23) Meher, L. C.; Vidya Sagar, D.; Naik, S. N. Renewable Sustainable Energy ReV. 2006, 10, 248. (24) Prakash, C. B. Global Changes Strategies International, Inc. (GCSI), Canada, 1998.

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Table 3 shows that biodiesel produced from soybean frying oil had a flash point similar to conventional diesel (67 C), while the mixture of soybean and cotton seed frying oil had a somewhat higher flash point (83 C). Thus, there is negligible fire risk during normal storage and handling of such biodiesel products. Meher et al.23 reported that the flash point of biodiesel ranges between 65 and 110 C, as measured in Austria, Czech Republic, France, Germany, Italy, and the U.S.A. Thus, the flash point of both biodiesels, evaluated in the present study, is within these limits. 3.2.6. Cloud and Pour Points. Biodiesel is less suitable for use at low temperatures than petrodiesel. The cloud point is the temperature at which a sample of the fuel starts to become cloudy, indicating that wax crystals have begun to form. At even lower temperatures, the fuel becomes a gel that cannot be pumped. The pour point is the temperature below which the fuel will not flow. As the cloud and pour points for biodiesel are higher than those for petroleum diesel, the performance of biodiesel under cold conditions is markedly worse than that of petroleum diesel. Table 3 shows that biodiesels produced from vegetable frying oils have higher cloud (-3 and -4 C) and pour (-6 and -7 C) points than those of conventional diesel (from -10 to -15 C for the cloud point and from -12 to -18 C for the pour point). Alcantara et al.,12 Strivastava et al.,20 and Varese et al.21 reported that the cloud points of biodiesels produced from different waste vegetable oils range between 1 and 13 C. Antolin et al.25 stated that the limits of the cloud point of biodiesel are 4 C for summer months and -1 C for winter months. Joshi et al.26 reported that the cloud point of biodiesel ranges between -3 and 12 C and the pour point ranges between -15 and 10 C. Finally, Nestor et al.27 state that the cloud and pour points of biodiesel range between -4 and 18 C and -13 and 12 C, respectively. Thus, the cloud and pour points of both biodiesels in the present study are between these limits. 3.2.7. Cold Filter Plugging Point (CFPP). The CFPP of a fuel reflects its cold-weather performance. At low operating
(25) Antolin, G.; Tinaut, F. V.; Briceno, Y.; Castano, V.; Perez, C.; Ramirez, A. I. Bioresour. Technol. 2002, 83, 111. (26) Joshi, R. M.; Pegg, M. J. Fuel 2007, 86, 143. (27) Nestor, J. R.; Soriano, N. U.; Migo, V. P.; Matsumura, M. Fuel 2006, 85, 25.

temperatures, fuel may thicken and might not flow properly, affecting the performance of fuel lines, fuel pumps, and injectors. The CFPP defines the fuel limit of filterability. The CFPP is a more useful index of both biodiesel and conventional diesel than the cloud point.24 Table 3 shows that biodiesels produced from vegetable frying oil have higher CFPPs (-4 and -5 C) than those of conventional diesel (from -15 to -7 C). Gomez et al.28 and Fabbri et al.29 reported that the CFPP of biodiesels ranges between -5 and 1 C. Thus, the CFPP point of both biodiesels in the present study are within these limits. 4. Conclusions Two waste frying oils (a soybean oil and a 50% mixture of soybean and cotton seed oil) were converted into biodiesel by the transesterification reaction with methanol. The operating conditions for this chemical conversion were studied, and key properties of these biodiesels were determined. Transesterification was carried out at different catalyst concentrations using mechanical stirring and ultrasonication. It was found that the optimum catalyst concentration was 2.0% NaOH. Ultrasonication was shown to be an efficient, time-saving procedure, offering a number of advantages as compared to mechanical stirring. On the basis of values of physical and chemical properties determined, it can be concluded that biodiesel can be used as an alternative fuel in conventional diesel engines.
Acknowledgment. This work was funded by the Archimedes European Program through the Greek Ministry of Education. Work was conducted at the University of Ioannina.

Note Added after ASAP Publication. There were numerous corrections made by the author to the original version of the paper published ASAP August 16, 2007; the corrected version was published ASAP September 4, 2007.
EF070102B
(28) Gonzalez Gomez, M. E.; Howard-Hildige, R.; Leahy, J. J.; Rice, B. Fuel 2002, 81, 33. (29) Fabbri, D.; Bevoni, V.; Notari, M.; Rivetti, F. Fuel 2007, 86, 690.