Waste Management 26 (2006) 487–494 www.elsevier.
Production of biodiesel from waste frying oils
Pedro Felizardo a, M. Joana Neiva Correia a,*, Idalina Raposo b, Joao F. Mendes c, ˜ d a Rui Berkemeier , Joao Moura Bordado ˜
´ Department of Chemical Engineering, Instituto Superior Tecnico, Av. Rovisco Pais, 1049-001 Lisboa, Portugal b ´ Escola Secundaria Alfredo dos Reis Silveira, Torre da Marinha, Av. 25 de Abril, 2840 Seixal, Portugal c ´ SPACE – Eco-Combustıveis. Rua 8 de Dezembro No. 494, 4760-016 Vila Nova de Famalicao, Portugal ˜ d Quercus – Associacao Nacional Conservacao da Natureza, Apartado 4333, 1503-003 Lisboa, Portugal ¸˜ ¸˜ Accepted 9 February 2005 Available online 17 June 2005
Abstract Waste frying oils transesteriﬁcation was studied with the purpose of achieving the best conditions for biodiesel production. Transesteriﬁcation reactions were carried out for 1 h using waste frying oils (WFOs), methanol, and sodium hydroxide as catalyst. In order to determine the best conditions for biodiesel production, a series of experiments were carried out, using methanol/WFO molar ratios between 3.6 and 5.4 and catalyst/WFO weight ratios between 0.2% and 1.0%. For oils with an acid value of 0.42 mg KOH/g, results show that a methanol/WFO ratio of 4.8 and a catalyst/WFO ratio of 0.6% gives the highest yield of methyl esters. Furthermore, an increase in the amount of methanol or catalyst quantity seems to simplify the separation/puriﬁcation of the methyl esters phase, as showed by a viscosity reduction and an increasing purity to values higher than 98% for methyl esters phase. Ó 2005 Elsevier Ltd. All rights reserved.
1. Introduction The increasing production of waste frying oils (WFOs) from household and industrial sources is a growing problem in Portugal and all around the world. This residue is regularly poured down the drain, resulting in problems for wastewater treatment plants and energy loss, or is integrated into the food chain through animal feeding, thus becoming a potential cause of human health problems (Costa Neto et al., 2000). There are several end-uses for this waste, such as the production of soaps or of energy by anaerobic digestion, thermal cracking (Zaher, 2003), and more recently the production of biodiesel, a fuel that can be used as a mineral diesel substitute for engines. The core process of the biodiesel production consists in the transesteriﬁcation of the raw materials, vegetable oils and fats, using a short
Corresponding author. Tel.: +351 21 8417344; fax: +351 21 8499242. E-mail address: firstname.lastname@example.org (M.J. Neiva Correia). 0956-053X/$ - see front matter Ó 2005 Elsevier Ltd. All rights reserved. doi:10.1016/j.wasman.2005.02.025
chain alcohol. Vegetable oils and fats are mainly constituted by triglycerides with minor amounts of mono and diglycerides (Fig. 1). The transesteriﬁcation reaction (Reaction 1) takes place between a lipid and an alcohol to produce an ester and a by-product, glycerol, also known as glycerine. This reaction occurs stepwise, with mono and diglycerides as intermediate products (Ullmanns, 1992). The fuel thus obtained performs in a similar way to fossil fuel, with the advantage of reducing greenhouse emissions because it is a renewable resource (Mittelbach and Tritthart, 1988; Leung, 2001; Al-Widyan et al., 2002; Dorado et al., 2003; Tashtoush et al., 2003; Ulusoy et al., 2004). Meher et al. (2004) published an excellent review of biodiesel production processes by transesteriﬁcation. The use of several low molecular weight alcohols and homogeneous acid and basic catalysts for transesteriﬁcation has been studied in recent years with success (Peterson et al., 1983; Schudardt et al., 1998; Khan, 2002; Knothe et al., 1997; Nye et al., 1983). Basic
Al-Widyan and Al-Shyoukh.. Haas et al.
Fig.1. The reference standards for gas chromatography (GC) were obtained from Sigma–Aldrich (Lisbon..488
P. Saponiﬁcation reaction.
. or esters in hydrolysis reactions (Reaction 2) and subsequent saponiﬁcation (Reaction 3) (Schudardt et al. the viscosity and acidity of the oil increases. This step consists in an acid catalyzed reaction with an alcohol in order to transform the free fatty acids into their corresponding esters. Hydrolysis reaction. in spite of their lower reactivity. because the reaction is faster (only 30 min compared to 1–8 h for the acid catalysis) and lead to the same yield of transesteriﬁcation (above 90% for both) (Schudardt et al. 1992. 2000. This reaction is undesirable.. 2001.
1998. as well as the incomplete conversion of the free fatty acids contained in WFO into alkyl esters. Schudardt et al. Canakci and Gerpen. and from local domestic consumers.. Portugal).. and the oil becomes darker and develops an unpleasant odour. Several studies concerning the production of methyl esters from ‘‘fresh’’ vegetable oils and fats (Freedman et al... The numerous fractions were blended in order to obtain two diﬀerent types of waste oils. Materials and methods WFO were collected in school cafeterias and local restaurants. Zhang et al. sodium and potassium hydroxides react with the alcohol to give water. because water can react with triglycerides. On the other hand.. Conneman and Fischer. Meher et al. 2002.. di.
2. Vaz Pereira (Lisbon..and triglycerides. Felizardo et al. fatty acids.. for oils with a high concentration of free fatty acids (acid value higher than 2 mg KOH/g). glycerides in the oil/ester phase are transesteriﬁed with basic catalysis. However. a pre-treatment step is recommended. Tashtoush et al.. During frying. 1998. environment. this reaction overcomes some of the drawbacks of chemical transesteriﬁcation. 2002. 2004).
H 2C HC H 2C
O O O
R1 R2 R3
COOR COOR COOR
OH OH OH
HC H2 C
Reaction 1. However. Transesteriﬁcation reaction. 1998).5%). 2003). Pereda Marın et al. 2003. Portugal).
homogeneous catalysts have surpassed the acid ones. Vegetable oils used in industrial or household frying undergo degradation by hydrolytic and oxidative reactions. 2003.. 2004). Mittelbach et al. After this pre-treatment. as well as low-cost raw materials such as used frying oils. Tomasevic and Siler-Marinkovic. 1997. 1984. Enzymatic catalysts like lipases are also able to catalyze the transesteriﬁcation of triglycerides. R2 and R3 represent the fatty acids chains. 1983. The production of biodiesel has been actively investigated in the past 20 years. 1984. where R1. Knothe et al. This work describes the optimum conditions for biodiesel production using waste frying oils as raw material in the transesteriﬁcation process. cause formation of various by-products and require high quality oils and water-free methanol (Schudardt et al. The recent concerns with sustainability. 2. both processes being responsible for changes in the chemical and physical properties. 1998. the production costs of the catalyst are signiﬁcantly greater than those of an alkaline one (Meher et al. sodium hydroxide commercial grade. soap stocks and animal fats (Nye et al. 2003a). 2000).. namely the diﬃculty of recovering glycerol. Methanol chromatographic grade (99. Structures of mono-. and dry magnesium sulphate (>99%) were sup´ plied by Jose M. and raw material costs have made the use of waste frying oils attractive to the industry. 1998). as compared to the fresh oil (Costa Neto et al. have been conducted. 1. According to the literature. Gonzalez ´ Gomez. / Waste Management 26 (2006) 487–494
H2C O COR1 HC OH H2C OH
H2C O COR1 HC O COR2 H2C OH
H2C O COR1 HC O COR2 H2C O COR3
H2C O R1 HC O R2 H2C O R3
COONa COONa COONa
HC OH H2C OH
Reaction 3.. especially if stimulated with economic beneﬁts associated with the use of blends of biodiesel and fossil diesel (Zhang et al. Good results concerning the reduction of the acid value were achieved even with high initial percentages of free fatty acids (Cana´ kci and Gerpen. Pre-treatment of the frying oil Homogenous samples of the two WFO that were prepared were dried over magnesium sulphate and subsequently ﬁltered under vacuum to remove any
Reaction 2. 2004). The methylate salts are more reactive than the corresponding hydroxides. 2003b). but are expensive. Peterson and Scarrah. sodium and potassium hydroxides can also lead to high reaction yields just by increasing the catalyst quantities.. ´ 2001. Sodium and potassium hydroxides and sodium and potassium methylates have been preferred as catalysts due to high yields in the transesteriﬁcation reaction. However.
the sulphated ashes were quantiﬁed according to ISO 3987 (1994). The temperature program was as follows: 140 °C for 5 min. respectively. Methyl heptadecanoate was used as an internal standard (Portuguese Standard NP EN ISO 5508.3.10 0.70 30.5 (determined by Hannus method – Portuguese Standard NP 941. Results and discussion A sample of 200 g of WFO (equivalent to 228. with a 0.42 and 2. Measurements of the density at 15 °C by the hydrometer method and of the kinematic viscosity at 40 °C were carried out according to ISO 3675 (1998) and ISO 3104 (1994). as well as the glycerol separation (Freedman et al.65 Oil sample 2 8. Eﬀect of WFO properties on the transesteriﬁcation reaction Freedman et al.. 2. 2004).07 mg of KOH/g of oil. the biodiesel produced from the WFO with the lower acid value had a purity higher than the one obtained from the more acidic frying oil.55
suspended matter and magnesium sulphate crystals. 1998) and the water content by the Karl–Fischer method (ISO 12937.3%).1. this procedure results in the saponiﬁcation of the free fatty acids.25 57.29 4. 1984). Puriﬁcation of methyl esters phase At the end of the reaction period (1 h). A magnetic bar was used for stirring. It was also observed that those ME layers could be more easily separated from the glycerol-rich phases than the ones produced using the more acidic WFO. 1997).65 4. 2002). The injector was set up for 250 °C. 1985). thus aﬀecting the yield in methyl esters. Sodium was determined by ﬂame photometry (EN 241.28 0. To determine the inﬂuence of the oil acid value on the production of biodiesel. with a DB-WAX 52 column from Supelco. Finally.42 and 2.02 27. heating until 240 °C at a rate of 4 °C/min and holding at 240 °C for 10 min. 2. The iodine value was calculated from the methyl esters composition (EN 14214. by as much as 14%. In all experiments. although the yield in methyl esters is similar for both oil samples. a mixture of methanol and sodium hydroxide was added to the oil and the transesteriﬁcation reaction began. together with the calculated mass of methyl esters (MEs) produced per 100 g of WFO (mME/100 g WFO) and the purity of methyl esters phases (% ME). The study was carried out using a molar ratio of methanol/WFO which varied from 3. For the latter. six experiments were conducted using WFOs with acid values of 0. The methyl ester composition was obtained by gas chromatography using a Varian Star 3400CX Gas Chromatograph. and an iodine value of 116. In the ﬁrst two experiments.. (1984) have studied the inﬂuence of the free fatty acids (FFA) and water content in the production process of biodiesel. The oil was heated until the desired temperature was reached (65 °C). The fatty acid composition of both samples was obtained by GC (Table 1). respectively. a water content of 0. Meher et al. The latter phase was washed with water.6 to 5.
3.4 and a catalyst quantity equivalent to 0.5% HCl solution and again with water to provide a puriﬁed biodiesel.13% by weight. If these requirements are not met it is still possible to produce biodiesel.9 and 130. the purity of the samples is quite diﬀerent.07% and 0. the glycerol rich-phase was separated from the methyl ester layer in a decantation funnel. but the yield of the reaction is reduced due to the deactivation of the catalyst and the formation of soaps. The ﬂash point was determined by the Pensky-Martens method (ISO 2719. 2003). The concentration of methanol was evaluated by heating at 75 °C a known mass of methyl esters until constant weight was achieved.07.62 2. as well as the FID detector. The reactor was kept at around 65 °C for 1 h (Freedman et al. The treated oil samples (here referred to as oil samples 1 and 2) presented.6 mmol considering a molar mass of 874. 1984. an acid value of 0.8 g/mol) was transferred to a two-neck Woulf ﬂask equipped with a thermometer and a reﬂux condenser.
. Felizardo et al.0 mass% of oil. The washed methyl esters were then dried over magnesium sulphate and ﬁltered under vacuum.30 0. Analyses The puriﬁed methyl esters were evaluated in a series of tests to determine if the biodiesel produced met the European Standard EN 14214 (2003). They have found that the oil acid value should be less than 1 mg KOH/g and that all raw materials should be anhydrous (water content <0. 2. 2000). a pre-treatment step would be advisable in order to obtain higher purities. at a pressure of 10 bar..60 55. while the acid value was obtained by titration (Portuguese Stan3. / Waste Management 26 (2006) 487–494 Table 1 Fatty acid composition (mass%) of WFO Fatty acid C16:0 C18:0 C18:1 C18:2 C18:3 C20:0 Oil sample 1 8.2– 1. 2000). Transesteriﬁcation procedure
dard NP 903. The experimental conditions are presented in Table 2.2.4.P. Although high acid values may be corrected by the addition of sodium hydroxide. Helium was used as carrier gas. At this point.
The inﬂuence of the catalyst/WFO ratio seems to be less important when the methanol/frying oil ratio is higher than 4. using a molar ratio methanol/oil of 6:1 with 1% potassium hydroxide or 0.0 0. it may be concluded that the best catalyst/WFO ratio is 0. Felizardo et al.4 80. Therefore.3 80.9 92. 1.8 99. at constant mass ratio of catalyst/ WFO.42 mg KOH/g.07 mNaOH/mWFO (%) 1.490
P. / Waste Management 26 (2006) 487–494
Table 2 Inﬂuence of acid value in methyl esters phase yield and purity Experiment 1 2 3 4 5 6 Acid value (mg KOH/g) 0. 0. Both reactions interfere with the separation of the glycerol rich phase and with the methyl esters puriﬁcation. Freedman et al.6 3.4 5.6) at 50 °C. Eﬀect of methanol/waste frying oil molar ratio The methanol/WFO ratio is one of the most important variables in methyl esters production.42 2. 1.6 4. consequently.4 5.6 83.2 4.8 5. Inﬂuence of the methanol/WFO molar ratio on the yield of biodiesel production.2 Purity (% ME) 95. not only because it determines the reaction rate. Experimental conditions: acid value of the oil: 0.42 2. it is diﬃcult to ﬁnd suﬃcient information about the methanolysis reaction of used frying oils in the literature. 2 and 3. the biodiesel purity and its apparent viscosity.2. n. it is possible to reduce the consumption of sodium hydroxide without aﬀecting the yield of methyl esters. reaction time: 1 h.5% sodium methoxide. but also because it can cause hydrolysis and saponiﬁcation.3.8%.0%.2 0.2%. Nye et al.8 87. 3.4 Methanol/WFO (mol/mol) 6
Fig.7 86. no information is available on the optimal value of the methanol/WFO molar ratio to be used for various NaOH/WFO mass ratios and vice versa measured in terms of the yield and purity of the methyl ester phase. }. the yield of the reactions (expressed as the mass of methyl esters produced per 100 g of WFO after 1 h
of reaction) increases directly with the excess of methanol.9
3. 0. for 24 h in the presence of 0.42 mg KOH/g WFO and for a reaction time of 1 h. more recently. and 1. 0. (1984) recommended the use of 1% NaOH or 0. 0.8. the results obtained for 0.9 70. However. the optimal conditions to produce biodiesel are a methanol/WFO molar ratio higher than 4. 0. To our knowledge.42 2. Eﬀect of sodium hydroxide/frying oil mass ratio The amount of catalyst used in the process is another variable to take into account.0% NaOH/ WFO mass ratios are presented below. depending
m M E/100 g of WFO
90 85 80 75 70 65 60 3 3.4%.5% NaOCH3 as the optimal concentrations of catalyst.4 5. De Filippis et al.5%.0 80.4% to 0.4% potassium hydroxide. (1984) obtained a maximum conversion (98–99% of methyl esters) by transesterifying reﬁned oil with methanol. Since no further data on the optimal sodium hydroxide concentrations are available in the literature. 2003).4 mME/100 g WFO 80.5. 2 shows that for the oil sample with an acid value of 0. and 1. 0.07 0. 2.0 MeOH/WFO (mol/mol) 3. As recognized by Tomasevic and Siler-Marinkovic (2003).2 and.0%.8%. As shown in Fig.6%. the use of methanol/WFO ratios higher than 4. 3. 3.2 is not advantageous in terms of the methyl esters yield. using a higher value may be of importance since this ratio inﬂuences the extent of the reaction and.0 1. Fig. Determination of the optimal conditions for biodiesel production As shown in Figs. Freedman et al. Tomasevic and Siler-Marinkovic (2003) have also achieved high purity fuels using the same molar ratio of 6:1 for methanol/frying oils. From Fig.6% because it allows the maximum yield of methyl esters to be achieved. concentrations of 0. In recent work (Tomasevic and Siler-Marinkovic.2%.
. j. Furthermore.0 1.3 84.8%. m.5% of KOH were studied and the optimum value found was 1% of potassium hydroxide.2 1. 2. the reaction yields after 1 h of reaction are maximized when the ratio of catalyst/ WFO ranges from 0. as presented in Section 3. (1983) achieved a fuel containing 74% of methyl esters by reacting WFO and methanol (molar ratio of 1:3. for 1 h at 60 °C.6%. (1995) and.07 0.4. It was also observed that the increase of the methanol excess facilitates the separation of the glycerol from the MEs phase.42.4%. catalyst/WFO mass ratio: r. 0.6 5. for a WFO with an acidity of 0.
this is an important property regarding fuel atomization. a NaOH/WFO mass ratio between 0. It is important to emphasize that these optimal values would correspond to methanol and catalyst consumptions lower than the ones cited in the literature (Freedman et al. Felizardo et al.42. }.4% 0.0%
6. Experimental conditions: acid value of the oil: 0. 1984). 3).P. 3.5 5 4. Tomasevic and Siler-Marinkovic. Characterization of biodiesel To determine if the biodiesel produced under the different experimental conditions met the speciﬁcations of the standard EN 14214 (2003). According to EN 14214 (2003). as well as fuel distribution.5. This property greatly inﬂuences fuel oxidation and the type of aging products and deposits formed in diesel engines injectors. Iodine value The iodine value is an important measure that allows determination of the unsaturation degree of the fuel.6% is the optimal value because it gives the higher yields. Concerning the catalyst mass ratio.8% 1.. 2003). increasing the consumption of methanol will inevitably increase its recovery costs. revealing the extent of the transesteriﬁcation reaction and the methyl esters phase purity (De Filippis et al.
on the alcohol excess.900 g/cm3.5 and 5. the viscosity of the methyl esters phase after washing).4% 0. The broken line (5 mm2/s) indicates the maximum value for viscosity (EN 14214.6. Analyses of several samples of the produced biodiesel revealed iodine values between 123 and 130. 3. 4. n. 2003). Addition of several inhibiting polymerization reagents to the frying oil is currently under research in order to determine their inﬂuence. 4. Since a heat-up stage is carried out in the pre-treatment step. minor quantities of radical quenching agents or antioxidants can be used. On an industrial scale. a molar ratio of 4.4. 5. In fact.8%. 3. / Waste Management 26 (2006) 487–494
95 90 85 80 75 70 65 60 55 50 0.0% 0. raising the viscosity of the raw material even further. Fig. 4. the kinematic viscosity must be between 3. greatly inﬂuence the fuel properties and especially its apparent viscosity (the same is to say.6% 0. methanol/WFO molar ratio: r. 5.0% 0. this is not a problem since methanol can be recovered from the glycerol and methyl esters phase. the biodiesel produced in this study had a density in the range of 0. waste frying oils diﬀer from ‘‘fresh’’ oils mainly due to oxidation and polymerization of triglycerides. 1995). methanol/WFO molar ratio: r. It is worth noting that the extent of the reaction.864–0. To prevent polymerization and the consequent viscosity increase. several samples of biodiesel were submitted to a series of tests.2% 0.. Kinematic viscosity at 40° C Even more than density. As mentioned before. These high values were expected since most of the frying oils used in
.2 may cause diﬃculties because the reaction yield is too sensitive to catalyst concentration changes (Fig. 3.5. 3. 1984.5.1 to 6. 3. as shown in Fig..2. Diﬀerent viscosities are due to the incomplete reaction of the frying oils or to the ineﬃcient biodiesel puriﬁcation. leaving conjugated or free glycerin in the methyl esters phase. However.5 4 3. 4.5. this quantity decreases when the methanol/WFO or the NaOH/WFO ratios are increased. Indeed.3 mm2/s.42. Density at 15 °C The standard for biodiesel states that the fuel should have a density between 0.8 or higher. n.3. Experimental conditions: acid value of the oil: 0.5 0. m. reaction time: 1 h. Therefore. reaction time: 1 h.5
Vi scosity (mm2/s)
m M E/ 100 g of WFO
6 5.4% and 0. 2 clearly shows that 0.900 g/cm3. the presence of glycerides changes the apparent viscosity of the methyl esters. The kine-
matic viscosity of the biodiesel samples produced in this work ranged from 4.1. as well as the experimental conditions used in biodiesel production. However. Inﬂuence of the catalyst/WFO mass ratio on the yield of biodiesel production.2. 3. further polymerization can occur.8.4. 4. This property is important mainly in airless combustion systems because it inﬂuences the eﬃciency of atomization of the fuel (Ryan et al. For biodiesel to be used in diesel engines.2% 0. m. The results obtained showed that for all the conditions studied.8% NaOH/WFO (m/m) 1. Inﬂuence of the biodiesel production conditions on the apparent fuel viscosity. }. methyl esters used as diesel fuel must have an iodine value below 120 g I2 per 100 g of sample.8.
Fig.860 and 0. 4.2.0 mm2/s. it is advisable to use a methanol/WFO ratio of 4.6% 0.6.
5.8. 5. 3. Acid value The acid value measures the content of free fatty acids in biodiesel. 220.127.116.11.
3. the inﬂuence of the NaOH/WFO ratio on the biodiesel purity is signiﬁcant.0% 0. Supple et al. Even for the less pure samples (<80% ME).. The water content in the biodiesel samples was thus reduced from 0. which is well below the required value. EN 14214 (2003) speciﬁes a maximum value of 5 mg/kg. / Waste Management 26 (2006) 487–494
Portugal are derived from sunﬂower seeds and are characterized by iodine values between 120 and 140. In order to determine how the methanol content inﬂuences the fuel ﬂash point.12% and 0.8% 1. 4.5 mg of KOH/g of sample.6% 0. 3. this property was determined for some of the samples. 3. On an industrial scale. the broken line (96.5. even when the raw material is derived from sunﬂower oils. the iodine value rises during the later stages of oil degradation and especially if the oil is exposed to temperatures higher than 180 °C. dewatering is usually carried out by distillation under vacuum (0.25.02% to 0. Water content Fuel contaminated with water can cause engine corrosion or react with the glycerides to produce soaps and glycerine.5. respectively. Therefore. reaction time: 1 h.8% and 0.
90 85 80 75 70 0. the produced biodiesels were routinely dried over anhydrous magnesium sulphate.492
P.02% and 0.2% of methanol in biodiesel. The maximum acid value found for the biodiesel produced in this work was 0.08% to 0. Flash point EN 14214 (2003) speciﬁes that biodiesel must have a ﬂash point higher than 120 °C.4% 0. n. The alcohol is easily removed from the esters phase during the washing step.3–5.6. Considering that the presence of free fatty acids inﬂuences fuel aging. due to elimination reactions of the oxidized triglyceride molecules. The increase of the purity is the net result of an eﬃcient removal of glycerol and suﬃcient reaction extent. the methanol content was within the speciﬁcations. Some preliminary results are encouraging as they show the feasibility of producing biodiesel with an iodine value lower than 120. 1984.5% in methyl esters.47.5%) indicates the minimum methyl esters purity (EN 14214. This technique. As shown in Fig.
. Methanol content Methanol is another possible contaminant of the methyl esters phase responsible for metal corrosion. (2002) reported that during frying the formation of C18:2 and C18:3 were enhanced. Tomasevic and Siler-Marinkovic. and in the laboratory biodiesel the methanol content varied from 0. Accordingly.5. 3. 5.11%.05 bar) at temperatures of 30–40 °C. m. Inﬂuence of the biodiesel production conditions in the methyl esters purity. It is well known that the content of sodium in biodiesel is mainly determined by the eﬃciency of the washing step.05% of water in fuels. respectively. especially up to 0. methanol/WFO molar ratio: r.2% 0. although for about 80% of the samples analyzed. 3. EN 14214 (2003) imposes a maximum content of 0. Purity of the methyl esters phase According to EN 14214 (2003). The sodium content of several biodiesel samples produced in this work was in the range of 2.9. }.5. 2003).8.04%. To evaluate the conformity of the biodiesel produced in this study to the European norm. particularly of aluminium. the minimum acceptable purity for biodiesel is 96. under similar operating conditions. Sodium content Because the presence of high amounts of sodium in biodiesel induces metal corrosion as well as saponiﬁcation of the methyl esters phase.21%. 4.3 mg/kg of fuel and only two productions were out of speciﬁcation. in a bench-scale batch column. These results indicate that the washing procedure used was eﬃcient in sodium removal.2. It is therefore possible to conclude that the biodiesel purity increases when the alcohol/WFO and catalyst/ WFO ratios are augmented up to 4.21% to 0.5.4.6%.15–0. EN 14214 (2003) speciﬁes a maximum content of 0. this parameter ranged 0. Furthermore. It is worth noting that the acceptable EN 14214 purity could be achieved with consumptions of methanol and catalyst lower than the ones cited in the literature (Freedman et al.6%. Methods to lower the iodine value of biodiesel by using reducing agents before transesteriﬁcation are cur´ rently under research at Instituto Superior Tecnico. all samples were analyzed by GC. the European Standard speciﬁes a maximum value of 0. ranging from 0. and for the decreasing of the fuel ﬂash point. 3.5.4. is not very eﬃcient and the water content in several samples of the biodiesel was consequently high. 2003). Felizardo et al. Experimental conditions: acid value of the oil: 0. two samples were also distilled.0%
NaOH/Frying Oil Ratio
Fig. In this study. The eﬀect of the molar ratio of methanol/WFO is also clearly illustrated in the same ﬁgure. although used in laboratory practice.
A pilot plant to produce biodiesel from high free fatty acid feedstocks. L. 3. which depend on the type of oil and temperature. 162. the mass fraction of methyl esters in the biodiesel phase can be correlated with viscosity by w ¼ a ln m þ b. 6 presents the correlation established between the methyl ester layer purity and its measured viscosity. Curitiba. Ramos. R2 = 0. m (mm2/s) is the measured viscosity and a and b are constants. M. Experimental evaluation of the transesteriﬁcation of waste palm oil into biodiesel. M. Quim. Utilization of ethyl ester of waste vegetable oils as fuel in diesel engines. M. Canakci. Fuel 82.
4. Al-Widyan. 1995. 1429–1436.. Ballesteros. Trans. Plot of methyl esters purity vs.85. Gomez. G.
.R. L. Exhaust emissions from a diesel engine fuelled with transesteriﬁed waste olive oil.6% give the highest yield of methyl esters and allow an eﬃcient separation/ puriﬁcation of the methyl esters phase. (R2 = 0. 2003. 23.8 and a catalyst/ waste frying oil weight ratio of 0. a methanol/waste frying oil ratio of 4.. Further studies will be developed to produce biodiesel on a pilot scale to meet the speciﬁcations of EN 14214.P. Technol. Van Gerpen.006%.7
1. 2000. Connemann. ln m.02% for sulphated ash.5
Ln ( )
1. Giavarini. 6 shows that. 3.M. J.07. Abu-Qudais. Lopez.9268.
Acknowledgement ´ Thanks are due to Professor Maria de Fatima Farelo ´ (Instituto Superior Tecnico. P.
Al-Widyan. Zagonel. Canakci. r. Lisboa) for her help in revising the manuscript.. This property is important since high values are generally associated with cocking of injectors and fuel ﬁlters clogging. However..P. J.. (1995) have established a fast analytical method to determine the methyl esters phase purity.. 253–256.. ð1Þ where w represents the mass fraction of methyl esters. M. Producao ¸˜ ´ ´ ´ de Biocombustıvel Alternativo ao Oleo Diesel Atraves da Transe´ steriﬁcacao de Oleo de Soja Usado em Frituras. M. 72 (11).85 R 2 = 0.J. (1995) was used in the present work and Fig.42 and 2. 85. 1399–1404. the proposed correlation can be considered of signiﬁcant value. Rossi. Conclusions The production of biodiesel from used frying oils is feasible by basic catalyzed transesteriﬁcation and the biodiesel produced has the quality required to be a diesel substitute.5% in the methanol content leads to a 50 °C decrease of the biodiesel ﬂash point. Scarsella. as shown by the viscosity reduction and increased purity of this layer. 945–954. Bioresour. ASAE 44. ASAE 46. although the correlation coeﬃcient of the simple linear equation ﬁtted to the experimental data is lower than the one obtained by De Filippis et al. M. The values obtained for the several productions were between 0. These studies are to be carried out in a full-automated machine and concern the optimization of the production of biodiesel on an industrial scale. Arnal.3
Fig.10. It is. The method proposed by De Filippis et al... G....9268
1. for samples with a 0. 76. Trans. just by making a single viscosity measurement at 40 °C. M. In: International Liquid Biofuels Congress. De Filippis et al. J. A. Soc. Technol. De Filippis.. Sorrentino. E.5% methanol content. interception.. Van Gerpen. it still allows a meaningful estimation of the degree of transesteriﬁcation.5. ¸˜ 531–537. Costa Neto. Experimental data. 91–103..6. meeting the fuel speciﬁcations. J. linear regression. worth noting that an increase of only 0. / Waste Management 26 (2006) 487–494
The results show that the samples of biodiesel containing less than 0.. M. Biodiesel in Europe 1998 – Biodiesel processing technologies. 2002. 2003.. Nova. J. Tashtoush. P. Correlation between viscosity of biodiesel and purity of methyl esters phase The content of methyl esters produced in the transesteriﬁcation reaction is a variable of the utmost importance in the industrial production of biodiesel. Al-Shyoukh. F.998)..1% of methanol had a ﬂash point from 160 to 170 °C. Transesteriﬁcation process for vegetable oils: a simple control method of methyl ester content. ——.055. 2001. The results show that after 1 h of reaction. The points presented in Fig. ´ ´ Dorado. J. Felizardo et al. According to these authors. À45. 1998. Fischer.
100 95 90 85 80 75 70 65 60 1.055x + 162.
Puri ty (% ME)
y = -45. Brasil. 6 correspond to the results obtained in several biodiesel production experiments using the WFO with acid values of 0. the measured ﬂash points (98–110 °C) were below the minimum acceptable value. Am.9
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