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Fuel 87 (2008) 34903496

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Biodiesel production from waste cooking oils


Anh N. Phan a,*, Tan M. Phan b
a b

School of Chemical Engineering and Advanced Materials, Newcastle University, NE1 7RU, UK Department of Science and Technology, HCMC, Viet Nam

a r t i c l e

i n f o

a b s t r a c t
Alkali-catalyzed transesterication of waste cooking oils, collected within Ho Chi Minh City, Vietnam, with methanol was carried out in a laboratory scale reactor. The effects of methanol/waste cooking oils ratio, potassium hydroxide concentration and temperature on the biodiesel conversion were investigated. Biodiesel yield of 8890% was obtained at the methanol/oil ratios of 7:18:1, temperatures of 3050 C and 0.75 wt% KOH. Biodiesel and its blends with diesel were characterized for their physical properties referring to a substitute for diesel fuel. The results showed that the biodiesel experienced a higher but much narrower boiling range than conventional diesel. Carbon residue content was up to 4 wt%. Blends with a percentage of the biodiesel below 30 vol% had their physical properties within EN14214 standard, which indicated that these could be used in engines without a major modication. Crown Copyright 2008 Published by Elsevier Ltd. All rights reserved.

Article history: Received 12 May 2008 Received in revised form 3 July 2008 Accepted 8 July 2008 Available online 15 August 2008 Keywords: Transesterication Biodiesel Waste cooking oil Boiling range Carbon residue

1. Introduction Increasing concerns regarding environmental impacts, the soaring price of petroleum products together with the depletion of fossil fuels have prompted considerable research to identify alternative fuel sources. Biofuel has recently attracted huge attention in different countries all over the world because of its renewability, better gas emissions and its biodegradability. It is estimated that biodiesel/bio-ethanol could replace approximately 10% of diesel fuel consumption within Europe and 5% of Southeast Asias total fuel demand. Biodiesel is superior to conventional diesel in terms of its sulphur content, aromatic content and ash point. It is essentially sulphur free and non-aromatic while conventional diesel can contain up to 500 ppm SO2 and 2040 wt% aromatic compounds. These advantages could be a key solution to reduce the problem of urban pollution since transport sector is an important contributor of the total gas emissions. Amongst vehicle fuels, diesel is dominant for black smoke particulate together with SO2 emissions and contributes to a one third of the total transport generated greenhouse gas emissions [31]. According to Utlu and Kocak [42], there was on average of a decrease of 14% for CO2, 17.1% for CO and 22.5% for smoke density when using biodiesel. Biodiesel production from vegetable oils has been extensively studied in recent literature reviews. There were more than 50

* Corresponding author. Tel.: +44 (0) 191 222 5747; fax: +44 (0) 191 222 5292. E-mail address: a.n.phan@ncl.ac.uk (A.N. Phan).

papers cited relating to biodiesel production from vegetable oils in the Fukuda et al.s work [17]. Many researchers have reported the biodiesel production in several ways: (a) the effect of operating parameters [3,15,16,29,36]; (b) the effect of the type of catalysts such as enzyme catalysts [17,20,32,33,38], heterogeneous catalysts [21,39] and acidic catalysts [4,28]. However, the raw material costs and limited availability of vegetable oil feedstocks are always critical issues for the biodiesel production. The high cost of vegetable oils, which could be up to 75% of the total manufacturing cost, has led to the production costs of biodiesel becoming approximately 1.5 times higher than that for diesel [30,44]. Nevertheless, the price of waste cooking oils (WCO) is 23 times cheaper than virgin vegetable oils. Consequently, the total manufacturing cost of biodiesel can be signicantly reduced [44]. In addition, a similarity in the quality of biodiesel derived from WCO and from vegetable oils could be achieved at an optimum operating condition [6]. Increasing food consumption has increased the production of a large amount of waste cooking oils/fats. It was, for example, 4.511.3 million litres a year in USA or 4 1056 105 ton/year in Japan [34]. The conversion of this amount of WCO into fuel also eliminates the environmental impacts caused by the harmful disposal of these waste oils, such as into drains [41]. Biodiesel from WCO (or used frying oils) has been recently investigated [6,1113,18,24,27,37,41,45]. However, the optimum conditions for biodiesel production (methanol/oils ratio and concentration of catalyst) are inconsistent. They strongly depend on the properties of WCO. Dorado et al. [10] found that the ester yield reached 90% at the methanol/oil ratio of 3.48:1 and 1.26 wt% KOH; while Encinar et

0016-2361/$ - see front matter Crown Copyright 2008 Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2008.07.008

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al. [11] revealed that the best results obtained at the molar ratio of 6:1 and 1 wt% KOH. According Zhang et al. [44], only rened/crude oils have acid value less than 1 could be used in an alkali-catalyzed process. A pre-treatment step was required for oils having acid value higher than 2 [13]. Nevertheless, some authors had also carried out successfully the alkali-catalyzed transesterication of WCO having an acid value up to 4.91 mg KOH/g [40]. Numerous research projects on the utilization of biodiesel as well as its blends in engines have been done [13,23,26]. However, most of these were focused on short-term tests on different types of direct injection engines in terms of gas emissions (CO, CO2, NOx, un-burnt hydrocarbons etc.) and engine performances (power output, specic fuel consumption). A suggested proportion of biodiesel in a blend used in engines, therefore, varied and could be up to 50 vol% [2,26]. Most of the research has not taken into account carbon deposit formation when fuelled with biodiesel. Carraretto et al. [5] have recently suggested that the most viable option for biodiesel is in boilers with a minor modication of nozzles and gaskets that give a comparable efciency and less fouling. Alkali catalysts used in transesterication can be potassium hydroxide, sodium hydroxide or alkali methoxides. However, potassium hydroxide was considered as a best catalyst for transesterication of used frying oils [11]. In this study, the transesterication of WCO was carried out for a reaction temperature of up to 70 C. The molar ratio of methanol/WCO ranged from 5:1 to 12:1 in the presence of KOH catalyst concentration varying from 0.5 wt% of oil to 1.5 wt% of the WCO. The physical properties of biodiesel and its blends were characterized for distillation curve, carbon residue, cloud and pour points, viscosity, density, caloric value and acid value. 2. Experiments 2.1. Materials WCO samples were collected from restaurants and shops within Ho Chi Minh City, Vietnam with 510 l each and ltered to remove inorganic residues. The WCO samples were obtained from different ways: (a) collecting after being used several times for frying purposes at small shops; (b) taking after being used once for big restaurants. The characteristics of the WCO samples are illustrated in Tables 1 and 2. Acid values of the samples varied from 0.67 to 3.64 mg KOH/g. The acid value was relatively low in the sample 4, where it was used once. The low level of free fatty acid content in the WCO samples could be an advantageous for an alkali catalyzed transesterication process. The samples had saponication values ranging from 264 to 272 mg KOH/g oil. Considering the composition of the samples, the WCO molecular weights can be calculated between 670.1 and 694.3 g/mol. This value was much lower than WCO from other research, which had molecular weight ranging from 866 to 873.4 g/mol [6,11].

Table 2 Quantitative of fatty acids in WCO samples Component g/100 g total fatty acid methyl ester Sample 1 C6:0 C8:0 C10:0 C12:0 C14:0 C15:0 C16:0 C16:1 C17:0 C18:0 C18:1 C18:2 C18:3 C20:0 C20:1 0 8.82 6.21 44.65 16.31 0.00 10.59 0.00 0.00 3.29 8.17 1.96 0.00 0.00 0.00 Sample 2 0.88 6.64 5.38 42.30 16.77 0.00 11.59 0.24 0.00 4.16 9.97 1.82 0.03 0.11 0.11 Sample 3 1.31 9.98 7.32 49.59 16.28 0.00 7.34 0.00 0.00 2.01 4.83 1.34 0.00 0.00 0.00 Sample 4 1.02 8.90 6.51 46.96 17.45 0.00 8.78 0.00 0.00 2.54 6.00 1.69 0.05 0.06 0.04

These WCO samples had 1015 times higher viscosity than diesel oil. They are composed mainly of saturated short length fatty acid alkyl chains, which was 4250 wt% of C12:0, 17 wt% C14:0, 10 wt% C16:0 and less than 10 wt% of unsaturated compounds (Table 2). Methanol and KOH used were obtained from Aldrich Company Ltd. Diesel was taken from commercial diesel (No. 2) with their characteristics listed in Table 1. The WCO samples were mixed together prior to the transesterication. 2.2. Transesterication The transesterication was carried out in a 500 ml three-neck glass ask connecting with a reux condenser using tap water to condense methanol vapour and a thermocouple probe. The mixture was agitated by using a stainless steel stirrer comprising of a turbine. The reactor was placed in a heated water bath. KOH pellets were dissolved in methanol before being poured in the reactor containing about 200 g WCO heated up to a desired temperature, which was 30 C, 50 C or 70 C. The reaction was kept at a desired temperature for 20 min, 40 min, 60 min, 90 min or 120 min. The molar ratio of methanol and WCO varied from 5:1 to 12:1 while the amount of KOH catalyst was ranging from 0.5 wt% to 1.5 wt% of the WCO. After a certain time, the mixture was poured into a separating funnel. The ester layer was separated by gravity and located in the upper layer. The glycerol, extra methanol and undesired products were in the lower layer and were decanted. The ester layer was washed several times with a small amount of hot water each until the washings were neutral. The ester layer was then dried over sodium sulphate and ltered. The conversation of biodiesel was determined as follows:

Conversion %

mester 100; moil 3 MW MWester


oil

Table 1 Physical properties of WCO samples and diesel Quality Acid number Iodine number Saponication number Density Flash point Cloud point Pour point Viscosity @40 C Unit mg KOH/g mg KOH/g mg KOH/g g/cm3 C C C mm2/s Sample 1 2.36 13.20 268.22 0.92 269 21.00 18.00 30.05 Sample 2 1.80 12.69 264.10 0.92 276 15.00 13.00 33.47 Sample 3 3.64 8.57 272.00 0.92 243 16.50 14.00 27.42 Sample 4 0.67 9.45 270.60 0.92 298 25.00 18.50 31.77 Diesel 0.11 0.83 69 0 <12 3.53

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where mester: weight of ester collected (g); moil: weight of the oil sample (g); MWoil: averaged molecular weight of oil sample.

MWoil 3

X
i

MWi %mi 38;

MWi: molecular weight of fatty acid i; %mi: percentage of fatty acid i in the raw material. MWester: averaged molecular weight of fatty acid ester.

MWester

X
i

MWi %mi 14:

2.3. Analysis Fatty acid quantitative was determined by using a Hitachi G-5000A GC (column length: 30 m; diameter: 0.25 mm, lm thickness: 0.25 lm). The physical properties of the raw samples, biodiesel and its blends with diesel were measured by using ASTM standard methods, including density (D1298), kinetic viscosity (D445), ash point (D93), cloud point (D2500), pour point (D97), distillation curve (D86) and carbon residue (D189), caloric value (D240) and acid value (D664). 3. Results and discussion 3.1. Transesterication of WCO with methanol 3.1.1. Effect of ratio of methanol to WCO The methanol/oil ratio is one of the most important factors affecting the yield of biodiesel. Although stoichiometric ratio requires 3:1, the transesterication is commonly carried out with an extra amount of alcohol in order to shift the equilibrium to the proposed product, methyl ester. According to Centikaya and Karaosmanoglu [6], for example, transesterication is insufcient at the ratios of methanol/oils below 5:1. Furthermore, the methanol/oil ratio is associated with operating parameters such as the type of catalyst used and the quality of oils. The optimum ratio of methanol/used frying oils was, for instance, 4.8 in the presence of sodium hydroxide [13]; while it could be up to 250 in the presence of acidic catalysts [45]. Shown in Fig. 1 is the effect of the methanol/oil ratio on the conversion of biodiesel at a temperature of 30 C in the presence of 0.75 wt% KOH. The conversion reached a value of above 50% in just 20 min. Increasing the ratio from 5:1 to 8:1 increased the conversion. It rose from 50% for the ratio of 5:1 to 64% for the ratio of 8:1.

The difference in the conversion between the ratios of 5:1 and 8:1 was about 24% in the rst 60 min and slightly decreased to 1316% for the last 60 min. The difference in the conversion was less than 2% when the methanol/WCO ratio increased from 8:1 to 9:1. A further increase in the methanol/WCO ratio above 9:1 caused a reduction in the conversion. It was 82% for the ratio of 12:1 compared to 88% for the ratio of 8:1 after 80 min as illustrated in Fig. 1. The reduction could be because the excess of methanol could interfere with the separation of ester product and by-products by increasing solubility of glycerol. Consequently, part of the diluted glycerol remained in the ester phase, leading to foam formation and therefore apparent lost ester product. In addition, the excess of methanol could also drive the combination of ester product and glycerol into mon-glycerides [11]. This indicated that the optimum molar ratio of methanol/WCO was 7:18:1, giving a biodiesel yield of approximately 8890% after 80 min. The optimum ratio in this study was in accordance with that obtained from other investigators [1]. Increasing the ratio also enhanced a settling process. The settling time took hours for the molar ratios below 7:1 while it was only approximately 30 min for the ratios of 7:1 and 8:1. The ester layer isolated in the cases of 7:1 and 8:1 was yellowish and transparent while it was translucent for the other cases. This indicated that there was a certain amount of un-reacted glycerides diluted in the ester phase at the ratios below 7:1.

3.1.2. Effect of concentration of catalyst Felizardo et al. [13] revealed that the optimum concentration of sodium hydroxide was 0.6 wt%. This value was much lower than the nding of Georgogianni et al. [18]. Leung et al. [25] also studied the effect of NaOH concentration on biodiesel derived from neat Canola and used frying oil. The results showed that the optimum value of NaOH concentration for neat Canola oil and used frying oil was 1.0 wt% and 1.1 wt%, respectively. It could be concluded that the concentration of alkali catalyst is strongly dependent on the type of oils used. Considering data from literature reviews, the concentration of KOH was tested in a range of 0.51.5 wt% of WCO. Fig. 2 shows the effect of concentration of KOH on the conversion at the methanol/WCO ratio of 8:1. Increasing KOH concentration from 0.5 wt% to 0.75 wt% increased the conversion. It was 82% and 90% at 0.5 wt% KOH and 0.75 wt% KOH, respectively during 120 min. However, the conversion reduced to 75% in the case of 1.5 wt% KOH. This could be explained by the fact that the forma-

100

100

90

90

0.75% 1.00% 0.50% 1.25% 1.50%

Conversion (%wt)

80

Conversion (%wt)
140

80

70
5:1 6:1 7:1 8:1 9:1 12:1

70

60

60

50

50

40 0 20 40 60 80 100 120

40 0 20 40 60 80 100 120 140

Time (min)
Fig. 1. Effect methanol/WCO ratio on the conversion of biodiesel at a temperature of 30 C and 0.75 wt% KOH.

Time (min)
Fig. 2. Effect of KOH concentration on the conversion of biodiesel at the methanol/ WCO ratio of 8:1 and a temperature of 30 C.

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tion of soap hindered the separation of the methyl ester phase during the washing step. The soap particles formed emulsions with water, which resulted in increased viscosity. This phenomenon did not occur at low KOH concentrations. As a consequence, the yields of biodiesel were low for the cases of 1 wt% and 1.5 wt% KOH. The optimum concentration of KOH in this study was proximate close to the nding of Felizardo et al. [13]. However, it was slightly lower than that from other research [11,36,40]. This was due to the lower free fatty acid content in the WCO samples. The higher free fatty acid requires an addition of KOH to compensate for this acidity. 3.1.3. Effect of temperature Transesterication can occur at different temperatures, depending on the properties of oils. It could be at ambient temperature [40]; or at a temperature close to the boiling temperature of methanol [13,43]. However, high reaction temperatures speed up the reaction and shortens the reaction time [8,30]. Freedman et al. [16] found that biodiesel yield depended on temperature in the rst 30 min reaction. It was, for example, 94%, 87% and 64% at the temperatures of 60 C, 45 C and 32 C, respectively. Fig. 3 shows the effect of temperature on the conversion at the methanol/oil ratio of 8:1 in the presence of 0.75 wt% KOH. Increasing the temperatures from 30 C to 50 C, the conversion increased 1013%. However, if the temperature increased up to 70 C, there was a slight reduction in the conversion. This is because high temperature enhances both transesterication and saponication reactions. 3.2. Characteristics of biodiesel and its blends with diesel 3.2.1. Distillation curve A distillation curve is used to characterize the volatility of fuel and its tendency to form soot and smoke and considered as an important indicator for long-term analysis of fuel performance relating to optimization and design engines. It is essential for biodiesel and its blends since biodiesel is oxygenated fuel which is the distinct difference to conventional diesel. Shown in Fig. 4a, the initial boiling point of the biodiesel (IBP) was 213 C compared to 162 C for diesel. A much narrower boiling range but higher value could be observed in the case of the biodiesel than in the case of diesel. The boiling temperatures kept almost constant at a value of 330 C from 20 vol% fraction to 70 vol% fraction while it increased steadily in the case of conventional diesel,

500
Biodiesel Diesel

400

Temperature(C)

300

200

100

0 IBP 5 10 20 30 40 50 60 70 80 90 95 FBP

% Volume Recovery

b
400

300

Temperature(C)

200

100

B5 B10 B15 B20 B25 B30 B50 B75

0 IBP 5 10 20 30 40 50 60 70 80 90 95 FBP

%Volume Recovery
Fig. 4. Distillation curves for (a) biodiesel and diesel and (b) biodiesel blends with diesel.

100

90

80

70

30C 50C 70C

60

50

40 0 20 40 60 80 100 120 140

Time (min)
Fig. 3. Effect of temperature on the conversion of biodiesel at 0.75 wt% KOH and the methanol/WCO ratio of 8:1.

which was an average of 1012 C/10 vol% recovery. This narrow range can be explained as the biodiesel consists mainly of alkyl esters that have a little difference in the boiling temperature. The difference in boiling points among pure fatty acid methyl esters was approximately 2030 C. The distillation curve behaviour was similar for the biodiesel obtained from this study to those obtained from soybean oil and rapeseed oil, which had a 810 C different boiling range from 10 vol% to 90 vol% [19]. Considering biodiesel obtained from other types of WCO [1], the boiling points at 10 vol%, 50 vol% in this study was 2030 C lower but was slightly higher at the boiling point at 90 vol%. This was because of the difference in the chemical properties of the raw materials. The WCO samples used in this study consisted mainly of saturated short alkyl chain fatty acids (C12 and C14) compared to other raw used frying oil samples being composed mainly of oleic (53%) and linoleic (33%). The nal boiling point (FBP), in contrast, was much lower in the biodiesel than in diesel. They were 348 C and 387 C for the biodiesel and for diesel, respectively. The lower FBP for the biodiesel was because the double bond of unsaturated of alkyl chains could be polymerised at high temperatures. This, therefore, hindered the volatilization of liquid at the end of the distillation process, which could lead to the formation of gums, carbon residue in the nozzles or on the surface of pistons causing corrosions. Smoke formation occurs mainly in the local fuel-rich zones where pyrolysis of the fuel is going on in accordance with a com-

Conversion (%wt)

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plicated multi-stage mechanism of fractioning and decomposing of fuel molecules with air. The low volatility of the biodiesel (high boiling point range) could cause a poor atomisation, leading to a potential formation of soot particles and a proportion of un-burnt and/or partially burned droplets. These droplets could potentially survive due to a poor mixing with air and therefore could impinge on cylinder walls and pistons or be released during the exhaust process. Knothe et al. [22] found that there was a greater varnish and deposits on the pistons and also a greater level of high molecular weight organic compounds absorbing to particles when fuelled with biodiesel than when fuelled with diesel. The high 10 vol% temperature of the biodiesel could also contribute to the formation of billowing clouds of white smoke during premixed combustion. Blends of the biodiesel with diesel are designated as B followed by a volumetric percentage of the biodiesel in the blend. For example, B5 stands for the blend of 5 vol% biodiesel and 95 vol% diesel. Shown in Fig. 4b, the trend of distillation curves of the blends was similar to that of diesel at a percentage of the biodiesel below 50 vol%. The percentage of diesel had little inuence on the IBP. The IBP was 170172 C for all the blends. However, the FBP decreased with increasing percentage of the biodiesel. It was 368 C for B5 while 354 C for B75. As expected, the mid-boiling point increased by increasing the proportion of the biodiesel. They were, for instance, 304 C, 328 C and 334 C for B20, B50 and B75. 3.2.2. Carbon residue Carbon residue is an important indicator to measure of the tendency to form carbonaceous deposits in engines, which can cause several operational problems such as blockage of nozzles, corrosion, cracking of components. As shown in Fig. 5, the carbon residue content increased exponentially with percentage of biodiesel. It was 0.15 wt%, 0.23 wt%, 0.27 wt% and 4.0 wt% for B10, B15, B20 and B100, respectively. The relation between the carbon deposit (y) and percentage of the biodiesel (x) in the blend could be described as follows by using a 95% condence limit:

of the disadvantages of biodiesel in considering it as a substitute fuel for engines. For biodiesel, the carbon residue is an indicator of not only the amount of the material left after vaporation and pyrolysis but also the amount of glycerides (free glycerol, partially reacted/un-reacted glycerides) and other residues remaining in the biodiesel product (free fatty acids and catalyst residue). The free glycerol and catalyst residue can be easily removed during the washing step whereas the content of glycerides can be only converted by using specic catalysts and reactions conditions or by further distillation products. According to Fernando et al. [14], increasing an amount of un-converted/partially converted glycerides increased the amount of carbon residue. Therefore, the formation of a high amount of residue could be due to the polymerisation of unsaturated alkyl chains (approximately 10 wt%) and the degradation of glycerides and free fatty acid remaining in the biodiesel at a high temperature. In addition, the degradation of glycerides at high temperature can also act as a catalyst for polymerisation of the unsaturated fatty acids [31]. Therefore, it is vital to have major modications in engines fuelled with 100% biodiesel in order to overcome operational problems as mentioned previously. Although not displayed in this work, the 10 vol% distillation residues from B50, B75 and B100 were brownish and sticky compared to those from diesel and other blends. 3.2.3. Other properties of biodiesel and its blends As shown in Table 3, the properties of the biodiesel from WCO in this study were in accordance with other investigators and within EN 14214 standard. The biodiesel had a density of 0.88 g/ml and was slightly higher than diesel, which is 0.83 g/ml. Flash point strictly corresponds to the methanol content and viscosity correlates with un-reacted triglycerides. According to Felizardo et al. [13], the ash point could decrease 50 C with increasing only 0.5% of methanol content in the ester phase. The ash point in this study was slightly lower than that from other research [6,11] but much higher than biodiesel obtained from used soybean oil and mixture frying oils [18]. The viscosity of the biodiesel in this study was 4.89 mm2/s, slightly lower than that from other investigators [9,35]. Generally, the viscosity of the biodiesel derived from WCO decreased 10 times compared to the original WCO samples. The properties of nal product strongly depend on the yield of methyl ester (purity of methyl ester phase). The presence of glyceride types, in particular, in the fuel can cause serious problems in commercial applications. According to EN 14214 biodiesel standard, there are strict limitations for both free and total glyceride contents of biodiesel and the level of methyl ester content. Although the amounts of free glyceride and total glyceride were not measured, the purity of biodiesel can be determined by using the viscosity measurement [7,13]. Regarding the measured viscosity of the biodiesel, the calculated methyl ester content in this study was approximately 9192%. This was slightly lower than the minimum level of methyl ester content, which is 96.5%. Once again, this explained the formation of high carbon residue of the biodiesel mentioned in the previous section. The ow properties, including cloud point and pour point, were much higher for the biodiesel than for conventional diesel. The cloud and pour points were 3 C and 0 C for the biodiesel while 0 C and <12 C for conventional diesel. This indicates that the biodiesel is less suitable in cold conditions. The cloud and pour points of the biodiesel derived from WCO in this study are higher than those from other research [10,18]. This is due to chemical properties of the raw WCO samples, consisting of 90% saturated fatty acid alkyl chains. The acid value indicates the content of free fatty acid in biodiesel. The value found in this study was 0.43 mg KOH/g. Referring to

y 0:1676 e0:0315x ;
with a correlation coefcient R = 0.9914. The level of carbon residue content at a percentage of the biodiesel above 20 vol% was exceeding the current diesel specication for carbon residue in the Petroleum Products Specications Regulations 2002 (PPSR), which is a maximum of 0.3 wt%. This is one

Carbon residue (%wt)

0 0 20 40 60 80 100 120

% Biodiesel
Fig. 5. Carbon residue (10% distillation residue).

A.N. Phan, T.M. Phan / Fuel 87 (2008) 34903496 Table 3 Biodiesel characteristics Quality Density @15 C, g/ml Viscosity @40 C, mm2/s Cloud point, C Pour point, C Flash point, C Acid value, max, mg KOH/g Water content, max, ppm EN 14214 0.860.90 3.55.0 >101 0.5 500 Centinkaya et al. [6] 0.88230.8874 5.296.46 9 3 176 0.289 480.07 Georgogianni et al. [16] 0.857 4.76 3 4 67 0.8 0.826 4.45 4 5 83 0.5 Encinar et al. [10] 0.890 (@25 C) 4.8 4.7 3.9 177

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This study 0.88 4.89 3 0 120 0.43 Trace

Table 4 Physical properties of biodiesel blends with diesel Quantity Unit Samples B5 Density Viscosity @40 C Cloud point Pour point Flash point Caloric value Water content Acid number g/ml mm2/s C C C kcal/kg wt% mg KOH/g 0.85 3.56 0 12 74 10,845 Trace 0.11 B10 0.85 3.72 0 11.5 80.5 10,750 Trace 0.12 B15 0.85 3.72 0 9.5 81 10,683 Trace 0.13 B20 0.85 3.75 0 9 82 10,615 Trace 0.16 B25 0.85 3.82 0 8.5 85 10,545 Trace 0.20 B30 0.86 3.90 0 8 86 10,462 Trace 0.23 B50 0.86 4.25 0 6 91 10,180 Trace 0.32 B75 0.88 4.64 0 4.5 106.5 10,100 Trace 0.35

EN14214 standard for bio-auto fuels, the biodiesel obtained from this study was found to be within the limits in terms of density, viscosity, ash point, acid value and water content. As observed in Table 4, increasing the percentage of the biodiesel resulted in a reduction in caloric value but an increase in other parameters such as acid number, viscosity and ash point. The reduction in caloric value for the biodiesel and its blends compared to diesel was due to the presence of oxygen in the biodiesel. 4. Conclusions Although being collected from different sources, there was little difference in properties among the WCO samples in terms of chemical and physical properties. This could then assist the implementation of biodiesel production process from waste cooking oils. In this study, biodiesel production from the WCO was carried out in the laboratory scale reactor. The results showed that the highest yield of biodiesel was obtained at the ratio of methanol/WCO of 7:1 8:1 during 8090 min at temperatures ranging 3050 C in the presence of 0.75 wt% KOH. Although most of the physical properties of the biodiesel were within standards for diesel fuel and for bioauto fuels (EN14214), the carbon residue was much higher in the biodiesel than in diesel. The carbon residue was 4.0 wt% for the biodiesel but only 0.05 wt% for diesel. Furthermore, the volatility characteristics of the biodiesel were much different to that of diesel as clearly projected in the distillation curve. There was a very narrow range of boiling temperature for biodiesel. The boiling temperature remained approximately 330 C from 20 vol% to 70 vol% fraction. Mixing the biodiesel with diesel improved signicantly the volatility and decreased the carbon deposits at a percentage of biodiesel in the blends below 50 vol%. The results obtained showed that the blend of 20 vol% the biodiesel and 80 vol% diesel (B20) could be applied in engines without major modication. References
[1] Alcantara R, Amores J, Canoira L, Fidalgo E, Franco MJ, Navarro A. Catalytic production of biodiesel from soy-bean oil used frying oil and tallow. Biomass Bioenergy 2000;18:51527. [2] Ali Y, Hanna MA, Leviticus LI. Emissions and power characteristics of diesel engines on methyl soyate and diesel fuel blends. Bioresour Technol 1995;52:18595.

[3] Antonlin G, Tinaut FV, Brceno Y, Castano V, Perez C, Ramirez AI. Optimisation of biodiesel production by sunower oil transesterication. Bioresour Technol 2002;83:1114. [4] Canakci M, Van Gerpen J. Biodiesel production via acid catalysis.Trans Am Soc Agric Eng 1999;5:120310. [5] Carraretto C, Macor A, Mirandola A, Stoppato A, Tonon S. Biodiesel as alternative fuel: experimental analysis and energetic evaluations. Energy 2004;29:2195211. [6] Cetinkaya M, Karaosmanoglu F. Optimisation of base-catalysed transesterication reaction of used cooking oil. Energy Fuels 2004;18: 188895. [7] De Filippis P, Giavarini C, Scarsella M, Sorrentino M. Transesterication process for vegetable oils: a simple control method of methyl ester content. J Am Oil Chem Soc 1995;72:1399404. [8] Demirbas A. Biodiesel fuels from vegetable oils via catalytic and non-catalytic supercritical alcohol transesterications and other methods: a survey. Energy Convers Manage 2003;44:2093109. [9] Dorado MP, Ballesteros E, Arnal JM, Gomez J, Lopez FJ. Exhaust emissions from a diesel engine fueled with transesteried waste olive oil. Fuel 2003;82:13115. [10] Dorado MP, Ballesteros E, Lopez FJ, Mittelbach M. Optimisation of alkalicatalyzed transesterication of Brassica Carinata oil for biodiesel production. Energy Fuels 2004;18:7783. [11] Encinar JM, Gonzalez JF, Rodriguez-Reinares A. Biodiesel from used frying oil. Variables affecting the yields and characteristics of the biodiesel. Ind Eng Chem Res 2005;44:54919. [12] Encinar JM, Gonzalez JM, Rodriguez-Reinares A. Ethanolysis of used frying oil. Biodiesel preparation and characterisation. Fuel Process Technol 2007;88:51322. [13] Felizardo P, Correia MJN, Paposo I, Mendes JF, Berkemeier R, Bordado JM. Production of biodiesel from waste frying oils. Waste Manage 2006;26: 48794. [14] Fernando S, Karra P, Hernandez R, Jha SK. Effect of incompletely converted soybean oil on biodiesel quality. Energy 2007;32:84451. [15] Freedman B, Buttereld RO, Pryde EH. Transesterication kinetics of soybean oil. JAOCS, J Am Oil Chem Soc 1986;63:137580. [16] Freedman B, Pryde EH, Mounts TL. Variables affecting the yields of fatty esters from transesteried vegetable oils. J Am Oil Chem Soc 1984;61:163843. [17] Fukuda H, Kondo A, Noda H. Biodiesel fuel production by transesterication of oils. J Biosci Bioeng 2001;92:40516. [18] Georgogianni KG, Kontominas MG, Tegou E, Avlonitis D, Vergis V. Biodiesel production: reaction and process parameters of alkali-catalysed transesterication of waste frying-oils. Energy Fuels 2007;21:30237. [19] Graboski MS, McCormick RL. Combustion of fat and vegetable oil derived fuels in diesel engines. Prog Energy Combust Sci 1998;24:12564. [20] Iso M, Chen B, Eguchi M, Kudo T, Shrestha S. Production of biodiesel fuel from triglycerides and alcohol using immobilized lipase. J Mol Catal B Enzym 2001;16:538. [21] Kim H-J, Kang B-S, Kim M-J, Park YM, Kim D-K, Lee J-S, et al. Transesterication of vegetable oil to biodiesel using heterogeneous base catalyst. Catal Today 2004;9395:31520. [22] Knothe G, Christopher AS, Ryan TW. Exhaust emissions of biodiesel, petrodiesel neat methyl esters and alkanes in a new technology engine. Energy Fuels 2006;20:4038.

3496

A.N. Phan, T.M. Phan / Fuel 87 (2008) 34903496 [35] Raheman H, Phadatare AG. Diesel engine emissions and performance from blends of karanja methyl ester and diesel. Biomass Bioenergy 2004;27:3937. [36] Rashid U, Anwar F. Production of biodiesel through optimized alkalinecatalysed transesterication of rapeseed oil. Fuel 2008;87:26573. [37] Refaat AA, Attia NK, Sibak HA, El Sheltawy ST, ElDiwani GI. Production optimisation and quality assessment of biodiesel from waste vegetable oil. Int J Environ Sci Technol 2008;5:7582. [38] Shimada Y, Watanabe Y, Sugihara A, Tominaga Y. Enzymatic alcoholysis for biodiesel fuel production and application of the reaction to oil processing. J Mol Catal B Enzym 2002;17:13342. [39] Suppes GJ, Dasari MA, Doskocil EJ, Mankidy PJ, Goff MJ. Transesterication of soybean oil with zeolite and metal catalysts. Appl Catal A: Gen 2004;257:21323. [40] Tomasevic AV, Siler-Marinkovic SS. Methanolysis of used frying oil. Fuel Process Technol 2003;81:16. [41] Utlu Z. Evaluation of biodiesel obtained from waste cooking oil. Energy Sources, Part A 2007;29:1295304. [42] Utlu Z, Kocak MS. The effect of biodiesel fuel obtained from waste cooking oil on direct injection diesel engine performance and exhaust emissions. Renew Energy 2008;33:193641. [43] Wang Y, Ou S, Liu P, Zhang Z. Preparation of biodiesel from waste cooking oil via two-step catalyzed process. Energy Convers Manage 2007;48:1848. [44] Zhang Y, Dube MA, McLean DD, Kates M. Biodiesel production from waste cooking oil: 2. Economic assessment and sensitivity analysis. Bioresour Technol 2003;90:22940. [45] Zheng Y, Kates MM, Dube A, McLean DD. Acid-catalyzed production of biodiesel from waste cooking oil. Biomass Bioenergy 2006;30:26772.

[23] Kocak MS, Ileri E, Utlu Z. Experimental study of emission parameters of biodiesel fuels obtained from Canola, Hazelnut, and waste cooking oils. Energy Fuels 2007;21:36226. [24] Kulkarni MG, Dalai AK. Waste cooking oil An economical source for biodiesel: A review. Ind Eng Chem Res 2006;45:290113. [25] Leung DYC, Guo Y. Transesterication of neat and used frying oil: optimisation for biodiesel production. Fuel Process Technol 2006;87:88390. [26] Lin Y-F, Wu Y-PG, Chang C-T. Combustion characteristics of waste-oil produced biodiesel/diesel blends. Fuel 2007;86:177280. [27] Liu C, Lin R, Meng Q. Technology for production of biodiesel with waste cooking oil. Speciality Petrochem 2007;24:669. [28] Lotero E, Liu Y, Lopez DE, Suwannakarn K, Bruce DA, Goodwin JG Jr. Synthesis of biodiesel via acid catalysis. Ind Eng Chem Res 2005;44(14):535363. [29] Ma F, Clements LD, Hana MA. The effects of catalyst, free fatty acids and water on transesterication of beef tallow. Trans Am Soc Agric Eng 1998;41:12614. [30] Ma F, Hanna MA. Biodiesel production: a review. Bioresour Technol 1999;70:115. [31] Nas B, Berktay A. Energy potential of biodiesel generated from waste cooking oil: an environmental approach. Energy Sources 2007;2:6371. [32] Nelson LA, Foglia TA, Marmer WN. Lipase-catalysed production of biodiesel. JAOCS, J Am Oil Chem Soc 1996;73:11915. [33] Nie K, Xie F, Wang F, Tan T. Lipase catalysed methanolysis to produce biodiesel: optimization of the biodiesel production. J Mol Catal B Enzym 2006;43:1427. [34] Pugazhvadivu M, Jeyachandran K. Investigations on the performance and exhaust emissions of a diesel engine using preheated waste cooking oil as a fuel. Renew Energy 2005;30:2189202.