Production of biodiesel from waste fryer grease using mixed methanol/ethanol system

Titipong Issariyakul, Mangesh G. Kulkarni, Ajay K. Dalai , Narendra N. Bakhshi

Catalysis and Chemical Reaction Engineering Laboratories, Department of Chemical Engineering, University of Saskatchewan, Saskatoon, Saskatchewan, Canada Accepted 30 April 2006

Abstract Transesterification of waste fryer grease (WFG) containing 56 wt.% free fatty acid (FFA) was carried out with methanol, ethanol, and mixtures of methanol/ethanol maintaining the oil to alcohol molar ratio of 1:6, and initially with KOH as a catalyst. Mixtures of methanol and ethanol were used for transesterification in order to use the better solvent property of ethanol and rapid equilibrium using methanol. Formation of soap by reaction of FFA present in WFG with KOH instigated difficulty in the separation of glycerol from biodiesel ester. To untangle this problem, two-stage (acid and alkali catalyzed) method was used for biodiesel synthesis. More than 90% ester was obtained when two-stage method was used compared to 50% ester in single stage alkaline catalyst. In the case of mixed alcohol, a relatively smaller amount of ethyl esters was formed along with methyl esters. Acid value, viscosity, and cetane number of all the esters prepared from WFG were within the range of the ASTM standard. Esters obtained from WFG showed good performance as a lubricity additive. Published by Elsevier B.V.
Keywords: Biodiesel; Lubricity; Transesterification; Waste fryer grease

1. Introduction Biodiesel has been defined as the mono alkyl esters of long chain fatty acids derived from renewable lipid feedstock, such as vegetable oils or animal fats. Biodiesel can be used as a substitute or an additive to diesel fuel. Compared to fossil-based diesel fuel, biodiesel possesses many advantages such as cleaner engine emissions, biodegradable, renewable and superior lubricating property [1]. In spite of the many advantages of biodiesel, it is not yet commercialized all over the world. The major problem is the cost of the raw material. Biodiesel obtained from neat vegetable oil is costly compared to the petroleum diesel fuel. Waste cooking oil is a promising alternative to

Abbreviations: WFG, Waste Fryer Grease; FFA, Free Fatty Acid; WME, Waste Fryer Grease Methyl Ester; WEE, Waste Fryer Grease Ethyl Ester; WMEE (3:3), Waste Fryer Grease Methyl Ethyl Ester prepared by reaction of WFG with 3:3 molar ratio of methanol to ethanol. Corresponding author. Tel.: +1 306 966 4771; fax: +1 306 966 4777. E-mail address: ajay.dalai@usask.ca (A.K. Dalai). 0378-3820/$ - see front matter. Published by Elsevier B.V. doi:10.1016/j.fuproc.2006.04.007

vegetable oil due to its reduced raw material cost. Restaurant waste oils and rendered animal fats are less expensive than food grade soybean oil [2]. Currently, all these waste oils are sold commercially as animal feed. But the European Union (EU) has put a ban since 2002 on feeding this mixtures to animal. The reason being, during frying many harmful compounds are formed and if the waste cooking oil is used as an additive to feeding mixtures for domestic animals then it would result in the return of harmful compounds back into the food chain through the animal meat [3]. Production of biodiesel from waste cooking oil is one of the better ways to utilize them efficiently and economically. Looking at the requirement of diesel fuel and availability of waste cooking oil, the biodiesel obtained from waste cooking oil can replace diesel fuel partially. In Canada, approximately 120,000 tonnes of yellow grease is produced per year [4]. Hence, a substantial amount of biodiesel fuel can be prepared from waste cooking oil, which would partly decrease the dependency on petroleum based fuel. In literature, many reports are available on the use of waste cooking oil for biodiesel production [1,3,5,6]. Used sunflower oil

was transesterified with methanol using alkaline catalysts such as KOH and NaOH and different molar ratios of methanol to oil (4.5:1, 6:1, and 9:1) [6]. The optimum conditions developed for production of good quality biodiesel from used sunflower oil were: molar ratio of methanol to oil 6:1, with 1% of KOH, at 25 C and reaction time of 30 min. Transesterification of processed waste cooking oil (citric acid was added to waste cooking oil to remove solids) and unprocessed waste cooking oil was carried out with methanol using KOH (1.75 wt.%) and 1:6 molar ratio of oil to alcohol at room temperature [7]. Excess catalyst was used to neutralize free fatty acids (FFA) present in waste cooking oil. The ester yield was 51 wt.% with processed waste oil and 58 wt.% with unprocessed waste cooking oil. A process was developed by Canakci [8] where the high free fatty acid (FFA) feedstock was initially treated using acidic catalyst to reduce the FFA level below 1%. The pre-treated feedstock with FFA less than 1% was then transesterified with methanol using alkaline catalyst. It was observed that two-step acid catalyzed esterification followed by alkaline catalyzed reaction improved the ester yield [8]. Methyl and ethyl esters of fatty acids are the most popular esters used as biodiesel. The methods of preparation of methyl and ethyl esters have their own advantages and disadvantages. In the case of methanolysis the solubility of oil in methanol is less and reaction is mass transfer limited. On the other hand, methanol makes higher equilibrium conversion due to higher reactive intermediate methoxide [9]. Unlike methanol, ethanol has better solvent properties and can be obtained from renewable resources. But the formation of emulsion after the transesterification of oil with ethanol makes the separation of ester very difficult. If mixture of methanol/ethanol is used for the transesterification reaction then this would take advantage of the better solvent properties of ethanol and desired equilibrium conversion using methanol. Also, esters obtained from mixture of alcohols may act as a good lubricity additive. Another advantage of using the mixture of methanol and ethanol is, if part of the methanol is replaced by ethanol, then there would be less dependency on the synthetic sources for methanol. The present work deals with the transesterification of WFG with methanol, ethanol and various mixtures of methanol and ethanol. Properties of methyl and ethyl esters prepared from various mixtures of methanol and ethanol were measured and compared with diesel fuel. Lubricity of the esters was also examined by M-ROCLE test using kerosene as a base fuel.
2. Materials and methods
Waste fryer grease (WFG) was obtained from Saskatoon Processing Co., Saskatoon, Saskatchewan. Anhydrous methanol (MeOH), 99.8%, and anhydrous ethanol (EtOH) were purchased from EMD Chemicals Inc., Darmstadt, Germany and Commercial Alcohol Inc., Brampton, ON, Canada respectively. Potassium hydroxide (KOH) from EMD Chemicals, Darmstadt, Germany and sulphuric acid (H2SO4) from EM Science, Darmstadt, Germany were used as catalysts in alkali and acid catalyzed reactions, respectively.

reaction. Solid portion of WFG was removed using a centrifuge. Water was removed by mixing WFG with 10 wt.% silica gel (28200 mesh) followed by stirring the mixture and vacuum filtration using Whatman filter paper (No. 40 Quantitative) for the removal of silica gel. This step was conducted twice to ensure complete removal of water.

2.2. Transesterification of WFG using alkali catalyst

Transesterification of WFG using alkaline catalyst was carried out using a two-step process. The two-step reaction utilized 100% excess methanol, 6:1 molar ratio of alcohol to oil and 1% KOH as a catalyst. In each step, 3 mol of alcohol and 0.5% KOH were used and reaction was carried out at 25 C for 30 min. After the first step the WFG having a high free fatty acid formed a thick soap which interfered with the glycerol separation. No further experiment was done with this method because of the saponification reaction.

2.3. Synthesis of biodiesel using two-stage (acid and alkali catalyzed) method
In order to avoid the problem of saponification, the two-stage method was used for synthesis of biodiesel from WFG. In the first stage, esterification of FFA present in WFG was carried out using sulphuric acid as a catalyst and in the second stage transesterification of neutral WFG was performed using KOH as a catalyst. Esterification of FFA was carried out as follows. A 50 g WFG was placed in a batch type reactor equipped with glass stopper, thermometer, and a magnetic stirrer. In another flask 2 wt.% of sulphuric acid with respect to WFG was mixed with alcohol (3:1 alcohol to WFG ratio plus 0.0088 mol extra alcohol for esterification of FFA in WFG) and then poured to the WFG. To avoid the evaporation of alcohols, the reaction temperature of 50 C was selected for methanol and mixture of alcohol and 60 C for ethanol. Depending on the decrease in acid value of WFG the esterification reaction was continued for 5 h. Water formed during the esterification reaction of free fatty acid and alcohol had an adverse effect during the alkali catalyzed transesterification reaction and was removed prior to the transesterification reaction. In order to remove water, the product of the esterification reaction was mixed with 10 wt.% silica gel and stirred for 15 min. After stirring, the mixture was filtered to remove the silica gel. Transesterification of neutral WFG was carried out using KOH as a catalyst. 1% KOH for transesterification with additional 1.144 g was properly mixed in alcohol to neutralize sulphuric acid and then poured to the reaction mixture. Transesterification reaction was carried out for 1 h at room temperature for methanol, and for mixture of alcohols and ethanol at 50 and 60 C, respectively.

2.4. Purification of ester

After transesterification the co-product glycerol was removed using a separating funnel. In the case of waste fryer grease ethyl ester (WEE) production, glycerol was not separated by gravity. To separate the glycerol from the ester phase, 12 g of pure glycerol was added to the reaction mixture and stirred for 15 min. The complete removal of glycerol was ensured by adding pure glycerol once for the upper layer and twice for the lower layer. The ester phase was then washed with hot distilled water to remove the catalyst. In the case of mixed esters and ethyl ester, the washing was done in a similar manner as done in methyl ester except that 0.1 wt.% tannic acid solution was used instead of distilled water in order to avoid the emulsion. Unreacted alcohol and water were removed using BCHI rotavapor at 90 C for 1.5 h. The complete removal of water and unreacted alcohol was confirmed by constant weight loss.

2.5. Ester characterization

The percentage of in purified ester phase was measured using highperformance liquid chromatography (HPLC), Hewlett-Packard 1100 series using refractive index detector and Phenogel 5u 100 A 300 7.80 mm 5 m column protected with guard column, equipped with ChemStation for LC 3D, Agilent Technologies. Tetrahydrofuran (THF) was used as a mobile phase. Fatty acid components of esters were identified using gas chromatographymass spectrometry (GCMS, Varian, Saturn 2000) with stabile wax column. Fatty acid composition of purified esters was measured using GC (Agilent 6890) with

2.1. Pre-treatment of WFG

The WFG obtained from Saskatoon processing co. was contaminated with water, solid particles, FFA and many other chemicals. Since water and FFA create a problem during transesterification, WFG was pre-treated before the

DB-23 column. Gas chromatograph-simulated distillation (Varian CP 3400 Gas chromatograph, specially configured for simulated distillation) was used to determine boiling point distribution of purified ester phase. The biodiesel esters were extensively characterized for their properties. Viscosity of esters was measured at 40 C using a Brookfield Digital viscometer Model DV-II. Water content of crude WFG and silica gel treated WFG was evaluated using a Karl Fisher Titrator (ATI ORION, 950 Ross). Fatty acid composition, acid value, heating value, cloud point, pour point, iodine number, and saponification number were determined as per the methods given in Table 1. Lubricity of the esters was measured by the Munson Roller on Cylinder Lubricity Evaluator (M-ROCLE) as per the method described by Lang et al. [10]. Cetane index and cetane number were measured by the methods given by Krisnangkura [11] and Patel [12] respectively.

Table 2 Properties of crude waste fryer grease Property Solid portion Total polar compounds Polymerized triglycerides Oxidized triglycerides Acid value Free fatty acid (FFA) Water content Saponification value Value 19% 22% 1.43% 4.72% 11.2 mg KOH g 1 5.6% 7.3% 177.87 mg KOH g 1 Method AOCS Cd 20-91 IUPAC, 2.508 (1987) IUPAC, 2.508 (1987) AOCS Te 1a-64 Karl Fischer method AOCS Cd 3-25

3. Results and discussion Properties of crude WFG are shown in Table 2. Initial water content of WFG was 7.3% w/w and after silica gel treatment the water content was reduced to 0.2 0.1% w/w. Crude WFG contains 5.6% free fatty acids which made alkaline catalyzed transesterification impractical. Apart from water and FFA, WFG was contaminated with various other chemicals due to exposure of cooking oil to a high temperature for a long period. Hence, the total polar content of WFG was 22%, which was much higher than that in the neat vegetable oil (0.46.4 mg/100 g) [13]. Due to the exposure of the cooking oil to a higher temperature for a long period of time some triglycerides got oxidized. Oxidized triglyceride content of WFG was 4.72%. Due to the same reason, some of the triglycerides got polymerized and the content of polymerized triglycerides in WFG was 1.43% (see Table 2). 3.1. Ester preparation As discussed earlier, in order to avoid the problem of saponification, two-stage method was used for the preparation of biodiesel from WFG. In the first stage, esterification of FFA in WFG was done using sulphuric acid as a catalyst. The decrease in acid value with time is shown in Fig. 1. The acid value of crude WFG was 11.2 and after 5 h of esterification the acid value decreased from 25 (this is due to addition of sulphuric acid) to 15. Since there was no significant decrease in acid value after 5 h, the first stage of esterification was stopped after 5 h. After the first stage, the transesterification of WFG was carried out using KOH as a catalyst. The amount of the ester phase collected after purification is shown in Table 3. When ethanol was used, the glycerol was not separated properly and hence, the amount of ester phase recovered was as low as
Table 1 Standard methods applied for ester characterization Property of esters Fatty acid compositions Acid value Heating value Cloud point Pour point Iodine number Saponification number Test method AOCS method Ca 5a-40 AOCS method Te 1a-64 ASTM D240-92 ASTM D2500 ASTM D97 AOCS method Tg 1-64 AOCS method Cd 3-25

31 g when 50 g of WFG was used for the reaction. Since there was no emulsification problem when methanol and mixtures of methanol/ethanol were used and the glycerol layer was separated easily, the weight of the ester phase collected was more than that of the ethyl ester phase (Table 3). Percentage of ester in ester phase as determined by HPLC was in the range of 8897% (Table 3). The HPLC analysis of crude WFG indicated the peak for polymerized triglycerides and after transesterification these polymerized triglycerides were converted to the dimeric or trimeric ester. In the present work, only pure esters were quantified and attempts were not made to quantify polymerized esters. Fatty acid components of WFG esters were detected by GCMS (Figs. 24). GCMS analysis showed that major fatty acid components in all esters were myristic acid (C14:0), palmitic acid (C16:0), palmitoleic acid (C16:1), stearic acid (C18:0), oleic acid (C18:1), linoleic acid (C18:2), linolenic acid (C18:3), arachidic acid (C20:0), eicosenoic (C20:1), and behenic acid (C22:0) with major contribution by oleic acid in all the esters. Fig. 4 shows that when WFG was transesterified with mixture of methanol/ethanol (3:3) {WMEE (3:3)} along with methyl, ethyl esters were also formed. Similar observation was also made with other mixtures of methanol and ethanol. The fatty acid composition of all the esters is presented in Table 4. All the esters showed oleic acid ( 51.1%) as a dominant fatty acid. In the case of WMEE (3:3), ethyl esters formed during transesterification were approximately 45% those of methyl esters i.e., the formation of ethyl esters was less compared to methyl. This can be explained by the fact that the reactivity of methoxide radicals is higher than that of ethoxide radicals [9]. In the case of esters formed by

Fig. 1. Acid value of WFG during esterification with methanol.

Table 3 Purified ester phase recovered from 50 g of WFG and ester percentage in ester phase by HPLC Ester WME WMEE (3:3) WMEE (3.5:2.5) WMEE (4:2) WMEE (4.5:1) WMEE (5:1) WEE Purified ester phase recovered (g) 41 41 42 43 45 45 31 Ester content in ester phase by HPLC (%) 96 88 91 94 91 94 97

3.2. Esters characterization 3.2.1. Acid value Acid value is defined as milligrams of potassium hydroxide necessary to neutralize fatty acids in 1 g of sample. Acid value of crude WFG was very high (11) but by using two-stage method, the acid value of WFG was reduced substantially to 1 and after transesterification the acid value of esters was within the limit of the ASTM standard (0.8 mg KOH g 1) as shown in Table 5. 3.2.2. Viscosity Viscosity of WFG was very high at 87.06 mm2/s. Higher viscosity of WFG was due to the presence of higher molecular weight molecules such as triglycerides, polymerized triglycerides and many other unknown heavier compounds formed during frying. After transesterification, esters showed substantial reduction in viscosity in the range of 4.685.89 mm2/s and met the ASTM standard of 1.96.0 mm2/s. There was not much difference in viscosity of methyl, ethyl and various mixtures of methyl/ethyl esters. Viscosity of biodiesel esters was 34.869.7% higher than that of reference diesel #2 (Table 5). But at 5% addition of biodiesel to the diesel fuel (B5) higher viscosity of biodiesel will not make much difference. It is reported in the literature that methyl esters obtained from heated rapeseed oil have no negative influence on engine performance [14].

reaction of WFG with 3.5:2.5, 4:2, 4.5:1.5, 5:1 molar ratio of methanol to ethanol, the percentage of ethyl esters of various fatty acids formed is compared to methyl esters. The percentage of ethyl esters formed along with methyl esters is as follows. Myristic acid 56, 45, 30, and 28%, palmitic acid 35, 27, 17, and 12%, palmitoleic acid 47, 36, 30, and 19%, stearic acid 51, 44, 33, and 28%, oleic acid 36, 28, 17, and 12%, linoleic acid 35, 29, 19, and 15%, linolenic acid 35, 28, 18, and 14%, arachidic acid 39, 29, 19, and 17%, and eicosenoic acid 36, 27, 17, and 13% when esters are prepared with 3.5:2.5, 4:2, 4.5:1.5, 5:1 molar ratio of methanol to ethanol, respectively. When methanol to ethanol molar ratio was increased less ethanol molecules were available for transesterification and ultimately less ethyl esters were formed.

Fig. 2. GCMS chromatogram of waste fryer grease methyl esters (WME).

Fig. 3. GCMS chromatogram of waste fryer grease ethyl esters (WEE).

3.2.3. Heating value Heating value is another important property of ester as it is aimed for use as diesel fuel substitute. Heating value of esters

was not much different from their parent oil waste fryer grease which ranged from 37.27 to 40.72 MJ/kg. These values were approximately 10% less than those of reference diesel #2

Fig. 4. GCMS chromatogram of waste fryer grease methyl ethyl ester (WMEE (3:3)).

Table 4 Fatty acid composition (wt.%) of esters prepared from WFG. Fatty acid Myristic (C14) Palmitic (C16) Palmitoleic (C16:1) Stearic (C18) Oleic (C18:1) Linoleic (C18:2) Linolenic (C18:3) Arachidic (C20) Eicosenoic (C20:1) Behenic (C22:1) Others
a

WME Methyl Ethyl Methyl Ethyl Methyl Ethyl Methyl Ethyl Methyl Ethyl Methyl Ethyl Methyl Ethyl Methyl Ethyl Methyl Ethyl Methyl Ethyl 0.42

WEE 0.41

WMEE (3:3) 0.33 0.19 6.66 2.46 0.67 0.34 4.26 2.48 36.96 14.57 9.01 3.69 2.08 0.87 0.42 0.18 0.73 0.31 0.21 N.I. 13.58

WMEE (3.5:2.5) 0.32 0.18 6.56 2.32 0.68 0.32 4.52 2.31 38.30 13.73 9.68 3.37 2.19 0.77 0.44 0.17 0.78 0.28 0.24 N.I. 12.84

WMEE (4:2) 0.33 0.15 6.90 1.91 0.73 0.26 4.74 2.07 40.63 11.39 10.14 2.89 2.38 0.66 0.48 0.14 0.81 0.22 0.24 N.I. 12.93

WMEE (4.5:1.5) 0.37 0.11 7.50 1.26 0.79 0.24 5.15 1.69 44.15 7.58 10.73 2.06 2.62 0.48 0.53 0.10 0.90 0.15 0.27 N.I. 13.32

WMEE (5:1) 0.39 0.11 7.83 0.94 0.83 0.16 5.35 1.49 46.07 5.67 10.98 1.65 2.71 0.37 0.53 0.09 0.94 0.12 0.27 N.I. 13.50

8.64 8.22 0.91 0.89 5.92 5.61 51.12 48.83 11.68 10.94 2.98 2.68 0.59 0.56 1.02 0.97 0.31 16.41 N.I. a 20.89

N.I. = not identified.

(Table 5). These data indicate that approximately 10 vol.% more biodiesel would be required compared to regular diesel fuel for the travel of the same distance. 3.2.4. Cloud and pour point Cloud point is the temperature at which a cloud of wax crystals first appears in the oil when it is cooled. Pour point is the lowest temperature at which the oil specimen can still be moved. Cloud point and pour point are used to measure the cold temperature usability of ester as fuel. Cloud point of esters was in the range of 1 to 2 C while pour point range was 3 to 6 C. There was a decrease in cloud and pour
Table 5 Properties of WFG esters compared to those of diesel fuel #2 and ASTM standard Sample Acid value Heating Density Viscosity Cloud Pour [mg KOH g 1] value @ 15 C @ 40 C point [C] point [MJ/kg] [g/cc] [mm2/s] [C] 40.17 37.27 40.72 40.05 40 40 40.1 39.82 45.47 N/A a 0.912 0.8822 0.8548 0.8873 0.8553 0.8778 0.8721 0.8862 0.845 N/A 87.06 4.68 4.98 5.89 5.66 5.04 5.38 4.94 3.47 1.96.0 1 2 1 1 0 0 1 5 N/A 3 6 4 4 4 3.5 3 15 N/A

point of mixed esters with a decrease in molar ratio of methanol to ethanol. Cloud and pour points of methyl ester were higher than their corresponding ethyl ester. These results fit well with a previous work [15]. Cloud point and pour point of the reference diesel fuel #2 were 5 and 15 C, respectively, which were much lower than those of WFG esters (Table 5). Higher cloud and pour points of esters may be due to the presence of some unknown compounds in WFG and formation of polymerized esters during transesterification. From these results it is clear that WFG esters would be a suitable candidate as a diesel fuel substitute in tropical countries and not in colder climate conditions such as in Canada. However, winterization of WFG or some additives may be necessary for the application of esters in cold temperature. 3.2.5. Iodine value The iodine value is a measure of unsaturation of oils and is expressed in terms of the number of cg of iodine absorbed per g of sample (% iodine absorbed). Iodine value is important to
Table 6 Iodine value, saponification value, cetane index, and cetane number of WFG and biodiesel esters Sample WFG WME WEE WMEE (3:3) WMEE (3.5:2.5) WMEE (4:2) WMEE (4.5:1.5) WMEE (5:1) Iodine value 94.50 85.83 82.56 84.57 81.42 82.42 82.68 83.24 Saponification value 174.47 174.35 169.70 171.37 170.68 172.30 173.75 174.47 Cetane index 55.72 58.29 59.89 59.12 59.96 59.43 59.11 58.85

WFG 11 WME 0.5 WEE 0.8 WMEE 0.7 (3:3) WMEE 0.6 (3.5:2.5) WMEE 0.7 (4:2) WMEE 0.4 (4.5:1.5) WMEE 0.3 (5:1) Diesel #2 0.002 ASTM 0.8
a

N/A = not available.

Table 8 M-ROCLE lubricity tests for esters prepared from WFG Fuel additive (1 vol.% in kerosene) BASE WME WMEE (3:3) WEE Coefficient of friction 0.117 0.114 0.114 0.113 Wear scar area (mm2) 0.338 0.294 0.265 0.293 Lubricity number 0.689 0.818 0.916 0.823

Hence, it is clear that all the esters prepared from WFG have good combustion quality.
Fig. 5. Boiling point vs. % off of waste fryer grease (WFG), waste fryer grease methyl ester (WME), waste fryer grease ethyl ester (WEE) and waste fryer grease methyl ethyl ester WMEE (3:3).

measure the oxidative stability of oil. Type of parent oil is the major parameter affecting the iodine value of the esters. Iodine value of WFG was very high (94.5). Since all esters were prepared from WFG, iodine values of the esters were close to those of the WFG and were in the range of 81.42 to 85.83 as shown in Table 6. The difference between methanol and ethanol used in transesterification didn't show a significant impact on iodine value. 3.2.6. Saponification value Saponification value is the amount of alkali necessary to saponify a definite quantity of sample and is expressed as the mg of potassium hydroxide (KOH) required to saponify 1 g of sample. Again, there was no significant difference in saponification value among esters prepared from WFG. Saponification values of esters were within the range of 169.70 to 174.47 (Table 6). 3.2.7. Cetane index Cetane index is used to evaluate combustion quality of esters. The higher the cetane index, the better the quality of esters as diesel fuel. Cetane index of all the esters prepared from WFG was within the range of 58.29 to 59.96 as shown in Table 6. Cetane index of methyl, ethyl and various mixtures of methyl/ethyl esters was almost the same. Cetane number is not much different from cetane index. The correlation reported by Patel [12] is given below: Cetane number cetane index 1:5 to 2:6: 1

3.2.8. Boiling point distribution Boiling point distributions of WFG, WFG esters, diesel fuel and kerosene base fuel are shown in Fig. 5. Waste fryer grease (WFG) showed higher boiling points than its esters, i.e., waste fryer grease methyl ester (WME), waste fryer grease ethyl ester (WEE), and waste fryer grease methylethyl ester {WMEE (3:3)}. This can be interpreted as the fact that large molecules, such as acylglycerols and polymerized materials present in WFG got converted into smaller molecules, i.e. esters after transesterification. Boiling point distributions of all the esters were approximately the same. Diesel fuel and kerosene were more volatile than WFG esters and boiling point of base fuel kerosene was much lower than that of the diesel fuel. But at 90% off the boiling points of WFG esters matched with that of diesel fuel. 3.2.9. Lubricity number Since the advent of ultra-low sulphur diesel fuel demand to meet environmental regulations, the sulphur removal process has been introduced in the petroleum industry. But ultra-low sulphur, unadditized diesel fuel has very poor fuel lubricity, resulting in a shorter diesel injection pump and engine lives. This is due to the fact that the processes such as hydrotreating in petroleum refineries that remove sulphur from diesel fuel also remove heterocyclic nitrogen and oxygen compounds that are known to provide the fuel with lubricity [16]. To restore the lubricity of diesel fuel refiners regularly add various lubricity additives in the diesel fuels. Fatty acid esters can act as a lubricity additive for diesel fuel. The dimensionless lubricity number ( LN) is used to determine how well a fuel provides lubrication to the engine and is calculated based on the roller wear scar stress, the elastic contact stress, and the coefficient of friction. The calculation and detailed method have been comprehensively described in a previous work [10]. In the present work, 1 vol.% of WME, WEE, and WMEE (3:3) were added to kerosene base fuel and lubricity was measured. Properties of the kerosene base fuel are shown in Table 7. Coefficient of friction, wear scar area, and lubricity number of kerosene base fuel treated at 1 vol.% of WME, WEE, and WMEE (3:3) are shown in Table 8. All the three esters showed substantial improvement in the lubricity. With 1 vol.% addition of WME, WEE and WMEE (3:3) to kerosene base fuel, lubricity numbers of the treated fuel were increased from 0.689 to 0.818, 0.916, and 0.823, respectively (Table 8). The LN of WMEE (3:3) was higher compared to

According to this correlation, all esters meet the ASTM standard {D 6751-02} ( 47) specified for the cetane number.

Table 7 Properties of the kerosene base fuel Fuel property Viscosity @ 40 C Density @ 15 C Acid value Heating value Lubricity number Value 1.33 mm2/s 0.775 g/ml 0.2 mg KOH g 1 44.32 MJ/kg 0.689

WME and WEE. The higher LN of WMEE (3:3) may be the contribution of some unknown compounds present along with the ester. At 1 vol.% treat rate of WMEE (3:3) in reference fuel kerosene, lubricity number of treated fuel showed an improvement of 33%. The wear scar and coefficient of friction also decreased substantially by addition of 1 vol.% of WFG esters in kerosene. 4. Conclusions WFG is an economic source for biodiesel production, yet the negative impact of free fatty acid (FFA) and water contained in WFG on transesterification method is still far from trivial. Appropriate pre-treatments are required in order to make WFG become a good feedstock for biodiesel production. Two-stage method for transesterification of WFG was found to be satisfactory in the preparation of biodiesel. Mixed methanolethanol system was used in order to use better solvent properties of ethanol and equilibrium conversion using methanol. In the case of mixed alcohol, along with methyl, ethyl esters were also formed in smaller amounts due to its less reactive intermediate ethoxide. Type of alcohol used in transesterification has a trivial effect on ester properties except for cloud point and pour point. Ethyl esters are better compared to methyl ester in terms of low temperature properties (cloud point and pour point). Biodiesel esters derived from WFG retain properties that meet the ASTM standard D6751-02 and comparable to those of reference diesel #2 except for the low temperature properties. Lubricity of the base fuel kerosene was improved by WFG esters. The lubricity of WMEE-treated fuel was better than that of WME and WEE-treated fuel. Higher cloud and pour points of WFG esters would make their use as diesel fuel substitute impractical in cold countries like Canada. But when used at 1 vol.% as a lubricity additive, then higher cloud and pour points of WFG esters would not be a major problem. Further investigation on lubricity of the mixed esters is being pursued. Acknowledgements The financial support for this project from BIOCAP, Canada and Natural Sciences and Engineering Research Council of

Canada (NSERC), Natural Resources Canada (NRCAN), AUTO21 Network of Centres of Excellence and Canada Research Chair (CRC) funding to Dr. A.K. Dalai is gratefully acknowledged. References
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