Fuel 95 (2012) 214220

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Fuel
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Evaluation of leather industry wastes as a feedstock for biodiesel production

Ertan Alptekin a,b, Mustafa Canakci a,b,, Huseyin Sanli b,c
a

Department of Automotive Engineering Technology, Kocaeli University, 41380 Kocaeli, Turkey Alternative Fuels R&D Center, Kocaeli University, 41275 Kocaeli, Turkey c Golcuk Vocational High School, Kocaeli University, 41650 Golcuk, Turkey
b

a r t i c l e

i n f o

a b s t r a c t
In this study, animal fat obtained from leather industry eshing wastes was used to produce methyl ester. The acid value of the eshing oil was 24.30 mg KOH g1 which corresponds to FFA level of about 12.15%. Therefore, it was needed to perform a pretreatment to the eshing oil. For this aim, sulfuric acid was used as a catalyst and methanol was used as alcohol for pretreatment reactions. The variables affecting the FFA level including alcohol molar ratio and catalyst amount were investigated by using the eshing oil. After reducing the FFA level of the eshing oil to less than 1%, the transesterication reaction was completed with alkaline catalyst. Potassium hydroxide, sodium hydroxide, potassium methoxide and sodium methoxide were used as catalyst and methanol was used as alcohol for transesterication reactions. The effects of catalyst type, catalyst amount and alcohol molar ratio on the fuel properties of produced methyl esters were investigated. The measured fuel properties of the eshing oil methyl ester (FOME) were compared to EN 14214 and ASTM D6751 biodiesel standards. According to results, the cold ow properties of FOME should be improved and the sulfur content of FOME should be investigated in detail. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 27 June 2011 Received in revised form 12 August 2011 Accepted 24 August 2011 Available online 9 September 2011 Keywords: Fleshing oil Alkaline catalyst Pretreatment Transesterication Biodiesel

1. Introduction Leather industry has an important role for countries economy in the light of its large scale of potential for employment, growth and exports. Turkish leather industry has taken a prominent place of the world leather trade with its high export productivity. There are 13 Leather Industrial Organized Zones functioning in Turkey and those are generally localized in the Marmara and Aegean regions [1]. The leather industry commonly uses hides and skins as raw materials, which are the by-products of meat and meat products industry. The leather industry is one of the considerably polluting industries and it produces highly quantity of fat-originated solid and liquid wastes while processing hides and skins [2]. These wastes cause environmental problems and must be utilized. Most of the solid waste in the leather production process is originated in the pre-tanning stages which are pre-eshing, eshing, shaving and trimming. Pre-eshing process is carried out so as to remove esh and to promote the penetration of the chemicals for better leather products. The fat content of the leather industry wastes is remarkable. However, these wastes are not evaluated effectively and there is almost no application method to recover these wastes.
Corresponding author at: Department of Automotive Engineering Technology, Kocaeli University, 41380 Kocaeli, Turkey. Tel.: +90 262 3032202; fax: +90 262 3032203. E-mail addresses: mustafacanakci@hotmail.com, canakci@kocaeli.edu.tr (M. Canakci).
0016-2361/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2011.08.055

One way to recover the leather industry wastes is using them as feedstock in biodiesel production due to their rich fat content [36]. Thus, the pollution caused from the leather industry wastes may be reduced and more valuable products can be obtained by converting them to biodiesel for countries like Turkey where there is a developed leather industry. Biodiesel is nontoxic, biodegradable and environmentally friendly fuel and it is an alternative fuel for diesel engines. Due to environmental benets of biodiesel, there are incentives about tax of biodiesel fuels. When B2 (2% biodiesel, 98% diesel fuel) is used in diesel engines, the biodiesel is excise tax free in Turkey. In general, biodiesel is produced from high quality food-grade vegetable oils. Using high-quality virgin oils makes biodiesel more expensive than diesel fuel. Therefore, low cost feedstocks are needed. Rendered animal fats, leather industry wastes and restaurant waste oils are appealing feedstocks to produce biodiesel. However, they often contain signicant amounts of free fatty acid (FFA). The fats with high FFA cannot be converted to biodiesel using alkaline catalysts. FFAs react with an alkaline catalyst and thus soaps are produced by this reaction. Soaps prevent the separation of the ester, glycerin and wash water [7]. This problem results in a diminished biodiesel yield. Acid catalysts are too slow to be suitable for converting triglycerides to biodiesel. However, they appear to be quite effective at converting FFAs to esters [8]. For these reasons, an acid catalyst can be used to esterify the FFAs to esters. The acid-catalyzed process is called as pretreatment. FFAs are converted to esters through the pretreatment of the feedstock with high FFA and thereby the FFA level

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reduces. The most commonly preferred catalysts are sulfuric, sulfonic, and hydrochloric acids as acid catalysts, and sodium hydroxide (NaOH), sodium methoxide (NaOMe), potassium hydroxide (KOH) and potassium methoxide (KOMe) as alkaline catalysts. Water is formed when KOH and NaOH are used to produce the methoxide. Water limits the completion of transesterication reaction. Therefore, industrial biodiesel processes run on alkoxides such as NaOMe and KOMe which can be bought as liquid form. They do not contain water and are usually commercially available as ready-to-use methanol solution [9]. Many researchers have investigated the availability of animal fats and waste oils for biodiesel production [1016]. However, almost no researchers have worked on the eshing oil especially with high FFA. Colak et al. [6] used the fat released from pre-eshings of sheep skins by boiling with water under high speed grinding. Because the FFA value of the eshing oil was about 1.2%, they did not perform a pretreatment reaction for the eshing oil. They used methanol and KOMe (30% in methanol) for transesterication and obtained high ester yield up-to 95%. Kolomaznik et al. [17] evaluated the leather industry tannery wastes for biodiesel production. The acid value of waste tannery fat was 10.6 mg KOH g1. They carried out the transesterication of the waste tannery fat with only KOH and methanol. However, the conversion to methyl ester was about 40% which was considerably low due to high FFA content of the fat. Therefore, they preferred tetramethylammonium hydroxide for esterication of FFA and obtained better re_ sults. Isler et al. [3] produced biodiesel from leather industry waste eshing fats. The acid value of the fat was 0.28 mg KOH g1. Therefore, the eshing fat was converted to biodiesel via transesterication. They used NaOH and methanol for determining optimum transesterication conditions to produce biodiesel. The fuel properties of the eshing oil biodiesel t the EN 14214 biodiesel standard specications except for cold plugging lter point and oxidation stability. The purpose of the present study was to produce biodiesel from the eshing oil with high FFA. Therefore, the optimization of pretreatment reaction was investigated with different acid catalyst amounts and alcohol molar ratios. After the optimum pretreatment parameters were determined, the optimization of biodiesel production from the eshing oil was investigated with different alkaline catalysts, catalyst amount and alcohol molar ratios. The methyl esters were characterized by determining its fuel properties according to the standard test methods.

generally between 5% and 25% [8]. The feedstock which has high FFA can cause foaming during transesterication. The researchers have suggested that the FFA level of the feedstock should be reduced to less than 1% before using an alkaline catalyst [18,19]. This was the initial target for the pretreatment. Because the acid value of the eshing oil was greater than 2 mg KOH g1, it was needed to perform a pretreatment to the feedstock. Some properties of the eshing oil are shown in Table 1a. The fatty acid composition of the eshing oil and other feedstocks are given in Table 1b. 2.1. Pretreatment and transesterication process Sulfuric acid (purity = 98%) was used as catalyst and methanol (purity P 99.7%) was used as alcohol for the pretreatment of the eshing oil. The esterication process of FFAs was repeated for different alcohol molar ratios and amounts of acid catalysts based on the FFA level of the eshing oil for 1 h at 60 C. In the calculations, the molecular weight of the FFA was calculated to be the average molecular weight of the fatty acids in the eshing oil. The experiments were performed in a laboratory scale apparatus. The eshing oil was added into the reaction ask equipped with reux condenser, magnetic stirrer and thermometer, and then it was heated. When the temperature reached to 60 C, the alcoholacid catalyst mixture was added into the fat. The nal mixture was stirred for 1 h at 60 C. The mixture was settled overnight and two phases was occurred. The upper phase consists of the alcoholwateracid mixture and the other phase mainly consists of the esteried fatty acids and unreacted eshing oil. The upper phase was separated from the other phase. After this step, the lower phase was subjected to a heating at 110 C for one hour to remove any remaining alcoholwater and it was ltered. The acid value of the fatester mixture was measured and recorded. In this study, KOMe solution (3035% in methanol), NaOMe solution (30% in methanol), KOH (purity = 85%) and NaOH (purity P 99%) were used as the catalysts for transesterication reactions to investigate the effect of catalyst type on the fuel properties of biodiesel. The catalyst amount was selected as 0.5%, 0.75% and 1% of the weight of the initial amount of fat in the eshing oil for KOH and NaOH catalysts while catalyst amounts were 0.35%, 0.70% and 1% of the weight of the initial amount of fat for KOMe and NaOMe. Additionally, neutralization amount was used, which was calculated from the Ref. [23]. Molar ratio between alcohol and fatester mixture was selected as 4.5:1, 6.0:1 and 7.5:1 for the transesterication reaction. Mean molecular weight of the eshing oil was found to be about 850 g mol1 according to the fatty acid composition for transesterication reactions. The transesterication process and laboratory apparatus were the same as those of pretreatment experiments except for catalyst. The reaction temperature was selected as 60 C, and reaction time was selected as 1 h. After the transesterication reaction, the glycerin layer was separated in a separating funnel and the ester layer was washed with warm water. After washing process, the methyl ester was subjected to a heating at 110 C to remove excess alcohol and water, and then ltered. The produced methyl esters were characterized in the Fuel Laboratory of the Department of Automotive Engineering Technologies (FLDAET), Alternative Fuels Research and Development Center in Kocaeli University (AFRDC) and Marmara Research Center The Scientic and Technological Research Council of Turkey (MRC-TUBITAK). The test methods used to determine the properties of the methyl esters are given below (unless otherwise stated, the tests were done in AFRDC); Density at 15 C (ASTM D4052), viscosity at 40 C (ASTM D445), ash point (ASTM D93), sulfur content (ASTM D2622), ester content (EN 14103 determined in MRC-TUBITAK), water content (EN ISO 12937), carbon residue (ASTM D4530), iodine value (EN 14111 determined in FLDAET), mono-, di- and tri-glyceride,

2. Materials and methods In this study, the eshing oil was obtained from the solid wastes recycle plant in Istanbul Leather Organized Industry, Istanbul-Turkey, where the eshing wastes are transformed into liquid form by an industrial process. The fat was in solid state at room temperature and it was subjected to a heating at 110 C for one hour to remove water and then ltered to remove the insoluble materials. The FFA level of the rendering plant feedstock is

Table 1a Some properties of the eshing and pretreated eshing oils. Property Density (at 25 C) Kinematic Viscosity (at 40 C) Acid value Water content Heat of combustion Iodine value Sulfur content Unit kg m3 mm2 s1 mg KOH g1 (% mass) kJ kg1 g l.100 g1 ppm Fleshing oil 907.1 43.33 24.30 0.3 39,572 75 >990 Pretreated eshing oil 902.2 24.91 1.52 0.3 39,270 68 >990

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Table 1b Fatty acid distribution of eshing oil, animal fats and vegetable oils. Product Fatty acid distribution C14:0 Fleshing oil PFOa FOMEb Fleshing oil (I) Fleshing oil (II) Chicken fat (I) Chicken fat (II) Rapeseed oil Sunower oil Soybean oil Yellow grease Brown grease
a b

Refs. C16:0 27.25 27.80 27.76 28.40 20.59 25.20 24.00 3.49 6.08 10.58 23.24 22.83 C16:1 5.10 5.05 4.95 8.10 4.60 7.80 5.80 3.79 3.13 C17:0 0.94 0.96 0.97 0.11 1.00 0.55 C18:0 13.23 13.27 13.40 10.67 8.36 5.90 5.80 0.85 3.26 4.76 12.96 12.54 C18:1 42.06 41.43 41.16 43.83 41.08 40.50 38.20 64.40 16.93 22.52 44.32 42.36 C18:2 2.04 2.09 2.19 1.80 2.97 18.40 23.80 22.30 73.73 52.34 6.97 12.09 C18:3 0.16 0.16 0.16 0.70 1.90 8.23 8.19 0.67 0.82 C20:0 0.21 0.21 0.22 0.84 0.10 0.36 0.14 0.20 [3] [6] [20] [21] [22] [22] [8] [8] [8]

C14:1 1.27 1.23 1.23 2.16 0.20

3.18 3.25 3.29 4.20 3.05 0.70 0.50 2.43 1.66

PFO: Pretreated eshing oil. FOME: Fleshing oil methyl ester.

Fig. 1. Effect of catalyst and methanol amount on the acid value of pretreated eshing oil.

total-free glycerin (EN 14105 determined in MRC-TUBITAK), methanol content (EN 14110), cold lter plug point (ASTM D6371), acid value (AOCS Cd 3a-64 determined in FLDAET), copper strip corrosion (ASTM D130 determined in FLDAET) and heat of combustion (ASTM D240). 3. Results and discussion After reducing the FFA level of the eshing oil to below 1%, transesterication reaction was completed with alkaline catalysts. In our previous study [24], it was clear that most of fuel properties such as ash point, acid value, methanol content, heat of combustion, copper strip corrosion and cold ow properties did not change signicantly with the reaction parameters (catalyst type, reaction temperature and reaction time). These reaction parameters especially affect viscosity and glyceride values. Therefore, in this study, the viscosity, density and ester yield values of produced FOMEs were determined at rst. Then, optimum reaction parameters were selected according to these values. Lastly, other fuel properties of FOME were characterized according to optimum reaction parameters. 3.1. Pretreatment of the eshing oil Sulfuric acid was used for the pretreatment of the eshing oil. The esterication process was repeated for different alcohol molar ratios (20:1, 30:1) and amounts of sulfuric acid (1%, 3%, 5%, 10%, 15%) based on the acid value of the eshing oil for 1 h reaction at 60 C. The initial experiments were performed with 1% sulfuric

acid and different methanol molar ratios. However, the acid value was only reduced to 22.12 mg KOH g1 with using 1% sulfuric acid and methanol molar ratio of 30:1. Therefore, greater amount of sulfuric acid were used. As shown in Fig. 1, the acid value of the eshing oil decreases with rising of sulfuric acid amount and methanol ratio in the pretreatment reaction. The acid value was reduced to 2.74, 1.90, 1.52 and 1.43 mg KOH g1 for 3%, 5%, 10% and 15% sulfuric acid with methanol molar ratio of 30:1, respectively. There is almost no difference between 10% and 15% sulfuric acid catalyzed pretreatments with methanol molar ratio of 30:1. The pretreatment with 10% sulfuric acid based on FFA level of the eshing oil and methanol molar ratio of 30:1 for 1 h at 60 C was thought to be sufcient for reducing acid value of the eshing oil less than 2 mg KOH g1 to get high ester yield after transesterication. Thus, these reaction parameters were selected for pretreatment. Some properties of the eshing oil and pretreated eshing oil was characterized to understand the effect of pretreatment on properties of eshing oil. The acid value of the eshing oil was reduced from 24.30 to 1.52 mg KOH g1. The viscosity, density, heat of combustion and iodine value of the eshing oil was reduced by pretreatment reaction. He et al. [25] stated that the sulfur content of animal fat may be high compared to vegetable oils. Also, in this study, the sulfur content of eshing oil was above 990 ppm which is the maximum measurement value of the sulfur analyzer. This means that sulfur content of the feedstock is important to get low sulfur content biodiesel after transesterication as will be stated in the characterization of fuel properties of the eshing oil methyl ester. 3.2. Density Density of a fuel directly affects the engine performance characteristics. Many performance characteristics such as cetane number and heating value are related with the density [2628]. Figs. 2a and 2b present the density values of the methyl esters produced from the eshing oil with KOH and NaOH catalysts. Generally, the density of FOME decreases with increasing the catalyst amount and methanol molar ratio. There is no signicant difference among the densities for transesterication reactions catalyzed with KOH and NaOH catalysts. The densities of FOMEs produced with KOH and NaOH are in the range of 875.2883.0 kg m3. The density of the eshing oil and pretreated eshing oil was measured at 25 C because they were in solid form at room temperature. After transesterication reactions, there were two phases as glycerin and ester layer. However, glycerin phase did not exist for KOMe and NaOMe catalyzed transesterication reactions except for 1% NaOMe catalyzed transesterication reactions. This

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means that the transesterication reaction was not completed. Therefore, the densities of methyl esters produced with KOMe and NaOMe catalysts were measured at 25 C, which were in solid form at room temperature. The densities of FOMEs produced with KOMe and NaOMe catalysts except for 1% NaOMe catalyzed transesterication reactions are in the range of 900.9901.5 kg m3. Therefore, these results were not shown in gures. For 1% NaOMe catalyzed transesterication reactions, the densities of FOMEs were 893.9, 892.0 and 892.2 for 4.5:1, 6.0:1 and 7.5:1 methanol molar ratios, respectively. In our previous study [24], the amount of NaOMe and KOMe catalysts were increased to up-to 2% for producing biodiesel from animal fat with high FFA. However, we obtained better results for KOH catalyzed reactions compared to NaOMe and KOMe catalyzed reactions like in the present study. 3.3. Viscosity Some of the physical properties limit the use of biodiesel in diesel engines, especially the viscosity [29]. The viscosity inuences the quality of combustion [3032]. Low viscosity can cause leakage in the fuel system, while high viscosity causes poor fuel atomization and incomplete combustion, increases the engine deposits [29,3335]. The viscosity values of the methyl esters produced from the eshing oil for transesterication reactions catalyzed with KOH and NaOH are illustrated in Figs. 3a and 3b. In general, the viscosity of FOMEs decreases with the increasing catalyst amount and methanol molar ratio. However, only a few FOMEs t the biodiesel viscosity standard according to EN 14214 as seen in Table 2a. The viscosities of FOMEs produced with KOMe and NaOMe catalysts except for 1% NaOMe catalyzed transesterication reactions are in the range of 23.9525.30 mm2 s1 which are close to that of the pretreated eshing oil. For 1% NaOMe catalyzed transesterication reactions, the viscosities of FOMEs were 14.40, 13.38 and 13.68 mm2 s1 for 4.5:1, 6.0:1 and 7.5:1 methanol molar ratios, respectively. 3.4. Ester yield Ester yield is one of the most important parameters, which affects the biodiesel cost. Ester yield was calculated by dividing the ester amount to the pretreated fat amount used for transesterication. The gathered ester yield results for KOH catalyzed transesterication are shown in Fig. 4a. The ester yield increased with the increasing of methanol molar ratio but the ester yield did not change signicantly for all reactions. Higher ester yields up-to 93.6% were obtained at KOH catalyzed reactions. After transesterication, ester and glycerol layer which was in solid form did not separate at NaOH catalyzed reactions and warm distilled water
Fig. 3b. The change in the viscosity of FOMEs with the different amount of NaOH and methanol. Fig. 2b. The change in the density of FOMEs with the different amount of NaOH and methanol.

Fig. 3a. The change in the viscosity of FOMEs with the different amount of KOH and methanol.

Fig. 2a. The change in the density of FOMEs with the different amount of KOH and methanol.

was added to encourage separation. The reason of this condition is probably the soaps of saturated fatty acids which tend to solidify at ambient temperature. Beside, the highest purity of NaOH stands for more alkali catalyst. More catalyst causes excessive soap which may gel and form a semi-solid mass [23]. For this reason, lower ester yields were obtained for NaOH catalyzed reactions as shown in Fig. 4b. Similarly, in our previous study [24], we found lower ester yields for biodiesel production from animal fat with high FFA for NaOH catalyzed reactions. Especially, for 1% NaOH catalyzed transesterication reactions, ester yield was lower than the others due to higher amount of glycerol layer which did not separate. According to the viscosity and density results, it seems that there

218 Table 2a Some properties of the eshing oil methyl esters. Property Ester yield Density (at 15 C) Kinematic viscosity (at 40 C) Free glycerin Monoglyceride Diglyceride Triglyceride Total glycerin

E. Alptekin et al. / Fuel 95 (2012) 214220

Unit (%) kg m3 mm2 s1 % (mass) % (mass) % (mass) % (mass) % (mass)

FOME 1 91.9 877.2 5.21 0.04 0.54 0.98 2.16 0.54

FOME 2 91.4 875.9 4.94 0.03 0.49 0.31 0.22 0.22

FOME 3 92.6 875.6 4.78 0.03 0.45 0.13 0.05 0.17

FOME 4 92.2 876.1 4.86 0.03 0.57 0.29 0.22 0.24

1: (1% KOH, 4.5:1 methanol molar ratio), 2: (1% KOH, 6.0:1 methanol molar ratio), 3: (1% KOH, 7.5:1 methanol molar ratio), 4: (0.75% KOH, 7.5:1 methanol molar ratio).

was no conversion of triglyceride to ester produced via KOMe and NaOMe catalysts. Nevertheless, the ester yield of FOMEs produced with KOMe and NaOMe catalysts except for 1% NaOMe catalyzed transesterication reactions reduced and the ester yields were in the range of 87.792.5%. For 1% NaOMe catalyzed transesterication reactions, the ester yields of FOMEs were 75.4, 77.8 and 80.8% for 4.5:1, 6.0:1 and 7.5:1 methanol molar ratios, respectively. 3.5. Mono-, di-, and tri-glycerides, total and free glycerin After transesterication, the resulting ester can contain unreacted starting material such as triglyceride, residual alcohol, and residual catalyst. Beside, traces of glycerol which is separated from biodiesel in the production process can also be found in the nal biodiesel product. Since transesterication is a stepwise process, monoglyceride and diglyceride formed as intermediates can also be found in biodiesel [36]. The total glycerin is dened as the sum of free and bound glycerol, and the bound glycerol is equal to the glycerol portion of the residual monoglyceride, diglyceride and triglycerides [37]. Free glycerol in biodiesel results from not quantitative separation during the production process or from formation by hydrolysis of remaining glycerides during longer storage [38]. The total and free glycerin amounts of biodiesel are two of the most important parameters to determine if the product is ready for commercial applications [3941]. According to viscosity and density results, only a few FOMEs are suitable for EN 14214 biodiesel standard for KOH and NaOH catalyzed reactions. As stated above, the ester yields for NaOH catalyzed reactions were lower than those of KOH. Therefore, the glyceride values of FOMEs produced with KOH were only determined. The glyceride values were given in Table 2b for FOME 1 (1% KOH, 4.5:1 methanol molar ratio), FOME 2 (1% KOH, 6.0:1 methanol molar ratio), FOME 3 (1% KOH, 7.5:1 methanol molar ratio) and FOME 4 (0.75% KOH, 6.0:1 methanol molar ratio). Although the viscosity of FOME 1 does not t the

Fig. 4b. The change in the ester yield of FOMEs with the different amount of NaOH and methanol.

viscosity standard for EN 14214, its glyceride values were characterized to understand the effect of methanol molar ratio on glyceride values. As seen in Table 2a, mono, di and triglyceride values reduced with increasing methanol molar ratio. Free glycerin values of FOMEs are slightly higher than the biodiesel standard values (%0.02) and these results show that it is not directly affected by reaction parameters. This means that free glycerin amount of the nal product depends on purication step rather than reaction parameters. On the other hand, it seems to be harder to remove free glycerin from ester for KOH catalyzed reactions compared to other experiments according to the results like in our previous study [24]. Total glycerin values of FOMEs also reduced with reduction of glyceride values. Although the total glycerin values t the biodiesel standards, mono-, di- and tri-glyceride values does not t the EN 14214 biodiesel standards for FOME 2. Standard glyceride values except for free glycerin were obtained only for FOME 3. Therefore, FOME 3 was used for further processing to reduce the free glycerin to t the biodiesel standards.

3.6. Characterization of fuel properties of the eshing oil methyl ester Six washings were done in the washing process of FOMEs and the water amount was half of the ester amount in volume. After determination of the glyceride values, it was seen that the free glycerin of FOME 3 was slightly higher than the biodiesel standard values (0.02%). In this case, FOME 3 was subjected to additional washing process to meet the biodiesel standard specication. This time, the amount of washing water was the same as the ester amount and FOME 3 was again washed for two times with warm distilled water. After washing process, the methyl ester was subjected to a heating at 110 C to remove water, and then ltered.

Fig. 4a. The change in the ester yield of FOMEs with the different amount of KOH and methanol.

E. Alptekin et al. / Fuel 95 (2012) 214220 Table 2b Fuel properties of eshing oil methyl ester (FOME 5). Property Density (at 15 C) Kinematic viscosity (at 40 C) Flash point Sulfur content Water content Acid number Methanol content Monoglycerides Diglycerides Triglycerides Free glycerin Total glycerin Ester content Carbon residue Iodine value Copper corrosion (3 h, at 50 C) CFPPa Heat of combustion
a

219

Unit kg m mm2 s1 C mg kg1 mg kg1 mg KOH g1 % (mass) % (mass) % (mass) % (mass) % (mass) % (mass) % (mass) % (mass) g l.100 g1 Degree of corrosion C kJ kg1
-3

EN-14214 860900 3.55.0 101 min 10 max 500 max 0.50 max 0.20 max 0.80 max 0.20 max 0.20 max 0.02 max 0.25 max 96.5 min 0.30 max 120 max No 1 max

ASTM-D6751-10 1.96.0 130 min S1515 max S500500 max 0.50 max 0.20 max 0.02 max 0.24 max 0.050 max No 3 max

Fleshing oil methyl ester 875.5 4.77 174.8 141 326.4 0.32 0.01 0.27 0.09 0.04 0.01 0.10 95.5 0.026 61 No 1 +11 39,954

This property changes according to climate of the region.

After this stage, the FOME 3 was renamed as FOME 5. Other fuel properties of FOME 5 were determined and given in Table 2b. The free glycerin of FOME 3 was reduced from 0.03% to 0.01% by additional washing process. Mono-, di- and tri-glyceride values were also decreased and thus the total glycerin of FOME 3 was reduced from 0.17% to 0.10%. The glyceride values t the biodiesel standards. The viscosity and density of FOME 5 were 4.77 mm2 s1 and 875.5 kg m3 which are in accordance with EN 14214 and ASTM D6751 biodiesel standards. On the other hand, the fatty acid composition of the eshing oil did not change signicantly after pretreatment and transesterication as seen in Table 1b. One of the most important advantages of biodiesel is its ash point being higher than that of diesel fuel. The ash point of FOME 5 was measured to be 174.8 C and this is much above the requirements. The excess methanol used in the biodiesel production process must be removed. The allowable methanol content level is specied in biodiesel standards as 0.2%. The methanol content of FOME 5 was 0.01%. The cold lter plugging point (CFPP) is used to characterize the cold ow operability of a fuel because it directly affects the utility of the fuel, especially in cold climate conditions. The CFPP was +11 C which was unacceptable to use this ester in winter temperate climates. The acid value is used to determine the amount of acid presents in the fuel which have inuence on fuel aging [42,43]. The acid value of FOME 5 was measured to be 0.32 mg KOH g1 which is much below the required biodiesel standards. The heat of combustion is a measure of the energy available from the fuel. It is used for estimating the fuel consumption compared to petroleum diesel fuel [44,45]. The heat of combustion of FOME 5 was 39,954 kJ kg1 and which is slightly lower than that of petroleum diesel fuel. The copper strip corrosion is used for the detection of the corrosiveness to copper of biodiesel fuels. The copper strip corrosion result gathered with FOME 5 was the lowest level of corrosiveness (No 1a). Carbon residue gives a measure of the carbon depositing tendencies of a fuel. While not directly correlating with engine deposits, this property is considered an approximation. The carbon residue of the FOME 5 was determined for 100% sample and it was 0.026% which is suitable for the biodiesel standards. Iodine value is a measure of the degree of unsaturation of a vegetable oil or animal fat. The iodine value is no listed in ASTM D6751 while it is listed in EN 14214 biodiesel standard to be maximum 120. The iodine value of FOME 5 was 61 and this is enough below the standard value. Water in the fuel builds up corrosion, and microbiological growth may occur

at a fuelwater interface. The water content value of the FOME 5 was measured to be 326.4 ppm and it ts the biodiesel standards. Oxidation stability of biodiesel is worse than petroleum diesel fuel. Therefore, biodiesel ages more quickly than petroleum diesel fuel. The oxidation stability of FOME 5 was not added to Table 2b. Because, the oxidation stability of FOME 5 was determined according to PetroOXYs Rapid Small Scale Oxidation Test (RSSOT) ASTM D7545 method which has been approved but not incorporated into ASTM fuel quality specications. The oxidation stability of FOME 5 was about 0.3 h while that of diesel fuel was about 2 h. Beside mono, di and triglycerides, ester content of a biodiesel gives information about purity of that. The ester content of FOME 5 was 95.5% and it is slightly lower than the standard of EN 14214. However, Schober et al. [46] stated that the ester content of an animal fat biodiesel may be lower than the real ester content. This situation causes from heptadecanoic acid (C17:0) in the fat. In their study, they developed a modied method for the determination of ester content based on EN 14103. They determined that biodiesel samples produced from waste animal fats and oils showed an increase in ester content between 2% and 7% compared to values measured according to EN 14103. Sulfur content of fuels has an effect on engine wear and deposits. Sulfur in the fuels is harmful for environmental and human health and it also affect emission values. Sulfur content must be maximum 10 ppm for EN 14214 and it has two standard values as S15 and S500 for ASTM D6751. S15 sulfur content standard allows maximum to be 15 ppm, whereas S500 sulfur content standard allows maximum to be 500 ppm. He et al. [25] stated that when animal fats and waste vegetable oils are used for biodiesel production, the sulfur content is expected to be higher due to the presence of sulfur-containing compounds such as proteins. In addition, water-washing of the biodiesel may be a critical step for sulfur removal to obtain fuel quality biodiesel, particularly if acid esterication is used as a pretreatment to lower FFAs. However, pretreatment with sulfuric acid of the high FFA feedstocks does not carry a signicant amount of sulfur over to the nished fuel according to their results. In this study, as seen in Table 1a, the sulfur content of the eshing oil and pretreated oil were considerably high and above 990 ppm which is the maximum measurement value of our sulfur analyzer. The reason of high sulfur content of the eshing oil may be the sulfur containing protein which is probably the keratin. On the other hand, high sulfur content of the eshing oil may be results of the industrial process of the solid wastes recycle plant where the eshing oil was

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obtained. Due to upper limit of sulfur analyzer, we cannot directly determine the effect of pretreatment reaction on the sulfur content of the eshing oil. The sulfur content of FOME 5 was measured to be 141 ppm after transesterication and this value ts the S500 standard. Nevertheless, we are now working on a study about the effect of pretreatment reaction and washing process on sulfur content of different animal fats and waste cooking oils with high FFA but low sulfur. 4. Conclusion This study deals with producing biodiesel from the eshing fat with high FFA. After the FFA level of the fat was reduced to less than 1%, the reaction was completed by using the alkaline catalysts. Optimum reaction conditions for pretreatment were determined as methanol molar ratio of 30:1, sulfuric acid amount of 10% based on FFA level of the eshing oil for 1 h at 60 C. Optimum reaction conditions for transesterication were determined as methanol molar ratio of 7.5:1, catalyst amount of 1% and catalyst type of KOH for 1 h at 60 C. The measured fuel properties t the biodiesel standards except for CFPP, ester and sulfur content. The cold ow properties of the FOME should be improved with cold ow enhancers or it may be mixed with petroleum diesel fuel which has better cold ow properties. Ester content of FOME is slightly below the requirement value for EN 14214. However, this property seems not to be absolutely suitable for the animal fats as stated above. According to results, the sulfur content of the biodiesel feedstock is very important to get low sulfur content biodiesel after transesterication. Therefore, the sulfur content of the feedstock must be determined. In addition, the effect of pretreatment on sulfur content of pretreated fat and removing sulfur from the feedstock or biodiesel should be investigated in detail for further studies. Acknowledgements This study was supported by grants from the Scientic Research Foundation of Kocaeli University and Izmit Municipality (Project Nos. 2008/APP002 and 2011/37). References
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