Renewable Energy 35 (2010) 269274

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Biodiesel production from residual oils recovered from spent bleaching earth
Yi-Pin Huang, James I. Chang*
Department of Safety, Health and Environmental Engineering, National Kaohsiung First University of Science and Technology, #1, University Blvd., Yenchao, Kaohsiung, Taiwan ROC

a r t i c l e i n f o
Article history: Received 22 December 2008 Accepted 21 July 2009 Available online 15 August 2009 Keywords: Solvent extraction Transesterication Financial analysis

a b s t r a c t
This work was to study technical and economic feasibilities of converting residual oils recovered from spent bleaching earth generated at soybean oil reneries into useable biodiesel. Experimental results showed that fatty acids in the SBE residual oil were hexadecenoic acid (58.19%), stearic acid (21.49%) and oleic acid (20.32%), which were similar to those of vegetable oils. The methyl ester conversion via a transesterication process gave a yield between 85 and 90%. The biodiesel qualities were in reasonable agreement with both EN 14214 and ASTM D6751 standards. A preliminary nancial analysis showed that the production cost of biodiesel from SBE oils was signicantly lower than the pre-tax price of fossil diesel or those made of vegetable oils or waste cooking oils. The effects of the crude oil price and the investment on the production cost and the investment return period were also conducted. The result showed that the investment would return faster at higher crude oil price. 2009 Elsevier Ltd. All rights reserved.

1. Introduction The commercial use of methyl esters or biodiesel as a diesel substitute began in Europe in the late 1980s. The world production has increased 100 fold to 10 million kiloliters (w9 million metric tons) in 2007 [1] since then. The application of biodiesel has been limited due to its higher cost than petroleum-based diesel. Approximately 5090% of the biodiesel production cost arises from the cost of raw material such as vegetable oils, animal fats, and waste cooling oils [27]. To lower the production cost of biodiesel and to expand its usage, using less expensive raw materials is desired. Waste vegetable oil adsorbed in spent bleaching earth (SBE) during the crude oil rening process is a potential candidate that has been overlooked in the past. SBE is an industrial waste generated at the vegetable oil rening industry after the discoloration (bleaching) of crude oil. The annual world generation of SBE is between 1.5 and 2.0 million tons based on the world edible oil production of 128.2 million metric tons in 2007 [8] and 1.21.6 kg of SBE generation per metric ton of edible oil production. SBE contains 2040% by weight of oil, fat and colored pigments [9] and may present a re hazard, if it is not stored or disposed properly [10]. The recovery of residual oils adsorbed in SBE has been studied by many researchers using solvent extraction [1115], supercritical CO2 extraction [16, 17] or lye extraction [18,19] in the past. Only

a small fraction of SBE generated worldwide is recovered and most of them are disposed at landlls. The oils in SBE are methyl esters of fatty acids such as those in vegetable oils [15,20]. Pizarro and Park [20] tried to produce biodiesel fuel by lipase-catalysis method using oils from SBE generated at the soybean, rapeseed and palm oils renery facilities. The highest conversion yield reached 55% (w/w) with palm oil after 96 h of reaction. Loh et al. [15] used both solvent and supercriticaluid (SC-CO2) extraction to recover oils from SBE generated at a palm oil rening industry. They found that those oils exhibited poor qualities in terms of free fatty acids content and peroxide value. Those oils were not suitable for food applications, but could be converted to their respective methyl esters for biodiesel applications. The purpose of this study was to investigate if a two-step esterication process that converts the residual oil adsorbed in SBE into methyl esters is technically and economically feasible. Experimental design and the response surface methodology were used to study the effects of the process variables on the biodiesel yield. A preliminary nancial analysis for a hypothetical 1000-ton/year biodiesel production unit was also conducted.

2. Materials and methods 2.1. Spent bleaching earth

* Corresponding author. Tel.: 886 7 601 1000x2315; fax: 886 7 601 1061. E-mail address: envjames@ccms.nkfust.edu.tw (J.I. Chang). 0960-1481/$ see front matter 2009 Elsevier Ltd. All rights reserved. doi:10.1016/j.renene.2009.07.014

SBE was provided by TTET Union Company, the largest edible oil producer in Taiwan with an annual production capacity of 300,000

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Y.-P. Huang, J.I. Chang / Renewable Energy 35 (2010) 269274

tons. The samples were taken from the SBE that passed with 294 kPa (42.6 psi) steam for primary recovery of oil in the plant. 2.2. Residual oil extraction Oil adsorbed in SBE was obtained by extraction with n-hexane (1:4 wt/wt ratio) in a soxhlet extractor. The extraction was continued for 6 h until the extracted hexane was colorless. Hexane was then removed in a rotary vacuum evaporator. The brown oil left was then subjected to esterication. 2.3. Residual oil esterication Residual oil (100 g) was mixed with 29 g of methanol and 1 g of NaOH (1 wt% of residual oil) in a 250 ml glass reactor that was equipped with an agitator and a water-cooled reux, and was heated with a temperature controlled water bath. The reaction time was 1 h and the temperature of the reactants was kept at 60  C. The product was then poured into a funnel and let it stay for 30 min. After the bottom part (water fraction) was removed, the oil layer was washed with 60  C distilled water to remove excess methanol and sulfuric acid. The esterication product was then titrated with potassium hydroxide to ensure that the concentration of free fatty acid (FFA) below 2%. If the FFA concentration was over 2%, the esterication process had to be repeated. The nal product with minimal FFA concentration was subjected to transesterication process. 2.4. Residual oil transesterication Esteried residual oil (100 g) was preheated to a specied temperature between 60 and 80  C rst, and then was mixed with methanol and 1 g of NaOH (1 wt% of oil). The reaction mixture was reuxed for a certain time period between 30 and 90 min. The reaction product was poured into a funnel and let it stay for 60 min. After the bottom glycerol/methanol layer was removed, the top methyl esters/methanol layer was rinsed with dilute acetic acid solution (1 wt %) and excess warm water at 60  C. The nal product was heated to 105  C to remove the residual water. 2.5. Experimental design To study the effects of the process variables on biodiesel conversion, a partial factorial central composite experimental design and a response surface methodology [21,22] were conducted. The temperature, reaction time and the methanol/oil molar ratio were selected as the inuence (independent) variables, and the conversion to biodiesel (%) were selected as the dependent variable. The range and levels of the variables that affect the transesterication reaction investigated are listed in Table 1. Fourteen experiments augmented with three replications at the center points were carried out. The effects of independent variables on the dependent variable were analyzed as a quadratic function:
2 2 2 Y a0 a1 X1 a2 X2 a3 X3 a11 X1 a22 X2 a33 X3

where Y is the predicted response (dependent variable); X1 (temperature), X2 (reaction time), X3 (methanol/oil molar ratio) are the independent variables; a0 the offset term; a1, a2 and a3 the linear coefcients; a11 and a22 are the squared terms; and a12, a13, a23 are interaction coefcients; e is the error. The graphical representation of Eq. (1) called the response surface could be used to determine the mutual interactions between test variables and their subsequent effect on the response [21]. The Design Expert 7.15 software was used for the regression analysis and the graphical presentation. 2.6. Analysis 2.6.1. Residual oils Fatty acid methyl esters were prepared by adding 2% sulfuric acidmethanol directly to the waste oil. The reaction was carried out at 50  C. Fatty acid composition was determined by gas chromatography of methylated fatty acids [20]. 2.6.2. Gas chromatography Fatty acid concentrations in SBE and transesteried products were determined by using a gas chromatograph (GC-2014, Shimadzu, Kyoto) coupled with a ame ionized detector and a BPx70 glass capillary column (30 m length, 0.25 mm i.d., 0.25 mm lm thickness, SGE International Pty, Ltd., Victoria, Australia) with a maximum temperature up to 260  C and a column pressure of 10 psi. Standard methyl esters of fatty acids were used as authentic samples and peak identication was done by comparing relative retention times. The peak areas were obtained from the computer and the percentage of the fatty acid was calculated as the ratio of the partial area to the total area. Triheneiconsaoin 21:TAG was used as an internal standard. 3. Results and discussion 3.1. Residual oil quality SBE used in this work passed with 294 kPa (42.6 psi) steam for primary recovery of oil in the plant. The amount of the residual oil extracted from SBE by n-hexane was only 21%, which was 710% less than those reported in Pizarro and Park [20] or Loh et al. [15]. A higher percentage could be obtained when methanol, ethanol or polar compounds were used as the solvent; however, the extracted oil contained pigments, suspended solids, polar and phosphorous compounds, which made the separation of the water and methyl esters or the methyl esters and triglycerides difcult. The residual oil recovered from SBE via hexane extraction was dark brown in color. It was transparent and had no suspended solids. The chemical composition and properties of the residual oil from SBE by different researchers are summarized in Table 2 for comparison. The density of the residual oil was close to rened soybean and palm oils, but the viscosity was two times higher. More than 80% of the fatty acids in the residual oil were saturated fatty acids such as palmitic acid (57.9%) and stearic acid (22.6%), whereas only 15% of fatty acids in rened soybean oil were saturated. The free fatty acid (FFA) of the recovered oil was 24.1%, which was much higher than those of rened soybean oil, palm oil or residual oils recovered from SBE as reported in Pizarro and Park [20] or Loh et al. [15]. 3.2. Esterication

a12 X1 X2 a12 X1 X2 a12 X1 X2 e

(1)

Table 1 Experimental range and levels of transesterication variables. Variables Temperature Reaction time (min) Methanol/oil molar ratio 1 60 30 6 0 70 60 9 1 80 90 12

The FFA content in the residual oil had to be lowered to avoid the saponication with caustic soda in the transesterication process, which converted triglycerides to methyl esters. In this study, FFA in

Y.-P. Huang, J.I. Chang / Renewable Energy 35 (2010) 269274 Table 2 Physical and chemical properties of soybean and extracted residual oil. Property Density (kg/m3) Color Viscosity (cP) Saponication value Free fatty acid (FFA) (%) Fatty acid Fatty acid composition (%) Myristic acid (14:0) Palmitic acid (16:0) Stearic acid (18:0) Oleic acid (18:1) Linoleic acid (18:2) Linolenic acid (18:3) Oil recovery (%) Reference Soybean oil 0.919 Yellow 37.7 193 1%< 89.6 0 11 4 24 54 7 [27] Palm oil 0.89 Dark 41.3 180 Oil extracted from SBE (soybean oil) Transparent 118 188 4.1 87.5 30 [20] Oil extracted from SBE (palm oil) Dark 11.5 88.1 1.1 44.8 5.1 38.6 10.6 0 30 [25]

271

Oil extracted from SBE (soybean oil) 0.88 Dark brown 8496 185 24.1 87.6 0 57.9 22.6 19.5 0 0 21 This work

89.4 1 37 4 46 10 1 [20,27]

oil was reduced to less than 2% by reacting methanol with oil in the presence of 1% sulfuric acid. Water in the residual oil was reduced by evaporation at 105  C prior to and after the esterication process. It would be difcult to reduce the FFA content in oil to the desired level of 2% or less if water was not removed prior to the esterication. Water would also result in soap formation in the transesterication process [23,24]. The FFA content in oil could be reduced to 1.77% after the oil was esteried twice with methanol at 60  C for an hour. 3.3. Transesterication-biodiesel production The pre-esteried oil with less than 2% of FFA was transesteried by methanol in the presence of 1 wt% of caustic soda. Experimental results of biodiesel conversion (%) are shown in Table 3. The quadratic polynomial equation obtained from the multiple regression analysis of the experimental data is listed below:
2 2 Y 87:08 0:76X1 0:53X2 1:40X3 0:60X1 0:26X2 2 0:16X3 0:04X1 X2 0:38X2 X3 0:30X1 X3

reaction time (X2) and the temperature (X1) were the variables with the second and the third largest effects. The dependence of the biodiesel conversion on inuencing parameters is shown graphically in the contour plots of Fig. 1. As shown in Fig. 1(a), there is a positive correlation between the biodiesel conversion and the reaction time and the temperature. The biodiesel conversion increases as the reaction and the temperature increase. The range of variation is around 3%. The biodiesel conversion increases as the temperature increases and the methanol/oil ratio decreases [Fig. 1 (b)]. The variation is 4%. As the reaction time increases and the methanol/oil ratio decreases, the biodiesel conversion increases [Fig. 1 (c)]. The variation is also 4%. 3.4. Biodiesel quality The biodiesel produced from the SBE residual oil was a clear yellow liquid. Its properties were in reasonable agreement with both EN 14214 and ASTM D6751 standards, as shown in Table 6. It had a higher cetane number and a lower iodine number than the biodiesel made from rened vegetable oils, because the residual oil contained signicantly more saturated fatty acids such as palmitic acid (hexadecenoic acid).

(2)
where Y is the observed response, the conversion to biodiesel (%), and X1, X2 and X3 are coded values of independent variables, temperature, reaction time and the methanol/oil molar ratio, respectively. The results of the analysis of variance (ANOVA) for the quadratic model are given in Table 4. That the value of Fmodel (20.15) larger than the Fisher distribution of F0.01,8, 9 (5.47) with a very low probability value of [(Pmodel > F) 0.003] at 99% condence level demonstrates a high signicance for this model. The high coefcient of determination (R2 0.96) indicates that the quadratic regression model approximates 96% of the real data points. Only 4% of the total variations are not represented by the model. A highadjusted coefcient of determination (Adj. R2 0.92) also advocates for a high signicance of the model. A low value of the coefcient of variation (CV 0.56%) indicates low dispersion of experimental data. The signicance of each regression coefcient is determined by the t-values and P-values. The larger the t-value and smaller the Pvalue are, the more signicant is the corresponding coefcient [22]. As shown in Table 5, the variable with the most signicant effect was the molar ratio of methanol/oil (X3). The linear forms of the

Table 3 Factorial composite design matrix of three variables in coded and natural units along with the observed responses (conversion to biodiesel). No. 1 2 3 4 5 6 7 8 9 10 11 12 13 14 15 16 17 X1 1 1 1 1 1 1 1 1 1 1 0 0 1 1 0 0 0 X2 1 1 1 1 1 1 1 1 0 1 1 1 1 0 0 0 0 X3 1 1 1 1 1 1 1 1 1 0 1 1 0 1 0 0 0 Temperature ( C) 60 80 60 80 60 80 60 80 60 60 70 70 80 80 70 70 70 Reaction time (min) 30 30 90 90 30 30 90 90 60 90 30 90 30 60 60 60 60 Methanol/ oil molar ratio 6 6 6 6 12 12 12 12 12 9 12 6 9 6 9 9 9 Conversion to biodiesel (%) 85.96 88.08 88.12 90.08 84.52 85.44 85.16 85.68 84.73 85.76 85.24 89.64 87.56 88.27 87.00 87.28 87.19

272 Table 4 Analysis of variance (ANOVA) for the quadratic model. Source of variation Model Residual Lack of t Pure error Total Sum of squares 43.20 1.67 1.63 0.04 44.86 Degree of freedom 9 7 5 2 16 Mean square 4.80 0.24 0.33 0.02

Y.-P. Huang, J.I. Chang / Renewable Energy 35 (2010) 269274

F-value 20.15 15.92

Probability >F 0.0003 0.0602

CV 0.56%, R2 0.96, R 0.98, Adj. R2 0.92.

3.5. Preliminary nancial analysis A nancial analysis for a hypothetical, 1000-ton/year biodiesel production unit using residual oil recovered from SBE was prepared. A processing unit of this size could process the amount of SBE (13-ton/day) generated by a 1000-ton/day soy oil rening plant. The income came from the biodiesel sale and the saving of the SBE disposal cost. The biodiesel was assumed to sell at 80% of the price of the petroleum-based diesel, the glycerine was sent for purication and the deoiled SBE was mixed with soy meal for animal feed. The credits from the deoiled SBE and the glycerine were not included in the nancial analysis. The investment was 750,000 US dollars based on the average cost quoted by three local engineering rms. The design parameters are listed as follows. C Operating days per year: 300 days. C Residual oil in SBE: 30.2% (oil recovered by steam stripping included). C Biodiesel conversion: 85%. C Maintenance cost: 3% of investment. C Unearned interest rate: 3%. C Depreciation: 7 years based on 70% of investment. C Solvent (n-hexane) loss 12.5 kg/ton of SBE. C Excess caustic soda and sulfuric acid usage: 50%. C Excess methanol usage: 20%. C Crude oil: $100/barrel; diesel:$836/ton; methanol: $510/ton; solvent (n-hexane): $1620/ton; sulfuric acid: $145.6/ton; caustic soda: $491.3/ton; low sulfur fuel oil: $646/ton. C SBE disposal cost: $60/ton. C Electricity consumption: 38.9 kwh/ton of biodiesel; 130% of the gure used by Hass et al. [6]; electricity: $0.075/kwh. C Low sulfur fuel oil consumption: 72.8 kg/ton of biodiesel; 130% of the energy equivalent of natural gas used by Haas et al.[6]. C Wastewater treatment cost: $12,000. As shown in Table 7, the cost per liter of biodiesel production is 0.37$, which is only 52.1% of the local pre-tax petroleum diesel price at 0.71$ in Taiwan, when the crude oil price is 100$. It is also lower than estimated prices of 0.81.5 $/l produced from vegetable

Table 5 The least square t and parameter estimates. Model term Intercept X1 X2 X3 X2 1 X2 2 X3 3 X1X2 X1X3 X2X3 Parameter estimate 87.08 0.76 0.53 1.40 0.60 0.26 0.16 0.04 0.38 0.30 Standard error 0.26 0.15 0.15 0.15 0.33 0.33 0.33 0.17 0.17 0.17 Computed t-value 330.02 5.21 3.63 9.60 1.81 0.77 0.49 0.24 2.26 1.79 P-value 0.0012 0.0083 <0.0001 0.1139 0.4654 0.6412 0.8144 0.0582 0.1172

Fig. 1. Response curve of biodiesel conversion. (a) Temperature and reaction time; (b) Temperature and methanol/oil molar ratio; and (c) Temperature and methanol/oil molar ratio.

Y.-P. Huang, J.I. Chang / Renewable Energy 35 (2010) 269274 Table 6 Biodiesel properties in comparison with the standards. Property Specic gravity, 25  C (kg/m3) Viscosity, 40  C (mm2/s) Water content (wt %) Sulfur content (wt %) Phosphorus (wt %) Methanol (wt %) Ash content (wt %) Flash point ( C) Cetane number Carbon residue (wt %) Acid number (mg KOH/g) Iodine value (I2/100 g) Caloric value (kJ/kg) ASTM D6751 0.88 1.96.0 0.05 0.015 max 0.001 max 0.2 max 0.008 130 min 47 min 0.05 max 0.5 max EN 14214 3.55.0 0.02 0.001 130 min 47 0.02 0.8 120 max Biodiesel This work 0.89 5.0 0.05 0.01 < 0.001< 0.01 0.02 max. 168 61 0.05 0.5 27 38,840 Testing methods ASTM D4052 ASTM D445 ASTM D2709 ASTM D5453 ASTM D4951 EN 14110 ASTM ASTM ASTM ASTM ASTM ASTM D93 D613 D4530 D664 D5768-2 D240 Table 8 Linear regression coefcients of chemical pricesa. Chemical Diesel (before tax) Low sulfur fuel oil n-Hexane Methanol Caustic soda Sulfuric acid
a

273

a 7.036 5.368 13.252 2.437 4.032 2.191

b 132.73 108.97 294.94 266.40 88.12 73.49

R2 0.928 0.961 0.972 0.849 0.853 0.901

Price ($/ton) a (crude oil price in $/bbl) b.

C 158:1am 53:9ah 25:9aNa 19:4as Po 158:1bm 53:9bh 25:9bNa 19:4bs 80:08aF Po bF 0:176Inv 54; 909 (4) I 800ad Po bd 234; 007 (5)

Production cost ($/liter)

oils such as soybean or rapeseed oils or the waste cooking oil in Taiwan by Wei and Li [5] or the production cost of 0.800.95$ in Europe [1]. Chemicals at the cost of 0.15$/l of diesel production or 39.4% of the total production cost is the predominant cost item. It is because a high solvent loss factor and a high excess methanol usage are assumed in the nancial analysis. The solvent loss in typical vegetable oil rening plants is 0.74.0 kg/ton of oil seed [25]. Higher emission factors between 6 and 19 kg/ton seed for small plants are reported by Richardson and Costigan [26]. An average value of 12.5 kg/ton for small plants is used for the solvent loss. The use of less expensive material such as mixed hexane as the extraction solvent and improving recovery efciencies of methanol and the solvent will denitely lower the production cost. Since the prices of chemicals and the diesel change with the crude oil price, the variation of crude oil price signicantly affects the production cost and the income. To study the impact of the crude oil price on the nancial analysis, the prices of chemicals in last two years were rst correlated with the crude oil prices;

where C, I, and Inv are cost, income, and investment, respectively. am, ah, aNa, as, ad, aF, bm, bh, bNa, bs, bd, bF are the linear regression coefcients of methanol, n-hexane, caustic soda, sulfuric acid, diesel and low sulfur fuel oil, respectively. $234,007 was the saving of the disposal cost of 3900 tons of SBE at 60$/ton. The last item of 54,909 was the sum of cost of labor ($35,000), wastewater treatment, and electricity. An additional unexpected cost of 10% was included in C. The investment return period could then be expressed as:

Irpmonths Inv 12=I C

where Irp is the investment return period.

(6)

0.55 0.50 0.45 0.40 0.35 0.30 0.25 40

$1,080,000 $900,000 $750,000

Pi ai Po bi

(3)

where Pi is the local price of chemical (methanol, n-hexane, caustic soda or sulfuric acid) in $/ton; ai and bi were regression coefcients of ith chemicals. The determination coefcients (R2) over 0.85 shown in Table 8 indicated that the predicted prices were in fair agreement with the real data points. The income and the cost could be expressed in terms of crude oil and the investment using the empirical relations of Eq. (3):

60

80

100

120

140

160

Crude oil price ($/bbl)

Table 7 Preliminary nancial analysis for a 1000-ton/year SBE-to-biodiesel plant. Item Cost Chemicals Utilities Labor (2 operators) Maintenance Depreciation Unearned interest 10% allowance Subtotal Income Biodiesel Avoided disposal cost Subtotal Prot Unit prot ($/ton) Investment return (month) Cost ($) 166,431 62,905 35,000 22,500 75,000 22,500 38,434 422,770 669,064 235,294 904,358 481,997 480.3 18.7 ($/l) 0.15 0.05 0.03 0.02 0.07 0.02 0.03 0.37 0.59 0.21 0.79 0.42 Percentage (%)

65

$1,080,000
55

$900,000 $750,000

Period (months)

39.4 14.9 8.3 5.3 17.7 5.3 9.1 100.0 74.1 25.9 100.0

45 35 25 15 5 30

50

70

90

110

130

150

170

Crude oil price ($/bbl)

Fig. 2. The effects of crude oil price and the investment on production cost and investment return period. (a) Production cost; and (b) investment return period.

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Y.-P. Huang, J.I. Chang / Renewable Energy 35 (2010) 269274 [5] Wei KD, Li CZ. The strategy of biofuel utilization and the cost/benet analysis of greenhouse reduction. Hsin Chu, Taiwan: Industrial Technology Research Institute; 2005. [6] Haas MJ, McAloon AJ, Yee WC, Foglia TA. A process model to estimate biodiesel production costs. Bioresour Technol 2006;97:6718. [7] Su CC. The agricultural policy and the development of biofuels in Taiwan, ROC. Taipei: Agriculture and Food Agency, Council of Agriculture; 2007. [8] Soystats. World vegetable oil consumption 2007. St. Louis, MO.: American Soybean Association; 2007. [9] Werner Z. Spent bleaching earth-practical solutions. INFORM 1994;5:1375. [10] Taylor DR, Jenkins DB. Factors affecting the pyrophorisity of spent bleaching clay. J Am Oil Chem Soc 1999;67:678. [11] Ong JTL. Oil recovery from spent bleaching earth and disposal of the extracted material. J Am Oil Chem Soc 1983;60:3145. [12] Kalam A, Joshi J. Regeneration of spent earth by wet oxidation. J Am Oil Chem Soc 1988;65:1536. [13] Aziz AR, Harcharan S, Elkanzi EM, Lam LS, Liew SH. Feasibility study of oil recovery from used bleaching earth using waste solvents. In: Porim international palm oil Congress (PIPOC) proceedings; 2001. p. 126133. [14] Yoo CK, Lin SW. Regeneration of spent bleaching clay. MPOB TT No. 230. Kuala Lumpur: Malaysian Palm Oil Board, Ministry of Plantation Industries and Communities; 2004. [15] Loh SK, Cheng SF, Choo YM, Ma AN. Atudy of residual recovered from spent bleaching earth: their characteristics and applications. Am J Appl Sci 2006;3(10):20637. [16] Waldmann C, Eggers R. De-oiling contaminated bleaching clay by high-pressure extraction. J Am Oil Chem Soc 1991;68(12):92230. [17] King JW, List GR, Johnson JH. Supercritical carbon dioxide extraction of spent bleaching clays. J Supercrit Fluids 1992;5:3841. [18] Norris FA. Industrial oil and fat products. In: Bailey, editor. 3rd ed. New York, NY: Wiley-Interscience; 1964. p. 7856. [19] Chang JI, Tai HS, Huang TH. Regeneration of spent bleaching earth by lyeextraction. Environ Prog 2006;25(4):3738. [20] Pizarrro AVL, Park EY. Lipase-catalyzed production of biodiesel fuel from vegetable oil contained in waste activated bleaching earth. Process Biochem 2003;38:107782. [21] Box GE, Hunter WG, Hunter JS. Statistics for experimenters: an introduction to design, data analysis, and model building. 1st ed. New York: Wiley Interscience; 1978. [22] Khuri AI, Cornell JA. Response surfaces: design and analysis. Marcel Dekker; 1987. [23] Ma FR, Hanna MA. Biodiesel production: a review. Bioresour Technol 2005;70:115. [24] Ramadhas AS, Jayaraj S, Muraleedharan C. Biodiesel production from high FFA rubber seed oil. Fuel 2005;84:33540. [25] UNECE/CLRTAP. Fat, edible and non-edible oil extraction synopsis sheet. Expert Group on Techno-Economic Issues, United Nations Economic Commission for Europe/Convention on Long-Range Transboundary Air Pollution; 2005. [26] Richardson S, Costigan G. SNAP 06 06 44, in UN/ECE-EMEP- CORINAIR atmospheric emission inventory guidebook, version 2; 1996. [27] Zamora A. Fatty acid composition of some common edible fats and oils. Bethesda, MD: Scientic Psychic; 2005.

The effects of crude oil price on the production cost are shown in Fig. 2 (a). The higher the crude oil price is, the higher the production cost. The investment return period covers a wide range from 13.2 months to 57.2 months as shown in Fig. 2(b), depending upon the crude oil price and the investment. Since the biodiesel price increases with the crude oil price, the investment return period decreases as the crude oil price increases. 4. Conclusion This study demonstrated that residual oils recovered from SBE generated at the soybean oil renery could be converted into biodiesel via a two-step esterication. The residual oil contained hexadecenoic acid (58.19%), stearic acid (21.49%) and oleic acid (20.32%), which were similar to those in vegetable oils. The biodiesel properties were found to be in reasonable agreement with both EN 14214 and ASTM D6751 standards. A preliminary nancial analysis showed that the production cost was lower than the diesel or biodiesel made of rened vegetable oils or waste cooking oils. The production cost and the investment return period were heavily affected by the crude oil price, since the chemicals were the predominant cost item. Future work will focus on improving the conversion of the transesterication reaction and using less expensive chemicals as the extraction solvent. Acknowledgement The authors express their gratitude to the National Science Council, ROC for nancial support and to TTET Union Company for providing SBE samples and related technical information. References
[1] ENERS. Production of biodiesel in the world. Lausanne, Switzerland: ENERS; 2008. Energy Concept. [2] Krawczyk T. Biodiesel. INFORM 1996;7(8):80122. [3] Connemann J, Fisher J. Biodiesel in Europe: biodiesel processing technologies. In: Paper presented at the international liquid biofuels Congress, Brazil; 1978. [4] 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.