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Fuel 92 (2012) 377380

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Fuel
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Short communication

An optimum biodiesel combination: Jatropha and soapnut oil biodiesel blends


Yi-Hung Chen , Tsung-Han Chiang, Jhih-Hong Chen
Department of Chemical Engineering and Biotechnology, National Taipei University of Technology, Taipei 106, Taiwan

a r t i c l e

i n f o

a b s t r a c t
Jatropha (Jatropha curcas) and soapnut (Sapindus mukorossi) oils are considered potential non-edible oil feedstocks for biodiesel production and present complementary fuel properties. Apparently, the poor oxidation stability of jatropha oil biodiesel and the high cold lter plugging point of soapnut oil biodiesel can be successfully improved to satisfy all biodiesel specications at an optimum blending ratio. The optimum biodiesel combination was further blended with diesel at various volumetric percentages to evaluate the variations of fuel properties. The biodieseldiesel blends up to B40 would show the satisfactory fuel properties. 2011 Elsevier Ltd. All rights reserved.

Article history: Received 23 April 2011 Received in revised form 28 July 2011 Accepted 3 August 2011 Available online 24 August 2011 Keywords: Soapnut oil Jatropha oil Diesel Cold lter plugging point Oxidation stability

1. Introduction Biodiesel (a mixture of mono-alkyl esters of saturated and unsaturated long-chain fatty acids) generally has a higher cetane number, cold lter plugging point (CFPP), density, and kinematic viscosity (kV), as well as a poorer oxidation stability, than petroleum diesel (a mixture of parafnic, naphthenic, and aromatic hydrocarbons) [1]. At the CFPP, the fuel forms solids of sufcient size to render an engine inoperable due to fuel lter plugging. Consequently, biodiesel with poor low-temperature ow properties may cause problems, such as clogging of the fuel lines and lters in the engine fuel system, which limit the use of biodiesel in cold climates [2]. Moreover, many properties, including the cetane number and heating value, are related to the density of the biodiesel [3]. The iodine value reects the total unsaturation, regardless of the relative proportion of mono-, di-, tri-, and other polyunsaturated compounds. A fuel with a high kV can produce undesired consequences, such as poor fuel atomization during the spray, engine deposits, wear on the fuel pump elements and injectors, and the need for additional energy to pump the fuel [4]. Because biodiesel has inferior oxidation stability due to its chemical structure, the blending of biodiesel with petroleum diesel usually deteriorates the oxidation stability of the fuel. Currently, oxidation stability is a major technical issue and concern in the use of biodieseldiesel blends, especially for their long-term storage. Furthermore, the use of edible oils for biodiesel production may be contrary to current social movements and energy policies.
Corresponding author. Tel.: +886 2 27712171x2539; fax: +886 2 87724328.
E-mail address: yhchen1@ntut.edu.tw (Y.-H. Chen). 0016-2361/$ - see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2011.08.018

Non-edible vegetable oils, mostly produced by seed-bearing trees and shrubs, could be an alternative oil source [5]. Jatropha curcas Linn is a owering plant species in the spurge family, Euphorbiaceae, which is native to North and South America, primarily Mexico and Brazil [6]. It is a non-edible oil-bearing plant widespread in arid, semi-arid, and tropical regions of the world [7]. J. curcas can help with land reclamation, erosion control, protection, and improvement of the microclimate. Recently, J. curcas has been considered one of the most promising potential oil sources for the production of biodiesel in Asia, Europe, and Africa. The major fatty acids in jatropha oil are oleic (9Z-octadecenoic, C18:1) and linoleic (9Z,12Z-octadecadienoic, C18:2) acids; thus, jatropha oil contains large amounts of unsaturated carboncarbon double bonds. Due to its fatty acid composition, jatropha oil biodiesel usually exhibits satisfactory properties in accordance with biodiesel specications, with the exception of oxidation stability. Sarin et al. [8] studied the jatropha and palm oil biodiesel blends to get an optimum mix of better low-temperature properties and improved oxidation stability. However, the CFPP and oxidation stability still cannot satisfy the biodiesel specications of EN 14214 standard simultaneously. The soapnut is the fruit of the soapnut tree, which is generally found in tropical and subtropical climates in various parts of the world, including Asia, the Americas, and Europe. Sapindus mukorossi Gaertn., a member of the Sapindaceae family, is a deciduous tree widely grown from Afghanistan in the west to China in the east, at altitudes ranging from 200 to 1500 m [9]. The integration of soapnut tree plantations along with community forestry in barren lands is considered to have great potential for the mass production of soapnut seeds, which are a potential non-edible oil feedstock for biodiesel production [7]. The major fatty acids in soapnut oil are oleic (9Z-octadecenoic, C18:1) and eicosenoic (11Z-eicosenoic, C20:1)

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acids [10], which contain one unsaturated carboncarbon double bond each. The high content of monounsaturated fatty acids in soapnut oil is remarkable in comparison with the common fatty acid proles of vegetable oils. Based on its fatty acid composition, soapnut oil biodiesel potentially exhibits superior oxidation stability. The objective of this study was to characterize the blending properties of the jatropha oil methyl esters (JME) and soapnut oil methyl esters (SNME), including the CFPP and oxidation stability. Based on the results, the fuel properties of the SNMEJME blend at an optimum ratio can meet all biodiesel specications. The optimum SNMEJME blend was also blended with petroleum diesel at different volumetric percentages to investigate the variations in the fuel properties. Consequently, this study successfully obtained an optimum combination of jatropha and soapnut oil biodiesels with respect to biodiesel specications. 2. Experimental 2.1. Materials Unrened jatropha and soapnut oils were extracted from the seeds of jatropha trees ( J. curcas) in Indonesia and soapnut trees (S. mukorossi) in Fujian, China, respectively. The content of free fatty acids in the jatropha and soapnut oils was 13.6 and 6.69 wt.%, respectively, which indicated the need for acid-catalyzed esterication pretreatment. ACS-certied methanol was obtained from Mallinckrodt Chemicals (Phillipsburg, NJ, USA). Sulfuric acid (H2SO4) (96.7% purity) and KOH pellets (85% purity) were purchased from SigmaAldrich (St. Louis, MO, USA) and Riedel-deHan (St. Gallen, Switzerland), respectively. Anhydrous magnesium sulfate was obtained from Showa (Tokyo, Japan). Commercial, ultra-low-sulfur diesel (610 ppm sulfur) was provided by Formosa Petrochemical Corp. (Taipei, Taiwan). 2.2. Experimental procedures For the esterication pretreatment of the jatropha or soapnut oil, 2.25 g (2.84 mL) of methanol and 0.05 g (0.027 mL) of H2SO4 were added per 1 g of free fatty acids, corresponding to a 20:1 molar ratio of methanol to free fatty acids and a H2SO4 concentration of 5% w/w based on the weight of the free fatty acids, respectively. The acid-catalyzed reaction mixture was vigorously mixed at 60 C for a reaction time of 1 h. The esterication reaction produced a byproduct of water. After the esterication pretreatment, the mixture would be settled overnight while a methanol water mixture rose to the top and can be removed accordingly. Afterwards, the methanolysis of the esteried oils was performed for another hour using a 6:1 molar ratio of methanol to oil, a reaction temperature of 60 C, and a KOH catalyst dosage based on an oil weight of 1% w/w. The solution settled overnight, which resulted in phase separation. Subsequently, the ester phase was washed twice with a saturated sodium chloride solution (three times the volume of the ester phase) to remove any residual methanol, KOH, or glycerol. Finally, the trace amounts of water in the biodiesels were removed by adding anhydrous magnesium sulfate, followed by ltration [11]. Nine biodieseldiesel blends were prepared by blending the biodiesel at proportions of 1%, 2%, 5%, 7%, 10%, 20%, 40%, 60%, and 80% by volume with diesel, which corresponded to B1, B2, B5, B7, B10, B20, B40, B60, and B80 fuels, respectively. 2.3. Analysis of fuel properties The acid value, cetane number, CFPP, density, ash point, iodine value, and kV were determined according to EN 14104, ASTM

D613, EN 116, EN ISO 3675, ASTM D93, EN 14111, and EN ISO 3104, respectively. In addition, the fatty acid methyl ester content (purity) and composition were analyzed according to EN 14103. The purity of the SNME and JME were 99.4% (m/m) and 99.7% (m/m), respectively. The caloric value was measured by using a plain jacket calorimeter (Parr Instrument Company, Model 1341, Moline, IL, USA). The oxidation stability was quantied with the induction period (IP) using Rancimat equipment model 873 (Metrohm, Herisau, Switzerland). The IP of the pure biodiesels was determined in accordance with Rancimat method EN 14112. The IP of the diesel and biodieseldiesel blends was determined by the modied Rancimat method EN 15751 in the European standard EN 590:2009. All determinations of IP were performed in duplicate, and the mean values were reported.

3. Results and discussion 3.1. Properties of SNMEJME blends The variations in caloric value, CFPP, and IP of the SNMEJME blends with the weight percentage of SNME (wt.%) are shown in Fig. 1. As shown, the caloric value of the SNMEJME blends slightly varied and had the average value of about 39.97 MJ/kg. On the other hand, the CFPP and IP signicantly increased at a higher blending ratio of the SNME. At rst, the CFPP remained approximately 1 C when the weight percentage of the SNME ranged from 10 to 30 wt.%. The CFPP then continuously and remarkably increased to 6 C at a higher weight percentage of the SNME. Notably, the CFPP of the SNMEJME blends had already increased to 0 C by blending the SNME at 35 wt.%. However, the IP of the SNMEJME blends was slightly improved by increasing the weight percentage of the SNME up to 60 wt.%. After this point, the oxidation stability of the SNMEJME blends started to dramatically increase with the weight percentage of the SNME. The oxidation stability of the SNMEJME blend was observed to be greater than 6 h when the SNME was 35 wt.% or higher in the blended biodiesel. As a result, the optimum SNMEJME blend consisted of the SNME and JME at a 35:65 weight ratio. The free acid methyl ester composition was comprised of methyl palmitate, methyl stearate, methyl oleate, methyl linoleate, methyl linolenate, methyl arachidate, and methyl eicosenoate of 10.7, 5.2, 47.5, 25.3, 1.0, 2.0, and 8.4 wt.%, respectively. The optimum SNMEJME blend had the acid value of 0.17 mg KOH/g, CFPP of 0 C, density of 880 kg/m3 at 15 C,

48

10

24

Calorific value (MJ/ kg)

18 44 5

CFPP (oC)

IP (h)

12

40

0 6

36

-5

20

40

60

80

0 100

Weight percentage of SNME (wt.%)


Fig. 1. Variations in caloric value, CFPP, and IP of the SNMEJME blends with weight percentage of SNME (wt.%). Symbol and line: experimental data and correlation, respectively. h, s, and 4: caloric value, CFPP, and IP, respectively.

Y.-H. Chen et al. / Fuel 92 (2012) 377380

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ester content of 99.6% (m/m), ash point of 171 C, an iodine value of 100 g I2/100 g, kV of 4.55 mm2/s at 40 C, and oxidation stability of 6.0 h. Furthermore, cetane number is an important descriptor of the ignition quality for the use of diesel fuel in an internal combustion engine. Low cetane number generally indicates longer ignition delay time that may worsen the engine performance and pollutant emissions [12]. The optimum SNMEJME blend has the cetane number of 55 which satises the standards for biodiesel of a minimum of 47 (ASTM D6751) or 51 (EN 14214). Therefore, the optimum SNMEJME blend can simultaneously satisfy the specications for oxidation stability and CFPP, thus obviating the need for the addition of antioxidants, which is a common procedure to provide acceptable oxidation stability. 3.2. Properties of SNMEJME and diesel blends The optimum SNMEJME blend was further blended with diesel at different volumetric percentages to study variations in the CFPP, density, kV, and IP of the biodieseldiesel blends. Clearly, the SNMEJME blend had higher CFPP, density, and kV, as well as inferior oxidation stability, in comparison to diesel. Thus, the density and kV of the biodieseldiesel blends remarkably increased with the volumetric percentage of the biodiesel (vol.%), as shown in Fig. 2. The density of the biodieseldiesel blend linearly increased with the volumetric percentage of the biodiesel, which indicated the volume additivity. Excellent agreement between the measured and estimated values of the density at 15 C of the biodieseldiesel blends was produced by the following equation:

48

24

Calorific value (MJ/kg)

18 44 0

CFPP (oC)

IP (h)

12

40

-5 6

36

-10

20

40

60

80

100

Volumetric percentage of biodiesel (vol.%)


Fig. 3. Variations in caloric value, CFPP, and IP of the biodieseldiesel blends with volumetric percentage of the biodiesel (vol.%). Symbol and line: experimental data and correlation, respectively. h, s, and 4: caloric value, CFPP, and IP, respectively.

Density kg=m3 43:5x 836 R2 0:999

easily satisfy the limits of density and kV in all current biodiesel diesel blend specications. In addition, the caloric value, CFPP, and IP for the biodiesel diesel blends as a function of the volumetric percentage of the biodiesel are shown in Fig. 3. Apparently, the caloric value of the biodieseldiesel blend linearly decreased with the volumetric percentage of the biodiesel, which also showed the physical mixing characteristics as described by the following equation:

where x is the volumetric percentage of the SNMEJME biodiesel (vol.%). Similar to the density, the kV of the biodieseldiesel blend also showed a linear relationship with the volumetric percentage of the biodiesel, which showed the physical mixing characteristics. The kV at 40 C can be described by Eq. (2) for the biodieseldiesel blends:

Calorific value MJ=kg 6:13x 46:03 R2 0:996

kV mm2 =s 1:44x 3:03 R2 0:991

where x is the volumetric percentage of the SNMEJME biodiesel (vol.%). According to these results, the biodieseldiesel blend could
900
6

880
5

Density (kg/m3)

860
4

840

where x is the volumetric percentage of the SNMEJME biodiesel (vol.%). When the volumetric percentage of the biodiesel was less than 40%, the CFPP of the biodieseldiesel blends was approximately 6 C, which satises the requirement of Grades A to C in EN 590 in Europe and CNS 1471 in Taiwan. However, the CFPP greatly increased with a higher volumetric percentage of the biodiesel from B40 to B100. In contrast, the IP of the biodieseldiesel blend signicantly decreased with higher volumetric percentage of the biodiesel, especially in the region of diesel to B40. The decreasing IP was caused by poor oxidation stability of the unsaturated free fatty methyl esters in the biodiesel. Nevertheless, all the biodieseldiesel blends still satised the oxidation stability requirement of 6 h specied in ASTM D7467. Accordingly, blending of biodiesel was recommended up to B40, in accordance with the properties of the biodieseldiesel blends. The suggested biodieseldiesel blends would have the CFPP of approximately 6 C, density of 836853 kg/m3 at 15 C, kV of 3.033.51 mm2/s at 40 C, and oxidation stability of 9.117.3 h. Consequently, the optimum combination of the SNME and JME was advantageous in obtaining satisfactory fuel properties and was successfully further blended with diesel to satisfy the current mandates. 4. Conclusions Soapnut oil methyl esters (SNME) and jatropha oil methyl esters (JME) showed the complementary fuel properties. A SNMEJME blending ratio of 35:65 by weight can successfully improve high cold lter plugging point (CFPP) of the SNME and poor oxidation stability of the JME to satisfy all of the biodiesel specications. The SNMEJME biodiesel and diesel blends up to B40 presented the CFPP of approximately 6 C, density of 836853 kg/m3 at 15 C, kinematic viscosity of 3.033.51 mm2/s at 40 C, and

KV (mm2/s)

820

800

20

40

60

80

2 100

Volumetric percentage of biodiesel (vol.%)


Fig. 2. Variations in density and kV of the biodieseldiesel blends with volumetric percentage of the biodiesel (vol.%). Symbol and line: experimental data and linear correlation, respectively. s and 4: density and kV, respectively.

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Y.-H. Chen et al. / Fuel 92 (2012) 377380 [4] Alptekin E, Canakci M. Determination of the density and the viscosities of biodieseldiesel fuel blends. Renew Energy 2008;33:262330. [5] Chen YH, Chen JH, Chang CY, Chang CC. Biodiesel production from tung (Vernicia montana) oil and its blending properties of different fatty acid compositions. Bioresour Technol 2010;101:95216. [6] USDA, ARS, National Genetic Resources Program, Germplasm Resources Information Network (GRIN). <http://www.ars-grin.gov/cgi-bin/npgs/html/ taxon.pl?20692>; 2010. [7] Chhetri AB, Tango MS, Budge SM, Watts KC, Islam MR. Non-edible plant oils as new sources for biodiesel production. Int J Mol Sci 2008;9:16980. [8] Sarin R, Sharma M, Sinharay S, Malhotra RK. JatrophaPalm biodiesel blends: an optimum mix for Asia. Fuel 2007;86:136571. [9] Haryana-online.com, Ritha. <http://www.haryana-online.com/Flora/ritha. htm>; 2007. [10] Misra RD, Murthy MS. Performance, emission and combustion evaluation of soapnut oildiesel blends in a compression ignition engine. Fuel 2011;90:25148. [11] Moser BR. Inuence of blending canola, palm, soybean, and sunower oil methyl esters on fuel properties of biodiesel. Energy Fuels 2008;22:43016. [12] Dunn RO. Cold weather properties and performance of biodiesel. In: Knothe G, Gerpen JV, Krahl J, editors. The biodiesel handbook. Urbana, Illinois: AOCS Press; 2005. p. 83121.

oxidation stability of 9.117.3 h. The use of the optimum biodiesel combination in a diesel engine would be the future work to study the combustion performance and pollutant emissions. Acknowledgment The authors would like to thank National Science Council of Taiwan for the nancial support. References
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