Fuel 85 (2006) 17431749 www.fuelrst.

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Fuel structure and properties of biodiesel produced by the peroxidation process

Cherng-Yuan Lin a,*, Hsiu-An Lin a, Lang-Bang Hung b
a

Department of Marine Engineering, National Taiwan Ocean University, Keelung 20224, Taiwan, ROC b Department of Food Science, National Taiwan Ocean University, Keelung 20224, Taiwan, ROC Received 4 October 2005; received in revised form 12 February 2006; accepted 10 March 2006 Available online 18 April 2006

Abstract Biodiesel is a clean alternative fuel, which can be used to reduce the emission pollution from diesel engines. The improvement of fuel properties of biodiesel through production technique was investigated in this study. A chemical production procedure of transesterication reaction combined with an additional peroxidation process was applied to produce the biodiesel. It was shown that the biodiesel produced by this method has a larger weight proportion of saturated carbon bonds, higher kinematic viscosity, and a higher ash point with less fuel residue collected after the fuel burning, than the biodiesel without the additional peroxidation process. Moreover, the peroxide value and the acid number increased while the thiobarbituric acid value, iodine value, combined relative oxidation rate, and number of double bonds of fatty acids reduced for the biodiesel produced with the additional peroxidation process. Therefore, it was concluded that the peroxidation process for biodiesel production can be used to improve the fuel properties of biodiesel. q 2006 Elsevier Ltd. All rights reserved.
Keywords: Peroxidation process; Fuel properties; Transesterication reaction

1. Introduction The diesel engine is widely used to provide the power source for on-land transportation vehicles, marine vessels and power plants. However, a diesel engine also emits various forms of pollutants in gaseous, liquid, and solid phases to the environment. These pollutants can endanger human health and damage the ecological environment [1]. The use of alternative clean fuel is one of the promising approaches for curtailing the amount of emission from diesel engines. Among those alternative fuels, biodiesel has shown great potential and is considered an environmentally friendly clean fuel or fuel additive [2]. Biodiesel, which is produced from vegetable oils, animal fats or waste cooking oils has been proven to emit lower emissions of particulate matter (PM), unburned hydrocarbon, carbon dioxide, carbon monoxide, polycyclic aromatic hydrocarbons (PAH), and nitric polycyclic hydrocarbons (nPAH) than petrodiesel [3]. Biodiesel has a superior lubricity, high

* Corresponding author. Tel./fax: C886 2 24622307. E-mail address: lin7108@mail.ntou.edu.tw (C.-Y. Lin).

0016-2361/$ - see front matter q 2006 Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2006.03.010

ash point and cetane number, high oxygen content, low poison, as well as high biodegradability [4,5]. Transesterication reaction is the most commonly applied technique to produce biodiesel [6]. Vegetable oil, waste cooking oil or animal fat, which is a composition of triglycerides reacts with alcohol, particularly methanol or ethanol with the help of a catalyst to form alkyl esters and glycerin during the transesterication reaction [7,8]. Because, the transesterication reaction is a reversible process, the use of excessive alcohol will simultaneously alter the status of the chemical equilibrium of the product mixture. The manufacturing process of biodiesel can be divided into three systems based on the type of catalyst used in the transesterication reaction, which are strong alkali, strong acid, and enzyme. The process of transesterication by a strong alkali catalyst has a short reaction time. Only a small quantity of catalyst is required in the transesterication reaction and it is therefore, widely applied in the commercialized biodiesel production. In contrast, the process of transesterication by a strong acid catalyst requires a longer reaction time but it tolerates more water and free fatty acids in the reactant mixture during the transesterication reaction, and is therefore, suitable to be used in the pre-treatment of waste cooking oil prior to carrying on with the strong alkali-catalyzed process. Moreover, the enzyme catalyst process has the disadvantages of both

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higher production cost and lower conversion rate, which prevents it from being applied to mass biodiesel production [9]. This study proposes to enhance fuel properties of biodiesel by improving its production technique. The peroxidation technique is applied in the elds of pharmaceuticals, foods and medicines to reduce the molecular structure of complex compounds by breaking their molecular structures. Both hydrogen peroxide and ozone have been used to destroy the molecular bonding of polysaccharide during the peroxidation reaction. Polysaccharide was found to have reduced viscosity and increased uidity and solubility after this process [10]. Transesterication reaction is used in this study to produce biodiesel from soybean oil. The peroxidation technique is followed in order to further improve the fuel properties of biodiesel. The fuel properties, such as the heating value, cetane number, and iodine value of the biodiesel produced from this process with and without the additional peroxidation process, as well as from a commercial biodiesel and ASTM no. 2D diesel were analyzed and compared. The advantages of this method of biodiesel production were evaluated as well.

petroleum ether and 0.5 wt% of water of the coarse biodiesel were then added into the biodiesel in turn to wash away the other impurities in the coarse biodiesel. The biodiesel was termed as sample 1 biodiesel after undergoing these processes. This was followed with a peroxidation process in order to further improve the fuel properties of the sample 1 biodiesel. Hydrogen peroxide (H2O2) of 1 wt% of the sample 1 biodiesel was added to stir and react with the sample 1 biodiesel in a reacting tank for 10 min when the peroxidation technology was applied. The reacting temperature was set at 60 8C. The p bonds in the unsaturated carbon bonds of the biodiesel are susceptible to being attacked by the components of hydrogen peroxide. As a result of chemical reaction, electrophilic addition on the methyl esters of the biodiesel takes place. The double bonds of the methyl esters then attached to the hydroxyl group of the hydrogen peroxide. Consequently, the unsaturated carbon bonds of the methyl ester become saturated ones. The methanol and the other unreacted impurities were thereafter distilled away at 70 8C to obtain the sample 2 biodiesel. 2.2. Testing of fuel properties

2. Experimental details 2.1. Biodiesel production Soybean oil was used as the raw oil to react with methanol in a molar proportion of 1:6 to produce biodiesel. The specications of the soybean oil are listed in Table 1 [11]. Sodium hydroxide (NaOH) of 1% on a mass base of the soybean oil was used as the catalyst and pre-mixed with methanol by a mechanical stirrer to form sodium methoxide and water. This mixture was thereafter added into a reacting tank to be mixed with the soybean oil using a mechanical homogenizer in order to undergo transesterication reaction. Because, the boiling point of methanol is 63 8C, the reacting temperature of the transesterication process was set at 60 8C in order to prevent the vaporization of the methanol from the reacting mixture during the biodiesel production process. It took 50 min to complete the transesterication reaction. After this process, the mixture was separated into two layers, coarse biodiesel and glycerol, by centrifuging or keeping it motionless by virtue of the difference in density between these two compounds. The unreacted methanol was distilled away from the coarse biodiesel at a temperature of 70 8C. The 50 wt% of
Table 1 Specications of raw oil for biodiesel production [11] Item Appearance Moisture and volatile matter (wt%) Insoluble impurities (wt%) Specic gravity Refraction rate Iodine value Acid number Saponication value Peroxide value Properties Lucid !0.09 !0.08 0.916 1.471 123 0.1 188 !0.9

Samples 1 and 2 biodiesels were tested for their fuel properties after they were produced. An oxygen combustion bomb calorimeter (1261 automatically adiabatic model, Parr Instrument Co., USA) [12] was used for the analysis of the heating values of both biodiesels. The ash points of the fuels were tested by a Pensky-Martens closed-cup tester. A Saybolt viscosimeter was used to measure the kinematic viscosities of the biodiesels. A gas chromatograp (GC-14A model made by Shimadzu, Inc., Japan) accompanied with a ame ionization detector was used to analyze the fatty-acid compositions and the weight proportions of the saturated and unsaturated carbon bonds of the biodiesel in this study. The acid number, which was expressed as mg KOH/g, was acquired by titrating 0.01 N potassium hydroxide to the mixture of tested fuel and chemical reagents [13]. The peroxide value and iodine value were determined by titrating 0.01 N sodium thiosulfate to the mixture of tested fuel and chemical reagents until the disappearance of the colors yellow and blue, respectively based on the analysis methods of American Oil Chemists Society [14]. The testing procedures are based on the analysis method of American Oil Chemists Society [2] and calculated by the following formula: Peroxide value Z SKB !N !1000=W Iodine value Z BKS !N !0:001269=W where S and B are the amounts (in unit of mL) of sodium thiosulfate titrated for the tested sample and blank sample, respectively; N is the molar concentration (in unit of mol/L) of sodium thiosulfate; and W is the weight (in unit of g) of the tested sample. The thiobarbituric acid (TBA) value was analyzed by an ultraviolet visible spectrometer [15]. The elemental compositions of the fuel residual collected from burning the tested

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fuel were analyzed by an energy dispersive spectrometer (EDS). The X-ray energy of the EDS activates pairs of electronelectron holes in the semi-conductor crystal to produce signals, which are transformed to the energy spectrogram [16]. The fuel properties of the biodiesel produced in this study were compared with those of a commercial biodiesel and ASTM no. 2D diesel. Each experiment was repeated three to ve times to calculate the mean values of the experimental data. The experimental uncertainty for saturated and unsaturated carbon bonds of the methyl esters of fatty acids are 3.1 and 2.6%, respectively. 3. Results and discussion The fuel properties of the samples 1 and 2 biodiesel, which were produced by the processes as described in this study, a commercial biodiesel and the ASTM no. 2D biodiesel were analyzed and listed in Tables 24. The heating values of these four fuels are compared in Fig. 1. The three kinds of biodiesel have lower heating values than the ASTM no. 2D diesel. The heating values of the samples 1 and 2 biodiesel are comparable with each other and are higher than that of the biodiesel produced by Monyem and Gerpen [2]. The samples 1 and 2 biodiesel have a lower heating value than that of the ASTM no. 2D diesel by about 12%. This is primarily due to the lower elemental carbon and higher elemental oxygen contents in the biodiesel. The peroxidation process does not seem to have a signicant inuence on the heating value of the produced biodiesel. The burning of the sample 2 biodiesel released the least fuel residual in comparison with the sample 1 biodiesel and the ASTM no. 2D diesel, as shown in Fig. 2. The oxygen content of sample 1 biodiesel was 9.09 wt%. After the additional peroxidation process, the oxygen content of sample 2 biodiesel became 9.94 wt%. This implies that the oxygen content of the biodiesel increased by 9.3% after the peroxidation process. The higher oxygen content in biodiesel results in a more extensive chemical reaction and consequently less carbon residue is produced. Therefore, the burning of the biodiesel, which was
Table 2 Comparison of fuel properties Property Fuel ASTM no. 2D diesel Heating value (cal/g) Flash point (8C) Viscosity (cst at 40 8C) Specic gravity Iodine value Peroxide value Acid number TBA 11035.7 65 2.5 0.836 Commercial biodiesel 9712.8 125 4.3 0.882 128.5 58.235 2.76 90.5 Sample 1 biodiesel 9715.2 128.4 3.8 0.869 127.7 9.32 1.24 73.12 Sample 2 biodiesel 9687.3 133.9 4.3 0.873 123.4 12.942 2.30 46.59

Table 3 Fuel properties of the commercial biodiesel Item Cetane Index C% H% O% S% Water Ash Carbon residue Property 45.8 76.96 11.85 9.41 0.017 0.026 0.0 0.04 Unit wt% wt% wt% wt% wt% wt% Test method ASTM D976

ASTM D4294 ASTM E1064 ASTM D976 ASTM D524

produced through transesterication reaction followed by the peroxidation process has the highest combustion efciency, and therefore, the least amount of black smoke is emitted from the exhaust manifold of that diesel engine. Hence, the peroxidation process for biodiesel production can promote the combustion characteristics and will reduce the emission of particulate matter. The elemental contents of the fuel residual after burning the ASTM no. 2D diesel, samples 1 and 2 biodiesel were analyzed by an energy dispersive spectrometer (EDS). The fuel residual is mainly composed of elemental carbon content, as shown in Table 5. The oxygen content in the fuel residual may be formed from burning both excess surrounding air and the oxygen component, which is contained in the samples 1 and 2 biodiesel. Trace elemental metallic contents such as Al and Na may be produced from the burning of the compositions of the ignition wire, which was used to incur the liquid fuel combustion. The fuel residue, after burning the sample 2 biodiesel, is shown to have the lowest carbon and the highest oxygen elemental contents among the three fuels in Table 5. This result of the fuel residue after being burned agrees approximately with the elemental contents of the fuel as shown in Table 4. The ash points of the three biodiesels and the ASTM no. 2D diesel are shown in Table 2. The sample 2 biodiesel has the highest ash point among these four fuels and is nearly twice that of the ASTM no. 2D diesel. A higher ash point indicates a higher degree of safety for the storage, transportation, and usage of liquid fuel. The kinematic viscosities of the ASTM no. 2D diesel, samples 1 and 2 biodiesel are 2.5, 3.8, and 4.3 cst, respectively as shown in Table 2. Chen [17] considered that the biodiesel produced from soybean oil was about 4.0 cst, which is lower than that of biodiesel produced from rapeseed oil and palm oil, which were 4.2 and 4.5 cst, respectively. The specication of kinematic viscosity is in the range of 1.9 6.0 cst in the ASTM D6751 biodiesel standard and 3.55.0 in the EN 14214 biodiesel standard. The kinematic viscosities of
Table 4 Fuel properties of the ASTM no. 2D diesel Item Cetane Index C% H% S% Property 50.9 86.13 13.93 0.34 Unit wt% wt% wt% Test method ASTM D976

ASTM D4294

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Fig. 1. Heating values of the tested fuels.

the biodiesel produced in this study are in the range of both the ASTM D6751 and EN 14214 biodiesel standards, although the kinematic viscosities of these two biodiesel are slightly higher than that of the ASTM no. 2D diesel fuel. Therefore, it may be inferred that no modication is required on the injection pump of a diesel engine when biodiesel is used as an alternative fuel. Based on previous studies on storage stability of biodiesel [4,1819], iodine value, peroxide value and the acid number can be used as the indicators of the storage stability of biodiesel. The iodine value can be used to represent the amount of unsaturated fatty acids in oil. A higher iodine value indicates a higher content of unsaturated fatty acids in oil. The iodine value of the soybean oil, which was used as the raw oil for the biodiesel production is 142. The iodine values of the samples 1 and 2 biodiesels are 127.7 and 123.4, respectively. The iodine value of the biodiesel produced from soybean oil by another researcher was 130 [17], which was close to the values of the samples 1 and 2 biodiesel. The sample 2 biodiesel was produced by transesterication reaction combined with a peroxidation process. The p bond in the unsaturated carbon bonds of methyl esters of the sample 1 biodiesel was susceptible to attack by the compound of hydrogen peroxide during the peroxidation process. The electrophilic addition on the methyl esters was produced from this chemical reaction. The original positions of the double bonds of the sample 1 biodiesel were thus connected with the hydroxyl group of the hydrogen peroxide. The weight proportion of the unsaturated carbon bond in the sample 2 biodiesel was thus reduced by 1.56 wt% from 83.41 to 81.85 wt% as shown in Fig. 3. In addition, the peroxidation process under long reacting time and high reacting temperature will incur a decrease in the number of double bonds such as the 18:3 and 18:2 carbon bonds, as well as an increase in the weight proportion of saturated fatty acids such as 18:0 and 16:0 carbon bonds. This leads to a decrease of the iodine number. Hence, the iodine value of the sample 2 biodiesel produced with the additional peroxidation

Fig. 2. Fuel residue collected in a crucible after burning in a bomb-type calorimeter for (a) ASTM no. 2D diesel, (b) sample 1 biodiesel, and (c) sample 2 biodiesel.

process was lower than that of the sample 1 biodiesel by 4.3, as shown in Table 2. Liu and White [18,19] heated up commercial soybean oil to 60 8C and 180 8C, respectively, in order to compare variations of carbon-bond structure variations for fatty acids of the soybean oil. They found that the increase of heating time caused a slight increase of fatty acids of 18:1, 18:0 and 16:0 carbon bonds, while it caused a gradual reduction of fatty acids of the 18:2 and 18:3 carbon bonds. In addition, when the soybean oil was heated to 180 8C, the fatty acids of 18:1, 18:2 and 18:3 carbon bonds were considerably reduced while the fatty acids of 18:1, 18:0 and 16:0 carbon bonds were signicantly increased. This infers that either increase of the heating time or the heating temperature of vegetable oil enhances the conversion rate of its unsaturated fatty acids to become saturated fatty acids.

C.-Y. Lin et al. / Fuel 85 (2006) 17431749 Table 5 Elemental compositions of fuel residue after burning, analyzed by energy dispersive spectrometer (EDS) Fuel ASTM no. 2D diesel Sample 1 biodiesel Sample 2 biodiesel Elemental compositions (wt%) C 89.62 82.91 81.26 O 3.52 8.01 8.59 Na 0.18 0.26 0.3 Al 0.8 1.16 1.21 Si 5.42 7.2 8.09 K 0.46 0.46 0.56

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The weight proportions of saturated and unsaturated fatty acids of the samples 1 and 2 biodiesel are shown in Fig. 3. The sample 2 biodiesel, which was produced with additional peroxidation reaction under longer heating time and higher heating temperature was found to have a larger weight proportion of saturated carbon bonds and lower unsaturated carbon bonds. The weight proportion of saturated carbon bonds was 16.59 wt% for the sample 1 biodiesel and 18.15 wt% for the sample 2 biodiesel. This implied that the saturated carbon bonds of the biodiesel were increased by 1.56 wt% when the peroxidation process was followed with transesterication reaction in the production of biodiesel. The structures of the carbon bonds of the samples 1 and 2 biodiesel were further analyzed and revealed in Fig. 4. The fatty acids of 18:1 carbon bonds was slightly increased from 22.26 wt% for the sample 1 biodiesel to 22.75 wt% for the sample 2 biodiesel. In contrast, the weight proportion of fatty acid of 18:2 carbon bonds was decreased from 57.19 wt% for the sample 1 biodiesel to 55.18 wt% for the sample 2 biodiesel. The weight proportion of fatty acid of 18:3 carbon bonds was also slightly reduced from 3.96 to 3.92 wt% when the additional peroxidation process was applied after the transesterication reaction in the production of biodiesel. This infers that the reacting time and reacting temperature during the biodiesel production may inuence the conversion quantity of the carbon bonds of fatty acid structure. An oxidation reaction between chemically unstable double bonds of fatty acids and the surrounding air can be accelerated under the operating condition of a high reacting temperature and a long reacting time. The number of double bonds of fatty

acids are thereby reduced, leading to an increase of the weight proportion of the saturated fatty acids for the biodiesel produced by the additional peroxidation process as shown in Figs. 3 and 4. The peroxide value is an indicator of the extent of peroxidation of fatty acid oil at its initial stage of storage. Liu and White [18,19] found that the peroxide value of soybean oil increased from 0.1 to 45.2 when the soybean oil remained at a temperature of 60 8C from 0 to 15 days. The peroxide value increased more substantially when the soybean oil was heated to an even higher temperature. The peroxide values of the commercial biodiesel, sample 1 biodiesel, and sample 2 biodiesel are 58.2, 9.3 and 12.9, respectively as shown in Table 2. The commercial biodiesel has a much higher peroxide value, which is primarily due to its longer storage time after its production compared to the other two biodiesels. Part of the commercial biodiesel has therefore, reacted with the surrounding air, resulting in a higher peroxide value. The sample 2 biodiesel was produced from the sample 1 biodiesel with an additional peroxidation reaction. Because, the peroxidation reaction was carried out at a higher temperature and with a longer reacting time, the peroxide value of the sample 2 biodiesel was therefore, slightly higher than that of the sample 1 biodiesel. The acid number can be used to estimate the quantity of free fatty acids in oil. A higher acid number indicates a larger content of free fatty acids in oil. The acid numbers of the commercial biodiesel, sample 1 biodiesel, and sample 2 biodiesel were 2.76, 1.24 and 2.30, respectively. This means

Fig. 3. Weight proportions of saturated and unsaturated carbon bonds of samples 1 and 2 biodiesel.

Fig. 4. Weight proportions of structures of carbon bonds for samples 1 and 2 biodiesel.

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C.-Y. Lin et al. / Fuel 85 (2006) 17431749 Table 7 TBA values for samples 1 and 2 biodiesel, commercial biodiesel, and commercial biodiesel after being peroxidized Property Fuel Sample 1 biodiesel TBA 73.12 Sample 2 biodiesel 46.59 Commercial biodiesel 92.5 Peroxidized commercial biodiesel 90.13

that the commercial biodiesel has the highest content of free fatty acids among the three biodiesels. The quantity of free fatty acids of the sample 1 biodiesel increased after the peroxidation process. As a result, the sample 2 biodiesel appeared to have a higher acid number than that of the sample 1 biodiesel. This result agrees well with those of Liu and White [18,19] who found that the acid number of fatty acid oil rose with the increase of either reacting temperature or reacting time of this oil. The (TBA) value is an important indicator of the degree of oil oxidation. A higher TBA value implies a greater extent of oil oxidization. The TBA values of the commercial biodiesel, samples 1 and 2 biodiesel are 90.5, 73.12, and 46.59, respectively as shown in Table 2. This implies that the commercial biodiesel has been oxidized the most seriously among these biodiesels. However, the sample 2 biodiesel has a larger acid number and a signicantly lower TBA value than the sample 1 biodiesel. Therefore, compared with the sample 1 biodiesel, the sample 2 biodiesel has a higher number of free fatty acids and a lower degree of oxidation. To verify the effects of the peroxidation process on the TBA and acid number, the commercial biodiesel was processed through the same peroxidation reaction used for the sample 1 biodiesel. The experimental results of acid number and TBA value for the sample 1, sample 2 biodiesel, commercial biodiesel, and peroxidized commercial biodiesel are shown in Tables 6 and 7. The commercial biodiesel, after the peroxidation process, had an increased acid number from 2.97 to 3.23 in Table 6 and a reduced TBA value, from 92.52 to 90.13, as shown in Table 7. These results in the trends before and after the peroxidation process for the commercial biodiesel agreed well with the acid number and TBA value for the samples 1 and 2 biodiesel. In other words, the peroxidation reaction stated in this study can cause an increase in acid number and a reduction of the TBA values for fatty acid oils. After relating the results of the TBA values and the acid number with those of the weight proportions of the structures of carbon bonds in Fig. 4, it was found that the extent of oil oxidation was inuenced by its storage time and reacting temperature. The p bonds in the unsaturated carbon bonds of the sample 1 biodiesel were susceptible to be attacked by hydrogen peroxide. At the same time, part of the elemental hydrogen content in the oil reacted with unsaturated carbon bonds such as C18:1, C18:2 and C18:3 to form saturated carbon bonds such as C18:0 in the biodiesel. Consequently, the number of double bonds decreased, resulting in a lower propensity towards oxidation. The TBA value of the sample 2 biodiesel was therefore, relatively lower than that of the sample
Table 6 Acid numbers for samples 1 and 2 biodiesel, commercial biodiesel, and commercial biodiesel after being peroxidized Property Fuel Sample 1 biodiesel Acid number 1.1 Sample 2 biodiesel 2.13 Commercial biodiesel 2.76 Peroxidized commercial biodiesel 3.23

Table 8 Combined relative oxidation rates for samples 1 and 2 biodiesel Fuel Sample 1 biodiesel Sample 2 biodiesel Combined relative oxidation rate 673.26 653.02

1 biodiesel, as shown in Table 2. The relative oxidation rates of the carbon bonds C18:3, C18:2 and C18:1 are 20:10:1, as calculated by Gunston [20]. The combined relative oxidation rates of the samples 1 and 2 biodiesel were obtained by multiplying the weight proportions of those carbon bonds, i.e. C18:3, C18:2 and C18:1 and their corresponding relative oxidation rates. The weight proportion of C18:2 in the sample 2 biodiesel was 55.18 wt% and was signicantly lower than that of the sample 1 biodiesel, which was 57.19 wt%, as shown in Fig. 4. There were no obvious differences between the weight proportions of C18:1 and C18:3 for the samples 1 and 2 biodiesel in Fig. 4. This is due to the fact that the combined relative oxidation rates of the sample 2 biodiesel was 653.02, which is lower than the combined relative oxidation rate of the sample 1 biodiesel, which was 673.26, as shown in Table 8. Therefore, the TBA value of the sample 2 biodiesel was lower than that of the sample 1 biodiesel in Table 2. 4. Conclusion The heating values of the three kinds of biodiesel were lower than that of the ASTM no. 2D diesel, which was primarily due to its lower carbon and higher oxygen elemental contents. The biodiesel produced by the additional peroxidation process was shown not to cause a signicant variation of heating value compared to the biodiesel without the additional process. However, among the tested fuels, after the burning process the biodiesel produced with the additional peroxidation process released the least amount of fuel residual. In addition, it also had the lowest carbon and the highest oxygen elemental contents in the fuel residual released after burning among the four fuels tested. The biodiesel produced by the peroxidation process also had the highest kinematic viscosity and the highest ash point among the four tested fuels. The peroxidation process caused the increase of the acid number, peroxide value, and weight proportion of the saturated carbon bonds while decreasing the iodine number and the number of double bonds of fatty acids. Part of the elemental hydrogen content in the hydrogen peroxide agent reacted with the unsaturated carbon bonds such as C18:3, C18:2 and C18:1 in the biodiesel during the

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peroxidation process. The number of unsaturated double carbon bonds of the biodiesel was reduced. The peroxidation process for biodiesel production therefore, caused a reduction of the combined relative oxidation rate and TBA value. Acknowledgements The authors gratefully acknowledge the nancial support from the National Science Council of Taiwan, ROC for this investigation under Project contract No. NSC 90-2212-E019-010. References
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