October 9th-11th 2013, Bandung, Indonesia

<BIODIESEL>

International Seminar on Biorenewable Resources Utilization for Energy and Chemicals 2013
In conjunction with Chemical Engineering Seminar of SoehadiReksowardojo 2013

1 Synthesis of Biodiesel Using Carbon-Based Solid Catalyst

2 Febri Raharningrum1,2, Yano Suryapradana1,2, Arif Hidayat2,3 and Arief
3 Budiman1,2
1
4 Chemical Engineering Department, Gadjah Mada University
5 Jalan Grafika 2 Yogyakarta 55281, Indonesia
2
6 Process System Engineering Research Group, Department of Chemical Engineering
7 Gadjah Mada University, Yogyakarta 55281 Indonesia
3
8 Chemical Engineering Department, University of Islam Indonesia
9 Jalan Kaliurang km 14,5 Yogyakarta 55584, Indonesia
10 Email: abudiman@chemeng.ugm.ac.id
11
12
13 Abstract. Biodiesel is mostly made from trans-esterification reaction using
14 homogenous catalysts. Problems related to homogenous catalysts are the
15 difficulty to separate the final product and the toxic that the waste contains. To
16 prevent this negative effect, it is suggested to use heterogeneous catalysts.
17 Several studies related to heterogeneous catalysts have been studied by
18 researchers since the use of heterogeneous catalysts instead of homogeneous
19 ones can be expected to eliminate the problems associated with homogeneous
20 catalysts. The solid-based catalysts are easily regenerated and have a less
21 corrosive nature, leading to safer, cheaper, and more environment-friendly
22 operations. In this paper, the trans-esterification of palm oil to biodiesel was
23 studied using KOH loaded on activated carbon (K-AC) as heterogeneous
24 catalyst. Reaction parameters such as temperature, percentage of catalyst
25 amount, and molar ratio of oil to methanol were optimized to reach the highest
26 conversion. Iodometry method was used to determine bonding glycerol in final
27 product. The highest conversion of glycerol, 22.71%, was obtained by using 3%
28 catalyst amount at 60 oC temperature and 1:6 molar ratio of palm oil to methanol.
29 The low conversion was probably due to the catalysts pore size which is not
30 large enough, causing only a few triglycerides able to pass through the pore and
31 react with KOH.

32 Keywords: Biodiesel; Heterogeneous catalyst; Trans-esterification; KOH loaded

33 activated carbon

34 1 Introduction
35 Biodiesel is defined as methyl ester which is derived from trans-

36 esterification reaction of vegetable oils, animal fats and used oil from

37 food industry using alcohol in the presence of catalyst. The idea of using
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38 vegetables oils as fuel for engine has been known for more than 100

39 years ago, but it was not widely used because refined crude oil were still

40 cheaper and more appropriate as fuel or diesel fuel (Mittelbatch and

41 Remschmidt, 2004).

42 Nowadays, crude oil price is increased and the resource of fossil oil is

43 limited. Furthermore, continued and increasing use of fossil oil will

44 worsen the green house effect caused by CO2. It has been a new concern

45 to find renewable energy that could lower the dependence of crude oil,

46 reduce greenhouse gas emissions, and would not deliver any toxic effect

47 to environment. Biodiesel is noteworthy for its similarity to petroleum

48 based diesel but with less worse impact.

49 There are several materials which can be used to make biodiesel and one

50 of them is palm oil. Palm oil is produced from palm mesocarp, which is

51 characterized by high content of palmeat acid and oleic acid. The

52 advantages of using palm oil as a raw material are the large amount of oil

53 palm plantations in Indonesia and the cheaper price than other edible oils

54 (Susila, 2004).
 Synthesis of Biodiesel Using Carbon-Based Solid Catalyst 3

55 Biodiesel is mostly made from reacting palm oil and alcohol with the

56 presence of homogenous catalysts. Problems related to homogenous

57 catalysts are the difficulty to separate the final product and the toxic that

58 the waste contains. To prevent this negative effect, it is suggested to use

59 heterogeneous catalysts (Di Serio et al, 2007). The solid-based catalysts

60 are easily regenerated and have a less corrosive nature, leading to safer,

61 cheaper, and more environment-friendly operations.

62 Activated carbon has been widely used for catalytic supports because of

63 the facts that it owns many desirable properties required for support.

64 They include the following: (1) it can be used in acid and base condition;

65 (2) it can be used in high temperature condition (650 C); (3) it can be

66 changed in pore structure for different purposes; (4) it can be modified in

67 terms of its surface properties to become hydrophobic; (5) it can be

68 recycled for metal by burning spent catalysts; and (6) it is cheap (de la

69 Puente & Menendez, 1998; Goncalves & Figueiredo, 2004; Illan-Gomez

70 et al., 1995).Various carbonaceous materials such as coal, lignite,

71 nutshells, wood, and peat are used in the production of commercial

72 activated carbon. However, abundance and availability of agricultural by-

73 products make them good sources of raw materials for activated carbons.
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74 Harvesting and processing of various agricultural crops result in

75 considerable quantities of agricultural by-products. Such agricultural by-

76 products are usually inexpensive, for which the effective utilization has

77 been desired.

78 KOH loaded on activated carbon (K-AC) is able to accelerate the trans-

79 esterification reaction because of its active sites that reacts with

80 triglyceride molecules. The advantages of using activated carbon as a

81 catalyst support are its sufficient surface area, inert, and stable in high

82 pressure or temperature. As a catalyst support, activated carbon pore size

83 should be large enough to react with triglyceride molecule

84 (approximation of molecular size is 2-4 nm).

85 2 Materials and Methods

86 2.1 Materials
87 The activated carbon used in this work was coconut shell activated

88 carbon, produced by physical activation process. Palm oil was purchased

89 from local market. Methanol (99.8%) were obtained from Merck.

90 2.2 Catalyst Preparation

91 A potassium containing solution was prepared by dissolving KOH in

92 deionized water. Activated carbon was sieved to size range from 20 to 30

 Synthesis of Biodiesel Using Carbon-Based Solid Catalyst 5

93 mesh, washed with deionized water to remove fines and dirt, oven dried

94 at 110 C for a day, cooled in a desiccator and stored in glass containers.

95 Activated carbon was divided in 10 g portions and placed in separate

96 Erlenmeyer flasks and 100 ml of potassium hydroxide solution with

97 initial concentration 0.10 g/ml was added. Activated carbon together with

98 the KOH solutions was then agitated in an orbital shaker at 180 rpm at

99 constanttemperature of 25 C for 24 h. The total loading content of the

100 potassium salts was 6.8% by weight based on the weight of activated

101 carbon.

102 2.3 Trans-esterification of palm oil

103 Trans-esterification reaction of palm oil was carried out in a three-neck

104 round-bottomed flask (250 ml) equipped with a condenser, magnetic

105 stirrer, and temperature indicator. A known amount of palm oil was

106 added to reactor then heated to the desired temperature (60oC). Methanol

107 was also heated to the desired temperature, then added to the reactor

108 filled already by palm oil. The temperature of the mixture was

109 maintained isothermal. A known amount of catalyst was added to the

110 mixture. The molar ratio of methanol to oil used in this study was 4, 6,

111 and 8. The trans-esterification reaction was carried out for 1-4 hours.

112 After the reaction time, the solution was centrifuged for 10 minutes.
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113 Glycerol was in the bottom layer, separated with pipettes from the methyl

114 ester layer.

115 2.4 Determination of biodiesel conversion

116 The glycerol produced from the trans-esterification was analyzed by

117 iodometry method to determine the bonding glycerol. The conversion of

118 biodiesel was determined using the following equation.

119 0

120 3 Results and Discussion

121 3.1 Catalyst Characterization

122 The physical properties of activated carbon and K-AC catalyst are

123 summarized in Table 1. The coconut shell activated carbon had a BET

124 surface area of 30.884 m2/g and a pore volume of 3.259 cm3/g. The K-

125 AC catalyst, on the other hand, exhibits lower specific surface area

126 (34.466 m2/g) and pore volume (0.4091 cm3/g), compared to activated

127 carbon.

128 Table 1. The physical properties of activated carbon and K-AC catalyst

Materials
Physical Properties
Activated Carbon K-AC catalyst
 Synthesis of Biodiesel Using Carbon-Based Solid Catalyst 7

BET surface area (m2/g) 30.884 34.466

Pore volume (cm3/g) 3.259e-02 4.091e-02
Mean pore diameter (nm) 2.11025 2.374
129

130 Fig. 3. FTIR spectra of activated carbon and K-AC catalyst

131 The FTIR spectra of the activated carbons are shown in Figure 3. The

132 activated carbon contained more bands than the K-AC catalyst. The

133 broad band between 3700 and 3400 cm-1, which is assigned to the OH

134 stretching vibration of the hydroxyl functional groups including

135 hydrogen bonding, was observed for activated carbon and K-AC catalyst.
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136 The band at about 2870 cm-1, was attributed to the aliphatic CH

137 stretching vibration. The stretching vibrations of the C=O and C=C

138 bonds yield bands in the 17601690 and 16801610 cm-1 regions.

139 3.2 Effect of the amount of catalyst

140 The amount of catalyst added to the mixture was varied from 1, 3 and 5%

141 by weight based on the amount of palm oil. The conversion of palm oil to

142 glycerol was increased from 19,9% at 1% K-AC to 22,71% at 3% (Table

143 1). The increase was due to an increase in the number of active basic sites

144 in the reaction. 5% amount of catalyst added to the mixture did not show

145 a significant increase. According to Le Chatelier principle, a reversible

146 reaction is limited by equilibrium condition. Increasing the amount of

147 catalyst would not affect the conversion if the catalyst has provided

148 sufficient basic sites and the reaction has reached its equilibrium.

149 Table 1. The effect of different process variables on the conversion of

150 glycerol

Palm oil : Methanol Temperature Amount of catalyst Conversion

ratio (oC) (%) (%)
1:4 60 3 21,74
1:6 60 3 22,71
1:8 60 3 22,31
1:6 50 3 20,61
1:6 55 3 19,61
 Synthesis of Biodiesel Using Carbon-Based Solid Catalyst 9

1:6 60 1 19.99
1:6 60 5 20.20

151 3.3 Effect of temperature

152 The temperature of reaction was varied from 50, 55, and 60oC. The

153 highest conversion was obtained by the reaction carried out at 60oC

154 (Table 1). This satisfies the Arrhenius principle, saying the increase of

155 reaction rate is parallel with the increase of temperature.

156 Trans-esterification reaction using solid catalyst can be assumed as a

157 pseudo-homogenous reaction. Due to the presence of stirrer, the

158 resistance of mass transfer from liquid to solid can be neglected,

159 therefore reactant and catalyst were in the same phase. Methanol to oil

160 ratio was set excessed so the concentration of methanol was constant.

161 3.4 Effect of solvent-to-solid ratio

162 Reaction was carried out in the presence of 3% the amount of catalyst at

163 60 oC. The highest conversion was obtained by palm oil to methanol ratio

164 1:6 (table 1). Basically, trans-esterification is a reversible reaction. The

165 purpose of methanol to palm oil ratio was set excessively from its

166 stoichiometry need is to alter the equilibrium towards product side. Yet,

167 palm oil to methanol ratio 1:8 did not obtain a significant higher

168 conversion because the equilibrium was already reached.

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169 Conclusion
170 KOH loaded on activated carbon (K-AC) as a heterogeneous catalyst can

171 be used as solid based catalyst for biodiesel production from trans-

172 esterification of palm oil. The operating condition to obtain the highest

173 conversion was: amount of catalyst 3%, methanol to oil ratio 6, and the

174 reaction temperature at 60oC.

175 Acknowledgements

176 This research was financially supported by the Directorate of Research

177 and Community Service of the Directorate General Higher Education,

178 The Ministry of Education and Culture, Republic of Indonesia.

179 References

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183 [2] Levenspiel, O., Chemical Reaction Engineering, p.39, John Wiley

184 and Sons, Inc., New York, 1999.

185 [3] Mittelbach, M., and Remschmidt, C., Biodiesel, The

186 Comprehensive Handbook, Boersedruck Ges.m.b.H., Vienna, 2004.

 Synthesis of Biodiesel Using Carbon-Based Solid Catalyst 11

187 [4] Illan-Gomez M.J., Linares-Solano A., Radovic L.R., Salinas-

188 Martinez de Lecea C., NO reduction by activated carbons: 2

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190 [5] de la Puente G., & Menendez J.A., On the distribution of oxygen-

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193 Ion, 112:103111, 1998.

194 [6] Goncalves F. & Figueiredo J.L., Development of carbon supported

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