Fuel 89 (2010) 14751479

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Fuel
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In situ production of fatty acid methyl ester from low quality rice bran: An economical route for biodiesel production
Hong Lei, Xuefeng Ding *, Hongxi Zhang, Xue Chen, Yunling Li, Hong Zhang, Zichen Wang
College of Chemistry, Jilin University, Qianjin Street 2699, Changchun 130012, China

a r t i c l e

i n f o

a b s t r a c t
Low quality rice bran was used to produce fatty acid methyl ester (FAME) via in situ extraction, esterication and transesterication process. The effects of the acid and alkaline catalysts on the ester yield, esterication and transesterication process were studied. When 75 ml of absolute methanol, 150 ml of petroleum ether, 0.75 g of concentrated sulfuric acid and 0.71 g of sodium hydroxyl were used, 16.69% (wFAME/wrice bran) of FAME was obtained. The esterication rate and the transesterication rate reached 98.83% and 80.47%. Based on the proposed route, the production process of FAME (biodiesel) could be simplied and the production cost could be reduced. Crown Copyright 2009 Published by Elsevier Ltd. All rights reserved.

Article history: Received 17 August 2009 Received in revised form 19 September 2009 Accepted 9 October 2009 Available online 29 October 2009 Keywords: In situ Rice bran Fatty acid methyl ester Biodiesel

1. Introduction FAME is environment friendly because of its alternative, nontoxic, biodegradable and renewable properties [1,2]. It can be used as renewable fuel or applied as green solvent [3,4]. It is commonly produced by esterifying or transesterifying the vegetable oils or animal fats with methanol [5,6]. Because of the Energy Crisis of the world and the environmental problems of the fossil fuel, FAME is studied in majority as biodiesel recent years. It can be used as neat or blend with conventional fossil derived petrodiesel. However, raw material is a key factor for the application of biodiesel. The price of oil-containing material is strongly inuencing biodiesel cost, generally in the proportion of 7080% [7]. In order to reduce the biodiesel cost, a number of efforts have been made, such as selecting cheap raw materials or simplifying process, and so on. Rice bran is a suitable material for biodiesel production. Firstly, the biodiesel production from rice bran oil (RBO) has good performance both in engine test and emission test [810]. The results show that the biodiesel production from crude rice bran oil is of good quality and it can be used as an alternative fuel in current diesel engines without any expensive modications. Secondly, steady material source supply is available when use rice bran to produce biodiesel, especially in China. China produces more than ten million tons of rice bran annually. As a by-product of rice milling, rice bran contains 1523% lipids. Due to the presence of active lipase in
* Corresponding author. Tel./fax: +86 431 85155358. E-mail address: dingxf@jlu.edu.cn (X. Ding).

the bran and the lack of economical stabilization methods, most bran is used as livestock feed or boiler fuel and most rice bran oil produced is not of edible grade [11]. As a result, great amount of rice bran was utilized unreasonably nowadays. Thirdly, rice bran is a low-cost feedstock option for biodiesel production [12]. Our investigation in the range of China shows that the price of the rice bran is much lower and steadier than that of soy bean, rapeseed and cottonseed in the latest decade. Although some in situ methods were studied to reduce the biodiesel cost [1317], the liquid phase and solid oil-containing materials were mixed together in all of these studies. An additional step was needed to separate the solid and liquid phases, and more fresh solvent was needed to wash the solid phase for a few times to make sure the oil was transferred completely. Based on the existing studies and problems, this study was initiated to provide an in situ method to synthesize FAME from low quality rice bran, and suggest an economical route for biodiesel production. The oil extraction process and the effect of some factors, such as solvent and catalyst dosage, on the esterication and transesterication process were investigated. 2. Materials and methods 2.1. Materials Rice bran was supplied by a local factory (Songyuan, Jilin, China). It was passed through a 16 mesh sieve to remove mechanical impurity and broken rice during rice milling. The average oil content of the rice bran was 18.6%, and the moisture content of

0016-2361/$ - see front matter Crown Copyright 2009 Published by Elsevier Ltd. All rights reserved. doi:10.1016/j.fuel.2009.10.008

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the rice bran was 8.9%. The free fatty acids (FFAs) content of the extracted rice bran oil was about 80%. Potassium periodate was purchased from Sinopharm Group Chemical Reagent Co., Ltd. (Shanghai, China). Calcium oxide was purchased from Jiangsu Menghe Chemical Reagent Plant (Jiangsu, China). Petroleum ether (3060 C) was obtained from Tianjin Tiantai Fine Chemicals Co., Ltd. (Tianjin, China). Other chemical reagents used in the study, hydrochloric acid, sodium hydroxide, potassium iodide, sodium thiosulfate, potassium dichromate, sulfuric acid (98%) and absolute methanol (up to 99.5% purity), were purchased from Beijing Beihua Fine Chemicals Co., Ltd. (Beijing, China). All the agents above were analytical grade and used without further purication. 2.2. Experimental procedure A simplied block ow diagram of experimental procedure was shown in Fig. 1, and the related details were described in the following subsections. 2.2.1. Extraction of rice bran oil Rice bran oil was extracted by 200 ml of absolute methanol with Soxhlets method, as shown in Fig. 2a. Fifty grams of rice bran was used in each extraction. The extraction rate was dened as the weight quotient of the rice bran oil and the rice bran. The extraction process was investigated by analyzing the acid value (AV) and the glycerin content of the rice bran oil at different extraction time. 2.2.2. Acid catalyzed esterication In this stage, experiments were done to determine the proper dosage of the acid catalyst. The apparatus was as same as the one in the rice bran oil extraction stage, as shown in Fig. 2a. The difference was that H2SO4 was added in the ask in this stage, and the free fatty acids in the extracted rice bran oil could be esteried in situ while the extraction process was ongoing. After a certain time, the reaction was stopped by adding calcium carbonate into the ask. Then the methanol was recycled by distillation, and the oil product was washed with distilled water three times (50 ml for each time). Finally, the oil product was dried in an oven at 80 C to remove the moisture. The yield rate was obtained by dividing the weight of the oil product by that of the rice bran,
Fig. 2. Apparatus for oil extraction and FAME synthesis (a) apparatus for oil extraction and in situ esterication and (b) apparatus for alkaline catalyzed transesterication.

and the conversion of FFAs in the rice bran oil to FAME was studied by analyzing the AV of the oil product. 2.2.3. Effect of the solvent Petroleum ether was used to improve the efciency of rice bran oil extraction and to reduce the dosage of the methanol. As the boiling point (b.p.) of the petroleum ether (3060 C) was lower than that of the methanol, it would reux in the Soxhlet apparatus and extract rice bran oil, while the methanol would remain in the ask and mainly take part in the esterication and transesterication reactions. Different volume ratios of petroleum ether and absolute methanol were investigated (see Table 1). 2.2.4. Alkaline catalyzed transesterication In this stage, rice bran oil was extracted and in situ esteried using H2SO4 as catalyst rstly. After the AV of the extracted oil was lowed down, the Soxhlets apparatus was changed with another one which had CaO in it (see Fig. 2b). Then, certain amount of NaOH was dissolved in 15 ml of absolute methanol, and the solution was dropped into the ask in 3 h. After the alkaline solution was completely dropped into the ask, the reaction was maintained for another 0.5 h. After the completion of the reaction, the product was poured into a separatory funnel, and settled to

Fig. 1. Simplied block ow diagram of experimental procedure.

H. Lei et al. / Fuel 89 (2010) 14751479 Table 1 Effect of petroleum ether on the yield rate of oil product during acid catalyzed esterication process. No. 1a 2b 3b 4b 5c 6c 7b
a b c

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V (methanol) (ml) 200 200 25 50 75 100 75

V (petroleum ether) (ml) 0 0 175 150 125 100 150

Extraction/esterication time (h) 5 5 3 3 Null Null 3

Average yield rate (%) 16.45 16.47 18.64 18.89 Null Null 18.49

No agitation. Agitation. Bumping.

separate into two layers. The upper oil layer was washed with distilled water three times (50 ml for each time). Then, the oil product was dried in an oven at 80 C to remove the moisture. Finally, the yield rate was calculated, and the AV and the glycerin content were analyzed, respectively. 2.3. Analytical methods Glycerin was released when the glycerides in the rice bran oil were transesteried with short chain alcohols. As a result, we chose to analyze the content of glycerin in the untransteried glycerides to determine the extent of transesterication (glycerin in untransteried glycerides was released by special treatment). The actual glycerin weight was analyzed according to the method of periodic acid oxidation, and the transesterication rate was calculated as Eq. (1).

Transesterification rate 1 wEP %=wRBO % 100%

1
Fig. 3. Process of rice bran oil extraction, using methanol as solvent.

where wEP % is the residual glycerin content of the ester product, and wRBO % is the glycerin content of rice bran oil. AV was determined as Chinese national standard (GB5530-85), which was quite similar to the AOCS Ofcial Method Cd 3d-63. The difference is that GB5530-85 using ethanol and ethyl ether as solvent, while AOCS Cd 3d-63 using anhydrous isopropyl alcohol and toluene. The conversion of FFAs in the feed stock oil into methyl esters was calculated by the following equation.

Esterification rate 1 AVEP =AVRBO 100%

where AVEP is the acid value of the ester product, and AVRBO is the acid value of rice bran oil. 3. Results and discussion 3.1. Process of rice bran oil extraction The process of rice bran oil extraction with methanol was shown in Fig. 3. It could be seen that the oil extraction could nish in 5 h. The average extraction rate was about 16.7% based on the weight of the rice bran. We divided the process of oil extraction into three sections. The possible fact of the extraction was supposed as follow. In the rst section (13 h), the increase of extraction rate showed that the rice bran oil was extracted consecutively. The slightly decrease of AV indicated the percentage of FFAs in the extracted rice bran oil decreased. In another words, the percentage of glycerides in the extracted rice bran oil was supposed to increase accordingly. However, a slightly decline of glycerin content was seen. According to the weight percentages of glycerin section in triglyceride (TG), diglyceride (DG) and monoglyceride (MG) molecules (i.e. TG < DG < MG), we considered that the increase of TG or DG in

the extracted rice bran oil led to the slightly decline of glycerin content. In the second section (35 h), the extraction rate kept increasing, and more rice bran oil was extracted. The increase of AV and glycerin content may be caused by the hydrolyzation of TG or DG. In the third section (57 h), the oil extraction was completed. But the AV increased rapidly, and the glycerin content decreased. This could be explained by the hydrolysis of the glycerides (especially MG). 3.2. Rice bran oil extraction and in situ acid catalyzed esterication The effects of the acid catalyst and solvent on the esterication of free fatty acids were investigated. The results showed that, AV decreased with the increase of H2SO4 (Fig. 4a), and the extraction efciency was improved with the aid of petroleum ether (Table 1). Besides, a synergistic effect between methanol and petroleum ether was observed. It could reduce the usage of methanol and acid catalyst. As petroleum ether made the acid catalyst, oil phase and methanol more miscible, H+ could attach to the carbonyl oxygen of FFAs more easily, and the hydroxyl oxygen of methanol could attack the carbonyl carbon of FFAs more easily, too. According to the mechanism of esterication, the esterication efciency was enhanced. As a result, for a xed amount of acid catalyst, we could use less amount of methanol to get a lower acid value with the aid of petroleum ether (Fig. 4c). However, even when the petroleum ether was used, the amount of methanol could not be decreased illimitably (Fig. 4d). The reason lied on the other basic rule, that the amount of the reactant methanol was one factor affecting the esterication of FFAs. Commonly, more amount of

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Fig. 4. Effects of the acid catalyst and solvent on the esterication of free fatty acids.

methanol led to a lower acid value, and vice versa (Fig. 4b). Nevertheless, as we described before, without petroleum ether, AVs could hardly be lowed down even though more methanol was used (Fig. 4a). There existed a synergistic effect between methanol and petroleum ether. Data of Nos. 5 and 6 in Table 1 suggested that the volume of the petroleum ester adopted relied on the capability of the Soxhlets apparatus. If the petroleum ester was not enough to full ll the Soxhlets apparatus, the temperature in the ask would increase till the methanol was distilled. As a result, as soon as the uid recycled back into the ask, the high temperature would cause the bumping of petroleum ester. Typically, in the case of No. 1 in Table 1, when 2 g of H2SO4 was used, the acid value could be lowed to 6.42 mg KOH/g. In the case of No. 7 in Table 1, when 0.75 g of H2SO4 was used, the acid value could be lowed to 5.09 mg KOH/g. As H2SO4 could also catalyze the transesterication of glycerides, the glycerin contents in both of these two cases were measured, and then the transesterication rates were calculated. The results showed that the transesterication rates were 47.32% and 8.98%, respectively. Therefore, alkaline catalyst was necessary to be used to catalyze the transesterication reaction. 3.3. The effect of NaOH on the transesterication process and FAME production The effect of the alkaline catalyst (NaOH) on the synthesis of FAME was shown in Table 2. In this stage, 50 g of rice bran, 75 ml of absolute methanol, 150 ml of petroleum ether and 0.75 g of H2SO4 were used in the in situ rice bran oil extraction and esterication process. According to the data of Nos. 14 in Table 2, the optimal dosage of NaOH was 0.71 g, and the relevant esterication and transesterication rates reached 98.83% and 80.47%. According to the oil extraction experiment, the FFAs content of the extracted rice bran oil was around 80% and the glycerides held another 20%. Thus, we could estimate that about

Table 2 Effect of the alkaline catalyst on the synthesis of FAME. No. 1a 2a 3a 4a 5b

a b

m (NaOH) (g)c 0.61 + 0.05 0.61 + 0.10 0.61 + 0.20 0.61 + 0.40 0.61 + 0.10

Yield rate (%) 16.92 16.69 14.62 14.45 13.19

Esterication rate (%) 98.83 98.83 98.84 98.95 98.84

Transesterication rate (%) 76.95 80.47 80.86 80.47 78.52

The methanol solvent of NaOH was dropped into the ask. The methanol solvent of NaOH was all added into the ask once in a time, and no desiccant was used. c About 0.61 g was the theoretical dosage of NaOH to neutralize H2SO4.

95.16% (i.e. 80% 98.83% + 20% 80.47% = 95.16%) of extracted rice bran oil was transformed to FAME. Comparing the data of Nos. 2 and 5 in Table 2, we could see that, it was necessary to drop NaOH solvent into the system, and the synchronous water removal was important. 4. Conclusions In summary, using low quality rice bran as raw material, FAME was synthesized via in situ method. When 50 g of rice bran, 75 ml of absolute ethanol, 150 ml of petroleum ether, 0.75 g of concentrated sulfuric acid and 0.71 g of sodium hydroxyl were used, 16.69% (wFAME/wrice bran) of FAME was obtained. The esterication rate and the transesterication rate reached 98.83% and 80.47%. About 95.16% of extracted rice bran oil was transformed to FAME. References
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