process safety and environment protection 8 6 ( 2 0 0 8 ) 441447

Contents lists available at ScienceDirect

Process Safety and Environment Protection

journal homepage: www.elsevier.com/locate/psep

Biodiesel production from waste oil feedstocks by solid acid catalysis

Bao-Xiang Peng, Qing Shu, Jin-Fu Wang , Guang-Run Wang, De-Zheng Wang, Ming-Han Han
Beijing Key Laboratory of Green Chemical Reaction Engineering and Technology, Department of Chemical Engineering, Tsinghua University, Beijing 100084, China

a b s t r a c t
Biodiesel is a non-toxic and biodegradable substitute for petroleum-based diesel. However, it is impractical to use rened edible oils to produce biodiesel due to its high cost and priority for food products, especially in China, while waste oils with high free fatty acids (FFAs) can be considered as the raw materials. In the present work, a solid acid catalyst comprising SO4 2 /TiO2 SiO2 was prepared, characterized and studied for its activity for the production of biodiesel from several low cost feedstocks with high FFAs. The solid acid catalyst can be recycled, easily removed and can simultaneously catalyze esterication and transesterication. The inuence of reaction parameters was studied, and the optimized reaction parameters are reaction temperature 200 C, molar ratio of methanol to oil 9:1 and catalyst concentration 3 wt.%. The catalyst showed good stability. A continuous process for biodiesel production from cheap raw feedstocks was proposed, and a 10,000-tonnes/year biodiesel production demonstration plant has been built. 2008 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved. Keywords: Biodiesel; Solid acid; Esterication; Transesterication; Waste oil feedstock

1.

Introduction

Due to the potential depletion of petroleum and environmental concerns about air pollution caused by the combustion of fossil fuels, the search for alternative fuels has gained much attention. Biodiesel (fatty acid methyl ester) derived from either the transesterication of triglycerides (vegetable oils or animal fats) or the esterication of free fatty acids (FFAs) with methanol is a potential substitute for petroleum-based diesel. Compared with conventional diesel, biodiesel has the advantages of being biodegradable, renewable, non-toxic, and low pollutant, especially SOx emission (Angina and Ram, 2000; Gerpen, 2005). The major obstacle to the commercialization of biodiesel from vegetable oil, in comparison to petroleum-based diesel, is primarily the high raw material cost (Haas, 2005; Haas et al., 2006; Kulkarni and Dalai, 2006; Zhang et al., 2003a). In recent years, China has been consuming approximately 22 million tonnes of rened edible oils annually, of which 50% was imported (source: National Grain & Oil Information Cen-

ter). Therefore, it is impractical in China to produce biodiesel from rened edible oils as feedstocks. The use of cheap raw feedstocks such as waste cooking oils, soapstock (byproduct of vegetable oil renery) and non-edible oils will improve the economical feasibility of biodiesel (Behzadi and Farid, 2007; Canakci, 2005; Ramadhas et al., 2005; Supple et al., 2002; Tomasevic and Siler-Marinkovic, 2003; Zhang et al., 2003b). In China, the potential amount of waste cooking oils and soapstock is about 2.5 and 1.0 million tonnes/year, respectively. Currently, many attempts have also been made to produce biodiesel from non-edible plant oils like karanja, jatropha, mahua and Chinese prickly ashseed oil (Ghadge and Raheman, 2005). Due to the high free fatty acid content and water in these cheap raw feedstocks, the use of a homogeneous base catalyst will cause saponication, which creates a serious problem of product separation and will ultimately substantially decrease methyl ester yield. In order to solve this problem, a two-step process (Canakci and Gerpen, 2001; Dorado et al., 2002; Talens et al., 2007; Zullaikah et al., 2005) is most commonly used to

Corresponding author. E-mail address: wangjf@otu.org (J.-F. Wang). Received 4 February 2008; Accepted 17 May 2008 0957-5820/$ see front matter 2008 The Institution of Chemical Engineers. Published by Elsevier B.V. All rights reserved. doi:10.1016/j.psep.2008.05.003

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deal with feedstocks with high FFAs. The rst step is the preesterication of FFAs with methanol, which is catalyzed by liquid acids. By this pretreatment, the FFA content of the oil is reduced to less than 1%. The second step, alkaline-catalyzed transesterication process, converts the products of the rst step to biodiesel and glycerol. Homogeneous acid catalysts show better adaptability to FFAs than base catalysts, and can catalyze esterication and transesterication simultaneously (Wang et al., 2006). However, the separation of the catalyst and serious environmental and corrosion-related problems limit their use. Since heterogeneous catalysts can provide a simple catalyst removal step and can be recycled, utilizing heterogeneous catalysis to produce biodiesel is becoming more popular (Petersonm and Scarrah, 1984; Serio et al., 2006). Compared with solid base catalysts, solid acid catalysts have lower catalytic activity but higher stability, thus, they can be used for feedstocks with large amount of FFAs without catalyst deactivation (Lotero et al., 2005). Many researchers have already made good progress on biodiesel production via heterogeneous acid catalysis (Meher et al., 2004). Solid acid catalysts, such as Amberlyst-15 (Chavan et al., 2001), SO4 2 /SnO2 (Chavan et al., 1996) and zeolites (Sasidharan and Kumar, 2004) used for triglyceride transesterication showed high catalytic activities. The esterication of FFAs by solid acid catalysts also had been explored. Sulfated zirconia (SO4 2 /ZrO2 ), sulfated tin oxide (SO4 2 /SnO2 ) and sulfated titanium oxide (SO4 2 /TiO2 ) are the representative catalysts that showed good catalytic activities (Kiss et al., 2006; Furuta et al., 2004a). Some of these solid acid catalysts, such as SO4 2 /TiO2 , showed high catalytic activity and good stability when used to catalyze esterication and transesterication simultaneously (Furuta et al., 2004b). However, they have not been generally used in the industrial production process, mainly because of the high catalyst cost and difculty in ltering the small catalyst particles. In the present study, we prepared large particles of the solid acid catalyst SO4 2 /TiO2 SiO2 (Chen and Wang, 2006), and evaluated its catalytic activity for biodiesel production from cheap raw materials. The effect of various reaction parameters on biodiesel yield, such as catalyst concentration, reaction temperature, molar ratio of methanol to oil and amount of FFAs was studied. A continuous process for biodiesel production from feedstocks with high FFAs was proposed, and the properties of the biodiesel product were obtained.

equipment (NOVA-4000) and nitrogen adsorption. The chemical compositions of the samples were characterized by XPS and element analysis (PHI Quantera SXM).

2.3.

Reaction procedure

In practical industrial production, waste vegetable oils used as feedstocks include corn, cottonseed, rapeseed and soybean acidied oils (derived from soapstocks by acidication), and non-edible oils like Chinese prickly ashseed oil. In this work, a mixed oil made by adding oleic acid to rened cottonseed oil was used. The reaction was carried out in a 250-mL autoclave equipped with a magnetic stirrer. The mixed oil and a known amount of catalyst were charged into the reactor. When the required temperature was reached, methanol with the same temperature was charged in by a pump, and the reaction was started by stirring. Samples were manually withdrawn at different times during the run. After several hours, the reaction mixture was cooled and separated by ltration. The ltrate was allowed to settle down to separate into two layers. The oil phase consisted of methyl esters, while the aqueous phase mainly contained water, methanol and glycerol.

2.4.

Method of analysis

2.
2.1.

Experimental
Catalyst preparation

High-performance liquid chromatography (HPLC, Shimadzu LC-10A) equipped with an ultraviolet photometric detector was used for analyzing the product samples. A Spherisorb ODS 2 column (250 mm 4.6 mm with 80 pore size and 5 m particle size) was used for the separation. The mobile phase was a mixture of acetone and acetonitrile in the volumetric ratio 50:50. The ow rate of the mobile phase was 1 mL/min, and the column temperature was set at 40 C. The components measured by the HPLC included triglycerides, diglycerides, monoglycerides, methyl esters and free fatty acids. Standard samples were used to establish the calibration charts. The calibration charts were used to calculate the weight percentage of the individual components from the integrated peak areas. The identities and relative proportions of fatty acids in the methyl ester product were determined by an Agilent GC-6890 gas chromatograph with a ame ionization detector. This was equipped with a 95% dimethylpolysiloxane capillary column (HP-5ms, 30 m 0.25 mm 0.25 m). The GC operating conditions were held at 60 C (2 min), heated at 10 C/min to 250 C, and held at 250 C (4 min). The injector and detector temperatures were set at 280 C. The helium ow rate was 2.0 mL/min.

3.
3.1.

Results and discussion

Structural properties of the catalyst

50 g SiO2 powder (Qingdao Haiyang Chemical Co., Ltd, China) was slowly added to 200 mL of 0.5 mol/L tetraisopropyl titanate solution of isopropyl alcohol, and was agitated under reux for 4 h. After ltering and drying at 110 C for 2 h, the powder was calcined at 450 C for 4 h. The resulting TiO2 SiO2 particles were soaked in a 0.5-mol/L H2 SO4 solution (10 mL H2 SO4 per 1 g SiO2 ) for 1 day, followed by ltering and drying. SO4 2 /TiO2 SiO2 was nally obtained by calcining at 500 C for 4 h.

The structural properties and composition of the catalyst are given in Table 1. The large specic surface area of the catalyst ensured good contact between the reactant molecules and catalytic active sites. The average pore diameter of the catalyst is Table 1 Properties of the catalyst (SO4 2 /TiO2 SiO2 )
Surface area (m2 /g) Average pore diameter (nm) Pore volume (mL/g) Ti (wt.%) S (wt.%) Si (wt.%) 258 10.8 1.1 6.7 2.2 37.4

2.2.

Catalyst characterization

The BET specic surface area and pore size distribution of the catalyst were measured using a Micrometrics adsorption

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Table 2 Properties of different feedstocks Oil type

Cottonseed acidied oil Corn acidied oil Rapeseed waste oil Soybean waste oil Chinese prickly ashseed oil

Acid value (mg KOH/g)

172 92 112 68 37.5

FFAs (wt.%)
86 46 56 34 18

Saponication value (mg KOH/g)

185 180 189 199 176

big enough so that the molecules of reactant and product can pass through the channels. Furthermore, the amounts of Ti and S on the surface of the catalyst are high. All these indicate the solid acid catalyst SO4 2 /TiO2 SiO2 will have high catalytic activity.

3.2.

The effect of reaction parameters

Table 2 presents the properties of ve cheap raw feedstocks. It can be seen that the acid values of these oils varied widely, from 37.5 to 170 mg KOH/g. Also the FFA content of these materials is high, with a maximum of 86%. As described above, a mixed oil made by adding oleic acid to rened cottonseed oil was used to study the inuence of the reaction parameters. The effect of temperature, catalyst concentration, molar ratio of methanol to oil, FFA content of oil and stability on biodiesel yield was examined. A mixed oil with 50% rened cottonseed oil and 50% oleic acid was used for most of the experiments. When we calculate the molar ratio of methanol to oil, 3 mol of FFAs is treated as 1 mol of triglyceride.

Fig. 2 Effect of temperature on ME yield. Reaction conditions: mixed oil (50% cottonseed oil and 50% oleic acid), molar ratio of methanol to oil 9:1 and catalyst concentration 3 wt.%. used for biodiesel production from cheap feedstocks with high FFA contents.

3.2.1.

Free fatty acids content of oil

The effect of FFA amount on the yield of esters was studied by adding 10, 30, 50 and 80 wt.% oleic acid to rened cottonseed oil. The reaction was carried out at 200 C, with a molar ratio of methanol to oil 9:1 and catalyst concentration 3 wt.%. Fig. 1 shows that the FFA content increased the yield of methyl ester, and the rate of esterication of oleic acid was much higher than the rate of transesterication of cottonseed oil. Several researchers (Warabi et al., 2004; Kulkarni et al., 2006) had also observed a similar phenomenon. The greater solubility of FFAs than cottonseed oil in methanol is one of the reasons. From the experiments, it can be concluded that SO4 2 /TiO2 SiO2 is very well suited for high FFA contents in the oil and the water produced by esterication. Therefore, SO4 2 /TiO2 SiO2 can be

3.2.2.

Reaction temperature

The inuence of the reaction temperature on the yield of biodiesel was evaluated using a mixed oil with 50% rened cottonseed oil and 50% oleic acid at 180, 200 and 220 C. The other reaction conditions were molar ratio of methanol to oil 9:1, and catalyst concentration 3 wt.%. From Fig. 2, it can be seen that the yield of methyl ester increased with temperature. The reaction rate at 200 C was signicantly faster than the reaction rate at 180 C, but just slightly slower than that at 220 C. On the other hand, for the reaction carried out at a higher temperature, a higher pressure is needed to ensure that the reaction takes place in the liquid phase which will increase the biodiesel production cost. So, the optimum temperature for this reaction is 200 C.

3.2.3.

Catalyst concentration

The amount of catalyst also affects the conversion efciency of the process. The effect of catalyst concentration (1, 3 and 5 wt.%) on the yield of methyl ester during the reaction of a mixed oil containing 50% oleic acid with methanol was studied (Fig. 3). The reaction took place at 200 C, and molar ratio of methanol to oil 9:1. With increase in catalyst concentration from 1 to 3 wt.%, the yield of methyl ester increased markedly from 84 to 92%. However, when the catalyst concentration was further increased to 5 wt.%, the reaction rate and methyl ester yield just slightly increased. The optimum catalyst concentration was chosen to be 3 wt.% for further studies. Fig. 1 Effect of the FFA content on ME yield. Reaction conditions: temperature 200 C; molar ratio of methanol to oil 9:1; catalyst concentration 3 wt.%.

3.2.4.

Molar ratio of methanol to oil

According to the reaction stoichiometry, the transesterication of triglycerides with methanol requires that the molar

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Fig. 3 Effect of catalyst concentration on ME yield. Reaction conditions: mixed oil (50% cottonseed oil and 50% oleic acid), reaction temperature 200 C, molar ratio of methanol to oil 9:1. ratio of methanol to oil be 3:1, while the esterication of FFAs with methanol requires 1:1 molar ratio of methanol to FFAs. Since 3 mol FFAs can be considered as 1 mol of triglyceride, the theoretical molar ratio of methanol to oils with a large amount of FFAs is still 3:1. Since the transesterication and esterication are reversible reactions, excess methanol shifts the equilibrium in the direction of ester formation. Fig. 4 shows that an increase in the molar ratio of methanol resulted in a signicant effect on the yield of ester when the molar ratio of methanol to oil was small. However, a further increase in the molar ratio of methanol to oil after 9:1 showed very limited effect on the yield of ester. Hence, a 9:1 molar ratio of methanol to oil is appropriate for this reaction. The excess methanol can be collected and recycled.

Fig. 5 Stability of the solid acid catalyst. Reaction conditions: mixed oil (50% rened cottonseed oil and 50% oleic acid), reaction temperature 200 C, reaction time 6 h, molar ratio of methanol to oil 9:1 and catalyst concentration 3 wt.%. experimental results indicated that SO4 2 /TiO2 SiO2 is a stable catalyst and suitable for long-term use.

3.3.

A continuous process for biodiesel production

3.2.5.

Stability

Besides the simple catalyst removal step and being environmental friendly, another main advantage of the solid acid catalyst is reusability. The catalyst was recycled to study the reusability. The data of the reusability of the catalysts are presented in Fig. 5. It shows that SO4 2 /TiO2 SiO2 has good stability. From the fresh use run to the completion of 4th reuse run, the yield of ME did not show obvious changes. The

Based on the experimental results, our group recently proposed a continuous process for biodiesel production from cheap raw feedstocks with high FFAs by solid acid catalysis (Wang et al., 2007). A schematic ow diagram of the process is shown in Scheme 1 to show the important steps in biodiesel production. The production process is carried out as follows: the raw feedstocks are rst pretreated by ltration and dehydration to remove impurities and water, respectively. Then, the feedstock ow through R-1, R-2 and R-3 in sequence, and vaporized methanol ows countercurrently. In a series of three reaction kettles, part of the methanol reacts with oils as a reactant, and excess methanol removes water from the system as a solvent, which increases the esterication conversion substantially and effectively decreases the acid value. Finally, excess methanol is puried in a methanol distillation tower (T1) for recycling, while the oil phase is rened at a biodiesel vacuum distillation tower (T2) to give the biodiesel product. Compared with conventional purifying procedures, such as water washing, decolorization and deodorization, the use of vacuum distillation for rening ensures a high product quality and yield. Using the proposed continuous process, a 10,000tonnes/year industrial biodiesel demonstration production plant has been built. The process has the following characteristics. The use of cheap feedstocks with high FFAs such as waste cooking oils, soapstocks and non-edible oils, instead of rened vegetable oil, decreases the cost greatly. The solid catalyst SO4 2 /TiO2 SiO2 has high catalytic activity, easy separation, and can catalyze biodiesel production by simultaneous esterication and transesterication.

3.4.

Biodiesel properties

Fig. 4 Effect of molar ratio of methanol to oil on ME yield. Reaction conditions: mixed oil (50% cottonseed oil and 50% oleic acid), reaction temperature 200 C and catalyst concentration 3 wt.%.

Waste edible vegetable oils or non-edible oils, such as corn, cottonseed, rapeseed, soybean acidied oils (derived from soapstocks by acidication), and Chinese prickly ashseed oil were used to produce biodiesel. The reaction was catalyzed by SO4 2 /TiO2 SiO2 , under the conditions of reaction temper-

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445

Scheme 1 Process ow diagram of biodiesel production by solid acid catalysis. R-1, R-2, R-3: reaction kettles. S-1: gas liquid separator. S-2: liquid liquid separator. T-1: methanol distillation tower. T-2: biodiesel vacuum distillation tower. Table 3 Fatty acid prole of biodiesel produced from different feedstocks Oil type Myristic,
Cottonseed acidied esters Corn acidied esters Rapeseed waste oil esters Soybean waste oil esters Chinese prickly ashseed esters
a

Fatty acid composition (wt.%) 14:0a Palmitic, 16:0

22.3 16.5 6.5 12.2 20.7

Stearic, 18:0
3.7 2.3 1.1 4.0 2.8

Oleic, 18:1
26.3 32.0 59.3 25.8 30.4

Linoleic, 18:2
46.5 47.8 25.9 52.3 26.8

Linolenic, 18:3
0.5 1.4 7.2 5.7 19.3

0.7 -

The alkyl chain contains 14 carbons and 0 double bonds.

Table 4 Topological index ( biodiesel (at 313 K) Oil type

Cottonseed acidied esters Corn acidied esters Rapeseed acidied esters Soybean acidied esters Chinese prickly ashseed esters

m)

and viscosity of
m

Viscosity, (calc) (mPa s)

3.475 3.513 3.569 3.536 3.490

9.725 9.788 9.880 9.825 9.759

ature 200 C, reaction time 6 h, molar ratio of methanol to oil 9:1 and catalyst concentration 3 wt.%. The products were then analyzed by gas chromatograph to determine the fatty acid distribution (Table 3). It mainly consists of saturated com-

pounds (myristic acid, palmitic acid and stearic acid) and other unsaturated compounds. Compared with unsaturated fatty acid methyl esters, saturated fatty acid methyl esters have higher cetane numbers and better stability, but they tend to crystallize at a high temperature which will cause a high cloud point and poor cold ow properties. However, the biodiesel produced from these cheap raw feedstocks is highly unsaturated, and its cold ow properties should be very good. The characteristic of fuel atomization is very important in a compression ignition engine. One of the main contributing factors that affect the atomization characteristic is the viscosity of the fuel. In the present work, we estimate the viscosity of biodiesel with different compositions using the topological index method based on the distance matrix and adjacent matrix of the molecular structure recently pro-

Table 5 Fuel properties of biodiesel from the demonstration plant and diesel Property Unit Biodiesel Diesel, ASTM D975 Biodiesel standards ASTM D 6751-02
Density at 20 C Viscosity at 40 C Flash point Pour point Water Sulfur Carbon residue Cetane number Caloric value

Method

DIN EN 14214
875900 3.55.0 >120 15 to 10 <0.05 50 <0.3 >49 SH/T 0604 GB/T 265 GB/T 261 SH/T 0248 SH/T 0246 GB/T 17040 GB/T 17144 GB/T 386-91 GB/T 384

kg/m mm2 /s C C % ppm % MJ/kg

880 3.48 175 6 0.01 9.8 0.25 53.4 41.8

850 2.60 68 35 to 15 0.02 500 0.17 4055 42

870900 1.96.0 >130 15 to 10 <0.03 50 4860

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posed (Shu et al., 2006). The estimated results are given in Table 4. The correlation between the viscosity () and the mean mixture topological index ( m ) of the biodiesel was expressed by regression:
n

= 5.96249 ln

10.08814; ln

=
i

Zi ln

(1)

where m is the mean topological index value of the biodiesel mixture, i is the topological index value of pure i component, and Zi is the mass fraction of pure i component. The fuel properties of biodiesel produced from cottonseed acidied oil, diesel and biodiesel standards are summarized in Table 5. It can be seen that most of the biodiesel properties are comparable with those of the diesel and biodiesel standards. The viscosity of biodiesel and conventional diesel is very close. The ash point of biodiesel is much higher than that of diesel, so its storage is relatively safe. The caloric value is slightly less than that of diesel because of their oxygen content. On the other hand, the presence of oxygen in the biodiesel helps to make the combustion of fuel more complete.

4.

Conclusions

The present study showed that the solid acid catalyst SO4 2 /TiO2 SiO2 is inexpensive and environment friendly, has high catalytic activity, and is stable for biodiesel production from cheap raw feedstocks with high FFAs. The proposed continuous process for the production of biodiesel has potential widespread applications on an industrial scale. The properties of the biodiesel derived from the demonstration plant are comparable with those of diesel and biodiesel standards.

Acknowledgements
The authors are grateful for the nancial support by the National Basic Research Program of China (No. 2004CB71970 6) and the Specialized Research Fund for the Doctoral Program of Higher Education (No. 20050003030).

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