Renewable Energy 38 (2012) 10e15

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Renewable Energy
journal homepage: www.elsevier.com/locate/renene

Biodiesel production using magnetically stabilized uidized bed reactor

Pingmei Guo a, b, Fenghong Huang a, b, *, Qingde Huang a, b, Chang Zheng b
a b

Oil Crops Research Institute, Chinese Academy of Agricultural Sciences, Wuhan 430062, China Hubei Energy Research Center of Oil Crops and Bio-diesel, Wuhan 430062, China

a r t i c l e i n f o
Article history: Received 11 February 2011 Accepted 2 June 2011 Available online 16 August 2011 Keywords: Biodiesel Nanometer magnetic catalytic particles Magnetically stabilized uidized bed reactor Transesterication

a b s t r a c t
A novel production process of biodiesel using magnetically stabilized uidized bed reactor (MSFBR) has been developed based on cottonseed oil and the reaction conditions were also studied. The reactant ow rate and magnetic eld intensity affects on the magnetic catalytic particles behavior in the column were performed, and the transesterication reaction conditions of cottonseed oil were investigated in MSFBR with nanometer magnetic catalytic particles. Under the suitable reaction conditions of methanol/oil molar ratio 8:1, 40 cm3 min1 ow rate, 225 Oe magnetic eld intensity and temperature of 65  C, the conversion efciency reaches to 97% in 100 min. The stability and recovery of the magnetic catalytic particles in MSFBR are much better than that in autoclave stirred reactor. The result shows that most of the resultant cottonseed oil biodiesel parameters comply with the limits established by representative biodiesel standards. 2011 Elsevier Ltd. All rights reserved.

1. Introduction Biodiesel, namely fatty acid methyl esters (FAME) is an alternative diesel fuel derived from vegetable oils or animal fats [1]. The main components of vegetable oils and animal fats are triglycerides or also known as esters of fatty acids attached to a glycerol. The most widely used industrial method for the commercial production of biodiesel from vegetable oils/fats is a base catalyzed transesterication process using sodium hydroxide (NaOH) or potassium hydroxide (KOH) as the homogeneous catalyst and methanol as the lower alcohol (Fig. 1) [2]. The advantage of this process is that the production of methyl esters at very high yields under mild conditions and reaction generally takes about an hour for completion [3]. Several edible and non-edible oils such as sunower oil [4], palm oil [5] and waste oil [6] have been transesteried for biodiesel production. However, homogeneous catalysts have some disadvantages: (1) they cannot be reused; (2) the complicated process of post treatment; (3) they produce large amounts of wastewater and pollution. In contrast, the advantages of solid catalyst are easy separation, simplicity in post treatments and they are environmentally friendly. However, their specic surface area is too small to contact liquid reactants abundantly which reduces biodiesel conversion. Nanometer catalytic particles have huge specic

* Corresponding author. Oil Crops Research Institute, Chinese Academy of Agricultural Sciences, No. 2 Xudong Er Road, Wuchang dist., Wuhan 430062, China. Tel.: 86 27 86827874; fax: 86 27 86815916. E-mail addresses: pmguo11@yahoo.cn (P. Guo), huangfh@oilcrops.cn (F. Huang). 0960-1481/$ e see front matter 2011 Elsevier Ltd. All rights reserved. doi:10.1016/j.renene.2011.06.010

surface area and high catalytic activity, but it is very difcult to recover for the recycling purposes. Nanometer magnetic catalytic particles combine the merits of the above catalystsdhuge specic surface area to contact the reactants, easily separated from the reagents through magnetic eld. Several researchers have reported this kind of catalysts. For example, Liu et al. prepared nanometer magnetic catalytic particles by loading CaO on Fe3O4 with Na2CO3 and NaOH as precipitator for biodiesel production in three-necked ask with stirring, and found the catalytic activity and recovery rate of the catalyst were much better than those of CaO [7]; Chen et al studied that the method of preparing biodiesel from Chinese tallow kernel oil by nanometer magnetic catalytic particles, and the esterication ratio is 96.78% under the optimal reaction conditions [8]. Nowadays, biodiesel is generally manufactured by nanometer magnetic catalytic particles using autoclave stirred reactor (ASR) or uidized bed reactors (FBR), but the ASR will destroy the structure of the catalysts and the used catalyst is signicantly deactivated. A FBR with CuO/activated carbon catalytic particles was demonstrated to show the signicantly improved removals of y ash and NO compared with the traditional reactor systems. However, mass transfer limitation in these catalytic particles still results in a considerable reduction in productivity [9] and [10]. Magnetically stabilized uidized bed reactor (MSFBR) offers a number of potential advantages over the conventional biodiesel reactors; it avoids destroying the structure of the nanometer magnetic catalytic particles, elimination of solid mixing, low pressure drop through the bed, ease of solid transportation as well as the possibility of operation at increased uid velocities and even countercurrent operation [11]. Several studies with MSFBR for

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2.3. Equipment In this study, MSFBR was supplied with a homogeneous magnetic eld surrounding the whole reaction column. The homogeneous magnetic eld was produced by a long solenoid which was covered by 1680 turns of copper wires. The height of the magnetic eld was 30 cm, and the inside and outside diameters were 19 cm and 50 cm respectively. The magnetic eld intensity was controlled by adjusting the current passing through the solenoid using a power supplier. MSFBR, a glass column with a heating jacket is illustrated in Fig. 2, its inner diameter and length was 8 cm and 40 cm respectively. Fig. 2 shows the schematic diagram of the experiment system. Temperature in the MSFBR was controlled by a temperature bath with the circulation system. 2.4. Procedure In all experiments, cottonseed oil and methanol were pumped into the mixing tank; the ow rate was controlled by metering pumps. Each reactor was lled with 60 g of nanometer magnetic catalytic particles. The mixture of cottonseed oil and methanol were preheated by the heating system. The reaction temperature was controlled by water bath through the circulating system. Different temperature (40  C, 50  C, 60  C, 65  C and 70  C), methanol and oil ratios (4:1, 5:1, 6:1, 7:1, 8:1, 9:1 and 10:1), ow rates (10 cm3 min1, 20 cm3 min1, 30 cm3 min1, 40 cm3 min1, 50 cm3 min1 and 60 cm3 min1) and magnetic eld intensity (from 200 Oe to 450 Oe) were used to investigate their effects on the transesterication reaction conversion efciency of cottonseed oil. 2.5. Product analysis Kinematic viscosity was measured following standards of GB/T 265 using a Paar-physica viscometer (diameter 0.6 mm). The test temperature was kept at 40  C. For gas chromatograph (GC) analysis, these tests were carried for washed methyl ester. The washing process consisted of acid neutralization which was followed by water washing. This was to remove sodium hydroxide and other impurities such as excess methanol, diglyceride and monoglyceride. A gas chromatograph (Agilent 6890N) equipped with a ame ionization detector (FID) was used for product analysis (i.e. methyl ester production and triglyceride and monoglyceride conversion). A DB-17HT (30.0 m 0.32 mm 0.15 mm) GC column was used. Samples were prepared by dissolving 1000 ml of product in 25 ml n-Hexane with the addition of 200 ml internal standards. About 1 ml of the sample was then injected into the column. The oven temperature program was set at a starting temperature of 160  C and held for 1 min, then increased to 195  C at a rate of 25  C/min, and then increased to 225  C at a rate of 10  C/min, nally it was increased to 360  C at a rate of 25  C/min and held for 12 min. The FID and injection temperatures were set at 370  C and 355  C. GC was calibrated by using stock solution of methyl olein, mono-olein, diolein, and tri-olein. Tricaprin was used as the internal standard. 3. Results and discussion 3.1. Characterization of cottonseed oil The physicochemical properties (such as acid value, moisture, saponication value, etc.) of cottonseed oil were determined as per Bureau of China Standard. The moisture, acid value and saponication value of cottonseed oil are 0.035%, 0.27 mgKOHg1 and 187.72 mgKOHg1, respectively. The fatty acid proles of cottonseed

Fig. 1. Transesterication of vegetable oil.

magnetic catalytic particles reactions have been reported in the literatures. Liu et al. immobilized Saccharomyces cerevisiae in magnetic particles, the magnetic catalytic particles have ability of oscillation and rotational motion in an altering magnetic eld, and ethanol productivity is increased by using the alternating magnetic eld [12]. The researchers found the MSFBR was an efcient system coupled with magnetic catalytic particles for process intensication of biocatalysis and biotransformation, and they mentioned that the transport of the molecules might be increased through the interface of the carrier surface. MSFBR shows similar and higher conversations when compared with conventional reactors [12e15]. The aim of this research is to develop a MSFBR with nanometer magnetic catalytic particles for the production of biodiesel. In this project, MSFBR to produce biodiesel is applied to study the effects of operation temperature, uid rate, magnetic eld intensity, methanol to oil molar ratio. 2. Materials and methods 2.1. Materials Cottonseed oil and methanol were used in this research as feedstock while nanometer magnetic catalytic particles Na2O$SiO2/ Fe3O4 were used as catalyst. Rened cotton seed oil was purchased from local food outlets, and it contained less than 0.6% free fatty acid (FFA) and less than 0.035% moisture, the density of the samples was 0.96 g cm3. Methanol was obtained from Chemical Company in China. Nanometer magnetic catalytic particles Na2O$SiO2/Fe3O4 was made in the laboratory, functional group, specic surface area, and average particle size of the sample was Na2O, 107.9 m2/g and 87.6 nm, respectively. All other chemical reagents were purchased from commercial chemical company and were of analytical grade. 2.2. Preparation of nanometer magnetic catalytic particles 2.2.1. Preparation of nano-Fe3O4 FeCl2 and FeCl3 were dissolved in the distilled water with the proportion of 4.5:1, and 20% ammonia was dropped into the solution with drastic stirring. After aging for 1 h, black precipitates were formed, and Cl1 was eliminated by washing many times. 2.2.2. Preparation of nano-Na2O$SiO2/Fe3O4 some Na2O$3SiO2 was dissolved in distilled water, then a certain amount (the proportion of Si to Fe was controlled to be 2.5:1) of magnetic core was added into the Na2O$3SiO2 solution. The solution of NaOH was titrated into the previous solution under vigorous stirring and aged for 2 h at 65  C, then the magnetic material was precipitated by placing at 2200 Gauss magnetic eld from permanent magnet NeFeB. The magnetic material was washed repeatedly until its pH value came to 7 and then dried for 12 h in a vacuum at 80  C. Finally, the sample was calcined for 2.5 h at 400  C to transform multiple oxides to achieve nanometer magnetic catalytic particles.

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Fig. 2. Schematic diagram of continuous experiment system using MSFBR.

oil are given in Table 1. The data listed in Table 1 for comparison purposes are the fatty acid proles of soybean and rapeseed. According to previous research studies [16] and [17], cottonseed oil has great potential for providing a source of triglycerides for biodiesel in terms of its fatty acid composition. 3.2. Transesterication of the cottonseed oil using MSFBR 3.2.1. Effects of uid ow rate and magnetic eld intensity on magnetic catalytic particles behavior in the column It is very important to stabilize the magnetic catalytic particles in the column and adjust the bed volume by applying different magnetic eld intensities. In order to determine the effects of magnetic eld, the reactor was lled 60 g of nanometer magnetic catalytic particles because this amount was found suitable for the column volume. And minimum magnetic eld intensities which enable the particles to suspend in the column were determined at different ow rates. During the relation study of magnetic eld intensity and uid ow rate, three phenomena are illustrated in Fig. 3 and Fig. 4. In the rst region, magnetic eld intensity almost increases linearly with the ow rate in order to keep the particles in the column. In this situation, the magnetic particles ll the whole column and there is no agglomeration of particles, which is shown schematically in Fig. 4A. As mentioned by some researchers, when a magnetic eld is applied to the magnetic catalytic particles, the particles are

magnetized by the applied eld and tend to align themselves due to the dipole interaction [19]. It is well known that in an applied magnetic eld, magnetic catalytic particles develop north and south poles and align themselves with the direction of the eld. The stronger the eld, the greater is the tendency for the particles to align [20]. For a uniformly stabilized bed with almost no relative particle movement, the eld force and the dipole force are greater than the viscous force [20]. Therefore, in Fig. 4A, the eld force and the dipole force should be just a little greater than the viscous force since the uniformly stabilized bed was obtained without any particle agglomeration. When the ow rate exceeded 60 cm3 min1, the magnetic eld intensity must be increased to keep the catalytic particles in the column, but partial agglomeration on the magnetic eld lines was observed and the bed volume began to shorten. The results are shown at the second region of Fig. 3 and in Fig. 4B. The phenomena can be explained that interparticle attractive forces cause magnetic particles to form agglomerates [19]. These agglomerates act essentially as one large particle and become more sensitive to ow than individual particles [21]. Therefore, it is not necessary to increase magnetic eld intensity at the same rate. In Fig. 4C, particles are fully agglomerated and the bed volume in the reactor is the minimum. The phenomena observed in the third region of Fig. 3 can be explained by the further particles agglomeration as further magnetic eld intensity increase to keep the particles in the column.

Table 1 Properties of cottonseed oil in comparison with the other oils. Fatty acid C12:0 C14:0 C14:1 C16:0 C16:1 C17:0 C17:1 C18:0 C18:1 C18:2 C18:3 C20:0 C20:1 C20:2 C22:0 C22:1 C22:2 C24:0 Saturated fatty acid Unsaturated fatty acid
a b

Cottonseed oil (%)a Soybean oil (%)b Rapeseed oil (%)b e e 0.5 20.4 0.3 e e 1.4 14.6 62.8 e e e e e e e e 22.3 77.7 e 0.1 e 10.8 0.2 0.1 0.1 3.9 24.7 50.1 7.4 0.4 0.7 e 0.3 1.2 e 0.2 15.8 84.2 e 0.1 e 3.2 0.3 0.1 e 1.3 33.40 14.50 7.0 0.6 8.7 0.3 e 29.3 0.4 1.0 6.3 93.7 Fig. 3. Minimum magnetic eld intensities to keep catalysts particles in the column at different uid ow rates.

[16]. [18].

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Fig. 4. Schematic illustration of hydrodynamic behavior of catalysts particles in the column. Fig. 6. Effect of molar ratio of methanol to oil on conversion efciency and kinematic viscosity.

From above observations and analysis, it is easy to draw the conclusion that only the rst region is suitable for the reactor operation. 3.2.2. Effect of reactant ow rate on conversion efciency and kinematic viscosity In order to nd out the effect of reactant ow rate or reaction time on transesterication conversion efciency and kinematic viscosity, the variation of conversion efciency with the reactant ow rate which is at the rst region of Fig. 3 is shown in Fig. 5. The test conditions were molar ratio of 9:1, reaction temperature of 70  C. Fig. 5 indicates that the kinematic viscosity increases rapidly from 6.4 mm2/s to 20.3 mm2/s when the ow rate changes from 10 cm3 min1 to 60 cm3 min1, and the conversion efciency is reduced from 96.5% to 85.9%. The trend of viscosity becomes slow when the ow rate is changed from 10 cm3 min1 to 40 cm3 min1 continually, and the conversion efciency changes from 96.5% to 96.3%. It can be seen that the transesterication efciency of cottonseed oil drops rapidly due to the poor mass transfer inside these catalytic particles when the reactant ow rate exceeds 40 cm3 min1. Similar results have been observed in other studies in which calcium oxide was used as immobilization matrices [22] and [23]. Therefore, reactant ow rate of 40 cm3 min1 and

magnetic eld intensity of 225 Oe were used in the following experiments, and at this time, the reaction time is 100 min. 3.2.3. Effect of methanol to oil molar ratio on conversion efciency and kinematic viscosity The methanol to oil molar ratio is one of the important factors that affect the conversion efciency of transesterication. Stoichiometrically, 3 mol of methanol is required for each mol of triglyceride, but in practice a higher molar ratio is used to obtain higher yield of FAME [24]. The research results obtained from Muniyappa et al. [25] show that the optimal methanol amount should be 2e10 times of the stoichiometrical one. In the present work, Fig. 6 shows the inuence of methanol to oil ratio on conversion efciency and kinematic viscosity. The studies were carried out with a reaction temperature of 70  C, ow rate of 40 cm3 min1 and magnetic eld intensity of 225 Oe under different methanol to oil molar ratios. It can be observed in Fig. 6 that, the conversion efciency increases sharply from 62.3% to 96.3% with the increasing of methanol to oil ratio from 4:1 to 8:1, and the kinematic viscosity decreases from 26.4 mm2/s to 6.4 mm2/s. Conversion efciency can meet the requirement of transesterication at the ratio of 8:1, 9:1, and 10:1. However, too high molar ratio of methanol to oil slows down the separation of the

Fig. 5. Effect of reactant ow rate on conversion efciency and kinematic viscosity.

Fig. 7. Effect of reaction temperature on conversion efciency and kinematic viscosity.

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reaction temperatures are shown in Fig. 7. The higher the temperature used, the more kinematic viscosity is reduced and a higher conversion efciency is achieved. The conversion efciency is only 74.4% at 40  C, and the viscosity is 25.9 mm2/s. As the temperature increases to 65  C, kinematic viscosity of the reactant drops to 6.3 mm2/s, and conversion efciency increases to 96.9%. These results are in accordance with the results obtained by Sarin et al. [23]. Thus, an optimal reaction temperature of 65  C was used for transesterication in the following experiments.

3.3. Lifetime comparison of nanometer magnetic catalytic particles in MSFBR and ASR for transesterication Transesterication of cottonseed oil was catalyzed by nanometer magnetic catalytic particles using MSFBR and ASR as the reactor, respectively. The transesterication conditions in MSFBR were methanol to oil molar ratio of 8:1, ow rate of 40 cm3 min1, magnetic eld intensity of 225 Oe, reaction time of 100 min, reaction temperature 65  C, and the transesterication reaction conditions in ASR have been researched [27], namely, catalyst dosage of 10%, molar ratio of methanol to oil 8:1, reaction time of 70 min, stirring speed of 400 r/min, reaction temperature of 65  C. For each reaction process, the test repeated 11 times using fresh oil. Fig. 8 indicates the conversion efciency is more than 90% for MSFBR after round 8, and after round 11, the conversion efciency still reaches to more than 60%. However, for ASR, the conversion efciency decreases to 16.9% after round 6, and after round 7, catalytic activity of nanometer magnetic catalytic particles is totally lost. Actually, after reaction, the catalyst almost can not be seen in ASR since its structure has been destroyed by ASR and the large amounts of catalyst has been dissolved into the methanol and poured out with the reaction products [7]. As shown in Fig. 8, the longer lifetime of the catalytic particles and higher biodiesel production are observed in MSFBR than in ASR. Similar observation has been found in the previous report with immobilized S. cerevisiae in magnetic particles in a MSFBR [12].

Fig. 8. The stability comparison of transesterication activity in MSFBR and autoclave stirred reactor.

glycerin phase and the methyl ester phase [26]. Therefore, the optimum quantity of methanol was determined to be 8:1 M ratio of methanol to oil. 3.2.4. Effect of reaction temperature on conversion efciency and kinematic viscosity Transesterication can occur at different temperatures, alkaline alcoholysis of vegetable oils is normally performed in the temperature range between 45  C and 65  C by the researchers [27]. The report from Liu et al. [7] shows that the methanolysis of Jatropha curcas oil carried out at 70  C lead to higher conversion efciency than at lower temperatures with nanometer magnetic particles Ca2Fe2O5 as catalyst. To study the effect of reaction temperatures on transesterication efciency in MSFBR, experiment trails were carried out at temperature of 40  C, 45  C, 50  C, 55  C, 60  C, 65  C and 70  C. The conversion efciency and kinematic viscosity at different

Table 2 Fuel properties of cottonseed oil biodiesel. Properties GB/T 20828e2007 Limits Density (20  C) (kg/m3) Kinematic viscosity (40  C) (mm2/s) Flash point ( C) Cold lter plugging point (CFPP) ( C) Sulfur content (weight %) Carbon residue (10% distillation residue) (weight %) Water content (weight %) Sulfate ash (weight %) Mechanical impurities (weight %) Copper corrosion, 3 h at 50  C Cetane number Oxidation stability at 110  C (hr) Acid value (mgKOH/g) Free glycerol (weight %) Total glycerol (weight %) 90% distillation temperature ( C) e Indicates no. a [24]. b [28]. c [29]. d [30]. e [31]. Test methods GB/T2540 GB/T 265 GB/T 261 GB/T 0248 GB/T 0689 GB/T 17144 GB/T 0246 GB/T 2433 GB/T 511 GB/T 5096 GB/T 386 GB/T 14112 GB/T 258 ASTMD 6584 ASTMD 6584 GB/T 6536 ASTM 6751 03 Limits Test methods e ASTM ASTM e ASTM ASTM 445 93 5453 4530 EN14214 Limits 0.86e0.90 3.5e5.0 120 min 0 max 0.010max 0.3 max 0.05max e e 1max 51min 6.0min 0.5 max 0.02 max 0.25 max e Test methods Methyl esters Soybean oil Cottonseed oil Rapeseed oil methyl estersa methyl esters methyl esters 881e885b,c 4.1e5.75b,c,d 168d 5d 873 6.2 175 6 0.01 0.14 0.018 0.015 0 1a 56 6.54 0.55 0.0018 0.0073 344

e 1.9e6.0 130min 4max 0.05max 0.3max 0.05max 0.020max 0 1max 49min 6.0min 0.80max 0.020max 0.240max 360max

e 1.9e6.0 130min e 0.050max 0.050max 0.05max 0.020max e 3max 47min e 0.80max 0.020max 0.240max 360max

EN ISO 3675 880 ENISO 3104 4.2 EN ISO 3679 165 DIN EN 116 9 EN ISO 20846 EN ISO 10370 EN e e EN EN EN EN EN EN e ISO 12937

ASTM 2709 ASTM 874 e ASTM 130 ASTM 613 e ASTM 664 ASTM 6584 ASTMD 6584 ASTM 1160

ISO 2160 ISO 5165 14112 14104 14105 14105

1a 50.4 0.25

48.84e56d,e 0.3e0.45c,d

331.7

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3.4. Fuel properties of cottonseed oil biodiesel The cottonseed oil methyl esters sample used to determine the fuel properties was prepared using the optimum conditions determined in the study. Some important fuel properties of cottonseed oil biodiesel are presented in Table 2, in which most of these parameters comply with the limits for representative Bidiesel Standards (GB/T 20828e2007, ASTM 6751 03 and EN14214) except that the cold lter plugging point (CFPP) and kinematic viscosity of cottonseed oil biodiesel are higher than that described by the specications for biodiesel because CFPP and kinematic viscosity are highly inuenced by the fatty acid proles of cottonseed oil [20]. 4. Conclusions Applied magnetic eld intensity in the MSFBR should be as low as possible to avoid diffusion and channeling problems coming from particle agglomeration. In the MSFBR system for biodiesel production, methanol/oil molar ratio, ow rate and magnetic eld intensity, reaction time and temperature are important variables, showing considerable effect on the transesterication reaction of cottonseed oil with nanometer magnetic catalytic particles in the MSFBR. Under the reaction conditions, it is possible to get higher activity and better stability performance from the MSFBR than ASR. The cottonseed oil biodiesel obtained has the fuel properties that basically comply with the limits established by representative Biodiesel Standards. Acknowledgments We are grateful for the nancial support given by the International Cooperation Project (No. 2008DFA61430), High Technology R&D Program (863 project) (No. 2009AA05Z437), National Science and Technology Support Program (No. 2009BADB1B10), Director Fund of Oil Crops Research Institute (No.1610172011014). References
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