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Study on membrane reactors for biodiesel production by phase behaviors of canola oil methanolysis in batch reactors. The membrane reactor has been reported to have higher molar ratios of methanol to oil but ultralow catalyst concentration. Results show that increasing the residence time of the whole reactant system within the two-phase zone is good for the separation operation through the membranes.
Study on membrane reactors for biodiesel production by phase behaviors of canola oil methanolysis in batch reactors. The membrane reactor has been reported to have higher molar ratios of methanol to oil but ultralow catalyst concentration. Results show that increasing the residence time of the whole reactant system within the two-phase zone is good for the separation operation through the membranes.
Study on membrane reactors for biodiesel production by phase behaviors of canola oil methanolysis in batch reactors. The membrane reactor has been reported to have higher molar ratios of methanol to oil but ultralow catalyst concentration. Results show that increasing the residence time of the whole reactant system within the two-phase zone is good for the separation operation through the membranes.
Study on membrane reactors for biodiesel production by phase behaviors
of canola oil methanolysis in batch reactors
Li-Hua Cheng a,b , Shih-Yang Yen b , Li-Sheng Su b , Junghui Chen b, * a Department of Environmental Engineering, Zhejiang University, Hangzhou 310027, PR China b R&D Center for Membrane Technology and Department of Chemical Engineering, Chung-Yuan Christian University, Chung-Li 32023, Taiwan, ROC a r t i c l e i n f o Article history: Received 30 December 2009 Received in revised form 10 March 2010 Accepted 20 March 2010 Keywords: Biodiesel Canola oil Kinetics Ternary phase diagram Membrane reactor a b s t r a c t In comparison with the general stirring batch reactor, the membrane reactor has been reported to have higher molar ratios of methanol to oil but ultralow catalyst concentration in the biodiesel production. In this research, the methanolysis of canola oil is conducted in a stirring batch reactor in the presence of NaOH as a catalyst. Based on the investigation of the effects of operating conditions, including methanol to oil molar ration, catalyst concentrations and temperatures, the time course of the reaction path for the reactant composition in the ternary phase diagram of oilFAMEMeOH offers an effective way to under- stand the operation of membrane reactors in the biodiesel production. The results show that increasing the residence time of the whole reactant system within the two-phase zone is good for the separation operation through the membranes. 2010 Elsevier Ltd. All rights reserved. 1. Introduction Biodiesel has been widely accepted to be an important compo- nent of the combined strategic approach to decrease our current dependence on fossil fuels. Biodiesel is the monoalkyl esters of long-chain fatty acids made from renewable biological sources, such as vegetable oils or animal fats. It is also known as fatty acid methyl ester (FAME). With emissions of less carbon monoxide, sul- fur compounds, particulate matter and unburned hydrocarbons ex- cept NO x , biodiesel is more advantageous as it is environmental friendly and non-toxic. Biodiesel is usually produced by transesterication of vegetable oils, largely consisting of triglycerides, with methanol. To produce high purity of biodiesel and to simplify product purication proto- cols, a membrane reactor has been reported to produce FAME in the presence of NaOH as a catalyst. The membrane reactor is useful in removing unreacted canola oil from the FAME product and shift- ing the reaction equilibrium to the product side (Dube et al., 2007). The transesterication is believed to occur at the surface of the oil droplets suspended in methanol, and hence a heterogeneous state is required to be maintained in the membrane reactor (Cao et al., 2007). The initial methanol to oil molar ratios of 11:1, 16:1, 23:1 and 46:1 had been tested, and it was reported that at least ratio of 12:1 was required for the collection of permeate. At a methanol to oil molar ratio of 24:1, the catalyst concentration can be reduced to 0.05 wt.% NaOH for the steady-state biodiesel production via the membrane reactor (Tremblay et al., 2008). With a focus on the inuences of catalyst concentration and residence time, the kinet- ics of canola oil transesterication was further investigated by Cao et al. (2009) in the continuous membrane reactor. In comparison with high molar ratio of methanol to oil but ultralow amount of catalyst concentration in the membrane reac- tor for biodiesel production, molar ratio of 6:1 and catalyst concen- tration high up to 520 folds are often used in kinetics study in the stirring batch reactor. Freedman et al. (1986) reported that the kinetics of the forward reaction, which described the base-cata- lyzed reaction of methanol and soybean at 6:1 molar ratio, con- sisted of a combination of second-order consecutive and fourth order shunt reactions. Noureddini and Zhu (1997) investigated the kinetics of the transesterication of soybean oil with methanol using NaOH as a catalyst, and studied the effect of mixing intensity and temperature on the reaction rates for a 6:1 methanol to soy- bean oil molar ratio and the catalyst concentration of 0.2 wt.%. A reaction mechanism was proposed, consisting of an initial mass transfer-controlled region followed by a second-order kinetically controlled region. Vicente et al. (2005) conducted a comprehensive study on the kinetics of sunower oil transesterication with a 6:1 methanol/oil molar ratio, and varied catalyst concentrations of 0.5, 1 and 1.5 wt.%. Based on the past work, the difference in the methanol to oil molar ratio and the amount of catalyst concentration between the membrane reactor and the stirring batch reactor are believed to be correlated closely with the biodiesel production process, i.e. 0960-8524/$ - see front matter 2010 Elsevier Ltd. All rights reserved. doi:10.1016/j.biortech.2010.03.095 * Corresponding author. Tel.: +886 3 2654107; fax: +886 3 2654199. E-mail address: jason@wavenet.cycu.edu.tw (J. Chen). Bioresource Technology 101 (2010) 66636668 Contents lists available at ScienceDirect Bioresource Technology j our nal homepage: www. el sevi er . com/ l ocat e/ bi or t ech transesterication which is characterized in the reversibility and mass transfer limitation. The reaction system is essentially hetero- geneous, as the oil and methanol, with lots of different properties in their polarity, are almost immiscible in the range from 298.15 to 333.15 K (Cerce et al., 2005). To overcome or rather, exploit this situation, the two-phase is maintained for the membrane reactor (Cao et al., 2007, 2009; Dube et al., 2007; Tremblay et al., 2008). However, as the conversion of the oil, the solubility of oil in meth- anol gradually increases till nally a homogeneous solution is formed since the product of FAME can act as a cosolvent (Zhou et al., 2006). Our previous work also showed that only when the feed bulk composition was controlled within the two-zone phase, the oil-rich phase was rejected by the membrane and the permeate was free of TG (Cheng et al., 2009). Even if the phase behavior of the typical system composed of oilFAMEMeOH is so important for affecting the operation performance, the investigation of the path controlling of the transesterication reaction has not been re- ported to our best knowledge. In the present work, the methanolysis of canola oil using NaOH as catalyst is investigated in a stirring batch reactor. The study is focused on the inuences of methanol to oil molar ratio and cata- lyst concentration on the product concentration. The path of the transesterication reaction within the reactor is characterized with the liquidliquid phase equilibrium for the system of oilFAME MeOH. Since the phase diagram is inuenced by the temperature, the paths of the product compositions in the reactor with the dif- ferent operating temperatures are studied and compared. For fur- ther comparison purpose, tting the kinetic model parameters (Freedman et al., 1986; Vicente et al., 2005), such as the rate con- stants and the corresponding activation energies, is also carried out in this study. 2. Methods 2.1. Materials The canola oil and its biodiesel came from Taiwan NJC Corpora- tion. Glycerine, monolein, diolein, triolein, butanetriol, tricaprin and methyl oleate were supplied by SigmaAldrich Co. Methanol and n-heptane were of HPLC grade. The water content of canola oil, canola ester and glycerol are 0.05%, 0.03% and 0.1%, respec- tively. The analysis of the supplied canola ester for the measure- ment of liquidliquid equilibrium showed that the actual methyl oleate (C18:1) content was 58.89 wt.%, and the overall content of C (C16:0C18:3) was 98.68% with TG, DG, MG and free fatty acids of 0.017%, 0.029%, 0.037% and 0.376%, respectively. 2.2. Equipment Reactions were carried out in a 250 mL three-necked batch reactor, where the total volume of reactants was 125 mL. The reac- tor was equipped with a reux condenser, a thermometer, and a stopper to remove samples. This reactor was immersed in a con- stant-temperature bath (Vicente et al., 2005). 2.3. Transesterication Transesterication conditions employed were shown in Table 1. The reactor was initially charged with the mixture of canola oil and methanol, placed in the constant-temperature bath with its associ- ated equipment, and then heated to a predetermined temperature. NaOH was dissolved in the minimal amount of methanol, and the solution was added to the agitated reactor. The reaction was timed as soon as the NaOH/MeOH solution was added to the reactor, and it continued for 2 h. During the reaction, samples of 0.5 mL were taken at the following reaction times: 1, 3, 5, 7, 10, 13, 16, 20, 25, 30, 45, 60, 90 and 120 min. The samples were quenched imme- diately in the corresponding volume of methanol containing the oxalic acid of 0.12 g/mL (Zhou, 2006) but not the chloric acid (Vicente et al., 2005) to stop the reaction. The precipitated sodium monooxalates were removed by centrifugation of 8000g for 15 min (HsiangTai CN-2200, Taiwan). The organic layers were evaporated at reduced pressure of 0.337 bar at 60 C using a rotav- apour (Buchi R-210, Switzerland). The methanol content in the reaction samples was calculated from the weight loss after evapo- ration and deduction of the methanol that has been added for the quenching purpose. The remaining mixture was then analyzed by capillary gas chromatography (Agilent 6890N) with a ame ioniza- tion detector (FID) employing an Ultra Alloy + -5 capillary column (Frontier Laboratories LTD, Japan) of 15 m length, 0.53 mm ID, 0.25 lm lmthickness according to ASTM-D6584 (2000) for simul- taneous determination of components including fatty acid methyl esters (FAME), monoglycerides (MG), diglycerides (DG), triglycer- ides (TG), and glycerine (GL). Methyl ester of oleic acid, 1-monoo- lein, 1,3-diolein, triolein, glycerine were used as standard samples to determine the retention time of FAME, MG, DG, TG and GL, respectively. The components, 1,2,4-Butanetriol and tricaprin, were used as internal standard 1 and 2, respectively. n-Heptane was used as the solvent for the preparation of GC samples. 2.4. Liquidliquid equilibrium of oilFAMEMeOH During the transesterication, the time course of three main components including MeOH, FAME and TG, was characterized with the ternary phase diagram of oilFAMEMeOH. The ternary phase diagram of oilFAMEMeOH rather than the intersolubilities between FAMEMeOHGlycerol, OilGlycerolMeOH and oil GlycerolFAME, has been used for the kinetics investigation at the initial stage (Gunvachai et al., 2007). The LLE experiments for this ternary system were carried out using a water bathed glass vessel with a magnetic stirrer. The experiments were performed in a glass vessel of 50 mL volume. Measurements of the boundary of LLE at atmospheric pressure and different temperatures from 20 to 60 C were carried out by turbidimetric analysis using the titra- tion method under isothermal conditions (Cerce et al., 2005; Zhou et al., 2006; Cheng et al., 2009). 2.5. Mathematical modeling for canola oil methanolysis As shown in Table 1, effects of methanol to oil molar ratio, cat- alyst concentration and temperature on the reaction rates were fo- cused in this study. The kinetic modeling approach of Vicente et al. (2005) was used. Six effective reaction rate constants k 0 1 k 0 6 , six reaction rate constants k 1 k 6 as shown in formula (1), and the Table 1 Details of the transesterication experiment. Methanol to oil molar ratio Reaction temperature (C) Catalyst concentration (wt.%) Run 1 6:1 60 0.1 Run 2 12:1 60 0.1 Run 3 24:1 60 0.1 Run 4 24:1 60 0.5 Run 5 24:1 60 0.05 Run 6 24:1 40 0.1 Run 7 24:1 40 0.5 Run 8 24:1 40 0.05 Run 9 24:1 20 0.1 Run 10 24:1 20 0.5 Run 11 24:1 20 0.05 6664 L.-H. Cheng et al. / Bioresource Technology 101 (2010) 66636668 labels were consistent with those used by Vicente et al. (2005). They were estimated from measurements performed on the com- positions of the reactor. TG MeOH ) * k 0 1 k 1 C k 0 2 k 2 C DG FAME DG MeOH ) * k 0 3 k 3 C k 0 4 k 4 C MG FAME MG MeOH ) * k 0 5 k 5 C k 0 6 k 6 C GL FAME 1 where k 0 i k i C, i 1; 2; . . . ; 6, indicating that the effective reaction constants k 0 i only depends on the catalyst concentration C and the rate constants of the catalyzed reaction k i . To calculate the effective rate constants, the minimum differ- ence (e) between all experiments and calculated concentrations of the components as shown in Eq. (2) can be used as the objective criterion of the correctness of the model for base-catalyzed transesterication. e min X n i1 X m t1 C exp i;t C fit i;t
2 2 where n is the number of the reactants, C i,t is the concentration of component i at time t and the superscript exp and t denote the experimental and tting value, respectively. 3. Results and discussion In order to fully understand the transesterication reaction path within the reactor, the time course of the component concentra- tion including TG, DG, MG, FAME, GL and MeOH was recorded, and then the composition path was characterized with the ternary phase diagram of oilFAMEMeOH. Eleven reactions are carried out by varying the methanol to oil ratio (6:1, 12:1 and 24:1), reac- tion temperature (20, 40 and 60 C), and catalyst concentration (0.05, 0.1 and 0.5 wt.% of canola oil). 3.1. Time course of product composition Fig. 1 shows the product composition variation during the cano- la oil methanolysis using 1150 rpm at 60 C, 0.1 wt.% of the NaOH, and methanol to oil molar ratio of 24:1. In this case, the slow rate region at the initial stage of the reaction is observed even though the stirring rate of 1150 rpm is adopted. Because of the high molar ratio of 24:1 and low catalyst concentration of 0.1 wt.%, the immis- cibility of canola oil in methanol is hard to be overcome as com- pared with the work of Vicente et al. (2005) where 6:1 of molar ration and 1.5 wt.% was used, and hence the mass transfer might still govern the kinetics of the reaction. As a result, increased mechanical agitation of 1150 rpm is necessary to promote a more rapid reaction though Vicente et al. found that the maximum value of impeller speed was 600 rpm (Vicente et al., 2005). Upon vigor- ous mixing, an emulsion is formed and the reaction is then con- trolled by the solubility of oil in the catalytically active phase (Gunvachai et al., 2007). The formation of FAME and byproduct of glycerol, accompanied by the consumption of methanol and TG, then increase rapidly until their equilibriums are approached as shown in Fig. 1, respectively. The concentration of intermediate MG does not show a signicant change during the whole transeste- rication reaction. By contrast, about 10 wt.% of the intermediate DG is detected during the rst few minutes of the reaction, fol- lowed by a decrease to nearly zero, a level maintained until the end of the reaction (Vicente et al., 2005). The difference in concen- tration variation of both DG and MG can be attributed to the high- est activation energy required for the second forward reaction step from DG to MG as will be shown in Section 3.3. Although Fig. 1 shows only one of the experimental results, similar time courses of composition for the other ten reactions have been obtained for other reaction conditions. Fig. 1 shows that oil, FAME and MeOH are the three major reaction components in the transesterication process. Therefore, the intersolubilities of those three components can be used to represent the main phase variation in the process of transesterication. This method has also been used in the past re- search (Gunvachai et al., 2007). 3.2. Effect of kinetics parameters 3.2.1. Effect of methanol to oil molar ratio Fig. 2 shows the effect of methanol to oil molar ratio on the composition path during the canola oil methanolysis using 0 20 40 60 80 100 120 0 10 20 30 40 50 60 MeOH / oil = 24:1, T = 60 o C, NaOH = 0.1 wt.% Reaction time (min) C o n c e n t r a t i o n
( w t . % ) TG DG MG FAME GL MeOH Fig. 1. Composition of reaction mixture during canola oil methanolysis (methanol to oil molar ratio = 24:1, temperature = 60 C, NaOH concentration in canola oil = 0.1 wt.%, stirring speed = 1150 rpm). 0 20 40 60 80 0 20 40 60 80 0 20 40 60 80 5 min wt.% Canola oil w t . %
C a n o l a
e s t e r w t . %
M e O H 1 min 3 min 7 min 10 min 20 min MeOH / oil = 24:1 MeOH / oil = 12:1 MeOH / oil = 6:1 Experimental LLE at 60 o C Fig. 2. Effect of methanol to oil molar ratio on the ternary composition paths of canola oil methanolysis (T = 60 C, 0.1 wt.% NaOH, stirring speed = 1150 rpm, samples were taken at reaction times of 1, 3, 5, 7, 10, 13, 16, 20, 25, 30, 45, 60, 90 and 120 min). L.-H. Cheng et al. / Bioresource Technology 101 (2010) 66636668 6665 1150 rpm at 60 C and 0.1 wt.% of the NaOH. As shown in Fig. 2, oil and methanol are not mutually soluble so that the initial reaction composition all starts from the bottom line of MeOHCanola oil, regardless of the initial methanol to oil molar ratio. However, with the increase of FAME ratio during the transesterication, the meth- anol to oil ratio shows signicant effect on the time for the reaction composition entering into the homogenous phase of the ternary system of oilFAMEMethanol. If the starting mixture at 60 C has a molar ratio of 6:1 (open triangle), only 3 min are required for the reaction to be homogenous. With the increase of methanol to oil, 10 and 20 min are required before homogenous liquid sys- tems are formed for molar ratio of 12:1 (open square) and 24:1 (open circle), respectively. This difference in the reaction path ex- plains partly well for the reasons that in the membrane reactor, molar ratio of 24:1 is usually adopted for the maintaining of two-phase status because the oil-rich phase can be rejected by the membrane barrier, whereas the lower amount of methanol (like 6:1) is good for the homogenous batch transesterication. Actually, the effect of the molar ratio on the performance of the membrane reactor for the biodiesel production has already been reported experimentally (Cao et al., 2007, 2009; Tremblay et al., 2008), but no clear explanation was given. In our experiments, the difference in the reaction path is used to explain why the high- er molar ratio is usually adopted in the membrane reactor. But 24:1 is not always necessary for the membrane reactor where the heterogeneous status is required. 3.2.2. Effect of temperature Fig. 3 shows both the effect of temperatures on the ternary phase diagram of oilFAMEMeOH, and the composition paths with the different reaction temperatures during the canola oil methanolysis using 1150 rpm at molar ratio of 24:1 and 0.1 wt.% of the NaOH. The liquidliquid equilibrium is apparently inu- enced by the temperature as shown in Fig. 3. The two-phase area extends to the higher concentration of the methyl esters at the lower temperature. For example, the two-phase area at 20 C is much broader than that at 60 C. Nearly 70 wt.% of methyl ester is needed to achieve a homogeneous phase at 20 C while only about 50 wt.% is required at 60 C. It indicates that it is preferable to operate the membrane reactor under the lower temperature in order to maintain as broad two-phase area as possible (Cheng et al., 2009). However, both the reaction rate and reaction conversion re- duce when the temperature drops from 60 to 20 C. As shown in Fig. 3, the nal FAME concentration is about 17 wt.% at the end of the 2 h of transesterication for the reaction temperature of 20 C (open circle), whereas nearly 50 wt.% of FAME is obtained for only 20 min of transesterication at temperature of 60 C (open triangular). Therefore, in the stirring batch reactor, the reac- tion temperature is required to be as high as possible for reducing the reaction time only if the methanol is not evaporated, but for the membrane reactor, the reaction temperature is required to be as low as possible for control of two-phase and avoiding the system at the homogenous phase. Cao et al. had pointed out that the transesterication was believed to occur at the surface of the oil droplets suspended in methanol, and heterogeneous phase is necessary for the operation of the membrane reactor (Cao et al., 2007). With the increase of the temperature, the nal FAME con- centration increases. However, the purity of FAME is deteriorated since the solubility of oil and other intermediates in the product increase with the temperature. Additionally, our experimental study as shown in Fig. 3 indicates that the reaction path remained on the same line irrespective of the increase in reaction tempera- ture for the constant methanol to oil molar ratio of 24:1 adopted in this case. 3.2.3. Effect of catalyst concentration Similar with that shown in Fig. 3, all reaction paths are still found on the same line as shown in Fig. 4, when the experiments are performed at 0.05, 0.1 and 0.5 wt.% of NaOH at the constant molar ration of 24:1. However, the time for the reaction to attain a steady state reduces with the increase of catalyst concentration whereas the nal equilibriumconcentration of each component re- mains almost the same. For the catalyst concentrations of 0.5, 0.1 and 0.05 wt.%, it takes 5, 20 and 45 min for the system to be homo- geneous as shown on the reaction path line in Fig. 4, and it will take 7, 25 and 60 min to achieve almost the same nal equilibrium FAME concentration, respectively. 0 20 40 60 80 0 20 40 60 80 0 20 40 60 80 20 min 2 hr wt.% Canola oil w t . %
C a n o l a
e s t e r w t . %
M e O H 20 o C 40 o C 60 o C Experimental LLE at 20 o C Experimental LLE at 40 o C Experimental LLE at 60 o C Fig. 3. Effect of reaction temperature on the ternary composition paths of canola oil methanolysis (MeOH:oil = 24:1, 0.1 wt.% NaOH, stirring speed = 1150 rpm, samples were taken at reaction times of 1, 3, 5, 7, 10, 13, 16, 20, 25, 30, 45, 60, 90 and 120 min). 0 20 40 60 80 0 20 40 60 80 0 20 40 60 80 wt.% Canola oil w t . %
C a n o l a e s t e r w t . % M e O H 20 min 3 5 min 45 min Experimental LLE at 60 o C NaOH = 0.5 wt.% NaOH = 0.1 wt.% NaOH = 0.05 wt.% Fig. 4. Effect of NaOH concentration on the ternary composition paths of canola oil methanolysis (MeOH:oil = 24:1, reaction temperature = 60 C, samples were taken at reaction times of 1, 3, 5, 7, 10, 13, 16, 20, 25, 30, 45, 60, 90 and 120 min). 6666 L.-H. Cheng et al. / Bioresource Technology 101 (2010) 66636668 The corresponding TG conversion in terms of 20 min is calcu- lated to be 61.1%, 87.2% and 100% for the catalyst concentrations of 0.05, 0.1 and 0.5 wt.%, respectively. The effect of catalyst on the concentration of reaction mixture is found apparently different from the work of Cao et al. using a continuous membrane reactor, where the overall TG conversion for the 0.05 wt.% catalyst is only 32.7% after 20 min (Cao et al., 2009). The lower TG conversion is partly attributed to two-phase maintained within the membrane reactor. Although oil molecules aggregate to form droplets dis- persed in the alcohol as an emulsion, which is conducive for the oil-rich phase rejection by the membrane (Cao et al., 2007, 2009), the mass-transfer effects is still apparent in the membrane reactor with the methanol to oil molar ratio of 24:1 and the catalyst concentration of 0.05 wt.%. The mass-transfer resulted from the two-phase maintenance in the membrane reactor also shows the necessity to make the transesterication and separation carried out in two different units, i.e. the transesterication in the stirring batch reactor as homogenously as possible followed by the separation in the membrane reactor. Additionally, the same TG conversion is found to be achieved by the ultralow catalyst concen- tration of 0.05 wt.% and that of 0.5 wt.% as shown in Fig. 4, indicat- ing the amount of catalyst can be reduced in this reactor without at the expense of TG conversion. To sum up, this above study is to explain why maintaining het- erogeneous reaction is important to the membrane reactor in the biodiesel production. Although this has been shown in literature (Cao et al., 2007, 2009; Tremblay et al., 2008), no strong evidence has been given to explain why the reaction with the heterogeneous behavior is good. Although the reactor is related to conventional reaction, the membrane reactor can simultaneously react and re- move part of feed and product. It is hard to investigate the phase behavior directly in the membrane reactor. Fortunately, the reac- tion mechanism and the phase equilibrium relationships of all those related components are the same irrespective of the reactor type. In this research, the methanolysis of canola oil in a stirring batch reactor is carried out. As a result, the phase behavior ob- tained from the batch reactor is investigated for the inference of the operation of the membrane reactor. 3.3. Kinetics for canola oil methanolysis For comparison purpose, the eleven reactions as shown in Table 1 are used for the calculation of the effective rate constants by the mathematical procedure (Vicente et al., 2005), as shown in Table 2. Similar results can be obtained for the values of the effective rate constant k 0 6 , corresponding the reverse third reaction, i.e. it is too small and can be negligible. Also k 0 3 is the highest only in all the reactions for the methanol to oil molar ratio of 24:1 as shown in Table 2. When the molar ratio is decreased to 12:1 and 6:1, k 0 4 is slightly larger than k 0 3 . However, the absolute values of k 0 3 and k 0 4 are about one order lower than the work of Vicente et al. (2005) in which the batch reactor with molar ratio of 6:1 at 65 C is adopted. By contrast, the order of k 0 3 and k 0 4 are comparable with that of Cao et al. (2009) where the membrane reactor and the same methanol to oil ratio are adopted. It shows that the molar ra- tio of methanol to oil, together with the catalyst concentration has signicant effect on the apparent reactive constants in the transe- sterication process. The effect of the reaction temperature on the rate constant k 1 , corresponding to the rst forward reaction as shown in Fig. 5, is found similar to the work of Vicente et al. (2005). That is, k 1 in- creases with the increase of temperature. Nevertheless, k 1 does not exceed k 5 , corresponding to the third forward reaction. As shown in Fig. 5, no cross point is formed for the Arrhenius plot of k 1 and k 5 . Although all calculated apparent constants increase with the reaction temperature as shown in Fig. 5, the combined effect of the molar ratio of methanol to oil and the catalyst concentration has made the Arrhenius plot of reaction rate versus temperature signicantly different from that of Vicente et al. (2005). The temperature dependence of the reaction rate is further cal- culated as shown in Table 3 for the NaOH-catalyzed reaction by canola oil. The results show that the activation energies are the largest for the second step reaction, with slightly higher value for the forward reaction than that of the reverse reaction. Neverthe- less, the calculated activation energies for the three-step reactions are larger than those reported by Vicente et al. (2005), but closer to those in Freedman et al. (1986) and those in Noureddini and Zhu (1997). The combined effect of molar ratio of methanol to oil and Table 2 Apparent rate constants. k 0 1 (mol/ L min) k 0 2 (mol/ L min) k 0 3 (mol/ L min) k 0 4 (mol/ L min) k 0 5 (mol/ L min) k 0 6 (mol/ L min) Run 1 0.0450 0.0260 0.1052 0.2983 0.1473 0.0006 Run 2 0.0121 0.0556 0.0871 0.3436 0.1934 0.0015 Run 3 0.0084 0.0675 0.3137 0.2836 0.1334 0.0007 Run 4 0.0470 0.3937 1.5660 1.2939 0.6072 0.0038 Run 5 0.0048 0.0277 0.1629 0.1509 0.0908 0.0004 Run 6 0.0039 0.0124 0.0066 0.0042 0.0043 0.0003 Run 7 0.0239 0.0679 0.0341 0.0199 0.0207 0.0018 Run 8 0.0020 0.0062 0.0033 0.0027 0.0015 0.0003 Run 9 0.0004 0.0040 0.0016 0.0016 0.0009 0.0000 Run10 0.0020 0.0218 0.0085 0.0076 0.0062 0.0001 Run 11 0.0002 0.0020 0.0008 0.0008 0.0005 0.0000 2.9 3 3.1 3.2 3.3 3.4 3.5 x 10 -3 -6 -5 -4 -3 -2 -1 0 1 2 3 4 1/T (k -1 ) l n
k k 1 k 2 k 3 k 4 k 5 k 6 Fig. 5. Arrhenius plot of reaction rate versus temperature (MeOH:oil = 24:1, stirring speed = 1150 rpm). Table 3 Activation energies and pre-exponential factors. TG ?DG DG ?TG DG ?MG MG ?DG MG ?FAME FAME ?MG Activation energies (Ea) (J/mol) 65431.2 58403.2 105093.0 102958.6 92540.5 67587.6 Pre-exponential factors (k 0 ) 2.0e + 10 0.9e + 10 5.0e + 17 1.7e + 17 2.2e + 15 3.4e + 9 L.-H. Cheng et al. / Bioresource Technology 101 (2010) 66636668 6667 catalyst concentration causes the difference from those had been previously reported. 4. Conclusions From the experimental results, increasing the residence time of the reaction path within the two-phase zone is inferred to be good for the simultaneous separation and reaction operations of the membrane reactor. In fact, in the membrane reactor, part of the components can be simultaneously removed by the membrane and the continuous removal of products helps shift the reaction equilibrium. Thus, the reaction paths for batch and membrane reactors are not the same. However, if the composition of the sys- tem can be well controlled, the residence time for the reaction path within the two-phase zone shown in the phase diagram of oil FAMEMeOH is longer than that in the conventional batch reactor. Based on the analysis, enhancing operation performance would be possible by integrating a pre-reactor before a membrane reactor. It is being undertaken in our lab. Acknowledgements The authors wish to express their sincere gratitude to the Cen- ter-of-Excellence (COE) Program on Membrane Technology from the Ministry of Education (MOE), ROC, and to the project Toward Sustainable Green Technology in the Chung Yuan Christian Univer- sity, Taiwan, under Grant CYCU-98-CR-CE. References ASTM-D6584, 2000. Test Method for Determination of Free and Total Glycerine in B-100 Biodiesel Methyl Esters by Gas Chromatography. ASTM, USA. Cao, P., Tremblay, A.Y., Dube, M.A., Morse, K., 2007. Effect of membrane pore size on the performance of a membrane reactor for biodiesel production. Ind. Eng. Chem. Res. 46, 5258. Cao, P., Tremblay, A.Y., Dube, M.A., 2009. Kinetics of canola oil transesterication in a membrane reactor. Ind. Eng. Chem. Res. 48, 25332541. Cerce, T., Peter, S., Weidner, E., 2005. Biodiesel-transesterication of biological oils with liquid catalysts: thermodynamic properties of oilmethanolamine mixtures. Ind. Eng. Chem. Res. 44, 95359541. Cheng, L.-H., Cheng, Y.-F., Yen, S.-Y., Chen, J., 2009. Ultraltration of triglyceride from biodiesel using the phase diagram of oilFAMEMeOH. J. Membr. Sci. 330, 156165. Dube, M.A., Tremblay, A.Y., Liu, J., 2007. Biodiesel production using a membrane reactor. Bioresour. Technol. 98, 639647. Freedman, B., Buttereld, R.O., Pryde, E.H., 1986. Transesterication kinetics of soybean oil. J. Am. Oil Chem. Soc. 63 (10), 13751380. Gunvachai, K., Hassan, M.G., Shama, G., Hellgardt, K., 2007. A new solubility model to describe biodiesel formation kinetics. Trans. I Chem. E, Part B, Process Saf. Environ. Prot. 85 (B5), 383389. Noureddini, H., Zhu, D., 1997. Kinetics of transesterication of soybean oil. J. Am. Oil Chem. Soc. 74 (11), 14571463. Tremblay, A.Y., Cao, P., Dube, M.A., 2008. Biodiesel production using ultralow catalyst concentrations. Energy Fuels 22, 27482755. Vicente, G., Martinez, M., Aracil, J., Esteban, A., 2005. Kinetics of sunower oil methanolysis. Ind. Eng. Chem. Res. 44, 54475454. Zhou, H., Lu, H.F., Liang, B., 2006. Solubility of multicomponent systems in the biodiesel production by transersterication of Jatropha curcas L. oil with methanol. J. Chem. Eng. Data 51, 11301135. Zhou, W.Y., 2006. Kinetics and Phase Behavior of Transersterication of Triglycerides. Ph.D. Thesis, University of Toronto, Canada. 6668 L.-H. Cheng et al. / Bioresource Technology 101 (2010) 66636668