DOI: 10.1002/ente.

201200026

Preparation of Biodiesel from Castor Oil Catalyzed by Novel Basic Ionic Liquid
Dong Fang,*[a] Chenning Jiang,[b] and Jinming Yang[b]
As a result of the shortage of fossil fuels and the demands on the control of environmental pollution, it is increasingly necessary to develop clean, alternative renewable energy sources and technology. Fatty acid methyl ester (FAME), as one of the most important biodiesel fuels, is a well-known for being clean, biodegradable, and renewable. Biodiesel is generally prepared from animal fats or vegetable oils through the transesterification of triglycerides (TGs) and methanol in the presence of catalysts such as inorganic acids (e.g., sulfuric acid) or alkali compounds (e.g., KOH, NaOH).[1] These catalysts have significant disadvantages such as being corrosive, nonrenewable, prone to saponification, and producing environmental pollution.[2] Hence, it is urgent to develop new environmentally benign catalysts for biodiesel production. For these reasons, the replacement of the current transesterification procedure with a more environmentally benign process involving the use of ionic liquids is an area worthy of investigation.[3] Functional basic ionic liquids (FBILs) combine the advantageous characteristics of organic and inorganic bases and are designed to replace traditional inorganic bases in clean processes.[4] Recently, FBILs containing the imidazolium cation have also been used for the synthesis of biodiesel.[5] The raw materials used to produce biodiesel can be obtained from a wide variety of bioresources, however, the factors of technical and economic feasibility, environmental effects, accessibility, and national policy concerns must also be considered.[6] It is practical to prepare biodiesel with nonedible oil,[7] and governmental policy currently states that all edible oils, such as rapeseed oil and soybean oil, are forbidden to be used as raw materials to produce biodiesel in China. As one of the most important renewable, nonedible oils, castor oil has potential for use in biodiesel production at a large scale. In view of the importance of biodiesel for energy technology, the limitations of the present synthetic methods, and the continuation of our previous explorations in green catalytic preparation of biodiesel with ionic liquids,[8] a basic ionic liquid 1-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene hydroxide ([BTBD]OH) was synthesized in this work (Scheme 1), and its use as a novel catalyst for the preparation of biodiesel by transesterification of castor oil with methanol was also investigated. To the best of our knowledge, the synthesis of biodiesel from castor oil catalyzed by [BTBD]OH has not been reported.

Scheme 1. Structure of [BTBD][OH] as the catalyst.

The procedure for preparation of [BTBD]OH involves a two-step atom-efficient reaction, and the new catalyst obtained was a somewhat-viscous light yellow liquid. The ionicliquid product did not fume or manifest any noticeable degree of vapor pressure. It is worthwhile to note that the treatment of the [BTBD]OH under vacuum at 250 8C for 72 h resulted in no loss of mass, which proved that [BTBD]OH possesses thermostability. This characteristic could help to recover and reuse the catalyst in the post-procedure. A solubility experiment showed that [BTBD]OH is miscible with water, partly soluble in polar solvents (such as methanol, ethanol, and acetone), and nearly insoluble in nonpolar solvents such as alkanes, aromatic hydrocarbons (such as toluene, benzene, and cyclohexane), and mineral or vegetable oils. To begin screening the potential catalysts, castor oil and methanol were employed as the model reactants at specific temperatures and times to compare their catalytic performances. In this study, tetrabutylammonium hydroxide ([TBA]OH), 1-butyl-3-methyl-imidazolium hydroxide ([Bmim]OH), and KOH were selected to compare with [BTBD]OH (Table 1).

[a] Prof. Dr. D. Fang Jiangsu Provincial Key Laboratory of Coastal Wetland Bioresources & Environmental Protection 50 Kai Fang Da Dao, Yancheng 224002 (P R China) E-mail: fang-njust@hotmail.com [b] C. Jiang, Prof. J. Yang School of Chemistry and Chemical Engineering Yancheng Normal University Yancheng 224002 (P R China) Supporting information for this article is available on the WWW under http://dx.doi.org/10.1002/ente.201200026.

Table 1. Effect of different catalytic system on transesterification.[a] Entry 1 2 3 4 5 Catalyst[c] KOH [TBA]OH [Bmim]OH [BTBD]OH t [h] 6.0 1.0 1.0 1.0 1.0 T [8C] 60 40 40 40 40 Yield [%][b] trace 82 65 88 96

[a] Reaction conditions: n (methanol)/n (castor oil) = 6:1. [b] Isolated yield. [c] All catalyst loadings were 0.9 wt %.

Energy Technol. 0000, 00, 1 4

 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

&1&

These are not the final page numbers!

It was found that no measureable biodiesel could be detected if a mixture of castor oil and methanol was stirred at 60 8C in the absence of a catalyst (entry 1, Table 1), indicating that the catalyst was absolutely necessary for this transesterification procedure. KOH was used as a standard basic catalyst for comparison with other FBILs as it showed relatively good catalytic performance in the transesterification reaction. All three FBILs (entries 35) were proved to be efficient (6596 % yields) in comparison with KOH. In case of FBILs, differing yields were obtained even though the anions of these FBILs were the same (OH). The order of catalytic performance was consistent with the number of nitrogen atom in the cations. The recycling performances of [TBA]OH, [Bmim]OH, and [BTBD]OH were also explored using the above reaction conditions. After completion of the reaction, the products were isolated from the catalytic system by decantation; the catalyst was reused in the next run after the removal of methanol and glycerol under atmospheric distillation and vacuum distillation (400 Pa), respectively. As shown in Figure 1, the [BTBD]OH could be reused at least six times and the decrease in yields was approximately 1 %. The very small degradation after each cycle might be

Table 2. Effect of the molar ratio of methanol to castor oil on the transesterification.[a] Entry 1 2 3 4 5 6 Molar ratio (methanol:castor oil) 3:1 4:1 5:1 6:1 7:1 8:1 t [h] 1.0 1.0 1.0 1.0 1.0 1.0 T [8C] 40 40 40 40 40 40 Yield [%][a] 76 84 88 96 96 93

[a] Isolated yield.

use of too much methanol did not bring an additional increase in the yields, probably because the concentration of catalyst was diluted by the excess methanol and some product was lost in the discarded liquid layer after the reaction. Additionally, the use of excess methanol would not facilitate scaling up this catalyst procedure. It is well known that reaction time has a significant effect on the equilibrium of the transesterification reaction, and therefore, the effect of reaction time on this procedure was also explored (Figure 2). From Figure 2 it is clear that

Figure 1. Reusability of FBILs for transesterification, & [TBA]OH; & [Bmim]OH; & [BTBD]OH.

the result of a slight loss of the catalyst after each cycle. This further indicated that [BTBD]OH was stable at relatively higher temperatures than ([Bmim]OH) and [TBA]OH. Combined with the use of traditional solvents and the simple catalytic procedure, the easy recycling nature is also an attractive property of the [BTBD]OH catalyst if environmental and economic factors are considered. Hence, [BTBD]OH should be the best catalyst for this procedure among the three FBILs. An excess of reactant (methanol) is usually necessary for the preparation of biodiesel by transesterification. To explore the catalyst behavior more fully, the mole ratio of methanol to castor oil was varied from 3:1 to 8:1, and the yields of FAME are listed in Table 2. As expected, as additional methanol was added to the reactant mixture, a higher the yield of target product was obtained under the same reaction conditions. The highest yield of biodiesel achieved was 96 % with a methanol/castor oil mole ratio of 6:1 in 1 h. However, the

Figure 2. Effect of the reaction time on the transesterification reaction yield.

[BTBD]OH was a very efficient catalyst for the transesterification reaction: initially, a drastic increase in yield could be observed with longer reaction times. Further increasing of reaction time did not improve the yields significantly as the transesterification reaction approached equilibrium, with an isolated yield over 96 % in 1.0 h, after which no additional biodiesel product formed when the reaction time was prolonged to 80 min. Hence, the optimal reaction time was 1.0 h for this procedure. The previous results indicated that the amount of catalyst also had a significant influence on the transesterification reaction. The effect of the of the catalyst/castor oil ratio (wt %) on the reaction (Figure 3) illustrated that there was an insufficient number of active sites for the transesterification reaction if the catalyst amount was too low. The yield increased with increasing amount of catalyst over the range
Energy Technol. 0000, 00, 1 4

&2&

www.entechnol.de

 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

These are not the final page numbers!

the catalyst. The ionic liquid can be recycled and reused for many times, and this procedure has the potential to be applied in for industrial biofuel production.

Experimental Section
Melting points were determined using an X-6 microscope melting apparatus and reported uncorrected. 1H NMR spectra were recorded using a Bruker DRX300 spectrometer (300 MHz) and 13 C NMR spectra were acquired using a Bruker DRX300 (75.5 MHz) spectrometer. Mass spectra were obtained with an automated Finnigan TSQ Quantum Ultra AM (Thermal) LC/MS spectrometer. Elemental analyses were recorded using a PerkinElmer 240C spectrometer. The concentration of the product was directly measured by using a Finnigan Trace DSQ GC-MS by quantifying the area under each chromatographic peak. The catalyst was synthesized by gradually adding n-butyl bromide (13.7 g, 0.10 mol) to a solution of 1,5,7-triazabicyclo[4.4.0]dec-5-ene (13.9 g, 0.10 mol) in 20 mL cyclohexane within 30 min under stirring. The mixture was then stirred under nitrogen atmosphere for 2 h at 80 8C. After reaction completion and cooling to room temperature, a white precipitate formed, which was then isolated by filtration, washed with cyclohexane, and dried under vacuum to give 94 % yield of the desired bromide product of 1-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene bromide (white solid, mp 300303 8C (dec)). KOH (2.81 g, 0.05 mol) and and 30 mL ethanol were added to the above bromide product (13.8 g, 0.05 mol), and the mixture was then stirred for 24 h at room temperature before filtering to remove the KBr. The filtrate was distilled to remove the ethanol solvent. The crude product (1-butyl-1,5,7-triazabicyclo[4.4.0]dec-5-ene hydroxide) was washed repeatedly with dichloromethane to remove unreacted starting material and the further dried under vacuum. 1 H NMR (300 MHz, D2O): d = 0.96 (t, 3 H, J = 7.02 Hz), 1.30 1.33 (m, 4 H), 1.491.51 (m, 2 H), 1.962.15 (m, 4 H), 2.532.57 (m, 4 H), 3.313.35 ppm (m, 4 H); 13C NMR (75.5 MHz): d = 14.4, 21.0, 22.0, 25.2, 30.5, 40.2, 41.7, 45.1, 45.7, 48.2, 152.7 ppm. Then, the castor oil was dehydrated at 140 8C under vacuum in a rotary evaporator for 2 h. Dehydrated castor oil, methanol, and [BTBD]OH were added to a flask charged with a reflux condenser and a magnetic stirring bar. The transesterification reaction was then performed for a length of time at the specific temperature with vigorous stirring. After reaction, the mixture was rapidly cooled to room temperature, transferred to a separator, and then held still to allow the reaction mixture to become biphasic. The upper phase mainly containing the desired biodiesel product could be isolated by simple liquid/liquid separation and decantation. The product was washed with water, dried under vacuum to give the target product, and the concentration of the product was directly measured by GC-MS. The bottom phase was a mixture of the ionic liquid with methanol and glycerol generated from the reaction; the catalyst could be recovered and reused by atmospheric distillation and vacuum distillation (400 Pa) to remove the methanol and glycerol respectively.

Figure 3. Effect of the catalyst amount on the transesterification reaction yield.

from 0.1 to 0.9 % before flattening at higher catalyst loadings. Thus, considering the reaction results and the cost of catalyst, the optimum catalyst amount was 0.9 % in this procedure. The effect of reaction temperature on the transesterification reaction is shown in Figure 4. A reaction yield of 56 % of biodiesel was obtained in 1.0 h at 20 8C, and the yield rose as the reaction temperature was increased from 20 to 50 8C.

Figure 4. Effect of reaction temperature on the transesterification reaction yield.

However, this increase became more gradual as the temperature was increased further, and a maximum isolated yield of 96 % was obtained for biodiesel product in 1.0 h at 40 8C, after which increasing the temperature further did not produce additional product. In conclusion, the basic ionic liquid [BTBD]OH was prepared and proved to be an efficient catalyst for the synthesis of biodiesel from castor oil and methanol, exhibiting a high yield of 96 % under optimal reaction conditions. The utilized procedure has the advantages of mild reaction conditions and a practical method for separation of the product from
Energy Technol. 0000, 00, 1 4

Acknowledgements
This work was financially supported by the Ministry of Science and Technology of P. R. Chinaand the Professional Talent Foundation of Yancheng Normal University.

 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.entechnol.de

&3&

These are not the final page numbers!

Keywords: catalysis transesterification

fuel

methanol

synthesis

[1] a) A. E. Farrell, R. J. Plevin, B. T. Tumer, A. D. Jones, M. Ohare, D. M. Kammen, Science 2006, 311, 506 508; b) D. E. Lpez, J. G. Goodwin, D. A. Bruce, E. Lotero, Appl. Catal. A 2005, 295, 97 105; c) J. M. Marchetti, V. U. Miguel, A. F. Errazu, Fuel 2007, 86, 906 910; d) S. Pinzi, I. L. Garcia, F. J. Lopez-Gimenez, M. D. Luque de Castro, G. Dorado, M. P. Dorado, Energy Fuels 2009, 23, 2325 2341; e) S. Yan, C. DiMaggio, S. Mohan, M. Kim, S. O. Salley, K. Y. S. Ng, Top Catal. 2010, 53, 721 736; f) A. A. Kiss, C. S. Bildea, J. Chem. Technol. Biotechnol. 2012, 87, 861 879; g) V. B. Borugadda, V. V. Goud, Renewable Sustainable Energy Rev. 2012, 16, 4763 4784. [2] a) B. A. D. Neto, M. B. Alves, A. A. M. Lapis, F. M. Nachtigall, M. N. Eberlin, J. Dupont, P. A. Z. Suarez, J. Catal. 2007, 249, 154 161; b) A. C. Dimian, Z. W. Srokol, M. C. Mittelmeijer-Hazeleger, G. Rothenberg, Top Catal. 2010, 53, 1197 1201; c) Y. C. Sharma, B. Singh, J. Korstad, Biofuels Bioprod. Biorefin. 2011, 5, 69 92; d) R. Chakraborty, S. K. Das, Ind. Eng. Chem. Res. 2012, 51, 8404 8414. [3] a) S. H. Ha, M. N. Lan, S. H. Lee, S. M. Hwang, Y. M. Koo, Enzyme Microb. Technol. 2007, 41, 480 483; b) M. Gamba, A. A. M. Lapis, J. Dupont, Adv. Synth. Catal. 2008, 350, 160 164; c) M. M. Soumanou, S. T. Djenontin, F. P. Tchobo, D. C. K. Sohounhloue, U. T. Bornscheuer, Lipid Technol. 2012, 24, 158 160; d) B. S. Souza, D. M. M. Pinho, E. C. Liopoldino, P. A. Z. Suarez, F. Nome, Appl. Catal. A 2012, 433/ 434, 109 114; e) T. Long, Y. Deng, S. Gan, J. Chen, Chin. J. Chem. Eng. 2010, 18, 322 327; f) M. H. Han, W. L. Yi, Q. Wu, Y. Liu, Y. C. Hong, D. Z. Wang, Renew. Biores. Techol. 2009, 100, 2308 2310; g) X. Z. Liang, J. G. Yang, Green Chem. 2010, 12, 201 204; h) N. I. Ruzich, A. S. Basi, Energy Fuels 2010, 24, 3214 3222; i) B. L. A. P. Devi, Z. Guo, X. Xu, AIChE J. 2011, 57, 1628 1637; j) A. H. M. Fauzi, N. A. S. Amin, Renewable Sustainable Energy Rev. 2012, 16,

[4]

[5]

[6]

[7]

[8]

5770 5786; k) B. Zhen, H. Li, Q. Jiao, Y. Li, Q, Wu, Y. Zhagn, Ind. Eng. Chem. Res. 2012, 51, 10374 10380; l) P. Lozano, E. Garcia-Verdugo, J. M. Bernal, D. F. Izquierdo, M. I. Burguete, G. SanchezGomez, S. V. Lius, ChemSusChem. 2012, 5, 790 798. a) B. C. Ranu, S. Banerjee, Org. Lett. 2005, 7, 3049 3052; b) K. Guo, B. N. Chen, J. Org. Chem. 2009, 74, 6999 7003; c) Y. Peng, G. Li, J. Li, S. Yu, Tetrahedron Lett. 2009, 50, 4286 4288; d) F. P. Yi, X. Zhang, H. Y. Sun, S. H. Chen, Acta Chim. Sinica 2012, 70, 741 746. a) A. A. M. Lapis, L. F. de Oliveria, B. A. D. Neto, J. Dupont, ChemSusChem 2008, 1, 759 762; b) J. H. Liang, X. Q. Ren, J. T. Wang, M. Jiang, Z. J. Li, J. Fuel Chem. Technol. 2010, 38, 275 280; c) X. F. Li, Y. Wang, H. Zhao, C. H. Li, Acta Petrolei Sin. 2012, 28, 200 206; d) S. Zhou, L. Liu, B. Wang, F. Xu, R. C. Sun, Chin. Chem. Lett. 2012, 23, 379 382. a) D. Y. C. Leung, Y. Gao, Fuel Process. Technol. 2006, 87, 883 890; b) H. J. Berchmans, S. Hirata, Bioresour. Technol. 2008, 99, 1716 1721; c) R. Luque, J. H. Clark, ChemCatChem. 2011, 3, 594 597; d) M. Snchez-Cant, L. M. Prez-Daz, R. Rosales, E. Ramirez, A. Apreza-Sies, I. Pala-Rosas, E. Rubio-Rosas, M. Aguilar-Franco, J. S. , J. M. Valente, Energy Fuels 2011, 25, 3275 3282; e) V. B. Veljkovic , Renewable Sustainable Energy Rev. Avramovic, O. S. Stamenkovic 2012, 16, 1193 1209; f) L. Daz, M. E. Borges, J. Agric. Food Chem. 2012, 60, 7928 7933. a) M. L. Wang, J. B. Morris, B. Tonnis, D. Pinnow, J. Davis, P. Raymer, G. A. Pederson, J. Agric. Food Chem. 2011, 59, 9250 9256; b) V. L. Gole, P. R. Gogate, Ind. Eng. Chem. Res. 2012, 51, 11866 11874. D. Fang, J. M. Yang, C. M. Jiao, ACS Catal. 2011, 1, 42 47.

Received: October 14, 2012 Revised: December 3, 2012 Published online on && &&, 0000

&4&

www.entechnol.de

 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

Energy Technol. 0000, 00, 1 4

These are not the final page numbers!

COMMUNICATIONS
Ionic powers: A basic ionic liquid is used as a catalyst for the preparation of biodiesel by transesterification of castor oil with methanol, the catalytic performance is compared with conventional catalysts and ionic liquids. A high yield of 96 % is achieved under optimal reaction conditions, and the green reaction procedure shows promise for industrial application. D. Fang,* C. Jiang, J. Yang && && Preparation of Biodiesel from Castor Oil Catalyzed by Novel Basic Ionic Liquid

Energy Technol. 0000, 00, 1 4

 2013 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim

www.entechnol.de

&5&

These are not the final page numbers!