Chemical Engineering Journal 174 (2011) 396399

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Chemical Engineering Journal

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Dimerization of fatty acid methyl ester using BrnstedLewis acidic ionic liquid as catalyst
Shiwei Liu a , Hongxia Zhou a , Shitao Yu a, , Congxia Xie b , Fusheng Liu a , Zhanqian Song a
a b

College of Chemical Engineering, Qingdao University of Science and Technology, No. 53 Zhengzhou Road, Qingdao 266042, China College of Chemistry and Molecular Engineering, Qingdao University of Science and Technology, No. 53 Zhengzhou Road, Qingdao 266042, China

a r t i c l e

i n f o

a b s t r a c t
The dimerization of fatty acid methyl ester was investigated using BrnstedLewis acidic ionic liquids (ILs) as catalysts. It is found that IL (3-sulfonic acid)-propyl-triethylammonium chlorozincinate [HO3 S(CH2 )3 NEt3 ]ClZnCl2 (x = 0.64, x: molar fraction of ZnCl2 , x = moles of ZnCl2 /(moles of ZnCl2 + moles of ammonium salt) was of good catalytic performance. Under the optimum conditions m(biodiesel):m(IL) 15:1, biodiesel 15 g, reaction temperature 240 C, and reaction time 5 h, the yield of product dimeric acid methyl ester was 96.8%. The reusability of IL was good and after it was used ve times, the dimeric acid methyl ester yield was still more than 94%. Otherwise, a synergetic effect of Brnsted and Lewis acid sites enhanced the catalytic performance of the IL. 2011 Elsevier B.V. All rights reserved.

Article history: Received 14 February 2011 Received in revised form 30 August 2011 Accepted 4 September 2011 Keywords: BrnstedLewis acidic ionic liquid Fatty acid methyl esters Dimerization Catalysis

1. Introduction Natural fats are converted into biodiesel (fatty acid methyl ester, FAME) in typical process of methanolysis. This process seems now more attractive because of a growing interest in biodiesel. However, even applying the latest and the most modern technology, the cost of biodiesel fuel is rather high. Thus there is a need to look for new ways to make the production of biodiesel fuel more economically attractive. One such alternative could be utilization of animal and vegetable fatty wastes for biofuel production. However, biodiesel from these wastes contains lots of carboncarbon double bonds which make the product unstable for use in an engine. Dimeric acid methyl esters (DAME), produced by the dimerization of unsaturated FAME, is an high value ne chemical, and widely used in the elds of polyamides, polymer applications and as anticorrosives, etc. [13]. The dimerization mechanism of FAME is similar to that of fatty acid [4,5]. It is that the catalyst promotes dehydrogenation and dimerization of FAMEs through a DielsAlder process. During the process of reaction, the unsaturated FAME containing one carboncarbon double bond forms the diene acid ester by dehydrogenation in the acidic catalyst. Then, the non-conjugated diene acid ester is conjugated to act as a diene and adds to a double bond of a normal (or conjugated) FAME, which acts as a dieneophile, to give the product. Usually a Brnsted acid is active for conjugation and a Lewis acid for the DielsAlder reaction. The crystalline clay

Corresponding author. Tel.: +86 532 84022719; fax: +86 532 84022719. E-mail address: yushitaoqust@126.com (S. Yu). 1385-8947/$ see front matter 2011 Elsevier B.V. All rights reserved. doi:10.1016/j.cej.2011.09.017

minerals, including bentonite, kaolinite, hectorite, etc., were used as catalysts in the dimerization. This is a commonly practiced commercial procedure and these catalysts are extremely effective for promoting the formation of DAME. However, these catalysts cannot be reused, and substantial quantities of DAME are retained by the clay and lost when the clay is disposed of. This results in considerable economic loss in addition to creating an environmental problem. Attempts to recover the DAME from the clay catalyst and lter cake by extraction with solvents such as hexane, heptane and other low boiling solvents have not been satisfactory because that DAME recovered in this way are discolored and unsuitable for most applications without further purication. Mesoporous molecular sieves were reported as catalysts in the dimerization [6,7]. They also have shortcomings, such as restricted accessibility to the matrixbound acidic sites, high molecular weight/active site ratios, and rapid deactivation from coking. Therefore, it is necessary to explore a new approach for the synthesis of DAME. In addition, compared with the expensive reagents, such as methyl oleate and methyl linoleate, biodiesel is more promising and economical as a feed for the preparation of DAME. As a kind of environmental-friendly catalyst, Brnsted or Lewis acidic ionic liquids (ILs) gets attention of researchers, and many organic reactions, such as esterication [8], dehydration [9], alkylation [10], acylation [11], and carbonylation [12], were reported with excellent selectivity, and the used ILs were of outstanding recyclability. In our laboratory, some BrnstedLewis acidic ILs were synthesized, characterized and used in the polymerization [13,14]. The results indicated that the BrnstedLewis acidic ILs was both Brnsted and Lewis acidic and had better catalytic performance

S. Liu et al. / Chemical Engineering Journal 174 (2011) 396399

397

C2H5 C2H5

C2H5 N+

_ ZnCl2 SO3H Cl (CH2)3

C2H5 C2H5

C2H5
+

_ ZnCl2 SO3H ZnCl3 N (CH2)3

C2H5 C2H5

C2H5 _ZnCl 2 + SO3H Zn Cl 2 5 N (CH2)3

C2H5 C2H5

C2H5

_ N + SO3H Zn3Cl7 (CH2)3

Scheme 1. Synthesis of IL [HO3 S(CH2 )3 NEt3 ]ClZnCl2 .

for the polymerization than the traditional catalysts. Due to the presence of Brnsted and Lewis acid sites, these ILs can selectively catalyze different reaction mechanisms to enhance the conversion and selectivity of the reaction. Therefore, we studied the dimerization of FAME using biodiesel as the feed in the presence of BrnstedLewis acidic ILs. 2. Materials and methods 2.1. Materials FAME (methyl palmitate 8.5 wt%, methyl stearate 5.1 wt%, methyl oleate 30.8 wt%, methyl linoleate 45.3 wt%, methyl linolenate 3.2 wt%, others 7.1 wt%, with the content of unsaturated FAME at 79.8 wt%), and other chemicals were obtained commercially and used without further purication. HP-LC spectra were measured with an Alltech ELSD-2000ES evaporative light-scattering detector (column: IP-18. Mobile phase: methanol. Flow rate: 1.0 mL/min. Column temperature: 25 C. Sample injection volume: 10 L 1% methanol solution). IR spectra were recorded by a Nicolet 510P FT-IR spectrometer in the range of 4500400 cm1 . NMR spectra were taken by a Bruker AV500 Fourier-Transform spectrometer with reference to SiMe4 , using solvent DMSO containing 5 wt% of the sample. 2.2. Preparation of ILs Using the procedure in the literature, 1,3-propane sultone was reacted with triethylamine to give 3-(triethylamine-N-yl)propane-1-sultonate (TEA-PS) as a white powder. Then TEA-PS was reacted with an equal mole of hydrochloric acid to give (3-sulfonic acid)-propyl-triethylammonium chloride [HO3 S(CH2 )3 NEt3 ]Cl as a white viscous liquid at room temperature. The BrnstedLewis acidic ILs were prepared by the reaction of [HO3 S(CH2 )3 NEt3 ]Cl with metal chlorides, including FeCl3 , ZnCl2 , CuCl and CuCl2 . The Lewis acidity of IL depended on the metal chloride mass. When the molar fraction of metal chloride was less than 0.5, IL only had Brnsted acidity and no Lewis acidity, and above this value, the obtained IL was BrnstedLewis acidic [13]. The reaction formula for the synthesis of IL [HO3 S(CH2 )3 NEt3 ]ClZnCl2 (x = 0.67) was shown in Scheme 1. [HO3 S(CH2 )3 NEt3 ]ClZnCl2 (x = 0.64): IR (KBr disc, cm1 ): 3351, 2989, 1621, 1484, 1455, 1396, 1255, 1228, 1151,
Table 1 Effects of kinds of catalysts on results of the reaction. Entry Catalysts

1039, 948, 813, 791, 735, 694, 598, 521. 1 H NMR (500 MHz, D2 O, ppm): 2.11 (m, 2H), 2.71(t, 2H), 3.71(s, 3H), 4.16(t, 2H), 7.25(s, 1H), 7.32(s, 1H), 8.53(s, 1H). 13 C NMR (500 MHz, D2 O, ppm): 24.75, 35.28, 46.94, 47.73, 122.12, 123.34, 134.75. 2.3. Dimerization of FAME In a typical experiment, 15 g biodiesel and 1 g IL were added and reacted at 240 C for 5 h in a ask under dry nitrogen. After the reaction, the reaction mixture was cooled to 120 C, and then the upper layer, containing the polymerized products and unreacted reactants, was separated from the IL layer at the bottom of the ask simply by decantation. The IL layer was reused directly in the cycle experiments. The product was obtained after removing unreacted reactants by distillation at 220 C under reduced pressure (5 mmHg) over 20 min. The yield of products (Y, %) was calculated by: Y (%) = Wp /WALL 100, where Wp is the mass of product, and WALL is the mass of the unsaturated FAME. All product samples were analyzed to determine the FAME, dimer, and trimer contents by HP-LC. 3. Results and discussion 3.1. Effects of different catalysts on the dimerization As can be seen from Table 1, comparing with the traditional catalysts, the examined ILs exhibited better catalytic performance. Especially, [HO3 S(CH2 )3 NEt3 ]ClZnCl2 (x = 0.67) exhibited good catalytic property with the yield of product more than 96.8% (entry 6). The components of the uncreated reactants were main saturated FAMEs (83.9 wt%), such as methyl palmitate (35.2 wt%), methyl stearate (15.1 wt%), methyl eicosanoate (7.6 wt%), methyl docosanoate (12.6 wt%), methyl tetracosanoate (8.0 wt%). The unsaturated FAMEs were only 14.1% (entry 6). It was indicated that most unsaturated FAMEs were dimerized. The good catalytic performance was due to the Brnsted and Lewis acidities of the IL and a synergetic effect. The Brnsted and Lewis acid sites of IL can selectively catalyze dehydrogenation, conjugation and dimerization, and the synergetic effect enhanced the catalytic performance of IL, which was similar to that of a zeolite [15]. The result from IL 1-butyl-3-methylimidazolium chlorozincinate [C4 mim]ClZnCl2 (x = 0.67) was also determined to show these effects on the

Y/%

Distribution/% FAME Dimer 88.6 93.6 96.0 97.4 94.3 95.7 91.1 96.3 94.8 95.59 93.0 Trimer 8.5 2.9 1.6 0.6 3.1 2.5 7.2 1.4 2.1 2.5 1.8

1 2 3 4 5 6 7 8 9 10 11

H2 SO4 (1 g) H2 SO4 + ZnCl2 (0.5 g + 0.5 g) ZnCl2 (2 g) [HO3 S(CH2 )3 NEt3 ]Cl [HO3 S(CH2 )3 NEt3 ]ClZnCl2 (x = 0.64) [HO3 S(CH2 )3 NEt3 ]ClZnCl2 (x = 0.67) [HO3 S(CH2 )3 NEt3 ]ClZnCl2 (x = 0.75) [HO3 S(CH2 )3 NEt3 ]ClFeCl3 (x = 0.67) [HO3 S(CH2 )3 NEt3 ]ClCuCl2 (x = 0.67) [HO3 S(CH2 )3 NEt3 ]ClCuCl3 (x = 0.67) [C4 mim]ClZnCl2 (x = 0.67)

40.7 32.5 37.3 39.5 78.0 96.8 95.3 88.9 32.4 35.9 24.3

2.9 3.5 2.4 2.0 2.6 1.8 1.7 2.2 3.1 2.0 5.2

398 Table 2 Effects of reaction conditions on the dimerization. T/ C t/h

S. Liu et al. / Chemical Engineering Journal 174 (2011) 396399

IL/g

Y/%

Distribution/% FAME Dimer 96.3 95.7 83.6 97.7 87.3 88.0 96.7 Trimer 2.1 2.5 14.4 1.1 11.7 9.5 1.2

220 240 270 240 240 240 240

5 5 5 4 6 5 5

1.0 1.0 1.0 1.0 1.0 1.5 0.5

88.3 96.8 97.2 90.2 97.5 96.2 81.3

1.6 1.8 2.0 1.2 1.0 2.5 2.1

Reaction conditions: Biodiesel 15 g.

catalytic performance of IL (entry 11). Among the chlorozincinate ILs (entries 57), the DAME yield increased with the molar fraction of ZnCl2 (x). When x value was 0.67, the dimerization of FAME was effectively catalyzed. However, when x reached 0.75, the yield of DAME did not increase further, but the trimer content in the product increased (entry 9). This can be explained by that, when the molar fraction of metal chloride (x) was more than 0.5, IL was Lewis acidic, and by increasing the x value, the Lewis acidity was increased [16], which increased the catalytic activity of IL. The metal chlorides had a decisive inuence on the catalytic performance of ILs (entries 6, 810). IL [HO3 S(CH2 )3 NEt3 ]ClZnCl2 (x = 0.67) showed the best catalytic performance (entry 8), and IL [HO3 S(CH2 )3 NEt3 ]ClCuCl (x = 0.67) had almost no catalytic activity (entry 9). These results can be explained by the difference in the Lewis acidic strength of IL. With the increase of the acidity of the metal chloride, the Lewis acidity of IL became stronger, and had a higher catalytic activity [10]. As a result, the catalytic activity of [HO3 S(CH2 )3 NEt3 ]ClZnCl2 (x = 0.67) was higher. 3.2. Effects of reaction conditions on the dimerization The effects of reaction conditions are shown in Table 2. The reaction temperature was very important for the dimerization. When the temperature was 220 C, the DAME yield was 88.3%. When the temperature reached 240 C, the DAME yield was 96.8%. However, the trimer content in the product was 14.4% when the temperature was increased to 270 C. This may be because the higher reaction temperature facilitated the dimerization of FAME to produce trimer. With increasing reaction time from 4 h to 6 h, the yield of product increased from 90.2% to 97.5%, and the trimer content also increased from 1.1% to 11.7%. When decreasing the IL dosage from 1.5 g to 0.5 g, the DAME yield decreased from 86.2% to 81.3%, and the trimer content also decreased from 9.5% to 1.2%. Both too long a reaction time and too small IL dosage were unfavorable to the quality of DAME. 3.3. Reusability of catalyst The reusability of [HO3 S(CH2 )3 NEt3 ]ClZnCl2 (x = 0.67) was investigated, and the results were given in Table 3. The results showed that the yield and composition of product were almost unchanged after [HO3 S(CH2 )3 NEt3 ]ClZnCl2 (x = 0.67) was used
Table 3 The reusability of the catalytic system. Cycle Y/% Distribution/% FAME 1 2 3 4 5 96.8 96.2 96.5 94.2 94.9 1.8 2.2 1.5 3.0 2.8 Dimer 95.7 94.9 97.3 93.4 95.0 Trimer 2.5 2.9 1.2 3.6 2.2

Transmittance /%
4000

3500

3000

2500

2000

1500

1000

500

Wavenumber

/cm-1

Fig. 1. FT-IR spectra of [HO3 S(CH2 )3 NEt3 ]ClZnCl2 (x = 0.64). (a) Unused IL and (b) repeatedly used ve times of IL.

repeatedly ve times. It is indicated that the BrnstedLewis acidic IL was of excellent reusability. This good reusability result could be explained by the following two points. First, in the structure of IL, the alkyl sulfonic acid group was covalently tethered in IL cation, and the anion [Zn2 Cl5 ] of IL was inert and stable in water and Brnsted acid. Therefore the acidity of IL was not easily lost. Second, the use of ZnCl2 increased the density of the IL, which gave an easier separation of IL from the reaction mixture, and the IL was not easily lost in the separation process. Therefore, its activity was stable. In order to investigate the intactness of the repeatedly utilized IL, IR spectra of the reusedve time and unused ILs were given in Fig. 1. As shown in Fig. 1, both IR spectra were similar, which indicated that the structure of the reused IL was unspoiled. 4. Conclusion The dimerization of FAME was investigated using BrnstedLewis acidic ILs as catalysts. IL (3-sulfonic acid)-propyltriethylammonium chlorozincinate [HO3 S(CH2 )3 NEt3 ]ClZnCl2 (x = 0.67) was of good catalytic property and the yield of product was 96.8%. The BrnstedLewis acidic sites of IL can selectively catalyze the dehydrogenation, conjugation and polymerization in the reaction, and a synergetic effect of Brnsted and Lewis acid sites enhanced the catalytic performance of the IL. Acknowledgments This work was nancially supported by the National Natural Science Foundation of China (30571463), the Program of Science & Research of Shandong Province (2011GGB01046) and the Doctor

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Foundation of Shandong Province (BS2010NJ006). The authors are grateful for the nancial support. References
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