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酸性离子液体具有催化活性好、选择性高及易于回收等优点,是一种应用前景非常好的环境友好的酸性催化剂,在生物柴油合成反应中具有重大的理论意义和应用价值.本文以油酸和甲醇为原料,探讨了7种不同酸性离子液体在生物柴油合成反应中的催化效应.研究表明,离子液体酸性越强,催化酯化活性越高;引入磺酸基团可大大增强离子液体Br?nsted酸性,使其在酯化反应中发挥溶剂/催化剂的双重作用,促进酯化反应向产物方向进行,达到高产率,因而1-丁基磺酸-3-甲基咪唑硫酸氢盐([BHSO3MIM]HSO4)催化效果最好.此外,系统研究了[BHSO3MIM]HSO4催化油酸与甲醇酯化反应,并采用响应面法优化了反应条件.结果发现,该反应的最适醇酸摩尔比、催化剂用量、反应温度及反应时间分别为4:1,10%(基于油酸的质量),130 oC和4 h;在此条件下,生物柴油产率为97.7%.[BHSO3MIM]HSO4连续使用10批次后,仍能保持初始催化活性的95.6%,表现出极好的操作稳定性.另外,利用该离子液体催化游离脂肪酸含量为72%的废油脂生产生物柴油,反应6 h可获得产率94.9%.可见,[BHSO3MIM]HSO4在酯化生产生物柴油方面具有巨大的应用潜力.

Acidic ionic liquids (ILs) are used as environmentally-friendly and promising acid catalysts for bio-diesel synthesis owing to their beneficial characteristics such as high catalytic activity, high selectiv-ity, and ease of recycling. In this paper, seven different acidic ILs were examined as catalysts in the synthesis of biodiesel from the esterification of oleic acid with methanol. It was found that the stronger the acidity of the IL, the higher its esterification activity. The introduction of a SO3H group into the IL greatly increases its Br?nsted acidity and results in a bifunctional nature of the ILs for use as either a catalyst or environmentally-friendly solution in the esterification reaction. All of these effects contribute to product formation. Of all the tested acidic ILs, 1-sulfobutyl-3- methylim-idazoliumhydrosulfate ([BHSO3MIM]HSO4) exhibited the best catalytic performance. The [BHSO3MIM]HSO4-catalyzed esterification of oleic acid with methanol was systematically explored, and the reaction conditions were optimized using a response surface methodology. The optimum molar ratio of methanol to oleic acid, catalyst amount, reaction temperature, and reaction time were 4:1, 10% (based on the mass of oleic acid), 130 °C, and 4 h, respectively, under these conditions, and a yield of methyl oleate (biodiesel) of 97.7% was achieved. Furthermore, [BHSO3MIM]HSO4 retained around 95.6% of its original catalytic activity after 10 successive reuses (4 h per period of use), showing excellent operational stability. In addition, the use of [BHSO3MIM]HSO4 for biodiesel syn-thesis from waste oils containing 72% of free fatty acids was examined, and yields as high as 94.9% after 6 h were obtained. Clearly, [BHSO3MIM]HSO4 shows considerable potential for the synthesis of biodiesel.

参考文献

[1] Fan X H;Burton R .[J].Open Fuels Energy Sci J,2009,2:100.
[2] Amin S .[J].Energy Conversion & Management,2009,50:1834.
[3] 闵恩泽.利用可再生油料资源发展生物炼油化工厂[J].化工学报,2006(08):1739-1745.
[4] Sheehan J;Camobreco V;Duffield J;Graboski M, Shapouri H.Over-view of Biodiesel and Petroleum Diesel Life Cycles[M].US:National Renewable Energy Lab,Golden,CO,2000
[5] 闵恩泽;张利雄.生物柴油产业链的开拓:生物柴油炼油化工厂[M].北京:中国石化出版社,2006:191.
[6] Zhang X Y;Ma Q;Cheng B B;Wang J Li J S Nie F D .[J].Journal of Natural Gas Chemistry,2012,21:774.
[7] Intarapong P;Iangthanarat S;Phanthong P;Luengnaruemitchai A Jai-In S .[J].J Energy Chem,2013,22:690.
[8] 杜泽学,唐忠,王海京,曾建立,陈艳凤,闵恩泽.废弃油脂原料SRCA生物柴油技术的研发与工业应用示范[J].催化学报,2013(01):101-115.
[9] Komintarachat C;Chuepeng S .[J].Industrial and Engineering Chemistry Research,2009,48:9350.
[10] Hu X T;Zhou Z;Sun D F;Wang Y T Zhang Z B .[J].Catalysis Letters,2009,133:90.
[11] 李明,陈登宇,朱锡锋.稻壳炭基固体酸催化剂的制备及其催化酯化反应性能[J].催化学报,2013(09):1674-1682.
[12] Alsalme A;Kozhevnikova E F;Kozhevnikov I V .[J].Applied Catalysis A:General,2008,349:170.
[13] Katada N;Hatanaka T;Ota M;Yamada K Okumura K Niwa M .[J].Applied Catalysis A:General,2009,363:164.
[14] Blagov S;Parada S;Bailer O;Moritz P;Lam D;Weinand R;Hasse H .Influence of ion-exchange resin catalysts on side reactions of the esterification of n-Butanol with acetic acid[J].Chemical Engineering Science,2006(2):753-765.
[15] Toukoniitty B;Mikkola J P;Eranen K;Salmi T Murzin D Y .[J].Catalysis Today,2005,100:431.
[16] 邓友全.[J].精细化工原料及中间体,2007(10):3.
[17] Elsheikh Y A;Man Z;Bustam M A;Yusup S Wilfred C D .[J].Energy Conversion & Management,2011,52:804.
[18] Ghiaci, M.;Aghabarari, B.;Habibollahi, S.;Gil, A. .Highly efficient Br?nsted acidic ionic liquid-based catalysts for biodiesel synthesis from vegetable oils[J].Bioresource Technology: Biomass, Bioenergy, Biowastes, Conversion Technologies, Biotransformations, Production Technologies,2011(2):1200-1204.
[19] Han, MH;Yi, WL;Wu, Q;Liu, Y;Hong, YC;Wang, DZ .Preparation of biodiesel from waste oils catalyzed by a Bronsted acidic ionic liquid[J].Bioresource Technology,2009(7):2308-2310.
[20] Wu Q;Chen H;Han M M;Wang D Z Wang J F .[J].Industrial and Engineering Chemistry Research,2007,46:7955.
[21] Liang X Z;Gong G Z;Wu H H;Yang J G .[J].FUEL,2009,88:613.
[22] 杨栋,谢文磊,王建龙.离子液体在生物柴油合成中的应用[J].中国油脂,2010(09):54-58.
[23] Fang D;Yang J M;Jiao C M .[J].ACS Catal,2010,1:42.
[24] Gui J Z;Cong X H;Liu D;Zhang X T Hu Z D Sun Z L .[J].CATALYSIS COMMUNICATIONS,2004,5:473.
[25] Zhang, L;Xian, M;He, YC;Li, LZ;Yang, JM;Yu, ST;Xu, X .A Bronsted acidic ionic liquid as an efficient and environmentally benign catalyst for biodiesel synthesis from free fatty acids and alcohols[J].Bioresource Technology: Biomass, Bioenergy, Biowastes, Conversion Technologies, Biotransformations, Production Technologies,2009(19):4368-4373.
[26] Zhen B;Li H S;Jiao Q Z;Li Y Wu Q Zhang Y P .[J].Industrial and Engineering Chemistry Research,2012,51:10374.
[27] 柏杨,张立明,满瑞林.酸离子液体在生物柴油酯交换反应中的催化活性[J].兰州理工大学学报,2010(03):81-85.
[28] 史娜,黄宝华,汪艳飞,黎子进,张煙,方岩雄.咪唑硫酸氢盐离子液体催化酯化反应[J].化学试剂,2009(06):423-426.
[29] 陶端健,周政,吕学铭,胡兴邦,吴有庭.离子液体催化酯化反应的研究进展[J].现代化工,2011(01):20-23.
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