基于B酸与L酸协同催化的乙酰丙酸酯化反应
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摘要
将甘蔗渣以碳化-磺化的方法制备出B酸催化剂(C-SO_3H),并与L酸CrCl_3协同催化乙酰丙酸(LA)和乙醇的酯化反应,通过单因素实验和正交实验优化乙酰丙酸酯化反应,探究最佳反应条件。结果表明,在B酸与L酸质量比为1∶1,反应摩尔比(LA∶EtOH)为1∶5,反应时间为8 h,反应温度为90℃的条件下,乙酰丙酸乙酯(ELA)的得率达89.7%。另外,对照组实验的结果说明,B酸与L酸在酯化反应中有一定的协同作用,提高了乙酰丙酸乙酯的得率。
The Bronsted acid catalyst(C-SO_3H) prepared by carbonization-sulfonation of sugarcane bagasse was applied to synergistically catalyze the esterification reaction of levulinic acid(LA) and ethanol with Lewis acid CrCl_3.The conditional parameters of the esterification reaction of levulinic acid was optimized by single factor experiment and orthogonal experiment to explore the optimal reaction conditions.The results showed that the yield of ethyl levulinate reached 89.7% when the mass ratio of Bronsted acid and Lewis acid was 1∶1,the reaction molar ratio(LA∶EtOH) was 1∶5,the reaction time was 8 h,and the reaction temperature was 90 ℃.In addition,the results of the control experiment showed that the Bronsted acid and the Lewis acid had a certain synergistic effect in the esterification reaction resulting in an increase in the yield of ethyl levulinate.
The Bronsted acid catalyst(C-SO_3H) prepared by carbonization-sulfonation of sugarcane bagasse was applied to synergistically catalyze the esterification reaction of levulinic acid(LA) and ethanol with Lewis acid CrCl_3.The conditional parameters of the esterification reaction of levulinic acid was optimized by single factor experiment and orthogonal experiment to explore the optimal reaction conditions.The results showed that the yield of ethyl levulinate reached 89.7% when the mass ratio of Bronsted acid and Lewis acid was 1∶1,the reaction molar ratio(LA∶EtOH) was 1∶5,the reaction time was 8 h,and the reaction temperature was 90 ℃.In addition,the results of the control experiment showed that the Bronsted acid and the Lewis acid had a certain synergistic effect in the esterification reaction resulting in an increase in the yield of ethyl levulinate.
引文
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[3]Peng L C,Lin L,Li H.Extremely low sulfuric acid catalyst system for synthesis of methyl levulinate from glucose[J].Industrial Crops&Products,2012,40(11):136-144.
[4]Xu G Z,Chang C,Zhu W N,et al.A comparative study on direct production of ethyl levulinate from glucose in ethanol media catalysed by different acid catalysts[J].Chemical Papers,2013,67(11):1355-1363.
[5]Kuwahara Y,Kaburagi W,Nemoto K,et al.Esterification of levulinic acid with ethanol over sulfated Si-doped Zr O2solid acid catalyst:Study of the structure-activity relationships[J].Applied Catalysis A General,2014,476(6):186-196.
[6]Peng L C,Zhuang J P,Lin L.Effects of Zr/Ti molar ratio in SO42-/Zr O2-Ti O2calcined at different temperatures on its surface properties and glucose reactivity in near-critical methano[J].Journal of Energy Chemistry,2012,21(2):138-147.
[7]Yan K,Wu G,Wen J,et al.One-step synthesis of mesoporous H4Si W12O40-Si O2catalysts for the production of methyl and ethyl levulinate biodiesel[J].Catalysis Communications,2013,34(34):58-63.
[8]Pileidis F D,Tabassum M,Coutts S,et al.Esterification of levulinic acid into ethyl levulinate catalysed by sulfonated hydrothermal carbons[J].Chinese Journal of Catalysis,2014,35(6):929-936.
[9]Cabiac A,Guillon E,Chambon F,et al.Cellulose reactivity and glycosidic bond cleavage in aqueous phase by catalytic and non catalytic transformations[J].Applied Catalysis A,General,2011,402(1):1-10.
[10]Lou W Y,Guo Q,Chen W J,et al.A highly active bagasse-Derived solid acid catalyst with properties suitable for production of biodiesel[J].Chemsuschem,2012,5(8):1533-1541.
[11]Namchot W,Panyacharay N,Jonglertjunya W,et al.Hydrolysis of delignified sugarcane bagasse using hydrothermal technique catalyzed by carbonaceous acid catalysts[J].Fuel,2014,116(1):608-616.
[12]Dehkhoda A M,West A H,Ellis N.Biochar based solid acid catalyst for biodiesel production[J].Applied Catalysis A General,2010,382(2):197-204.
[13]Liu Y,Chen J,Yao J F,et al.Preparation and properties of sulfonated carbon-silica composites from sucrose dispersed on MCM-48[J].Chemical Engineering Journal,2009,148(1):201-206.