微波辅助SnCl4/H2SO4二元体系催化纤维素醇解制备乙酰丙酸甲酯
收稿日期: 2015-11-09
修回日期: 2015-12-28
网络出版日期: 2016-02-01
基金资助
国家自然科学基金(No.21502095)、江苏省自然科学基金(No.BK20150872)和江苏省生物质绿色燃料和化学品重点实验室开放基金(No.14003)资助项目.
Microwave-Assisted Alcoholysis of Cellulose to Methyl Levulinate Catalyzed by SnCl4/H2SO4
Received date: 2015-11-09
Revised date: 2015-12-28
Online published: 2016-02-01
Supported by
Project supported by the National Natural Science Foundation of China (No. 21502095), the Natural Science Foundation of Jiangsu Province (No. BK20150872) and the Opening Fund from Jiangsu Key Laboratory of Biomass-based Green Fuels and Chemicals (No. 14003).
黄耀兵 , 杨涛 , 刘安凤 , 周新成 , 潘晖 . 微波辅助SnCl4/H2SO4二元体系催化纤维素醇解制备乙酰丙酸甲酯[J]. 有机化学, 2016 , 36(6) : 1438 -1443 . DOI: 10.6023/cjoc201511015
Microwave irradiation technology was used to assist the conversion of cellulose to methyl levulinate (ML) in methanol solution in the presence of mixed catalysts. The reactions were carried out in a microwave reactor and cellulose was rapidly converted into ML with a highest yield of 61.5% by the use of SnCl4/H2SO4 as catalyst. The catalysts ratios, reaction time and reaction temperature were optimized and found to have great influences on both the ML product yield and the selectivity. Besides, an appropriate amount of water, which may participate the breakage of the glucosidic bond of cellulose, is highly desirable for the full conversion of cellulose. Several other biomass derived carbohydrates such as starch, sucrose and inulin were also tested in the optimized system and 48%~60% ML yields were achieved. Finally, the mixed catalysts can be recycled and reused for at least five times without much decrease in catalytic activity.
Key words： cellulose; methyl levulinate; microwave irradiation; alcoholysis
[1] Chen, X.; Han, Z. Q.; Kong, F. H.; Hu, X. T. Prog. Chem. 2007, 19, 1091 (in Chinese). (陈曦, 韩志群, 孔繁华, 胡徐腾, 化学进展, 2007, 19, 1091.)
[2] Hu, L.; Sun, Y.; Lin, L. Prog. Chem. 2012, 24, 483 (in Chinese). (胡磊, 孙勇, 林鹿, 化学进展, 2012, 24, 483.)
[3] Wu, S. C.; Wang, C. L.; Gao, Y. J.; Zhang, S. C.; Ma, D.; Zhao, Z. B. Chin. J. Catal. 2010, 31, 1157 (in Chinese). (吴树昌, 王春雷, 高勇军, 张少春, 马丁, 赵宋保, 催化学报, 2010, 31, 1157.)
[4] Peng, L. C.; Lin, L.; Li, H. Prog. Chem. 2012, 24, 801 (in Chinese). (彭林才, 林鹿, 李辉, 化学进展, 2012, 24, 801.)
[5] Runge, T.; Zhang, C. Ind. Eng. Chem. Res. 2012, 51, 3265.
[6] Yang, Z.; Fu, Y.; Guo, Q. X. Chin. J. Org. Chem. 2015, 35, 273 (in Chinese). (杨珍, 傅尧, 郭庆祥, 有机化学, 2015, 35, 273.)
[7] Zhang, T.; Chang, C. Chem. Ind. Eng. Prog. 2012, 31, 1224 (in Chinese). (张婷, 常春, 化工进展, 2012, 31, 1224.)
[8] Joshi, H.; Moser, B. R.; Toler, J.; Smith, W. F.; Walker, T. Biomass Bioenergy 2011, 35, 3262.
[9] Chia, M.; Dumesic, J. A. Chem. Commun. 2011, 47, 12233.
[10] Huang, Y.; Dai, J.; Deng, X.; Qu, Y.; Guo, Q.; Fu, Y. ChemsusChem 2011, 4, 1578.
[11] Alexandre, D.; Nadine, E.; Franck, R. ACS Sustainable Chem. Eng. 2014, 2, 1338.
[12] Climent, M. J.; Corma, A.; Iborra, S. Green Chem. 2014, 16, 516.
[13] Melero, J. A.; Morales, G.; Iglesias, J.; Paniagua, M.; Hernandez, B.; Penedo, S. Appl. Catal., A 2013, 466, 116.
[14] Huang, Y. B.; Yang, T.; Zhou, M. C.; Pan, H.; Fu, Y. Green Chem. 2016, 18, 1516.
[15] Liu, D.; Lin, L.; Zeng, S. S.; Peng, L. C. Chem. Ind. Forest Prod. 2013, 33, 66 (in Chinese). (刘娣, 林鹿, 曾姗姗, 彭林才, 林产化学与工业, 2013, 33, 66.)
[16] Yu, K. M. K.; Tsang, S. C. Catal. Lett. 2011, 141, 259.
[17] Tominaga, K.; Mori, A.; Fukushima, Y.; Shimada, S.; Sato, K. Green Chem. 2011, 13, 810.
[18] Ma, H.; Long, J. X.; Wang, F. R.; Wang; L. F.; Li, X. H. Acta Phys. Chim. Sin. 2015, 31, 973 (in Chinese). (马浩, 龙金星, 王芙蓉, 王乐夫, 李雪辉, 物理化学学报, 2015, 31, 973.)
[19] Sun, P. Q.; Zhao, S. Q.; Chang, Q.; Chen, J. W. J. Zhengzhou Univ. 2014, 35, 22 (in Chinese). (孙培勤, 赵世强, 常春, 陈俊武, 郑州大学学报, 2014, 35, 22.)
[20] Ding, D. Q.; Xi, J. X.; Wang, J. J.; Liu, X. H.; Lu, G. Z.; Wang, Y. Q. Green Chem. 2015, 17, 4037.
[21] Hishikawa, Y.; Yamaguchi, M.; Kubo, S.; Yamada, T. J. Wood Sci. 2013, 59, 179.
[22] Li, J.; Huang, Y. B.; Guo, Q. X.; Fu, Y. Acta Chim. Sinica 2014, 72, 1223 (in Chinese). (李江, 黄耀兵, 郭庆祥, 傅尧, 化学学报, 2014, 72, 1223.)
[23] Wu, X.; Fu, J.; Lu, X. Carbohydr. Res. 2012, 358, 37.
[24] Chang, C.; Jiang, X. X.; Zhang, T. Adv. Mater. Res. 2012, 512, 388.
[25] Peng, L.; Lin, L.; Li, H.; Yang, Q. Appl. Energ. 2011, 88, 4590.
/
| 〈 |
|
〉 |
