物理化学学报 >> 2015, Vol. 31 >> Issue (5): 973-979.doi: 10.3866/PKU.WHXB201503171

催化和表面科学 上一篇    下一篇

酸性离子液体催化纤维素在生物丁醇中转化为乙酰丙酸丁酯

马浩, 龙金星, 王芙蓉, 王乐夫, 李雪辉   

  1. 华南理工大学化学与化工学院, 广州510640
  • 收稿日期:2015-01-20 修回日期:2015-03-16 发布日期:2015-05-08
  • 通讯作者: 李雪辉 E-mail:cexhli@scut.edu.cn
  • 基金资助:

    国家自然科学基金(21336002, 21276094)及教育部博士点基金(20130172110043)资助项目

Conversion of Cellulose to Butyl Levulinate in Bio-Butanol Medium Catalyzed by Acidic Ionic Liquids

MA Hao, LONG Jin-Xing, WANG Fu-Rong, WANG Le-Fu, LI Xue-Hui   

  1. School of Chemistry and Chemical Engineering, South China University of Technology, Guangzhou 510640, P. R. China
  • Received:2015-01-20 Revised:2015-03-16 Published:2015-05-08
  • Contact: LI Xue-Hui E-mail:cexhli@scut.edu.cn
  • Supported by:

    The project was supported by the National Natural Science Foundation of China (21336002, 21276094) and Doctoral Fund of Ministry of Education of China (20130172110043).

摘要:

研究了几种磺酸功能化离子液体催化纤维素在生物丁醇中转化为乙酰丙酸丁酯的性能. 系统考察了催化剂的酸强度, 用量, 反应温度, 时间和溶剂对纤维素转化效率和产物分布规律的影响. 实验结果表明酸度最强的磺酸功能化离子液体1-(4-磺酸丁基)-3-甲基咪唑硫酸氢盐([C4H8SO3Hmim]HSO4)能够有效地催化纤维素转化为乙酰丙酸丁酯, 且在优化的反应条件下纤维素的转化率高达98.4%, 乙酰丙酸丁酯的产率为31.1%, 同时共生产物甲酸丁酯、水溶性产物和生物油的产率分别为33.4%、20.6%和23.8%. 该催化体系具有一定的耐水性能, 水的添加量为0.2 mL时并不会严重影响纤维素的转化率. 此外, 酸性离子液体催化剂还表现出了良好的重复使用性能, 使用六次后仍然保持较高的活性.

关键词: 磺酸功能化离子液体, 纤维素, 乙酰丙酸丁酯, 甲酸丁酯, 生物燃料

Abstract:

Butyl levulinate (BL) is one of the most important biochemicals derived from cellulose, and it is of particular interest in industrial applications. Efficient synthesis of BL from cellulose in bio-butanol (bio-BuOH) medium has been investigated in the presence of acidic SO3H-functionalized ionic liquid (SFIL) catalysts. The results showed that the acid strength of the SFILs, catalyst dosage, reaction temperature, reaction time, and solvent composition significantly affected the conversion of cellulose and the yield of the target products. Using the strongest acidic SFIL 1- (4-sulfobutyl)-3-methylimidazolium hydrosulfate ([C4H8SO3Hmim]HSO4) as the catalyst, 98.4% of cellulose could be converted into 31.1% of BL accompanied with 33.4%, 20.6%, and 23.8% of butyl formate (BF), water soluble products (WSPs), and biofuel (Biof), respectively, under the optimized conditions. This catalytic system was water-tolerant, and the addition of 0.2 mL water did not significantly decrease its ability for conversion of cellulose. Furthermore, this acidic SFIL catalyst could be recycled up to six consecutive times without loss of catalytic activity.

Key words: SO3H-functionalized ionic liquid, Cellulose, Butyl levulinate, Butyl formate, Biofuel