马艳华,朱宪,万雪亮,姬文琦,田玲

• 1:上海大学环境与化学工程学院化工系

摘要(Abstract)：

研究了纤维素在亚临界水中无催化水解及分别添加ZnCl2、FeCl3、CuCl2、AlCl3对水解反应的影响。实验结果显示,无催化剂时,葡萄糖的收率在280℃,60s及(7.0±0.2)MPa时达到最大为14.3%。添加ZnCl2、FeCl3、CuCl2及AlCl3均能促进纤维素的水解及葡萄糖的降解。纤维素的水解及葡萄糖的降解反应级数均为一级。利用一级反应模型对纤维素在260℃水解及葡萄糖的降解反应进行数据拟合,求得了纤维素的水解速率常数(k),葡萄糖的生成速率常数(k1)及葡萄糖的降解速率常数(k2)。添加AlCl3体系中纤维素的水解速率常数(k)大于葡萄糖的降解速率常数(k2),有利于葡萄糖的生成,在260℃,120s及(5.2±0.2)MPa时,葡萄糖收率达到最大为46.05%。添加ZnCl2、CuCl2及FeCl3体系中葡萄糖的降解速率常数(k2)大于纤维素的水解速率常数(k),不利于葡萄糖的生成。XRD分析显示,金属氯化物的加入并没有破坏纤维素的晶体类型,水解残渣仍然保持纤维素Ⅰ型晶体结构。

关键词(KeyWords)： 纤维素;亚临界水;金属氯化物;水解反应;葡萄糖

Abstract:

Keywords:

基金项目(Foundation): 上海市重点资助项目(S30109)

作者(Author): 马艳华,朱宪,万雪亮,姬文琦,田玲

参考文献(References)：

• [1]ZHU Xian(朱宪),YAN Lei(杨磊),ZHAO Liang(赵亮)et al.The hydrolysis technology optimization for amino acids production from feather in sub-critical water(近临界水中羽毛水解制备氨基酸的工艺优化)[J].J Chem Eng of Chinese Univ(高校化学工程学报),2008,22(6):1032-1036.
• [2]Piroska S,Tomoaki M,Tomoko O.Liquefaction of cellulose in hot compressed water using sodium carbonate.Products distribution at different reaction temperatures[J].J of Chem Eng of Jap,1998,31(4):571-576.
• [3]Ehara K,Saka S.Decomposition behavior of cellulose in supercritical water,subcritical water,and their combined treatments[J].J Wood Sci,2005,51(2):148-153.
• [4]Sasaki M,Fang Z,Fukushima Y et al.Dissolution and hydrolysis of cellulose in subcritical and supercritical water[J].Ind Eng Chem Res,2000,39(8):2883-2890.
• [5]ZHUANG Xin-shu(庄新姝),WANG Shu-rong(王树荣),LUO Zhong-yang(骆仲泱)et al.Experimental research and products analysis of cellulose hydrolysis under extremely low acids(纤维素低浓度酸水解试验及产物分析研究)[J].Acta Energiae Solaris Sinica(太阳能学报),2006,27(5):519-523.
• [6]Nguyen Q A,Tucker M P.Dilute acid/metal salt hydrolysis of lignocellulosics[P].USP:6,423,145B1,2002-07-23.
• [7]LüXiu-yang(吕秀阳),Sakoda Akiyoshi(追田章义),Suzuki Motoyuki(铃木基之).Kinetics and product distributions of cellulose decomposition in near critical water(纤维素在近临界水中的动力学和产物分布)[J].J Chem Ind and Eng(Cina)(化工学报),2001,52(6):556-559.
• [8]Sasaki M,Kabyemela B M,Malaluan R M et al.Cellulose hydrolysis in subcritical and supercritical water[J].J Supercritical Fluids,1998,13(3):261-268.
• [9]Kruse A,Gawlik A.Biomass conversion in water at330-410℃and30-50MPa.Identification of key compounds for indicating different chemical reaction pathways[J].Ind Eng Chem Res,2003,42(2):267-279.
• [10]Maldas D,Shiraishi N.Liquefaction of biomass in the presence of phenol and H2O using alkalies and salts as the catalyst[J].Biomass and Bioenergy,1997,12(4):273-279.
• [11]Li F,Chen Z L.Research progress on dissolution and functional modification of cellulose in ionic liquids[J].Journal of Molecular Liquids,2008,142(1):1-5.
• [12]Zhuang X S,Yuan Z H,Ma L L et al.Kinetic study of hydrolysis of xylan and agricultural wastes with hot liquid water[J].Biotechnology Advances,2009,27(5):578-582.
• [13]Ott L,Lehr V,Urfels S et al.Influence of salts on the dehydration of several biomass-derived polyols in suband supercritical water[J].J Supercritical Fluids,2006,38(1):80-93.
• [14]LI Song-ye(李松晔),LIU Xiao-fei(刘晓非),ZHUANG Xu-pin(庄旭品)et al.Ultrasonic treatment of cotton pulp cellulose(棉浆粕纤维素的超声波处理)[J].Chinese Journal of Applied Chemistry(应用化学),2003,20(11):1030-1034.