留言板

尊敬的读者、作者、审稿人, 关于本刊的投稿、审稿、编辑和出版的任何问题, 您可以本页添加留言。我们将尽快给您答复。谢谢您的支持!

姓名
邮箱
手机号码
标题
留言内容
验证码

玉米秸秆纤维素在亚/超临界乙醇中液化生成酮类化合物的机理探讨

陶红秀 解新安 汤成正 田文广

陶红秀, 解新安, 汤成正, 田文广. 玉米秸秆纤维素在亚/超临界乙醇中液化生成酮类化合物的机理探讨[J]. 燃料化学学报(中英文), 2013, 41(01): 60-66.
引用本文: 陶红秀, 解新安, 汤成正, 田文广. 玉米秸秆纤维素在亚/超临界乙醇中液化生成酮类化合物的机理探讨[J]. 燃料化学学报(中英文), 2013, 41(01): 60-66.
TAO Hong-xiu, XIE Xin-an, TANG Cheng-zheng, TIAN Wen-guang. Mechanism of ketones formation from cellulose liquefaction in sub- and supercritical ethanol[J]. Journal of Fuel Chemistry and Technology, 2013, 41(01): 60-66.
Citation: TAO Hong-xiu, XIE Xin-an, TANG Cheng-zheng, TIAN Wen-guang. Mechanism of ketones formation from cellulose liquefaction in sub- and supercritical ethanol[J]. Journal of Fuel Chemistry and Technology, 2013, 41(01): 60-66.

玉米秸秆纤维素在亚/超临界乙醇中液化生成酮类化合物的机理探讨

基金项目: 国家自然科学基金(21176097); 广东省科技计划国际合作(2009B050700037)。
详细信息
    通讯作者:

    解新安(1964-),副教授,博士,主要从事生物质能利用与开发,食品加工过程模拟,能量系统优化等研究。Tel:020-85280266,E-mail:xinanxie@scau.edu.cn。

  • 中图分类号: TK6

Mechanism of ketones formation from cellulose liquefaction in sub- and supercritical ethanol

  • 摘要: 利用间歇式高压反应釜,在反应温度320℃、反应时间60 min条件下,研究乙醇用量对玉米秸秆纤维素液化生成酮类化合物的作用。当乙醇添加量为0时,酮类化合物的产率仅为1.25%。随着乙醇用量由0增加到160 mL,生物油产率不断的升高,酮类化合物产率增加至18.38%,乙醇促进了纤维素液化生成酮类化合物。利用GC/MS和FT-IR对生物油进行了定性分析,结果表明,在亚/超临界乙醇中,酮类化合物主要通过三条路径形成,纤维素脱水形成了含-C=O的活性纤维素,活性纤维素按逆Diels-Alder机理进行开环、脱水、异构化形成了4-羟基-4-甲基-2-戊酮等脂肪族酮类化合物;在乙醇自由基作用下,活性纤维素中C-O-C、C-C等键断裂、开环,形成环戊烯酮等脂环族酮类化合物,环戊烯酮与多种中间产物发生缩合、酯化形成2-甲酸基-1-苯基乙酮等芳香族酮类化合物;在高浓度乙醇自由基作用下,芳香族酮类化合物进一步发生裂解形成酸类、酮类等化合物。根据对酮类化合物生成机理的分析,建立了纤维素在亚/超临界乙醇中液化生成酮类化合物的反应网络。
  • 谢文, 袁兴中, 曾光明, 佟婧怡, 李辉. 催化剂对亚临界水中生物质液化行为的影响[J]. 资源科学, 2008, 30(1): 129-133. (XIE Wen, YUAN Xing-zhong, ZENG Guang-ming, TONG Jing-yi, LI Hui. Effects of catalysts on biomass liquefaction in subcritical water[J]. Resources Science, 2008, 30(1): 129-133.)
    曹洪涛. 生物质在亚/超临界水条件下液化研究[D]. 长沙: 湖南大学环境科学与工程学院, 2008. (CAO Hong-tao. The research on the liquefaction of biomass in sub- and supercritical water[D]. Changsha: Hunan University, 2008.)
    常胜, 赵增立, 张伟, 郑安庆, 吴文强, 李海滨. 不同种类生物油化学组成结构的对比研究[J]. 燃料化学学报, 2011, 39(10): 746-753. (CHANG Sheng, ZHAO Zeng-li, ZHANG Wei, ZHENG An-qing, WU Wen-qiang, LI Hai-bin. Comparison of chemical composition and structure of different kinds of bio-oils[J]. Journal of Fuel Chemistry and Technology, 2011, 39(10): 746-753.)
    DEMIRBAS A. Mechanism of liquefaction and pyrolysis reactions of biomass[J]. Energy Convers Manage, 2000, 41(6): 633-646.
    DEMIRBAS A. The influence of temperature on the yields of compounds existing in bio-oils obtained from biomss samples via pyrolysis[J]. Fuel Process Technol, 2007, 88(6): 591-597.
    邵千钧, 彭锦星, 修树东, 文先红. 竹子在超临界甲醇中的热解油产物分析[J]. 太阳能学报, 2007, 28(9): 984-987. (SHAO Qian-jun, PENG Jin-xing, XIU Shu-dong, WEN Xian-hong. Analysis of oil products by pyrolysis of bamboo in supercritical methanol[J]. Acta Energiae Solaris Sinica, 2007, 28(9): 984-987.)
    彭锦星, 邵千钧, 陈丰农, 陈奋学, 袁伯增. 基于超临界乙醇的竹子与聚乙烯共液化研究[J]. 太阳能学报, 2009, 30(8): 1139-1144. (PENG Jin-xing, SHAO Qian-jun, CHEN Feng-nong, CHEN Fen-xue, YUAN Bo-zen. Experimental study on co-liquefaction of bamboo and PE in supercritical ethanol[J]. Acta Energiae Solaris Sinica, 2009, 30(8): 1139-1144.)
    郑朝阳, 解新安, 陶红秀, 郑璐丝, 李雁. 亚/超临界乙醇液化秸秆纤维素解聚反应研究与机理初探[J].燃料化学学报, 2012, 40(5): 526-532. (ZHENG Chao-yang, XIE Xin-an, TAO Hong-xiu, ZHENG Lu-si, LI Yan. Depolymerization of stalk cellulose during its liquefaction in sub- and supercritical ethanol[J]. Journal of Fuel Chemistry and Technology, 2012, 40(5): 526-532.)
    LI J, KAZAKOV A, DRYER F L. Experimental and numerical studies of ethanol decomposition reactions[J]. J Phys Chem A, 2004, 108(38): 7671-7680
    曹洪涛, 袁兴中, 曾光明, 佟婧怡, 李辉华. 超/亚临界水条件下生物质和塑料的共液化[J]. 林产化学与工业, 2009, 29(1): 95-99. (CAO Hong-tao, YUAN Xing-zhong, ZENG Guang-ming, TONG Jing-yi, LI Hui, WANG Li-hua. Co-liquefaction of biomass with plastic in sub- and supercritical water[J]. Chemistry and Industry of Forest Products, 2009, 29(1): 95-99.)
    WANG G, LI W, LI B-Q, CHEN H-K, BAI J. Direct liquefaction of sawdust under syngas with and without catalyst[J]. Chem Eng Process: Process intensification, 2007, 46(3):187-192.
    SUN P-Q, HENG M-X, SUN S-H, CHEN J-W. Analysis of liquid and solid products from liquefaction of paulownia[J]. Energy Convers Manage, 2011, 52(2): 924-933.
    LU Q, YANG X-C, DONG C-Q, ZHANG Z-F, ZHANG X-M, ZHU X-F. Influence of pyrolysis temperature and time on the cellulose fast pyrolysis products: Analytical Py-GC/MS study[J]. J Anal Appl Pyrolysis, 2011, 92(2): 430-438.
    DEMIRBAS A. Mechanism of liquefaction and pyrolysis reactions of biomass[J]. Energy Convers Manage, 2000, 41(6): 633-646.
    龙玉峰. 麦草/聚酯混合超临界乙醇液化及其机理的研究[D]. 江苏: 江南大学, 2009. (LONG Yu-feng. Study on liquefaction mechanism and liquefaction of wheat straw mixed with polyester in supercritical ethanol[D]. Jiangsu: Jiangnan University, 2009.)
    李辉, 袁兴中, 曾光明, 佟婧怡, 谢文. 混合溶剂对稻草亚/超临界液化行为影响初探[J]. 农业工程学报, 2008, 24(5): 200-203. (LI Hui, YUAN Xing-zhong, ZENG Guang-ming, TONG Jing-yi, XIE Wen. Effect of mixed solvent on the sub- and supercritical liquefaction of agricultural waste[J]. Transactions of the CSAE, 2008, 24(5): 200-203.)
    LIU Z-G, ZHANG F-S. Effect of various solvents on the liquefaction of biomass to produce fuels and chemical feedstocks[J]. Energy Convers Manage, 2008, 49(12): 3498-3504.
    谭洪.生物质热裂解机理实验研究[D]. 浙江: 浙江大学,2005. (TAN Hong. Mechanism study of biomass pyrolysis[D]. Zhejiang: Zhejiang University, 2005.)
    黄金保, 刘朝, 魏顺安, 黄晓露, 李豪杰. 纤维素热解形成左旋葡聚糖机理的理论研究[J]. 燃料化学学报, 2011, 39(8): 590-594. (HUANG Jin-bao, LIU Chao, WEI Shun-an, HUANG Xiao-lu, LI Hao-jie. A theoretical study on the mechanism of levoglucosan formation in cellulose pyrolysis[J]. Journal of Fuel Chemistry and Technology, 2011, 39(8): 590-594.)
    SHEN D K, GU S. The mechanism for thermal decomposition of cellulose and its main products[J]. Bioresour Technol, 2009, 100(24): 6496-6504.
    耿中锋. 纤维素热裂解机理的理论和实验研究[D]. 天津: 天津大学, 2010. (GENG Zhong-feng. Theoretical and experimental study on mechanism of cellulose pyrolysis[D]. Tianjin: Tianjin University, 2010.)
    HUANG H-J, YUAN X-Z, ZENG G-M, WANG J-Y, LI H, ZHOU C-F, PEI X-K, YOU Q, CHEN L. Thermalchemical liquefaction characteristics of microalgae in sub- and supercritical ethanol[J]. Fuel Process Technol, 2011, 92(1): 147-153.
  • 加载中
计量
  • 文章访问数:  1876
  • HTML全文浏览量:  21
  • PDF下载量:  710
  • 被引次数: 0
出版历程
  • 收稿日期:  2012-08-07
  • 修回日期:  2012-10-08
  • 刊出日期:  2013-01-31

目录

    /

    返回文章
    返回