化工学报 ›› 2017, Vol. 68 ›› Issue (10): 3788-3794.DOI: 10.11949/j.issn.0438-1157.20170533

• 催化、动力学与反应器 • 上一篇    下一篇

NHPI催化分子氧选择性氧化木质素模型分子中的C-C键

刘长军1, 陈宁1, 刘颖颖2, 鲁厚芳1, 梁斌1,2, 唐思扬1, 岳海荣1, 谭平华3   

  1. 1 四川大学化学工程学院, 四川 成都 610207;
    2 四川大学 CCUS与CO2矿化利用研究中心, 四川 成都 610207;
    3 西南化工研究设计院有限公司, 四川 成都 610225
  • 收稿日期:2017-05-02 修回日期:2017-06-28 出版日期:2017-10-05 发布日期:2017-10-05
  • 通讯作者: 刘长军,liuchangjun@scu.edu.cn;谭平华,kinghuatan@163.com
  • 基金资助:

    国家自然科学基金项目(21406146,21476150,21336008)。

Oxidative C-C bond cleavage of lignin model compound with O2 in presence of N-hydroxyl phthalimide

LIU Changjun1, CHEN Ning1, LIU Yingying2, LU Houfang1, LIANG Bin1,2, TANG Siyang1, YUE Hairong1, TAN Pinghua3   

  1. 1 School of Chemical Engineering, Sichuan University, Chengdu 610207, Sichuan, China;
    2 Center of CCUS and CO2 Mineralization and Utilization, Sichuan University, Chengdu 610207, Sichuan, China;
    3 Southwest Research & Design Institute of Chemical Industry, Chengdu 610225, Sichuan, China
  • Received:2017-05-02 Revised:2017-06-28 Online:2017-10-05 Published:2017-10-05
  • Supported by:

    supported by the National Natural Science Foundation of China(21406146, 21476150, 21336008).

摘要:

以1,2-二苯乙烷为模型分子,考察了N-羟基邻苯二甲酰亚胺(NHPI)对分子氧氧化断裂木质素分子中C-C键的催化作用,比较了Cu、Co和Mn的多种可溶性盐对NHPI催化活性的促进作用,探究了工艺条件对1,2-二苯乙烷氧化的影响规律。结果表明:NHPI能够在温和条件下催化分子氧氧化1,2-二苯乙烷中的C-C键断裂生成苯甲醛和苯甲酸。可溶性的Cu、Co和Mn盐都具有助催化作用,其中乙酸锰的助催化作用最强。确定了二苯基乙酮为氧化的初级反应产物。发现提高反应温度、增加乙酸锰用量以及延长反应时间,有利于C-C键的氧化断裂和提高小分子产物的选择性。优化的反应条件为NHPI为底物物质的量的10%,乙酸锰和NHPI之比为1:10,反应温度90℃,氧气分压1.0 MPa,反应时间8 h,C-C键的氧化断裂产物苯甲醛和苯甲酸的总选择性可达76.5%。

关键词: 生物质, 催化, 氧化, 降解, 生物燃料

Abstract:

The catalytic effects of N-hydroxyl phthalimide combined with various transition metal salts on the oxidative breakage of C-C bond of lignin by O2 under mild conditions were studied.1,2-diphenylethane was adopted as the model compound of lignin C-C bond.It was found that Mn (OAc)2 showed the highest promotion effect on the catalytic activity of NHPI among the soluble cobaltous,manganous and cupric salts.The oxidative breakage of C-C bonds led to the production of benzyl aldehyde and benzoic acid with high selectivity.1,2-Diphenyl ethanone was found to be the primary product.Either increase the reaction temperature,Mn (OAc)2 amount as well as the reaction time favored the C-C bond cleavage.Total selectivity of benzyl aldehyde and benzoic acid up to 76.5% was achieved in acetic acid under the conditions of 90℃ and 1.0 MPa O2 for 8 h by using 10% NHPI and 1% Mn (OAc)2 with respect to the amount of benzyl phenyl ether as the catalyst.

Key words: biomass, catalysis, oxidation, degradation, biofuel

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