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

doi:10.11949/j.issn.0438-1157.20170533

Abstract

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

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

CLC Number:

O643.32
O625

LIU Changjun, CHEN Ning, LIU Yingying, LU Houfang, LIANG Bin, TANG Siyang, YUE Hairong, TAN Pinghua. Oxidative C-C bond cleavage of lignin model compound with O₂ in presence of N-hydroxyl phthalimide[J]. CIESC Journal, 2017, 68(10): 3788-3794.

刘长军, 陈宁, 刘颖颖, 鲁厚芳, 梁斌, 唐思扬, 岳海荣, 谭平华. NHPI催化分子氧选择性氧化木质素模型分子中的C-C键[J]. 化工学报, 2017, 68(10): 3788-3794.

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

NHPI催化分子氧选择性氧化木质素模型分子中的C-C键

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