NHPI催化分子氧选择性氧化木质素模型分子中的C-C键

doi:10.11949/j.issn.0438-1157.20170533

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 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 Bin^1,2, TANG Siyang¹, YUE Hairong¹, TAN Pinghua³

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/Abstract

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

中图分类号:

O643.32
O625

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.

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.

参考文献 38

[1]	PAULY M, KEEGSTRA K. Cell-wall carbohydrates and their modification as a resource for biofuels[J]. The Plant Journal, 2008, 54(4):559-568.
[2]	LIU C, WANG H, KARIM A M, et al. Catalytic fast pyrolysis of lignocellulosic biomass[J]. Chemical Society Reviews, 2014, 43(22):7594-7623.
[3]	MA R, GUO M, ZHANG X. Selective conversion of biorefinery lignin into dicarboxylic acids[J]. ChemSusChem, 2014, 7(2):412-415.
[4]	WYMAN C E, DALE B E, ELANDER R T, et al. Coordinated development of leading biomass pretreatment technologies[J]. Bioresource Technology, 2005, 96(18):1959-1966.
[5]	NIMMANWUDIPONG T, RUNNEBAUM R C, BLOCK D E, et al. Catalytic reactions of guaiacol:reaction network and evidence of oxygen removal in reactions with hydrogen[J]. Catalysis Letters, 2011, 141(6):779-783.
[6]	LI C, ZHAO X, WANG A, et al. Catalytic transformation of lignin for the production of chemicals and fuels[J]. Chemical Reviews, 2015, 115(21):11559-11624.
[7]	CALVO-FLORES F G, DOBADO J, GARC A J I, et al. Lignin and Lignans as Renewable Raw Materials:Chemistry, Technology and Applications[M]. West Sussex:John Wiley & Sons, Ltd, 2015:521.
[8]	叶跃元. 木质素解聚新工艺及机理研究[D]. 广州:华南理工大学, 2012. YE Y Y. Process and mechanism research on lignin depolymerization[D]. Guangzhou:South China University of Technology, 2012.
[9]	蒋挺大. 木质素[M]. 2版. 北京:化学工业出版社, 2009. JIANG T D. Lignin[M]. 2nd ed. Beijing:Chemical Industry Press, 2009.
[10]	GELLERSTEDT G. Softwood kraft lignin:raw material for the future[J]. Industrial Crops and Products, 2015, 77:845-854.
[11]	舒日洋, 徐莹, 张琦, 等. 木质素催化解聚的研究进展[J]. 化工学报, 2016, 67(11):4523-4532. SHU R Y, XU Y, ZHANG Q, et al. Progress in catalytic depolymerization of lignin[J]. CIESC Journal, 2016, 67(11):4523-4532.
[12]	HALMA M, LACHENAL D, MARLIN N, et al. H2O2 oxidation of lignin model dimers catalyzed by copper(Ⅱ)-phenanthroline[J]. Industrial Crops and Products, 2015, 74:514-522.
[13]	OUYANG X P, TAN Y D, QIU X Q. Oxidative degradation of lignin for producing monophenolic compounds[J]. Journal of Fuel Chemistry and Technology, 2014, 42(6):677-682.
[14]	ZHOU X F. Catalytic oxidation and conversion of kraft lignin into phenolic products using zeolite-encapsulated Cu(Ⅱ)[H4] salen and[H2] salen complexes[J]. Environmental Progress & Sustainable Energy, 2015, 34(4):1120-1128.
[15]	OUYANG X, RUAN T, QIU X. Effect of solvent on hydrothermal oxidation depolymerization of lignin for the production of monophenolic compounds[J]. Fuel Processing Technology, 2016, 144:181-185.
[16]	YANG Q, SHI J, LIN L, et al. Characterization of changes of lignin structure in the processes of cooking with solid alkali and different active oxygen[J]. Bioresource Technology, 2012, 123:49-54.
[17]	RAHIMI A, AZARPIRA A, KIM H, et al. Chemoselective metal-free aerobic alcohol oxidation in lignin[J]. Journal of the American Chemical Society, 2013, 135(17):6415-6418.
[18]	HANSON S K, BAKER R T, GORDON J C, et al. Aerobic oxidation of pinacol by vanadium(V) dipicolinate complexes:evidence for reduction to vanadium(Ⅲ)[J]. Journal of the American Chemical Society, 2009, 131(2):428-429.
[19]	HANSON S K, BAKER R T, GORDON J C, et al. Mechanism of alcohol oxidation by dipicolinate vanadium(V):unexpected role of pyridine[J]. Journal of the American Chemical Society, 2010, 132(50):17804-17816.
[20]	HANSON S K, BAKER R T, GORDON J C, et al. Aerobic oxidation of lignin models using a base metal vanadium catalyst[J]. Inorganic Chemistry, 2010, 49(12):5611-5618.
[21]	HANSON S K, WU R, SILKS L A P. Mild and selective vanadium-catalyzed oxidation of benzylic, allylic, and propargylic alcohols using air[J]. Organic Letters, 2011, 13(8):1908-1911.
[22]	SEDAI B, DÍAZ-URRUTIA C, BAKER R T, et al. Comparison of copper and vanadium homogeneous catalysts for aerobic oxidation of lignin models[J]. ACS Catalysis, 2011, 1(7):794-804.
[23]	HANSON S K, WU R, SILKS L A P. C-C or C-O bond cleavage in a phenolic lignin model compound:selectivity depends on vanadium catalyst[J]. Angewandte Chemie International Edition, 2012, 51(14):3410-3413.
[24]	ZHANG G, SCOTT B L, WU R, et al. Aerobic oxidation reactions catalyzed by vanadium complexes of bis(phenolate) ligands[J]. Inorganic Chemistry, 2012, 51(13):7354-7361.
[25]	SCHEUERMANN M L, LUEDTKE A T, HANSON S K, et al. Reactions of five-coordinate platinum(IV) complexes with molecular oxygen[J]. Organometallics, 2013, 32(17):4752-4758.
[26]	SEDAI B, DÍAZ-URRUTIA C, BAKER R T, et al. Aerobic oxidation of β-1 lignin model compounds with copper and oxovanadium catalysts[J]. ACS Catalysis, 2013, 3(12):3111-3122.
[27]	HANSON S K, BAKER R T. Knocking on wood:base metal complexes as catalysts for selective oxidation of lignin models and extracts[J]. Accounts of Chemical Research, 2015, 48(7):2037-2048.
[28]	DÍAZ-URRUTIA C, SEDAI B, LECKETT K C, et al. Aerobic oxidation of 2-phenoxyethanol lignin model compounds using vanadium and copper catalysts[J]. ACS Sustainable Chemistry & Engineering, 2016, 4(11):6244-6251.
[29]	SHELDON R A, ARENDS I W C E. Catalytic oxidations mediated by metal ions and nitroxyl radicals[J]. Journal of Molecular Catalysis A:Chemical, 2006, 251(1/2):200-214.
[30]	KISHIOKA S Y, YAMADA A. Kinetic study of the catalytic oxidation of benzyl alcohols by phthalimide-n-oxyl radical electrogenerated in acetonitrile using rotating disk electrode voltammetry[J]. Journal of Electroanalytical Chemistry, 2005, 578(1):71-77.
[31]	ISHⅡ Y, SAKAGUCHI S, IWAHAMA T. Innovation of hydrocarbon oxidation with molecular oxygen and related reactions[J]. Advanced Synthesis & Catalysis, 2001, 343(5):393-427.
[32]	ISHⅡ Y, SAKAGUCHI S. Recent progress in aerobic oxidation of hydrocarbons by n-hydroxyimides[J]. Catalysis Today, 2006, 117(1/2/3):105-113.
[33]	IWAHAMA T, SYOJYO K, SAKAGUCHI S, et al. Direct conversion of cyclohexane into adipic acid with molecular oxygen catalyzed by n-hydroxyphthalimide combined with Mn(acac)2 and Co(OAc)2[J]. Organic Process Research & Development, 1998, 2(4):255-260.
[34]	SHIRAISHI T, TAKANO T, KAMITAKAHARA H, et al. Studies on electro-oxidation of lignin and lignin model compounds(Part 2):N-hydroxyphthalimide (NHPI)-mediated indirect electro-oxidation of non-phenolic lignin model compounds[J]. Holzforschung:International Journal of the Biology, Chemistry, Physics, & Technology of Wood, 2012, 66(3):311-315.
[35]	PINHEIRO F G C, SOARES A K L, SANTAELLA S T, et al. Optimization of the acetosolv extraction of lignin from sugarcane bagasse for phenolic resin production[J]. Industrial Crops and Products, 2017, 96:80-90.
[36]	GÜVENATAM B, HEERES E H J, PIDKO E A, et al. Decomposition of lignin model compounds by lewis acid catalysts in water and ethanol[J]. Journal of Molecular Catalysis A:Chemical, 2015, 410:89-99.
[37]	ISHⅡ Y, IWAHAMA T, SAKAGUCHI S, et al. Alkane oxidation with molecular oxygen using a new efficient catalytic system:N-hydroxyphthalimide (NHPI) combined with Co(acac)n (n=2 or 3)[J]. The Journal of Organic Chemistry, 1996, 61(14):4520-4526.
[38]	ZHOU Y, LIN S, BIAN Y, et al. Aerobic oxidation of aromatics catalyzed by CoSPc and NHPI[J]. Indian Journal of Chemistry-Section B Organic and Medicinal Chemistry, 2016, 55B(5):624-628.

NHPI催化分子氧选择性氧化木质素模型分子中的C-C键

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

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 38

相关文章 15

编辑推荐

Metrics

本文评价

[1]	胡超, 董玉明, 张伟, 张红玲, 周鹏, 徐红彬. 浓硫酸活化五氧化二钒制备高浓度全钒液流电池正极电解液[J]. 化工学报, 2023, 74(S1): 338-345.
[2]	宋瑞涛, 王派, 王云鹏, 李敏霞, 党超镔, 陈振国, 童欢, 周佳琦. 二氧化碳直接蒸发冰场排管内流动沸腾换热数值模拟分析[J]. 化工学报, 2023, 74(S1): 96-103.
[3]	张义飞, 刘舫辰, 张双星, 杜文静. 超临界二氧化碳用印刷电路板式换热器性能分析[J]. 化工学报, 2023, 74(S1): 183-190.
[4]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[5]	杨百玉, 寇悦, 姜峻韬, 詹亚力, 王庆宏, 陈春茂. 炼化碱渣湿式氧化预处理过程DOM的化学转化特征[J]. 化工学报, 2023, 74(9): 3912-3920.
[6]	吴雷, 刘姣, 李长聪, 周军, 叶干, 刘田田, 朱瑞玉, 张秋利, 宋永辉. 低阶粉煤催化微波热解制备含碳纳米管的高附加值改性兰炭末[J]. 化工学报, 2023, 74(9): 3956-3967.
[7]	米泽豪, 花儿. 基于DFT和COSMO-RS理论研究多元胺型离子液体吸收SO₂气体[J]. 化工学报, 2023, 74(9): 3681-3696.
[8]	李艺彤, 郭航, 陈浩, 叶芳. 催化剂非均匀分布的质子交换膜燃料电池操作条件研究[J]. 化工学报, 2023, 74(9): 3831-3840.
[9]	陈哲文, 魏俊杰, 张玉明. 超临界水煤气化耦合SOFC发电系统集成及其能量转化机制[J]. 化工学报, 2023, 74(9): 3888-3902.
[10]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[11]	郑佳丽, 李志会, 赵新强, 王延吉. 离子液体催化合成2-氰基呋喃反应动力学研究[J]. 化工学报, 2023, 74(9): 3708-3715.
[12]	陈美思, 陈威达, 李鑫垚, 李尚予, 吴有庭, 张锋, 张志炳. 硅基离子液体微颗粒强化气体捕集与转化的研究进展[J]. 化工学报, 2023, 74(9): 3628-3639.
[13]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[14]	陈杰, 林永胜, 肖恺, 杨臣, 邱挺. 胆碱基碱性离子液体催化合成仲丁醇性能研究[J]. 化工学报, 2023, 74(9): 3716-3730.
[15]	李锦潼, 邱顺, 孙文寿. 煤浆法烟气脱硫中草酸和紫外线强化煤砷浸出过程[J]. 化工学报, 2023, 74(8): 3522-3532.

NHPI催化分子氧选择性氧化木质素模型分子中的C-C键

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

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

参考文献 38

相关文章 15

编辑推荐

Metrics

本文评价

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