配合物[C10H9N]2CuBr2的制备、结构分析及其对乙醇氧化羰化反应的催化活性

doi:10.11949/j.issn.0438-1157.20150013

摘要/Abstract

摘要：

以CuBr₂和4-甲基喹啉为原料, 在乙醇溶剂中制备了含溴铜(Ⅱ)配合物。通过FTIR、EA、XRD和ICP-AES表征, 初步确定了配合物分子结构为[C₁₀H₉N]₂CuBr₂;采用密度泛函理论计算对其结构、自然原子电荷和前线轨道进行分析, 进一步确定分子结构的可靠性, 并将该配合物应用于乙醇氧化羰化合成碳酸二乙酯催化反应中。结果表明, 在催化剂浓度为0.075 g·ml^-1, 反应温度为100℃, 反应压力为3.5 MPa, 反应时间为4 h的条件下, 乙醇的转化率达到21.5%。通过探讨反应机理, 认为该配合物催化剂稳定性适中, 有利于主反应控制步骤CO的插入反应, 有助于中间体的形成, 从而使催化活性得到提高。

关键词: 配合物, 密度泛函理论, 氧化羰化, 催化剂, 转化率

Abstract:

The copper coordination compound [C₁₀H₉N]₂CuBr₂ was prepared by the reaction of 4-methylchinolin with copper bromide in ethanol solution. The compound was characterized with FTIR, EA, ICP-AES and XRD, and its catalytic performance in oxidative carbonylation of ethanol was investigated. The density functional theory (DFT) calculations were performed to analyze its structure, natural atomic charges and frontier orbital energy levels. The introduction of ligand could improve catalytic activity to prepare diethyl carbonate. The per pass conversion of ethanol could reach 21.5% under the reaction conditions of temperature 373 K, pressure 3.5 MPa, time 4 h and mass concentration of catalyst in ethanol 0.075 g·ml^-1. Reaction mechanism study showed that the compound had moderate stability, which benefited insertion of CO (the rate-controlling step) and formation of intermediate. Therefore, reaction activity was enhanced.

Key words: compound, density functional theory, oxidative carbonylation, catalyst, conversion

中图分类号:

TQ253.2

徐凯, 王新, 刘定华, 刘晓勤, 孙林兵. 配合物[C₁₀H₉N]₂CuBr₂的制备、结构分析及其对乙醇氧化羰化反应的催化活性[J]. 化工学报, 2015, 66(6): 2089-2097.

XU Kai, WANG Xin, LIU Dinghua, LIU Xiaoqin, SUN Linbing. Preparation and structure of [C₁₀H₉N]₂CuBr₂ and its catalytic activity in oxidative carbonylation of ethanol[J]. CIESC Journal, 2015, 66(6): 2089-2097.

参考文献 22

[1]	Meng Xianyang (孟现阳), Zhen Pingjun (甄平军), Wu Jiangtao (吴江涛). Measurements of viscosity and density of diethyl carbonate [J]. Journal of Chemical Industry and Engineering (China) (化工学报), 2008, 59 (11): 2695-2700.
[2]	Su Yuehua (苏跃华), Jiang Xuanzhen (姜玄珍). Atmospheric vapor-phase carbonylation synthesis of diethyl carbonat [J]. Modern Chem. Ind. (现代化工), 2002, 22 (2): 33-34.
[3]	Zhang P, Zhang Z, Wang S, Ma X. A new type of catalyst PdCl2/Cu-HMS for synthesis of diethyl carbonate by oxidative carbonylation of ethanol [J]. Catalysis Communications, 2007, 8 (1):21-26.
[4]	Liu Dinghua (刘定华), Xu Ming (徐明), Chen Zhensong (陈振松), Liu Xiaoqin (刘晓勤). Study on reaction performance of copper salt in oxidative carbonylation of ethanol [J]. Journal of Chemical Engineering of Chinese Universities (高校化学工程学报), 2013, 27 (3): 425-430.
[5]	Romano U, Tesel R, Mauri M M, Rebora P. Synthesis of dimethyl carbonate from methanol, carbon monoxide, and oxygen catalyzed by copper compounds [J]. Industrial & Engineering Chemistry Product Research and Development, 1980, 19 (3): 396-403.
[6]	Cipriani G, Micucci L, Romano U, Tesei R. Method for the preparation of esters of carbonic acid [P]: US, 4218391. 1980-08-19.
[7]	Zhao Qiang (赵强), Li Zhong (李忠), Xie Kechang (谢克昌).Advance in the catalysts for synthesis of dimethyl carbonate (DMC) via liquid-phase oxidative carbonaylation of methanol [J]. Industrial Catalysis (工业催化), 2006, 14 (5): 9-13.
[8]	Liu Dinghua (刘定华), Jiang Zhiyang (姜志样), Liu Xiaoqin (刘晓勤), Zhong Qin (钟秦). Preparation of bromine-containing copper-organic coordination compound and its catalytic performance in oxidative carbonylation of methanol [J]. CIESC Journal (化工学报), 2010, 60 (7): 1714-1718.
[9]	Xiong H, Mo W, Hu J, Bai R, Li G. CuCl/phen/NMI in homogeneous carbonylation for synthesis of diethyl carbonate: highly active catalyst and corrosion inhibitor [J]. Industrial & Engineering Chemistry Research, 2009, 48 (24):10845-10849.
[10]	Yang Xiong (杨雄), Liu Dinghua (刘定华), Sun Linbing (孙林兵), Liu Xiaoqin (刘晓勤). CuBr /DMAP/DMA catalyzed oxidative carbonylation for diethyl carbonate synthesis [J]. Journal of Chemical Engineering of Chinese Universities (高校化学工程学报), 2014, 28 (5): 992-997.
[11]	Kornecki K P, Briones J F, Boyarskikh V, Fullilove F, Autschbach J, Schrote K E, Lancaster K M, Davies H M L, Berry J F. Direct spectroscopic characterization of a transitory dirhodium donor-acceptor carbene complex [J]. Science, 2013, 342 (6156): 351-354.
[12]	Struble M D, Scerba M T, Siegler M, Lectka T. Evidence for a symmetrical fluoronium ion in solution [J]. Science, 2013, 340 (6128): 57-60.
[13]	Upadhyay K K, Kumar A, Upadhyay S, Mishra P C Mishra. Synthesis, characterization, structural optimization using density functional theory and superoxide ion scavenging activity of some Schiff bases [J]. Journal of Molecular Structure, 2008, 873 (1): 5-16.
[14]	Kurt M, Yurdakul ?. Molecular structure and vibrational spectra of lepidine and 2-chlorolepidine by density functional theory and ab initio Hartree-Fock calculations [J]. Journal of Molecular Structure, 2005, 730 (1): 59-67.
[15]	Duttwyler S, Chen S, Takase M K, Wiberg K B, Bergman R G, Ellman J A. Proton donor acidity controls selectivity in nonaromatic nitrogen heterocycle synthesis [J]. Science, 2013, 339 (6120): 678-682.
[16]	Du Zhiping, Xiong Lihua, Lin Zhikun, Li Xuli, Ding Yigang, Wu Yuanxin. Oxidative carbonylation of methanol to dimethyl carbonate over Cu (Ⅱ)-1,10-phenanthroline bromide complexes [J]. Chinese Journal of Chemical Engineering, 2014, 22: 1117-1121.
[17]	Raab V, Merz M, Sundermeyer J. Ligand effects in the copper catalyzed aerobic oxidative carbonylation of methanol to dimethyl carbonate (DMC) [J]. Journal of Molecular Catalysis A: Chemical, 2001, 175 (1): 51-63.
[18]	Chen Junrong (陈俊蓉), Cai Jing (蔡静), Li Quan (李权), Zhao Keqing (赵可清). Theoretical studies of molecular interaction between alcohols and N, N-dimethylacetamide [J]. Acta Chimica Sinica-Chinese Edition (化学学报), 2008, 66 (5): 536-540.
[19]	Hu J C, Cao Y, Yang P. A novel homogeneous catalyst made of poly(N-vinyl-2-pyrrolidone)-CuCl2 complex for the oxidative carbonylation of methanol to dimethyl carbonate [J]. Journal of Molecular Catalysis A: Chemical, 2002, 185 (1/2): 1-9.
[20]	Zhang Liqing (张立庆), Shi Chen (史辰), Wang Jingfeng (王静峰). Thermodynamic analysis of the synthesis of diethyl carbonate by oxidative carbonylation of ethanol [J]. Chemical Engineering of Oil & Gas (石油与天然气化工), 2004, 33 (3): 152-154.
[21]	Liu D H, He J, Sun L B, Liu X Q, Zhong Q. Cupric bromide-derived complex: an effective homogeneous catalyst for oxidative carbonylation of methanol to dimethyl carbonate [J]. Journal of the Taiwan Institute of Chemical Engineers, 2011, 42 (4): 616-621.
[22]	Liu T C, Chang C S. Vapor-phase oxidative carbonylation of ethanol over CuCl-PdCl2/C catalyst [J]. Applied Catalysis A: General, 2006, 304: 72-77.

配合物[C₁₀H₉N]₂CuBr₂的制备、结构分析及其对乙醇氧化羰化反应的催化活性

Preparation and structure of [C₁₀H₉N]₂CuBr₂ and its catalytic activity in oxidative carbonylation of ethanol

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