催化学报

催化学报 ›› 2012, Vol. 33 ›› Issue (4): 736-742.DOI: 10.3724/SP.J.1088.2012.11121

• 研究论文 • 上一篇    

Cu(phen)Cl2 催化甲醇氧化羰基化合成碳酸二甲酯

杜治平*, 周彬, 黄丽明, 黄晨, 吴元欣, 王存文, 孙炜   

  1. 绿色化工过程教育部重点实验室, 湖北省新型反应器与绿色化学工艺重点实验室, 武汉工程大学化工与制药学院, 湖北武汉 430073
  • 收稿日期:2011-11-30 修回日期:2012-01-20 出版日期:2012-04-13 发布日期:2015-09-09

Synthesis of Dimethyl Carbonate from Oxidative Carbonylation of Methanol Catalyzed by Cu(phen)Cl2

DU Zhiping*, ZHOU Bin, HUANG Liming, HUANG Chen, WU Yuanxin, WANG Chunwen, SUN Wei   

  1. Key Laboratory for Green Chemical Process of Ministry of Education, Hubei Key Laboratory of Novel Chemical Reactor and Green Chemical Technology, School of Chemical Engineering and Pharmacy, Wuhan Institute of Technology, Wuhan 430073, Hubei, China
  • Received:2011-11-30 Revised:2012-01-20 Online:2012-04-13 Published:2015-09-09

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摘要： 以 CuCl2 和邻菲啰啉 (phen) 为原料, 在甲醇和乙醇混合溶剂中制备了 Cu(phen)Cl2, 采用傅里叶红外光谱、热重分析和 H2 程序升温还原对其进行了表征, 并研究了其在甲醇氧化羰基化合成碳酸二甲酯 (DMC) 反应中的催化性能. 结果表明, Cu(phen)Cl2 不仅具有较高的热稳定性, 而且因 phen 与 Cu(II) 间的 σ-π 配位作用而具有较高的催化活性. 在催化剂浓度 0.011 mol/L, 反应温度 150 °C, 反应压力 4.0 MPa 和 p(CO)/p(O2) = 19 的条件下, 生成 DMC 的转化数 (TON) 可达 51.5. 研究还发现, 反应存在诱导期, 且 TON 随温度呈“M”形变化, 据此提出了新的羰氧化反应机理.

关键词: 碳酸二甲酯, 甲醇, 氧化羰基化, 氯化铜, 邻菲啰啉, 配合物

Abstract: The copper coordination compound Cu(phen)Cl2 was prepared by the reaction of 1,10-phenanthroline with cupric chloride in the mixed solution of methanol and ethanol and was characterized by infrared spectroscopy, thermogravimetric analysis, and temperature-programmed reduction. Their catalytic performance for the oxidative carbonylation of methanol to dimethyl carbonate (DMC) was investigated. The results showed that Cu(phen)Cl2 had the high thermal stability and exhibited the high catalytic performance due to the effect of the σ-π coordination bond between phen and Cu(II). The turnover number (TON) could reach 51.5 mol of DMC per mol of Cu, under the conditions of reaction temperature 150 °C, total pressure 4.0 MPa, p(CO)/p(O2) = 19 (below the explosion limit of CO) and the catalyst concentration in methanol 0.011 mol/L. It was also found that there was an induction period at the early reaction stage, and the change of TON was the “M” type with the increase of temperature. Further, a novel reaction mechanism was suggested.

Key words: dimethyl carbonate, methanol, oxidative carbonylation, cupric chloride, phenanthroline, complex