淀粉基炭负载纳米铜催化合成碳酸二甲酯

doi:10.1016/S1872-2067(12)60640-8

催化学报 ›› 2013, Vol. 34 ›› Issue (9): 1734-1744.DOI: 10.1016/S1872-2067(12)60640-8

淀粉基炭负载纳米铜催化合成碳酸二甲酯

任军, 郭长江, 杨雷雷, 李忠

太原理工大学煤科学与技术教育部和山西省重点实验室, 山西太原 030024

收稿日期:2013-04-20 修回日期:2013-06-19 出版日期:2013-09-16 发布日期:2013-08-28
通讯作者: 任军
基金资助:
国家自然科学基金(20606022, 20936003和21276169); 国家重点基础研究发展计划(973计划, 2012CB723100); 山西省自然科学基金(2010011014-5); 山西省高等学校优秀青年学科带头人项目(TYAL).

Synthesis of dimethyl carbonate over starch-based carbon-supported Cu nanoparticles catalysts

Jun Ren, Changjiang Guo, Leilei Yang, Zhong Li

Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China

Received:2013-04-20 Revised:2013-06-19 Online:2013-09-16 Published:2013-08-28
Supported by:
This work was supported by the National Natural Science Foundation of China (20606022, 20936003 and 21276169), the National Basic Research Program of China (973 Program, 2012CB723100), the Natural Science Foundation of Shanxi Province (2010011014-5), and the Program for the Top Young Academic Leaders of Higher Learning Institutions of Shanxi (TYAL).

摘要/Abstract

摘要：

以硝酸铜和可溶性淀粉为原料, 经过溶胶-凝胶化过程、高温炭化和KOH活化得到炭负载铜催化剂(Cu/C), 采用扫描电镜、透射电镜、X射线衍射、热重-差热分析仪、N₂吸附和CO程序升温脱附对催化剂结构进行了表征, 并考察了它在甲醇氧化羰基化合成碳酸二甲酯(DMC)反应中的催化活性. 结果表明, 活化温度和KOH用量对催化剂的表面结构及金属铜粒子尺寸影响显著, 当活化温度为850℃, KOH:C=1 (质量比)时, Cu/C催化剂的比表面积达到1690 m²/g, 铜纳米粒子平均晶粒尺寸为30.4 nm, 催化活性最高, DMC时空收率达到235.7 mg·g^-1·h^-1, 甲醇转化率和DMC选择性分别为1.6%和76.5%.

关键词: 淀粉, 溶胶凝胶法, 炭载体, 氢氧化钾活化, 碳酸二甲酯

Abstract:

Carbon-supported Cu (Cu/C) catalyst was prepared from Cu(NO₃)₂ and starch, by the sol-gel method, subsequent high temperature carbonization and KOH activation. Catalyst samples were characterized by scanning and transmission electron microscopies, X-ray diffraction, thermogravimetric analysis, N₂ adsorption-desorption and CO temperature-programmed desorption. Their catalytic performance in the oxidative carbonylation of methanol to dimethyl carbonate (DMC) in a fixed-bed reactor was investigated. The activation temperature and KOH content greatly influenced the catalyst microstructure and catalytic performance. The Cu/C catalyst prepared at activation temperature of 850℃ and KOH/C mass ratio of 1 exhibited the best catalytic activity. Its specific surface area and mean Cu particle size were 1690 m²/g and 30.4 nm, respectively. The space time yield was 235.7 mg·g^-1·h^-1, and the methanol conversion and selectivity for DMC were 1.6% and 76.5%, respectively.

Key words: Starch, Sol-gel method, Carbon support, Potassium hydroxide activation, Dimethyl carbonate

任军, 郭长江, 杨雷雷, 李忠. 淀粉基炭负载纳米铜催化合成碳酸二甲酯[J]. 催化学报, 2013, 34(9): 1734-1744.

Jun Ren, Changjiang Guo, Leilei Yang, Zhong Li. Synthesis of dimethyl carbonate over starch-based carbon-supported Cu nanoparticles catalysts[J]. Chinese Journal of Catalysis, 2013, 34(9): 1734-1744.

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淀粉基炭负载纳米铜催化合成碳酸二甲酯

Synthesis of dimethyl carbonate over starch-based carbon-supported Cu nanoparticles catalysts

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