催化学报

催化学报 ›› 2010, Vol. 31 ›› Issue (7): 851-856.

• 研究论文 • 上一篇    

无氯 Cu/AC 催化剂的制备及其催化气相甲醇氧化羰基化反应性能

王瑞玉, 李忠, 郑华艳, 谢克昌   

  1. 太原理工大学煤科学与技术教育部山西省重点实验室, 山西太原 030024
  • 收稿日期:2010-07-25 出版日期:2010-07-25 发布日期:2010-07-25

Preparation of Chlorine-Free Cu/AC Catalyst and Its Catalytic Properties for Vapor Phase Oxidative Carbonylation of Methanol

WANG Ruiyu, LI Zhong*, ZHENG Huayan, XIE Kechang   

  1. Key Laboratory of Coal Science and Technology of Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
  • Received:2010-07-25 Online:2010-07-25 Published:2010-07-25

PDF

906

被引次数

44

摘要： 以 Cu2(NO3)(OH)3/AC (活性碳) 为催化剂前驱体, 在惰性气氛中于不同温度热处理分别制得无氯的 CuO/AC, Cu2O/AC 和 Cu0/AC 催化剂, 并用于甲醇直接气相氧化羰基化合成碳酸二甲酯 (DMC) 反应. 结果表明, 200 °C 处理制得的催化剂中, Cu 物种以 CuO 为主. 随着处理温度的升高, 催化剂中 CuO 含量逐渐降低, 而 Cu2O 含量增加; 400 °C 制备的催化剂中, Cu 物种仅以 Cu2O 形式存在; 而 450 °C 以上处理时则以 Cu0 形式存在. 随着热处理温度的提高, 相应催化剂活性逐渐增加, 表明 CuO, Cu2O 和 Cu0 均具有催化活性, 其活性大小的顺序为 CuO < Cu2O < Cu0. 在 140 °C, CO:MeOH:O2 = 4:10:1, SV = 5 600 h?1 条件下, 450 °C 处理制备的 Cu0/AC 催化剂表现出较高的催化甲醇氧化羰基化活性, 其中甲醇转化率达 11.5%, DMC 的时空收率和选择性分别为 261.9 mg/(g•h) 和 76.0%.

关键词: 甲醇, 氧化羰基化, 铜, 活性炭, 无氯催化剂, 热处理, 碳酸二甲酯

Abstract: Chlorine-free CuO/AC, Cu2O/AC, and Cu0/AC catalysts (AC: activated carbon) were prepared by heat treatment of Cu2(NO3)(OH)3/AC in an inert atmosphere, and their catalytic properties for the direct vapor-phase oxidative carbonylation of methanol to dimethyl carbonate (DMC) were investigated. When the Cu2(NO3)(OH)3/AC was heated at 200 °C, the main copper species on AC was CuO. With the heating temperature rising, the CuO content decreased and the Cu2O content increased on the AC support. The Cu species existed as Cu2O when the heating tempareture was 400 °C and as Cu0 when the heating tempareture was 450 °C. The catalytic activity also increased with the heating temperature rising. This indicated that the CuO, Cu2O, or Cu0 was active, and the catalytic activity increased in the order CuO < Cu2O < Cu0. Under the conditions of 140 °C, CO:MeOH:O2 = 4:10:1, and SV = 5 600 h?1, the Cu0/AC catalyst prepared at 450 °C had excellent catalytic activity, and the methanol conversion, space time yield, and selectivity for DMC reached 11.5%, 261.9 mg/(g•h), and 76.0%, respectively.

Key words: methanol, oxidative carbonylation, copper, active carbon, chlorine free catalyst, heat treatment, dimethyl carbonate