催化学报

催化学报 ›› 2011, Vol. 32 ›› Issue (2): 345-351.DOI: 10.3724/SP.J.1088.2011.00914

• 研究论文 • 上一篇    下一篇

铜基催化剂上甘油脱水制备羟基丙酮

牛莎莎 1,2, 朱玉雷 1,3, 郑洪岩 3, 张维 1,2, 李永旺 1,3   

  1. 1中国科学院山西煤炭化学研究所, 山西太原 030001; 2中国科学院研究生院, 北京 100049; 3中科合成油技术有限公司, 山西太原 030032
  • 收稿日期:2010-09-13 修回日期:2010-11-18 出版日期:2011-01-26 发布日期:2014-06-25

Dehydration of Glycerol to Acetol over Copper-Based Catalysts

NIU Shasha1,2, ZHU Yulei1,3,*, ZHENG Hongyan3, ZHANG Wei1,2, LI Yongwang1,3   

  1. 1Shanxi Institute of Coal Chemistry, Chinese Academy of Sciences, Taiyuan 030001, Shanxi, China; 2Graduate University of Chinese Academy of Sciences, Beijing 100049, China; 3Synfuels China Co. Ltd, Taiyuan 030032, Shanxi, China
  • Received:2010-09-13 Revised:2010-11-18 Online:2011-01-26 Published:2014-06-25

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1662

被引次数

42

摘要： 采用共沉淀法制备了一系列铜基催化剂, 在 N2 中于高压釜中, 考察了其催化甘油脱水制备羟基丙酮的反应性能. 结果表明, Cu/SiO2 催化剂具有较高的催化甘油脱水活性, 但目的产物羟基丙酮易与反应产生的 H2  生成 1,2-丙二醇, 使得羟基丙酮选择性不高. 因此, 在固定床反应器上详细考察了在优选的 Cu/SiO2 催化剂上反应气氛、温度和空速对甘油脱水性能的影响. 与纯 H2  或 N2  相比, 在 5% H2 -95% N2  混合气气氛下反应, Cu/SiO2 催化剂表现出较高的活性和羟基丙酮选择性. 采用 H2 -N2 混合气作为反应气氛, 在一定程度上抑制了 N2 气氛下催化剂的失活和 H2  气氛下羟基丙酮的过度加氢. 在 220 oC, 常压, 5% H2 -95% N2  混合气气氛和 WHSV = 0.08 h-1 条件下, 甘油转化率和羟基丙酮选择性分别高达 98.8% 和 84.6%.

关键词: 甘油, 羟基丙酮, 脱水, 铜基催化剂

Abstract: A series of Cu-based catalysts were prepared by the co-precipitation method, and their catalytic properties for the dehydration of glycerol to acetol were tested under N2 atmosphere in a stainless steel autoclave. The results showed that the Cu/SiO2 catalyst had higher catalytic activity than other catalysts. However, acetol can easily react with hydrogen that originated from the reaction process to 1,2-propanediol, leading to the low selectivity for acetol. Therefore, a fixed-bed reactor was selected to further investigate the effects of reaction atmosphere, reaction temperature, and WHSV on dehydration of glycerol over the Cu/SiO2 catalyst. In comparison with pure H2 or pure N2 atmosphere, the Cu/SiO2 catalyst exhibited significantly higher activity and selectivity for acetol under the mixed atmosphere of 5% H2-95% N2. Under the mixed atmosphere, Cu/SiO2 showed a slower deactivation rate compared with N2 atmosphere and a more proper hydrogenation than that under H2 atmosphere. Under the optimal reaction conditions of 220 oC, WHSV of 0.08 h-1, and ambient 5%H2/N2 pressure, glycerol conversion and selectivity for acetol can be as high as 98.8% and 84.6%, respectively.

Key words: glycerol, acetol, dehydration, copper-based catalyst