催化学报

催化学报 ›› 2012, Vol. 33 ›› Issue (7): 1203-1208.DOI: 10.3724/SP.J.1088.2012.20204

• 研究论文 • 上一篇    下一篇

草酸处理对丙烷氨氧化催化剂 Sb-V-O 结构和催化性能的影响

汪国军1,2, 郭耘1, 卢冠忠1,*   

  1. 1华东理工大学工业催化研究所, 上海 200237; 2中石化上海石油化工研究院, 上海 201208
  • 收稿日期:2012-02-03 修回日期:2012-04-03 出版日期:2012-06-21 发布日期:2012-06-21

Effect of Oxalic Acid on the Structure and Catalytic Performance of Sb-V-O Catalyst for Propane Ammoxidation

WANG Guojun1,2, GUO Yun1, LU Guanzhong1,*   

  1. 1Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, China; 2Shanghai Research Institute of Petrochemical Technology, China Petroleum & Chemical Corporation, Shanghai 201208, China
  • Received:2012-02-03 Revised:2012-04-03 Online:2012-06-21 Published:2012-06-21

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摘要： 以不同量的草酸处理钒的起始原料, 采用共沉淀法制备了 VSb3 混合氧化物催化剂, 运用 N2 低温吸附、X 射线衍射、X 射线光电子能谱和 H2 程序升温还原等方法对催化剂进行了表征, 并考察了其在丙烷氨氧化反应中的催化性能. 结果表明, 草酸的处理可使所得样品中 V 处于较低的价态, 从而有利于活性相 SbVO4 的生成. 当草酸/V (摩尔比) 为 3 时, 所制 VSb3 混合氧化物中存在较多的活性相 SbVO4, 且其表面具有适量 Sb 和 V 的分布, 使催化剂具有良好的氧化/还原性能平衡, 因而在丙烷氨氧化反应中表现出更高的活性和丙烯腈选择性.

关键词: 丙烷, 氨氧化反应, 丙烯腈, 锑, 钒, 混合氧化物, 草酸, 处理

Abstract: VSb3 mixed oxide catalyst samples for propane ammoxidation were prepared by a coprecipitation method with the vanadium starting materials treated with different amounts of oxalic acid in the preparation process. The VSb3 mixed oxide catalyst prepared with vanadium starting materials treated with nitric acid and the catalyst without treatment were also prepared for comparison. The effects of the oxalic acid amount on the physicochemical properties of the VSb3 mixed oxide catalyst were investigated by low-temperature N2 adsorption, X-ray diffraction, X-ray photoelectron spectroscopy, and H2 temperature-programmed reduction, and its catalytic performance for propane ammoxidation to acrylonitrile was tested. The results showed that the addition of oxalic acid in preparation process can keep V at a low valence, which generates a greater amount of SbVO4 phase that is vital active sites for propane ammoxidation. In the catalyst prepared with the oxalic acid/V molar ratio of 3, more SbVO4 phase can be formed, and Sb and V with suitable valence and appropriate concentration could disperse on the catalyst surface, resulting in better balance between oxidation and reduction capability. Therefore, both the conversion of propane and the selectivity for acrylonitrile can be obviously enhanced over the VSb3 mixed oxide catalyst prepared by treating vanadium starting materials with oxalic acid.

Key words: propane, ammoxidation, acrylonitrile, antimony, vanadium, mixed oxide, oxalic acid, treatment