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化学学报
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化学学报 ›› 2001, Vol. 59 ›› Issue (7): 1139-1144. 上一篇    下一篇

研究论文

改性钛锆复合氧化物催化环己酮肟气相Beckmann重 排反应

毛东森;卢冠忠;陈庆龄;谢在库;张玉贤   

  1. 华东理工大学工业催化所;上海石油化工研究院.上海(200137)
  • 发布日期:2001-07-15

Vapor-phase beckmann rearrangement of cyclohexanone oxime over modified titania-zirconia catalyst

Mao Dongsen;Lu Guanzhong;Chen Qingling;Xie Zaiku;Zhang Yuxian   

  1. Shanghai Res Inst of Petroleum Chem Tech.Shanghai(200137)
  • Published:2001-07-15

PDF

431

被引次数

30 | 6

制备了经SO4^2-,PO4^3-,MoO3,WO3和B2O3改性的钛锆复合氧化物(TiO2-ZrO2)催化剂，并用常压连续流动固定床微型反应器考察了它们对环己酮肟气相Beckmann重排反应制己内酰胺的催化性能。结果表明，在反应温度300℃时,B2O3/TiO2-ZrO2具有较高的己内酰胺选择性(97.0%)和收率(96.7%),且明显高于B2O3/TiO2和B2O3/ZrO2催化剂，用N2吸附和NH3-TPD，CO2-TPD等方法对催化剂的经表面积、孔容、孔分布和表面酸、碱性分别进行了测定，讨论了这些物化性能对催化剂活性、选择性和稳定性的影响。

关键词: 钛锆复合氧化物, 催化活性, 环己酮肟, 气相反应, 钛化合物, 锆化合物, 氧化硼, 己内酰胺, 贝克曼重排

The vapor-phase Beckmann rearrangement of cyclohexanone oxime to ε- caprolactam was examined over a variety of TiO2-ZrO2 mixed oxides modified by addition of sulfate, phosphate, and oxides of molybdenum, tungsten as well as boron. The catalytic reactions were performed in a continuous folw fixed-bed micro-reactor under atmospheric pressure. Boron oxide (B2O3) modified TiO2-ZrO2(B2O3/TiO2-ZrO2) showed the highest selectivity (97.0%) and yield(96.7%) of ε-caprolactam among the catalysts examined. Thses catalysts were characterized by nitrogen adsorption and temperature- programmed desorption of ammonia and carbon dioxide techniques. The effect of the physio-chemical properties of these catalysts on their catalytic performance was examined. The catalytic properties of B2O3/TiO2-ZrO2 were better than those of B2O3/TiO2 and B2O3/ZrO2.

Key words: CATALYTIC ACTIVITY, CYCLOHEXANONE-OXIME, GAS PHASE REACTION, TITANIUM COMPOUNDS, ZIRCONIUM COMPOUNDS, BORON OXIDE, CAPROLACTAM, BECKMANN REARRANGEMENT

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