物理化学学报 >> 2003, Vol. 19 >> Issue (06): 492-497.doi: 10.3866/PKU.WHXB20030603

研究论文 上一篇    下一篇

丙烷选择氧化制丙烯醛催化剂中Ce的作用

张昕;万惠霖;翁维正;杨乐夫;伊晓东   

  1. 清华大学化学系 一碳化学与化工国家重点实验室,北京　100084;
  • 收稿日期:2002-09-13 修回日期:2002-11-20 发布日期:2003-06-15
  • 通讯作者: 张昕 E-mail:zhangxinzhangcn@yahoo.com.cn

Role of Ce on Selective Oxidation of Propane to Acrolein over Ce-Ag-Mo-P-O Catalysts

Zhang Xin;Wan Hui-Lin;Weng Wei-Zheng;Yang Le-Fu;Yi Xiao-Dong   

  1. State Key Laboratory of C1 Chemistry and Technology,Department of Chemistry,Tsinghua University,Beijing　100084;
  • Received:2002-09-13 Revised:2002-11-20 Published:2003-06-15
  • Contact: Zhang Xin E-mail:zhangxinzhangcn@yahoo.com.cn

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摘要： 考察了一系列助剂如:Cu、Zn、Mn、W、Ce、Pr、Nd等对Ag-Mo-P-O催化剂丙烷选择氧化制丙烯醛的影响.其中添加助剂Ce的Ag-Mo-P-O催化性能较好.添加Ce降低了丙烷氧化反应的活化能并有利于中间产物丙烯转化为丙烯醛.采用BET、XRD、H2-TPR、O2-TPD、C3H8-TPD和EPR等方法,研究了含Ce催化剂的结构和性质.结果表明,助剂Ce改善了催化剂的可还原性,并调变了催化剂中Mo5＋/Mo6＋比例,有利于催化剂上丙烷选择氧化生成丙烯醛,这可能归因于催化剂中形成Ce3＋＋Mo6＋Ce4＋＋Mo5＋氧化-还原循环的缘故.

关键词: 丙烷, 选择氧化, 丙烯醛, 还原性, Mo5＋/Mo6＋摩尔比, 助剂Ce

Abstract: Role of Ce on the catalytic performance of Ce-Ag-Mo-P-O catalyst in selective oxidation of propane to acrolein was investigated.In order to establish the relationship between the catalytic performance and properties,the properties of Ag0.3Mo0.5P0.3Ox and Ce-doped Ag0.3Mo0.5P0.3Ox catalysts have been comparatively characterized by BET,XRD,H2-TPR,O2-TPD,C3H8-TPD and EPR.The addition of Ce to Ag0.3Mo0.5P0.3Ox catalyst distinctly improved the conversion of propane and the selectivity of acrolein.Ce0.1 Ag0.3Mo0.5P0.3Oy catalyst exhibited the highest selectivity and yield of acrolein in this reaction.The activation energy of propane oxidation was lower on the Ce0.1 Ag0.3Mo0.5P0.3Oy than on the Ag0.3Mo0.5P0.3Ox catalyst.Propene was a possible intermediate for the formation of acrolein in selective oxidation of propane on these catalysts.The proper addition of Ce enhanced the conversion of intermediate propene to acrolein.On the other hand,the addition of Ce improved the reducibility and Mo5＋/Mo6＋ ratio,furthermore,it caused a stronger adsorption of propane on the catalysts.The addition of Ce to the catalysts modified the properties by the formation of redox cycle “Ce3＋＋Mo6＋Ce4＋＋Mo5＋” in the catalysts.Such modification determined the catalytic performance of the catalysts in selective oxidation of propane to acrolein.

Key words: Propane, Selective oxidation, Acrolein, Reducible properties, Mo5＋/Mo6＋ molar ratio, Promoter Ce