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钾助剂对Rh/Al2O3催化富氢条件下CO选择氧化反应性能的影响

Effect of Potassium Promoter on Reaction Performance of Rh/Al2O3 Catalyst for CO Selective Oxidation in H2-Rich Streams

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【作者】 陈光文李淑莲袁权焦凤君

【Author】 CHEN Guangwen*, LI Shulian, YUAN Quan, JIAO Fengjun ( Dalian Institute of Chemical Physics, The Chinese Academy of Sciences, Dalian 11 6023, Liaoning , China)

【机构】 中国科学院大连化学物理研究所中国科学院大连化学物理研究所 辽宁大连116023辽宁大连116023辽宁大连116023

【摘要】 采用程序升温与原位FT-IR,CO程序升温脱附和X射线衍射等技术研究了钾对Rh/Al2O3催化剂上CO吸附态和表面吸附物种的影响.结果表明,钾未改变金属铑上CO吸附的形态,但削弱了CO的吸附强度;在程序升温(真空中)的动态过程中,120℃时CO线式吸附完全脱除,180℃时CO桥式吸附完全脱除;助剂钾明显促进了表面甲酸盐和碳酸盐物种的形成,同时减弱了Al-Rh的相互作用.讨论了钾存在时甲酸盐和碳酸盐物种的形成机理.

【Abstract】 It is indispensable to remove CO to less than 50×10 -6 from a H2-rich feed gas for proton exchange membrane fuel cells. The promoting effect of potass ium on the Rh/Al2O3 catalyst has been found in the CO preferential oxidation with O2 under H2-rich streams, CO conversion as high as 99.82% can be ach ieved, and methanation can be restrained. In this paper, the effect of potassium promoter on CO adsorption states and surface chemisorbed species in the CO sele ctive oxidation process under H2-rich streams over Rh/Al2O3 was investiga ted by in situ temperature-programming and FT-IR, CO-TPD and XRD. The res ults indicate that CO adsorption states on Rh/Al2O3 are not changed, but the CO adsorption intensity is weakened when potassium is added. The linear and br idged CO adsorbed on active sites of Rh-K/Al2O3 is fully desorbed at 120 and 180 ℃, respectively. The mechanism of formate and carbonate species format ion is also discussed. The experimental results of catalytic activity show that there exists an optimum loading of potassium on the Rh/Al2O3 catalyst to obt ain both higher CO conversion and less methane product.

【基金】 国家自然科学基金(20176057,20122201,20490200);国际科技合作重点项目计划(2001CB711203)资助.
  • 【文献出处】 催化学报 ,Chinese Journal of Catalysis , 编辑部邮箱 ,2005年09期
  • 【分类号】O643.32
  • 【被引频次】13
  • 【下载频次】282
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