铜物种对Cu/Fe2O3水煤气变换反应催化剂性能的影响

doi:10.3866/PKU.WHXB201311271

物理化学学报 >> 2014, Vol. 30 >> Issue (1): 157-163.doi: 10.3866/PKU.WHXB201311271

铜物种对Cu/Fe₂O₃水煤气变换反应催化剂性能的影响

林性贻, 马俊涛, 陈崇启, 詹瑛瑛, 郑起

福州大学化肥催化剂国家工程研究中心, 福州 350002

收稿日期:2013-09-02 修回日期:2013-11-27 发布日期:2014-01-01
通讯作者: 林性贻 E-mail:linxingyi@fzu.edu.cn
基金资助:
福建省教育厅A类科技项目(JA08021)

Influence of Copper Species on Performance of Cu/Fe₂O₃ Catalysts for Water Gas Shift Reaction

LIN Xing-Yi, MA Jun-Tao, CHEN Chong-Qi, ZHAN Ying-Ying, ZHENG Qi

National Engineering Research Center of Chemical Fertilizer Catalyst, Fuzhou University, Fuzhou 350002, P. R. China

Received:2013-09-02 Revised:2013-11-27 Published:2014-01-01
Contact: LIN Xing-Yi E-mail:linxingyi@fzu.edu.cn
Supported by:
The project was supported by the Education Department of Fujian Province Class A Science & Technology Program, China (JA08021).

摘要/Abstract

摘要：

采用共沉淀法制备了系列铜负载量不同的Cu/Fe₂O₃水煤气变换(WGS)催化剂，并考察了铜负载量对催化剂结构和水煤气变换反应性能的影响. 结果表明，Cu/Fe₂O₃催化剂呈现出良好的水煤气反应性能，当CuO质量分数为20%时，催化剂的WGS性能最优，250 ℃时CO转化率高达97.2%，同时热稳定性也最好. 运用X射线粉末衍射(XRD)、N₂物理吸脱附和H₂程序升温还原(H₂-TPR)等手段对Cu/Fe₂O₃催化剂的物相、织构特征及还原性能进行了表征，结果表明，CuFe₂O₄物种的存在极大地改善了催化剂的还原性能和WGS反应活性. 这是由于CuFe₂O₄特殊的尖晶石结构有利于Cu微晶的稳定；同时，CuFe₂O₄在低温下即被还原为单质铜，有利于促进催化剂体系中电子的转移. 此外，通过(NH₄)₂CO₃溶液处理，研究了独立相CuO对Cu/Fe₂O₃催化剂WGS反应性能的影响，结果发现，独立相CuO的存在，有利于H原子在各组分传递，从而促进催化剂的CuFe₂O₄的还原，改善Cu/Fe₂O₃催化剂的WGS反应性能.

关键词: 水煤气变换, Cu/Fe₂O₃催化剂, 铜负载量, CuFe₂O₄

Abstract:

A series of Cu/Fe₂O₃ catalysts with different Cu loadings were prepared using a co-precipitation method, and the relationship between their structures and catalytic activities for the water gas shift (WGS) reaction was carefully examined. It was found that the as-prepared Cu/Fe₂O₃ catalysts exhibit excellent WGS performances, in particular, the one containing 20% (w) CuO (CF-20) shows the best catalytic activity, with CO conversion of 97.2% at 250 ℃. Its catalytic stability is also outstanding during the temperature range of 250-400 ℃. X-ray diffraction (XRD), N₂ physisorption, and H₂ temperature program reduction (H₂-TPR) techniques were used to characterize the crystal phases, textures, and reduction properties of the Cu/Fe₂O₃ catalysts. The results show that the generation of CuFe₂O₄, which has a spinel structure in stabilizing Cu microcrystals and is easier to be reduced at low temperature, resulting in enhancing their reduction properties and facilitating electrons transfer between Cu and Fe₂O₃, thus greatly improving the catalytic performance. Furthermore, (NH₄)₂CO₃ solution treatment of the as-prepared catalysts was performed to study the effect of bulk CuO existed in the Cu/Fe₂O₃ catalysts. The result suggests that the bulk CuO is favor for H atom transfer between Cu and Fe₂O₃, thus promoting the reduction of CuFe₂O₄, finally improving the catalytic performance.

Key words: Water gas shift, Cu/Fe₂O₃ catalyst, Copper loading, CuFe₂O₄

林性贻, 马俊涛, 陈崇启, 詹瑛瑛, 郑起. 铜物种对Cu/Fe₂O₃水煤气变换反应催化剂性能的影响[J]. 物理化学学报, 2014, 30(1), 157-163. doi: 10.3866/PKU.WHXB201311271

LIN Xing-Yi, MA Jun-Tao, CHEN Chong-Qi, ZHAN Ying-Ying, ZHENG Qi. Influence of Copper Species on Performance of Cu/Fe₂O₃ Catalysts for Water Gas Shift Reaction[J]. Acta Phys. -Chim. Sin. 2014, 30(1), 157-163. doi: 10.3866/PKU.WHXB201311271

链接本文: https://www.whxb.pku.edu.cn/CN/10.3866/PKU.WHXB201311271

https://www.whxb.pku.edu.cn/CN/Y2014/V30/I1/157

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铜物种对Cu/Fe₂O₃水煤气变换反应催化剂性能的影响

Influence of Copper Species on Performance of Cu/Fe₂O₃ Catalysts for Water Gas Shift Reaction

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