Al2O3改性CuO/Fe2O3催化剂水煤气变换反应性能

doi:10.3866/PKU.WHXB201501091

物理化学学报 >> 2015, Vol. 31 >> Issue (4): 757-763.doi: 10.3866/PKU.WHXB201501091

Al₂O₃改性CuO/Fe₂O₃催化剂水煤气变换反应性能

林性贻, 殷玲, 范言语, 陈崇启

福州大学化肥催化剂国家工程研究中心, 福州350002

收稿日期:2014-11-13 修回日期:2015-01-05 发布日期:2015-04-03
通讯作者: 林性贻 E-mail:linxingyi@fzu.edu.cn
基金资助:
国家自然科学基金(21346007)资助项目

Performance of Al₂O₃-Modified CuO/Fe₂O₃ Catalysts in the Water-Gas Shift Reaction

LIN Xing-Yi, YIN Ling, FAN Yan-Yu, CHEN Chong-Qi

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

Received:2014-11-13 Revised:2015-01-05 Published:2015-04-03
Contact: LIN Xing-Yi E-mail:linxingyi@fzu.edu.cn
Supported by:
The project was supported by the National Natural Science Foundation of China (21346007).

摘要/Abstract

摘要：

采用分步共沉淀法制备了不同Al₂O₃含量(0%-15% (w))的CuO/Fe₂O₃催化剂, 并进行水煤气变换反应(WGSR)评价测试. 制得的催化剂中含有复合物CuFe₂O₄, 其晶粒尺寸, 氧化还原性质和表面Cu分散通过相应表征手段加以研究. X 射线粉末衍射(XRD), 拉曼(Raman)光谱, N₂物理吸附, N₂O分解和CO₂程序升温脱附(CO₂-TPD)等表征技术说明适量Al₂O₃的加入可以促进尖晶石CuFe₂O₄发生由四方相向立方相的转变, 阻止催化剂中Cu烧结, 增大表面Cu分散, 增加弱碱性位点的数量. 此外, 采用H₂程序升温还原(H₂-TPR)技术探究改性的CuO/Fe₂O₃催化剂的还原性能. 关联结果发现, Al₂O₃掺杂在增大铜物种的耗氢量, 降低其还原温度方面起着重要的作用. 即Al₂O₃的添加促进CuO/Fe₂O₃催化剂中铜铁物种之间的协同作用. 结合活性测试和表征结果,适量的Al₂O₃ (10%(w))改性的催化剂具有较小的Cu颗粒尺寸、较大的Cu分散、较强的还原性能、较多数量的弱碱性位点, 因此具有更好的初始活性和热稳定性.

关键词: CuFe₂O₄, 水煤气变换反应, Al₂O₃改性, Cu分散, 弱碱性位点, N₂O分解

Abstract:

The water-gas shift reaction (WGSR) has been carried out over CuO/Fe₂O₃ catalysts modified by different loadings of Al₂O₃ (0%-15% (w)), prepared by a stepwise co-precipitation method. Composite mixture CuFe₂O₄ was produced, and the crystalline size, redox property, and surface metallic Cu dispersion were manipulated. The appropriate introduction of Al₂O₃ can promote the phase transition of spinel CuFe₂O₄ from tetragonal to cubic, inhibit aggregation of Cu-crystallite, improve Cu dispersion, and increase the amount of weak basic sites, as confirmed using powder X-ray diffraction (XRD), Raman spectroscopy, N₂ physisorption, N₂O decomposition, and temperature-programmed desorption of carbon dioxide (CO₂-TPD) techniques. In addition, a temperature-programmed reduction of hydrogen (H₂-TPR) technique was used to investigate the reducibility of the modified CuO/Fe₂O₃ catalysts. It was found that the Al₂O₃-doping plays an important role in increasing the hydrogen consumption of the copper species, and decreasing reduction temperature. This means that the Al₂O₃ can promote a synergistic interaction between the copper and iron species in the CuO/Fe₂O₃ catalysts. Overall, the Al₂O₃-modified catalyst (10%(w)) has a smaller Cu particle size, better Cu dispersion, greater reducibility, and larger amount of weak basic sites, resulting in a much higher initial catalytic activity and better thermal stability.

Key words: CuFe₂O₄, Water-gas shift reaction, Al₂O₃-modification, Cu dispersion, Weak basic site, N₂O decomposition

MSC2000:

O643.3

林性贻, 殷玲, 范言语, 陈崇启. Al₂O₃改性CuO/Fe₂O₃催化剂水煤气变换反应性能[J]. 物理化学学报, 2015, 31(4): 757-763.

LIN Xing-Yi, YIN Ling, FAN Yan-Yu, CHEN Chong-Qi. Performance of Al₂O₃-Modified CuO/Fe₂O₃ Catalysts in the Water-Gas Shift Reaction[J]. Acta Phys. -Chim. Sin., 2015, 31(4): 757-763.

参考文献

(1) Jacobson, M. Z.; Colella, W. G.; Golden, D. M. Science 2005, 308, 1901. doi: 10.1126/science.1109157
(2) Spivey, J. J. Catal. Today 2005, 100, 171. doi: 10.1016/j.cattod.2004.12.011
(3) Maroño, M.; Sánchez, J. M.; Ruiz, E. Int. J. Hydrog. Energy 2010, 35, 37. doi: 10.1016/j.ijhydene.2009.10.078
(4) Tanaka, Y.; Utaka, T.; Kikuchi, R.; Sasaki, K.; Eguchi, K. Appl. Catal. A: Gen. 2003, 242, 287. doi: 10.1016/S0926-860X(02)00529-X
(5) Panagiotopoulou, P.; Kondarides, D. I. Catal. Today 2006, 112, 49. doi: 10.1016/j.cattod.2005.11.026
(6) Panagiotopoulou, P.; Christodoulakis, A.; Kondarides, D. I.; Boghosian, S. J. Catal. 2006, 240, 114. doi: 10.1016/j.jcat.2006.03.012
(7) Andreevaa, D.; Idakiev, V.; Tabakova, T.; Ilieva, L.; Falaras, P.; Bourlinos, A.; Travlos, A. Catal. Today 2002, 72, 51. doi: 10.1016/S0920-5861(01)00477-1
(8) Jacobs, G.; Williams, L.; Graham, U.; Thomas, G. A.; Sparks, D. E.; Davis, B. H. Appl. Catal. A: Gen. 2003, 252, 107. doi: 10.1016/S0926-860X(03)00410-1
(9) Budiman, A.; Ridwan, M.; Kim, S. M.; Choi, J.W.; Yoon, C. W.; Ha, J. M.; Suh, D. J.; Suh, Y.W. Appl. Catal. A: Gen. 2013, 462-463, 220.
(10) Wang, S. R.; Li, X. B.; Yin, Q. Q.; Zhu, L. J.; Luo, Z. Y. Catal. Commun. 2011, 12, 1246. doi: 10.1016/j.catcom.2011.04.019
(11) Lin, X. Y.; Zhang, Y.; Yin, L.; Chen, C. Q.; Zhan, Y. Y.; Li, D. L. Int. J. Hydrog. Energy 2014, 39, 6424. doi: 10.1016/j.ijhydene.2014.02.018
(12) Kameoka, S.; Tanabe, T.; Tsai, A. P. Catal. Lett. 2005, 100, 89. doi: 10.1007/s10562-004-3091-z
(13) Lin, X. Y.; Ma, J. T.; Chen, C. Q.; Zhan, Y. Y.; Zheng, Q. Acta Phys. -Chim. Sin. 2014, 30, 157. [林性贻, 马俊涛, 陈崇启, 詹瑛瑛, 郑起. 物理化学学报, 2014, 30, 157.] doi: 10.3866/PKU.WHXB201311271
(14) Du, X.; Yuan, Z. S.; Cao, L.; Zhang, C. X.; Wang, S. D. Fuel Process Technol. 2008, 89, 131. doi: 10.1016/j.fuproc.2007.07.002
(15) Ayastuy, J. L.; Fernández-Puertas, E.; González-Marcos, M. P.; Gutiérrez-Ortiz, M. A. Int. J. Hydrog. Energy 2012, 37, 7385. doi: 10.1016/j.ijhydene.2012.02.007
(16) Li, L.; Zhan, Y. Y.; Zheng, Q.; Zheng, Y. H.; Lin, X. Y.; Li, D. L.; Zhu, J. J. Catal. Lett. 2007, 118, 91. doi: 10.1007/s10562- 007-9155-0
(17) Dandekar, A.; Vannice, M. A. J. Catal. 1998, 178, 621. doi: 10.1006/jcat.1998.2190
(18) Faungnawakij, K.; Shimoda, N.; Fukunaga, T.; Kikuchi, R.; Eguchi, K. Appl. Catal. B: Environ. 2009, 92, 341. doi: 10.1016/j.apcatb.2009.08.013
(19) de Faria, D. L. A.; Venâncio S. S.; de Oliveira, M. T. J. Raman Spectrosc. 1997, 28, 873.
(20) Martin, T. P.; Merlin, R.; Huffman, D. R.; Cardona, M. Solid State Commun. 1977, 565.
(21) Liu, Y.; Zhang, Y.; Feng, J. D.; Li, C. F.; Shi, J.; Xiong, R. J. Exp. Nanosci. 2009, 4, 159. doi: 10.1080/17458080902929895
(22) Reddy, G. K.; Gunasekera, K.; Boolchand, P.; Dong, J. H.; Smirniotis, P. G. J. Phys. Chem. C 2011, 115, 7586. doi: 10.1021/jp2003084
(23) Xu, J. F.; Ji, W.; Shen, Z. X.; Tang, S. H. J. Solid State Chem. 1999, 147, 516. doi: 10.1006/jssc.1999.8409
(24) Sing, K. S.W.; Everett, D. H.; Haul, R. A.W.; Moscou, L.; Pierotti, R. A.; Rouquerol, J.; Siemieniewska, T. Pure Appl. Chem. 1985, 57, 603.
(25) Kruk, M.; Jaroniec, M. Chem. Mater. 2001, 13, 3169. doi: 10.1021/cm0101069
(26) Jensen, J. R.; Johannessen, T.; Livbjerg, H. Appl. Catal. A: Gen. 2004, 266, 117. doi: 10.1016/j.apcata.2004.02.009
(27) Wang, S. R.; Guo, W.W.; Wang, H. X.; Zhu, L. J.; Yin, S.; Qiu, K. Z. New J. Chem. 2014, 38, 2792. doi: 10.1039/c4nj00134f
(28) Chen, C. Q.; Ruan, C. X.; Zhan, Y. Y.; Lin, X. Y.; Zheng, Q.; Wei, K. M. Int. J. Hydrog. Energy 2014, 39, 317. doi: 10.1016/j.ijhydene.2013.10.074
(29) Zhu, Y. Y.; Wang, S. R.; Zhu, L. J.; Ge, X. L.; Li, X. B.; Luo, Z. Y. Catal. Lett. 2010, 135, 275. doi: 10.1007/s10562-010-0298-z
(30) Zhu, X. L.; Shen, M.; Lobban, L. L.; Mallinson, R. G. J. Catal. 2011, 278, 123. doi: 10.1016/j.jcat.2010.11.023
(31) Lin, X. Y.; Chen, C. Q.; Ma, J. T.; Fang, X.; Zhan, Y. Y.; Zheng, Q. Int. J. Hydrog. Energy 2013, 38, 11847. doi: 10.1016/j.ijhydene.2013.07.001
(32) Li, L.; Song, L.; Wang, H. D.; Chen, C. Q.; She, Y. S.; Zhan, Y. Y.; Lin, X. Y.; Zheng, Q. Int. J. Hydrog. Energy 2011, 36, 8839. doi: 10.1016/j.ijhydene.2011.04.137
(33) Khan, A.; Smirniotis, P. G. J. Mol. Catal. A: Chem. 2008, 280, 43. doi: 10.1016/j.molcata.2007.10.022
(34) Estrella, M.; Barrio, L.; Zhou, G.; Wang, X. Q.; Wang, Q.; Wen, W.; Hanson, J. C.; Frenkel, A. I.; Rodriguez, J. A. J. Phys. Chem. C 2009, 113, 14411.
(35) Tabakova, T.; Idakiev, V.; Avgouropoulos, G.; Papavasiliou, J.; Manzoli, M.; Boccuzzi, F.; Ioannides, T. Appl. Catal. A: Gen. 2013, 451, 184. doi: 10.1016/j.apcata.2012.11.025

[1]	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 .
[2]	毛江洪;倪哲明;潘国祥;胥倩. Cu催化水煤气的变换反应机理[J]. 物理化学学报, 2008, 24(11): 2059 -2064 .
[3]	江凌;王贵昌;关乃佳;吴杨;蔡遵生;潘荫明;赵学庄;黄伟;李永旺;孙予罕;钟炳. CO在某些过渡金属表面吸附活化的DFT研究[J]. 物理化学学报, 2003, 19(05): 393 -397 .
[4]	郭向云,钟炳,彭少逸. N₂O分解反应中复杂动力学行为的模拟[J]. 物理化学学报, 1995, 11(10): 873 -875 .
[5]	郭向云, 钟炳. N₂O分解反应的蒙特卡罗模拟[J]. 物理化学学报, 1994, 10(08): 733 -736 .

Al₂O₃改性CuO/Fe₂O₃催化剂水煤气变换反应性能

Performance of Al₂O₃-Modified CuO/Fe₂O₃ Catalysts in the Water-Gas Shift Reaction

PDF (PC)

赞

可视化

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 5

Metrics

本文评价

推荐阅读 10