한국수소및신에너지학회논문집 (Transactions of the Korean hydrogen and new energy society)

  • 제28권1호
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  • Pages.1-8
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  • 2017
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  • 1738-7264(pISSN)
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  • 2288-7407(eISSN)
한국수소및신에너지학회 (The Korean Hydrogen and New Energy Society)
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수성가스전이반응(Water Gas Shift Reaction)을 위한 Ce 첨가에 따른 Cu/Mn 촉매의 활성 연구

Effect of Ce Addition on Catalytic Activity of Cu/Mn Catalysts for Water Gas Shift Reaction

  • 박지혜 (충남대학교 에너지과학기술대학원) ;
  • 임효빈 (한국에너지기술연구원) ;
  • 황라현 (충남대학교 에너지과학기술대학원) ;
  • 백정훈 (충남대학교 에너지과학기술대학원) ;
  • 구기영 (한국에너지기술연구원) ;
  • 이광복 (충남대학교 화학공학교육과)
  • PARK, JI HYE (Graduate School of Energy Science and Technology, Chungnam National University) ;
  • IM, HYO BEEN (Korea Institute of Energy Research) ;
  • HWANG, RA HYUN (Graduate School of Energy Science and Technology, Chungnam National University) ;
  • BAEK, JEONG HUN (Graduate School of Energy Science and Technology, Chungnam National University) ;
  • KOO, KEE YOUNG (Korea Institute of Energy Research) ;
  • YI, KWANG BOK (Department of Chemical Engineering Education, Chungnam National University)
  • 투고 : 2017.01.18
  • 심사 : 2017.02.28
  • 발행 : 2017.02.28
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초록

Cu/Mn/Ce catalysts for water gas shift (WGS) reaction were synthesized by urea-nitrate combustion method with the fixed molar ratio of Cu/Mn as 1:4 and 1:1 with the doping concentration of Ce from 0.3 to 0.8 mol%. The prepared catalysts were characterized with SEM, BET, XRD, XPS, $H_2$-TPR, $CO_2$ TPD, $N_2O$ chemisorption analysis. The catalytic activity tests were carried out at a GHSV of $28,000h^{-1}$ and a temperature range of 200 to $400^{\circ}C$. The Cu/Mn(CM) catalysts formed Cu-Mn mixed oxide of spinel structure ($Cu_{1.5}Mn_{1.5}O_4$) and manganese oxides ($MnO_x$). However, when a small amount of Ce was doped, the growth of $Cu_{1.5}Mn_{1.5}O_4$ was inhibited and the degree of Cu dispersion were increased. Also, the doping of Ce on the CM catalyst reduced the reduction temperature and the base site to induce the active site of the catalyst to be exposed on the catalyst surface. From the XPS analysis, it was confirmed that maintaining the oxidation state of Cu appropriately was a main factor in the WGS reaction. Consequently, Ce as support and dopant in the water gas shift reaction catalysts exhibited the enhanced catalytic activities on CM catalysts. We found that proper amount of Ce by preparing catalysts with different Cu/Mn ratios.

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참고문헌

  1. M. Mikkelsen, M. Jorgensen and F. C. Krebs, "The teraton challenge. A review of fixation and transformation of carbon dioxide", Energy Environ. Sci., Vol. 3, No. 1, 2010, pp. 43-81. https://doi.org/10.1039/B912904A
  2. H. B. Im, S. J. Kwon, C. K. Byun, H. S. Ahn, K. Y. Koo, W. L. Yoon and K. B. Yi, "Effect of Support Geometry on Catalytic Activity of Pt/CeO2 Nanorods in Water Gas Shift Reaction", Trans. of the Korean Hydrogen and New Energy Society, Vol. 25, No. 6, 2014, pp. 577-585. https://doi.org/10.7316/KHNES.2014.25.6.577
  3. C. Rhodes, G. J. Hutchings and A. M. Ward, "Water-gas shift reaction: finding the mechanistic boundary", Catalysis Today, Vol. 23, No. 1, 1995, pp. 43-58. https://doi.org/10.1016/0920-5861(94)00135-O
  4. C. K. Byun, H. B. Im, J. H. Park, J. H. Baek, J. M. Jeong, W. L. Yoon and K. B. Yi, "Enhanced Catalytic Activity of Cu/Zn Catalyst by Ce Addition for Low Temperature Water Gas Shift Reaction", Clean Technology, Vol. 21, No. 3, 2015, pp. 200-206. https://doi.org/10.7464/ksct.2015.21.3.200
  5. R. J. Smith, M. Loganathan and M. S. Shantha, "A Review of the Water Gas Shift Reaction Kinetics", International Journal of Chemical Reactor Engineering, Vol. 8, 2010, Review R4.
  6. J. H. Baek, J. M. Jeong, J. H. Park, K. B. Yi and Y. W. Rhee, "Effect of Al Precursor Addition Time on Catalytic Characteristic of Cu/ZnO/Al2O3 Catalyst for Water Gas Shift Reaction", Trans. of the Korean Hydrogen and New Energy Society, Vol. 26, No. 5, 2015, pp. 423-430. https://doi.org/10.7316/KHNES.2015.26.5.423
  7. F. S. Stone and D. Waller, "Cu-ZnO and Cu-ZnO/Al2O3 catalysts for the reverse water-gas shift reaction. The effect of the Cu/Zn ratio on precursor characteristics and on the activity of the derived catalysts", Topics in catalysis, Vol. 22, No. 3-4, pp. 305-318. https://doi.org/10.1023/A:1023592407825
  8. Y. Tanaka, T. Utaka, R. Kikuchi, T. Takeguchi, K. Sasaki, and K. Eguchi, "Water gas shift reaction for the reformed fuels over Cu/MnO catalysts prepared via spinel-type oxide", Journal of Catalysis, Vol. 215 No. 2, 2003, pp. 271-278. https://doi.org/10.1016/S0021-9517(03)00024-1
  9. H. S. Roh, D. W. Jeong, K. S. Kim, I. H. Eum, K. Y. Koo and W. L. Yoon, "Single stage water-gas shift reaction over supported Pt catalysts", Catalysis letters, Vol. 141, No. 1, 2011, pp. 95-99. https://doi.org/10.1007/s10562-010-0480-3
  10. L. Z. Linganiso, V. R. R. Pendyala, G. Jacobs, B. H. Davis, D. C. Cronauer, A. J. Kropf and C. L. Marshall, "Low-Temperature Water-Gas Shift: Doping Ceria Improves Reducibility and Mobility of O-Bound Species and Catalyst Activity", Catalysis letters, Vol. 141, No. 12, 2011, pp. 1723-1731. https://doi.org/10.1007/s10562-011-0720-1
  11. J. B. Park, J. Graciani, J. Evans, D. Stacchiola, S. D. Senanayake, L. Barrio and J. A. Rodriguez, "Gold, Copper, and Platinum Nanoparticles Dispersed on CeOx/TiO2 (110) Surfaces: High Water-Gas Shift Activity and the Nature of the Mixed-Metal Oxide at the Nanometer Level", Journal of the American Chemical Society, Vol. 132, No. 1, 2009, pp. 356-363. https://doi.org/10.1021/ja9087677
  12. A. Wootsch, C. Descorme and D. Duprez, "Preferential oxidation of carbon monoxide in the presence of hydrogen (PROX) over ceria-zirconia and alumina-supported Pt catalysts", Journal of Catalysis, Vol. 225, No. 2, 2004, pp. 259-266. https://doi.org/10.1016/j.jcat.2004.04.017
  13. G. K. Reddy, K. Gunasekara, P. Boolchand and P. G. Smirniotis, "Cr-and Ce-Doped Ferrite Catalysts for the High Temperature Water− Gas Shift Reaction: TPR and Mossbauer Spectroscopic Study", The Journal of Physical Chemistry C, Vol. 115, No. 4, 2010, pp. 920-930. https://doi.org/10.1021/jp102959p
  14. H. Lu, X. Kong, H. Huang, Y. Zhou and Y. Chen, "Cu-Mn-Ce ternary mixed-oxide catalysts for catalytic combustion of toluene", Journal of Environmental Sciences, Vol. 32, 2015, pp. 102-107. https://doi.org/10.1016/j.jes.2014.11.015
  15. J. E. Park, J. H. Park, S. D. Yim, C. S. Kim and E. D. Park, "A Comparative Study of Commercial Catalysts for Methanol Steam Reforming", Korean Chemical Engineering Research, Vol. 49, No. 1, 2011, pp. 21-27. https://doi.org/10.9713/kcer.2011.49.1.021
  16. J. Papavasiliou, G. Avgouropoulos and T. Ioannides, "Steam reforming of methanol over copper-manganese spinel oxide catalysts", Catalysis Communications, Vol. 6, No. 7, 2005, pp. 497-501. https://doi.org/10.1016/j.catcom.2005.04.015
  17. Y. Tanaka, T. Takeguchi, R. Kikuchi and K. Eguchi, "Influence of preparation method and additive for Cu-Mn spinel oxide catalyst on water gas shift reaction of reformed fuels", Applied Catalysis A: General, Vol. 279, No. 1, 2005, pp. 59-66. https://doi.org/10.1016/j.apcata.2004.10.013
  18. X. Du, Z. Yuan, L. Cao, C. Zhang and S. Wang, "Water gas shift reaction over Cu-Mn mixed oxides catalysts: effects of the third metal", Fuel Processing Technology, Vol. 89, No. 2, 2008, pp. 131-138. https://doi.org/10.1016/j.fuproc.2007.07.002
  19. J. Chen, W. Shi and J. Li, "Catalytic combustion of methane over cerium-doped cobalt chromite catalysts", Catalysis Today, Vol. 175, No. 1, 2011, pp. 216-222. https://doi.org/10.1016/j.cattod.2011.03.061
  20. J. Papavasiliou, G. Avgouropoulos and T. Ioannides, "Combined steam reforming of methanol over Cu-Mn spinel oxide catalysts", Journal of Catalysis, Vol. 251, No. 1, 2007, pp. 7-20. https://doi.org/10.1016/j.jcat.2007.07.025