Reaction Characteristics of Thermochemical Methane Reforming on Ferrite-Based Metal Oxide Mediums

페라이트계 금속 산화물 매체 상에서 열화학 메탄 개질 반응 특성

  • Cha, Kwang-Seo (Department of Fine Chemical Engineering and Applied Chemistry, Chungnam National University) ;
  • Lee, Dong-Hee (Department of Fine Chemical Engineering and Applied Chemistry, Chungnam National University) ;
  • Jo, Won-Jun (R&D Division, Korea Gas Corporation) ;
  • Lee, Young-Seak (Department of Fine Chemical Engineering and Applied Chemistry, Chungnam National University) ;
  • Kim, Young-Ho (Department of Fine Chemical Engineering and Applied Chemistry, Chungnam National University)
  • 차광서 (충남대학교 정밀응용화학과) ;
  • 이동희 (충남대학교 정밀응용화학과) ;
  • 조원준 (한국가스공사 연구개발원) ;
  • 이영석 (충남대학교 정밀응용화학과) ;
  • 김영호 (충남대학교 정밀응용화학과)
  • Published : 2007.06.15

Abstract

Thermochemical 2-step methane reforming, involving the reduction of metal oxide with methane to produce syngas and the oxidation of the reduced metal oxide with water to produce pure hydrogen, was investigated on ferrite-based metal oxide mediums. The mediums, CoFZ, CuFZ, or MnFZ, were composed of the mixture of M(M=Co, Cu or Mn)-substituted ferrite as an active component and $ZrO_2$ as a binder, respectively. The WZ medium, composed of the mixture of $WO_3$ and $ZrO_2$, was also prepared to compare. With an addition of $ZrO_2$, the surface area of the mediums was slightly increased and the sintering of active components was greatly suppressed during the reduction. The higher reactivity of the reduced mediums for water splitting was confirmed by the temperature programmed reaction. From the results of the thermochemical 2-step methane reforming, the reactivity of $CH_4$ reduction and water splitting with ferrite-based metal oxide mediums was relatively higher than that with WZ, and the order of reactivity of the mediums was MnFZ>CoFZ>CuFZ>WZ.

Keywords

References

  1. T. Kodama, H. Ohtake, S. Matsumoto, A. Aoki, T. Shimizu, and Y. Kitayama, 'Thermochemical methane reforming using a reactive $WO_{3}$/W redox system', Energy, Vol. 25, 2000, p. 411 https://doi.org/10.1016/S0360-5442(99)00084-5
  2. T. Shimizu, K Shimizu, Y. Kitayama, and T. Kodama, 'Thermochemical methane reforming using $WO_{3}$ as an oxidant below 1173 K by a solar furnace simulator', Solar Energy, Vol. 71, 2001, No.5, p. 315 https://doi.org/10.1016/S0038-092X(01)00058-5
  3. T. Kodama, T. Shimizu, T. Satoh, and K-I. Shimizu, 'Stepwise production of CO-rich syngas and hydrogen via methane reforming by a $WO_{3}$-redox catalyst', Energy, Vol. 28, 2003, p. 1055 https://doi.org/10.1016/S0360-5442(03)00093-8
  4. T, Kodama, T. Shimizu, T. Satoh, M. Nakata, and K-I. Shimizu, 'Stepwise production of CO-rich syngas and hydrogen via solar methane reforming by using a Ni(II)-ferrite redox system', Solar Energy, Vol. 73, 2002, No.5, p. 363 https://doi.org/10.1016/S0038-092X(02)00112-3
  5. G. J. Hwang, C. S. Park, S. H. Lee, I. T Seo, and J. W. Kim, 'Ni-ferrite-based thermochemical cycle for solar hydrogen production', J. Ind. Eng. Chem., Vol. 10, 2004, No.6, p. 889
  6. T. Kodama, 'High-temperature solar chemistry for converting solar heat to chemical fuels', Progress in Energy and Combustion Science, Vol. 29, 2003, pp 567 https://doi.org/10.1016/S0360-1285(03)00059-5
  7. Kodama, T., Kondoh, Y., Yamamoto, R., Andou H., and Satou N. 'Thermochemical hydrogen production by a redox system of $ZrO_{2}$-supported Co(II)-ferrite', Solar Energy, Vol. 78, 2005, pp 623 https://doi.org/10.1016/j.solener.2004.04.008
  8. N. Laosiripojana, S. Assabumrungrat 'Methane steam reforming over Ni/Ce - $ZrO_{2}$ catalyst: Influences of Ce - $ZrO_{2}$ support on reactivity, resistance toward carbon formation, and intrinsic reaction kinetics' Applied Catalysis A: General Vol. 290, 2005, pp 200 https://doi.org/10.1016/j.apcata.2005.05.026
  9. T. Murota, T. Hasegawa, S. Aozasa, H. Matsui, M. Motoyama., 'Production method of cerium oxide with high storage capacity of oxygen and its mechanism' J. Alloys Comp. Vol. 193, 1993, pp 298 https://doi.org/10.1016/0925-8388(93)90377-Y
  10. J. Kaspar, P. Fomasiero, M. Graziani., 'Use of $CeO_{2}$-based oxides in three-way catalysis' Catalysis Today Vol. 50, 1999, pp 285 https://doi.org/10.1016/S0920-5861(98)00510-0
  11. 김진웅, 최승철, 주오심, 정광덕, '열화학싸이클 수소제조를 위한 $[Cu_{0.5}Mn_{0.5}]Fe_{2}O_{4}$의 열적 거동 한국수소 및 신에너지학회 논문집 Vol. 15, 2004, No.1, pp 32
  12. Tamaura, Y, Kojima, M., Sano, T., Ueda, Y, Hasegawa N. and Tsuji M. 'Thermodynamic evaluation of water splitting by a cation-excessive(Ni, Mn) ferrite', Int. J. Hydrogen Energy, Vol. 23, 1998, pp 1185 https://doi.org/10.1016/S0360-3199(98)00007-X
  13. 류재춘, 이동희, 김영호, 양현수, 박주식, 황갑진, 김종원, ' $M/Fe_{2}O_{3}$[M=Rh, Ce 및 Zr]혼합 산화물의 산화-환원 반응을 이용한 수소 저장 특성, 한국수소 및 신에너지학회 논문집 Vol. 17, 2006, No.1, pp 21