Korean Chemical Engineering Research

The Korean Institute of Chemical Engineers (한국화학공학회)
권호 표지
DOI QR코드

DOI QR Code

Study on Effects of Ni/Al2O3 Catalysts Added with Mo on Durability Improvement in Steam Reforming Reactions

Mo를 첨가한 Ni/Al2O3 촉매의 수증기 개질반응에서의 내구성 증진 특성연구

  • Won, Jong Min (Department of Environmental Energy Engineering, Kyonggi University) ;
  • Park, Gi Woo (Department of Environmental Energy Engineering, Kyonggi University) ;
  • Lee, Jin Woo (LIG Nex one) ;
  • Hong, Sung Chang (Department of Environmental Energy Engineering, Kyonggi University)
  • 원종민 (경기대학교 환경에너지공학과) ;
  • 박기우 (경기대학교 환경에너지공학과) ;
  • 이진우 (LIG 넥스원(주) 기계연구센터 Project 6팀) ;
  • 홍성창 (경기대학교 환경에너지공학과)
  • Received : 2016.01.29
  • Accepted : 2016.04.14
  • Published : 2016.08.01
Download PDF
⟨ Previous Next ⟩

Abstract

In this study, we characterized steam reforming reactions and surface of $Ni/Al_2O_3$ catalysts. Ni-Mo based catalysts were prepared by loading Mo as the co-catalyst and reaction activities of the Ni-Mo based catalysts were compared with those of Ni-based catalysts. Through the $H_2$-TPR and XPS analysis it was confirmed that this characteristic efficiency. $O_2$-TPO analysis was performed to examine the deposition characteristics, bonding structures and evaporation characteristics of carbon deposited on the surface of catalysts after long run experiments were performed for steam reforming reactions. As the results, it was found that durability was improved in Ni-Mo based catalysts inhibiting formation of graphitic carbon species which reduced reaction activities of the catalysts by strongly interacting with Ni in the steam reforming reaction.

본 연구에서는 $Ni/Al_2O_3$ 촉매의 수증기 개질반응 및 표면 특성을 조사하였다. 조촉매로써 선정된 Mo를 담지하여 제조한 Ni-Mo계 촉매를 Ni계 촉매와 반응활성 비교결과 효율증진 인자를 확인할 수 있다. $H_2$-TPR 및 XPS 분석을 통하여 효율이 저하되는 특성을 확인하였다. 수증기 개질반응 long run 실험 후 촉매표면에 침적된 carbon의 침적특성 및 결합구조, 기화특성을 확인하기 위하여 $O_2$-TPO 분석을 수행하였다. 본 연구를 통하여 수증기 개질반응에서 Ni과 강한 상호작용으로 결합하여 촉매의 반응활성 저하를 일으키는 graphitic carbon 종 형성을 억제함으로 Ni-Mo계 촉매에서 내구성이 증진됨을 확인할 수 있다.

Keywords

References

  1. Hohlein, B., Boe, M., Bogild-Hansen, J., Brekerhoff, P., Colsman, G., Emonts, B., Menzer, R. and Riedel, E., "Hydrogen from Methanol for Fuel Cells in Mobile Systems: Development of a Compact Reformer," J. Power Sources, 61, 143-147(1996). https://doi.org/10.1016/S0378-7753(96)02357-9
  2. Jung, S. J., "Green Energy and Environmental Catalysts," Asan Foundation Research Series, 299, 517-519(2010).
  3. De, C., Rune, L., Hallvard, S. and Anders, H., "Hierarchical Multiscale Modeling of Methane Steam Reforming Reactions," Ind. Eng. Chem. Res., 50, 2600-2612(2011). https://doi.org/10.1021/ie1006504
  4. Zhai, X., Cheng, Y. H., Zhang, Z. T., Jin, Y. and Cheng, Y., "Steam Reforming of Methane over Ni Catalyst in Micro-channel Reactor," Int. J. Hydrogen Energy, 36, 7105-7113(2011). https://doi.org/10.1016/j.ijhydene.2011.03.065
  5. Rostrup-Nielsen, J. R., "New Aspects of Syngas Production and Use," Catal. Today, 63, 159-164(2000). https://doi.org/10.1016/S0920-5861(00)00455-7
  6. Liu, C. J., Ye, J. Y., Jiang, J. J. and Pan, Y. X., "Progresses in the Preparation of Coke Resistant Ni-based Catalyst for Steam and $CO_2$ Reforming of Methane," Chem. Cat. Chem., 3, 529-541(2011).
  7. Kim, D. H. and Lee, T. J., "Kinetics of Methane Steam Reforming," Korean Chem. Eng. Res., 29, 396-406(1991).
  8. Kimura, T., Miyazawa, T., Nishikawa, J., Kado, S., Okumura, K., Miyao, T., Naito, S., Kunimori, K. and Tomishige, K., "Development of Ni Catalysts for Tar Removal by Steam Gasification of Biomass," Appl. Catal. B., 68, 160(2006). https://doi.org/10.1016/j.apcatb.2006.08.007
  9. Coll, R., Salvado, J., Farriol, X. and Montane, D., " Steam Reforming Model Compounds of Biomass Gasification Tars: Conversion at Different Operating Conditions and Tendency Towards Coke Formation," Fuel Process. Technol., 74, 19-31(2001). https://doi.org/10.1016/S0378-3820(01)00214-4
  10. Wu, C. and Williams, P. T., "Nickel-based Catalysts for Tar Reduction in Biomass Gasification," Biofuels, 2, 451-464(2011). https://doi.org/10.4155/bfs.11.113
  11. Jo, Y. B., "The Study of Carbon Deposit on Nickel Catalyst for the Carbon Dioxide Reforming of Methane," Ph.D. Dissertation, Department of chemical engineering, Chonnam national university, Gwang-Ju, Korea(2001).
  12. Rostrup-Nielsen, J. R., "Catalytic Steam Reforming," Catalysis, 5, 1-117(1984).
  13. Vernon, P. D. F., Green, M. L. H. Cheetham, A. K. and Ashcroft, A. T., "Partial Oxidation of Methane to Synthesis Gas, and Carbon Dioxide as An Oxidising Agent for Methane Conversion," Catal. Today, 13, 417-426(1992). https://doi.org/10.1016/0920-5861(92)80167-L
  14. Trimm, D. L., "The Formation and Removal of Coke from Nickel Catalyst," Catal. Rev. Sci. Eng., 16, 155-189(1977). https://doi.org/10.1080/03602457708079636
  15. Hofer, L. J. E., Sterling, E. and McCartney, J. T., "Structure of Carbon Deposited from Carbon Monoxide on Iron, Cobalt and Nickel," J. Phys. Chem., 59, 1153-1155(1955). https://doi.org/10.1021/j150533a010
  16. Jens, R. N. and David, L. T., "Mechanisms of Carbon Formation on Nickel-containing Catalysts," J. Catal., 48, 155-165(1977). https://doi.org/10.1016/0021-9517(77)90087-2
  17. Moon, K. I., Kim, C. H., Choi, J. S., Lee, S. H., Kim, Y. G. and Lee, J. S., "Carbon Dioxide Reforming of Methane over Nickel Based Catalysts II. Deposition of Cokes," Korean Chem. Eng. Res., 35, 890-894(1997).
  18. Rostrup-Nielsen, J. R., "Catalysis, Science and Technology," Springer-Verlag, 5, 1-118(1984).
  19. Choudary, V. R., Rajput, A. M. and Mamman, A. S., "NiO-Alkaline Earth Oxide Catalysts for Oxidative Methane-to-Syngas Conversion: Influence of Alkaline Earth Oxide on the Surface Properties and Temperature-Programmed Reduction/Reaction by $H_2$ and Methane," J. Catal., 178, 576-585(1998). https://doi.org/10.1006/jcat.1998.2197
  20. Cheng, Z., Wu, Q., Li, J. and Zhu, Q., "Effects of Promoters and Preparation Procedures on Reforming of Methane with Carbon Dioxide over Ni/$Al_2O_3$ Catalyst," Catal. Today, 30, 147-155(1996). https://doi.org/10.1016/0920-5861(95)00005-4
  21. Calride, J. B. and et al., "New Catalysts for the Conversion of Methane to Synthesis Gas: Molybdenum and Tungsten Carbide," J. Catal., 180, 85-100(1998). https://doi.org/10.1006/jcat.1998.2260
  22. Wan, H., Li X., Ji, S., Huang, B., Wang, K. and Li, C., "Effect of Ni Loading and $Ce_x-Zr_{i-x}O_2$ Promoter on Ni-Based SBA-15 Catalysts for Steam Reforming of Methane," J. Nat. Chem., 16, 139-147(2007). https://doi.org/10.1016/S1003-9953(07)60039-5
  23. Maluf, S. S. and Assaf, E. M., "Ni Catalyst with Mo Promoter for Methane Steam Reforming," Fuel, 88, 1547-1553(2009). https://doi.org/10.1016/j.fuel.2009.03.025
  24. Numaguchi, B., Eida, H. and Shoji, K., "Reduction of $NiAl_2O_4$ Containing Catalysts for Steam Methane Reforming Reaction," Int. J. Hydrogen Energy, 22, 1111-1115(1997).
  25. Hu, C. W., Yao, J., Yang, H. Q., Chen, Y. and Tian, A. M., "On the Inhomogeneity of Low Nickel Loading Methanation Catalyst," J. Catal., 166, 1-7(1997). https://doi.org/10.1006/jcat.1997.1469
  26. Tadeusz, B., Wojciech, G. and Andrzej, D., "Effects of Small $MoO_3$ Additions on the Properties of Nickel Catalysts for the Steam Reforming of Hydrocarbons III. Reduction of Ni-Mo/$Al_2O_3$ Catalysts," Appl. Catal. A: Gene., 270, 27-36(2004). https://doi.org/10.1016/j.apcata.2004.03.044
  27. Schouten, F. C., Kaleveld, E. W. and Bootsma, G. A., "AES-LEED-Ellipsometry Study of the Kinetics of the Interaction of Methane with Ni(110)," Surf. Sci., 63, 460-474(1977). https://doi.org/10.1016/0039-6028(77)90359-4
  28. Alstrup I., "A New Model Explaining Carbon Filament Growth on Nickel, Iron, and Ni Cu Alloy Catalysts," J. Catal., 109, 241-251(1988). https://doi.org/10.1016/0021-9517(88)90207-2
  29. Rudnitskii, L. A., Solboleva, T. N. and Alekseev, A. M., "Hysteresis of Thermogravimetric Curves of Nickel Catalysis for Methane Conversion in $CH_4+CO_2$ Mixture," Reaction Kinetics Catal. Lett., 26, 149-151(1984). https://doi.org/10.1007/BF02063882