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

The Korean Hydrogen and New Energy Society (한국수소및신에너지학회)
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Hydrothermal Pressure Effect over Preparation of MoS2: Catalyst Characterization and Direct Methanation

수열 압력 제조 조건이 MoS2 촉매 특성과 직접 메탄화 반응에 미치는 영향

  • PARK, JEONGHWAN (Clean Fuel Research Center, Korea Institute of Energy Research) ;
  • KIM, SEONGSOO (Biomass and Wastes Energy Laboratory, Korea Institute of Energy Research) ;
  • KIM, JINGUL (Department of Chemical Engineering, Soonchunhyang University)
  • 박정환 (한국에너지기술연구소 청정연료연구센터) ;
  • 김성수 (한국에너지기술연구소 바이오자원순환연구실) ;
  • 김진걸 (순천향대학교 나노화학공학과)
  • Received : 2018.04.02
  • Accepted : 2018.04.30
  • Published : 2018.04.30
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Abstract

After $MoS_2$ catalyst was prepared at 1, 30, and 70 atm, the hydrothermal pressure effect over preparation of $MoS_2$ was investigated in terms of catalyst characterization and direct methanation. Multifaceted characterization techniques such as XRD, BET, SEM, TPR, EDS, and XPS were used to analyze and investigate the effect of high pressure over the preparation of surface and bulk $MoS_2$ catalyst. Result from XRD, SEM, and BET demonstrated that $MoS_2$ was more dispersed as preparation pressure was increased, which resulted finer $MoS_2$ crystal size and higher surface area. EDS result confirmed that bulk composition was $MoS_2$ and XPS result showed that S/Mo mole ratio of surface was about 1.3. TPR showed that $MoS_2$ prepared at 30 atm possessed higher active surface sites than $MoS_2$ prepared at 1 atm and these sites could contribute to higher CO yield during methanation. Direct methanation was used to evaluate the CO conversion of the both catalysts prepared at 1 atm and 30 atm and reaction condition was at feed mole ratio of $H_2/CO=1$, GHSV=4800, 30 atm, temperature($^{\circ}C$) of 300, 350, 400, and 450. $MoS_2$ prepared at 30 atm showed more stable and higher CO conversion than $MoS_2$ prepared at 1 atm. Faster deactivation was occurred over $MoS_2$ prepared at 1 atm, which indicated that preparation pressure of $MoS_2$ catalyst was the dominant factor to improve the yield of direct methanation.

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References

  1. S. Jang, N. Park, and T. Lee, "Reactivity Test of Ni-based Catalysts Prepared by Various Preparation Methods for Production of Synthetic Natural Gas", Trans. of the Korean Hydrogen and New Energy Society, Vol. 22, No. 2, 2011, pp. 249-256.
  2. D. Hu, J. Gao, Y. Ping, L. Jia, P. Gunawa, Z. Zhong, G. Xu, F. Gu, and F. Su, "Enhanced Investigation of CO Methanation over Ni/Al2O3 Catalysts for Synthetic Natural Gas Production", Ind. Eng. Chem. Res., Vol. 51, No. 13, 2012, pp. 4875-4886. https://doi.org/10.1021/ie300049f
  3. X. Bai, S. Wang, T. Sun. and S. Wang, "The Sintering of Ni/Al2O3 Methanation Catalyst for Substitute Natural Gas Production", Reaction Kinetics, Mechanisms and Catalysis, Vol. 112, No. 2, 2014, pp. 437-451. https://doi.org/10.1007/s11144-014-0700-8
  4. S. Ma, Y. Tan. and Y. Han, "Methanation of Syngas over Coral Reef-like Ni/Al2O3 Catalysts", Journal of Natural Gas, Vol. 20, No. 4, 2011, pp. 435-440. https://doi.org/10.1016/S1003-9953(10)60192-2
  5. Y. D. Yoo, S. H. Kim, Y. Yun, and G. T. Jin, "Conversion Technology from Coal to Synthetic Natural Gas", Trans. of the Korean Hydrogen and New Energy Society, Vol. 12, No. 3, 2009, pp. 38-57.
  6. O. Liu, X. Dong, X. Mo, and W. Lin, "Selective Catalytic Methanation of CO in Hydrogen Rich Gases over Ni/ZrO2 Catalyst", J. of Natural Gas Chemistry, Vol. 17, 2008, pp. 268-272. https://doi.org/10.1016/S1003-9953(08)60062-6
  7. A. W. Naumann and A. S. Behan, "Molybdenum Disulfide Catalyst and the Preparation thereof", US Patent 4243554, Jan. 6, 1981, pp. 1-14.
  8. L. Alvarez, J. Espino, C. Ornelas, J. L. Rico, M. T. Cortez, G. Berhault, and G. Alonso, "Comparative Study of $MoS_2$ and Co/$MoS_2$ Catalysts Prepared by ex situ/in situ Activation of Ammonium and Tetrealkylammonium Thiomolybdates", J. Mol. Catal. A: Chemical, Vol. 210, 2004, pp. 105-117. https://doi.org/10.1016/j.molcata.2003.09.002
  9. P. Afanasiev, "The Influence of Reducing and Sulfiding Conditions on the Properties of Unsupported MoS2 based Catalysts", J. Catal., Vol. 269, 2010, pp. 269-280. https://doi.org/10.1016/j.jcat.2009.11.004
  10. R. R. Chianelli, G. Berhault, and B. Torres, "Unsupported Transition Metal Sulfide: 100 Years of Science and Application", Catal. Today, Vol. 147, 2009, pp. 275-286. https://doi.org/10.1016/j.cattod.2008.09.041
  11. J. Liu, E. Wang, Z. Li, B Wang, X. Ma, S. Qin, and Q. Sun, "Investigation of Sulfur-Resistant, Highly Active Unsupported $MoS_2$ Catalysts for Synthetic Natural Gas Production from CO Methanation", Fuel Processing Technology, Vol. 110, 2013, pp. 249-257. https://doi.org/10.1016/j.fuproc.2013.01.003
  12. R. R. Chianelli, "Carbon containing Molybdenum and Tungsten Catalysts", US Patent 4508847, Apr. 2, 1985.
  13. J. Happel, M. A. Hnatow, and L. Bajars, "Method of Making High Activity Transition Metal Catalysts", US Patent 4491639, Jan. 1, 1985, pp. 1-12.
  14. G. Alonso, R. R. Chianelli, S. Fuentes, and B. Torres, "Molybdenum Sulfide/Carbide Catalysis", US Patent 7223713 B2, May 29, 2007.
  15. Q. Li, M. Li, and C. Li, "Simple Solution Route to Uniform $MoS_2$ Particles with Randomly Stacked Layers", Material Research Bulletin, Vol. 39, 2004, pp. 981-988. https://doi.org/10.1016/j.materresbull.2004.03.017
  16. Y. Yoneyama and C. Song, "A New Method for Preparing Highly Active Unsupported Mo Sulfide Catalytic Activity for hydrogenolysis", Catalysis Today, Vol. 50, 1999, pp. 269-276.
  17. G. Alonso, G. Berhault, F. Paraguay, E. Rivera, S. Fuentes, and R. R. Chianelli, "Mesoporous Carbon Containing $MoS_2$ Materials formed from in situ Decomposition of Tetraalkylammonium Thiomolybdates", Materials Research Bulletin, Vol. 38, 2003, pp. 1045-1055. https://doi.org/10.1016/S0025-5408(03)00066-7
  18. R. R. Chianelli and G. Berhault, "Symmetrical Synergism and the Role of Carbon in Transition Metal Sulfide Catalytic Materials", Catalysis Today, Vol. 53, 1999, pp. 357-366. https://doi.org/10.1016/S0920-5861(99)00130-3
  19. H. Wang, P. Skeldon, and G. Thompson, "XPS Studies of $MoS_2$ Formation from Ammonium Tetrahtiomolybdate Solution", Surf. Coating Tech., Vol. 91, 1997, pp. 200-207. https://doi.org/10.1016/S0257-8972(96)03186-6
  20. J. Happel and M. A. Hnatow, "Direct Methanation - New Method of Converting Synthesis Gas to Substitute Natural Gas", http://web.anl.gov/PCS/acsfuel/preprint%20archive/Files/27_1_LAS%20VEGAS_03-82_0109.pdf.