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CN 34-1054/N

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A general theoretical model for the reaction rate of Ni catalyzed methane steam reforming reaction

  • Key Laboratory of Strongly-Coupled Quantum Matter Physics, Chinese Academy of Sciences

  • Department of Physics, School of Physical Sciences, University of Science and Technology of China, Hefei 230026,China

Cite this:
https://doi.org/10.3969/j.issn.0253-2778.2016.12.006
  • Received Date: 16 June 2016
  • Accepted Date: 26 October 2016
  • Rev Recd Date: 26 October 2016
  • Publish Date: 30 December 2016
    Abstract

  • Abstract

    Methane steam reforming (MSR) reaction rate is an important factor affecting the performance of methane fueled solid oxide fuel cell (SOFC). Ni is the most common catalyst for MSR in SOFC. There are large discrepancies in the Ni catalyzed MSR kinetic models proposed by different experiments. Moreover, the experiments for all the MSR kinetic models use methane with relatively high steam content, rendering the kinetic models unsuitable for the study of low steam methane fueled SOFCs.The major MSR kinetic models are surveyed here with the analysis of their similarities and differences. Based on the analysis and a new MSR kinetic model found for methane with low steam content, a unifying MSR kinetic model applicable for any steam content was deduced. The model is capable of explaining the confusion phenomenon that different steam reaction orders are observed by different experiments. It also provides good fits to the experimental data obtained under conditions such as different steam compositions and different working temperatures.

    Abstract

    Methane steam reforming (MSR) reaction rate is an important factor affecting the performance of methane fueled solid oxide fuel cell (SOFC). Ni is the most common catalyst for MSR in SOFC. There are large discrepancies in the Ni catalyzed MSR kinetic models proposed by different experiments. Moreover, the experiments for all the MSR kinetic models use methane with relatively high steam content, rendering the kinetic models unsuitable for the study of low steam methane fueled SOFCs.The major MSR kinetic models are surveyed here with the analysis of their similarities and differences. Based on the analysis and a new MSR kinetic model found for methane with low steam content, a unifying MSR kinetic model applicable for any steam content was deduced. The model is capable of explaining the confusion phenomenon that different steam reaction orders are observed by different experiments. It also provides good fits to the experimental data obtained under conditions such as different steam compositions and different working temperatures.
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    • References(23)
  • [1]
    CHA S W, COLELLA W, PRINZ F B. Fuel Cell Fundamentals[M]. New York: John Wiley & Sons, 2006: 8.
    [2]
    MURRAY E P, TSAI T, BARNETT S A. A direct-methane fuel cell with a ceria-based anode[J]. Nature, 1999, 400(6745): 649-651.
    [3]
    SANGTONGKITCHAROEN W, ASSABUMRUNGRAT S, PAVARAJARNV, et al. Comparison of carbon formation boundary in different modes of solid oxide fuel cells fueled by methane[J]. Journal of Power Sources, 2005, 142(1): 75-80.
    [4]
    PETERS R, DAHL R, KLTTGEN U, et al. Internal reforming of methane in solid oxide fuel cell systems[J]. Journal of Power Sources, 2002, 106(1): 238-244.
    [5]
    MBODJI M, COMMENGE J M, FALK L, et al. Steam methane reforming reaction process intensification by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation[J]. Chemical Engineering Journal, 2012, 207: 871-884.
    [6]
    VIPARELLI P, VILLA P, BASILE F, et al. Catalyst based on BaZrO3 with different elements incorporated in the structure: Ⅱ. BaZr(1-x) RhxO3 systems for the production of syngas by partial oxidation of methane[J]. Applied Catalysis A: General, 2005, 280(2): 225-232.
    [7]
    AHMED K, FOGER K. Kinetics of internal steam reforming of methane on Ni/YSZ-based anodes for solid oxide fuel cells[J]. Catalysis Today, 2000, 63(2): 479-487.
    [8]
    BRUS G. Experimental and numerical studies on chemically reacting gas flow in the porous structure of a solid oxide fuel cells internal fuel reformer[J]. International Journal of Hydrogen Energy, 2012, 37(22): 17 225-17 234.
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    DEGRD R, JOHNSEN E, KAROLIUSSEN H. Methane reforming on Ni/zirconia SOFC anodes[R]. Pennington, NJ: Electrochemical Society, 1995.
    [10]
    LEE A L, ZABRANSKY R F, HUBER W J. Internal reforming development for solid oxide fuel cells[J]. Industrial & Engineering Chemistry Research, 1990, 29(5): 766-773.
    [11]
    MOGENSEND. Methane steam reforming kinetics over Ni-YSZ anode materials for Solid Oxide Fuel Cells[D]. Technical University of Denmark: Topsoe Fuel Cell A/S, 2011.
    [12]
    LIU J, BARNETT S A. Operation of anode-supported solid oxide fuel cells on methane and natural gas[J]. Solid State Ionics, 2003, 158(1):11-16.
    [13]
    WANG B, ZHU J, LINZ. A theoretical framework for multiphysics modeling of methane fueled solid oxide fuel cell and analysis of low steam methane reforming kinetics[J]. Applied Energy, 2016, 176: 1-11.
    [14]
    ZEPPIERI M, VILLA P L, VERDONEN, et al. Kinetic of methane steam reforming reaction over nickel-and rhodium-based catalysts[J]. Applied Catalysis A: General, 2010, 387(1): 147-154.
    [15]
    BEBELIS S, ZERITIS A, TIROPANIC, et al. Intrinsic kinetics of the internal steam reforming of CH4 over a Ni-YSZ-cermet catalyst-electrode[J]. Industrial & Engineering Chemistry Research, 2000, 39(12): 4 920-4 927.
    [16]
    BODER M, DITTMEYER R. Catalytic modification of conventional SOFC anodes with a view to reducing their activity for direct internal reforming of natural gas[J]. Journal of Power Sources, 2006, 155(1): 13-22.
    [17]
    ACHENBACH E, RIENSCHE E. Methane/steam reforming kinetics for solid oxide fuel cells[J]. Journal of Power Sources, 1994, 52(2): 283-288.
    [18]
    KING D L, STROHM JJ, WANG X, et al. Effect of nickel microstructure on methane steam-reforming activity of Ni-YSZ cermet anode catalyst[J]. Journal of Catalysis, 2008, 258(2): 356-365.
    [19]
    WANG B, JIANG Z, LIN Z. Multi-physics modeling of solid oxide fuel cell fueled by methane and analysis of carbon deposition[J]. Chinese Journal of Chemical Physics, 2015, 28(3): 299-307.
    [20]
    KRATZER P, HAMMER B, NO J K. A theoretical study of CH4 dissociation on pure and gold-alloyed Ni (111) surfaces[J]. The Journal of Chemical Physics, 1996, 105(13): 5 595-5 604.
    [21]
    YANG H, WHITTENJ L. Dissociative chemisorption of CH4 on Ni(111)[J]. The Journal of Chemical Physics, 1992, 96(7): 5 529-5 537.
    [22]
    STEWART C N, EHRLICH G. Dynamics of activated chemisorption: Methane on rhodium[J]. The Journal of Chemical Physics, 1975, 62(12): 4 672-4 682.
    [23]
    LEMONIDOU A A, VASALOS I A. Carbon dioxide reforming of methane over 5 wt.% Ni/CaO-Al2O3 catalyst[J]. Applied Catalysis A: General, 2002, 228(1): 227-235.
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    [1]
    CHA S W, COLELLA W, PRINZ F B. Fuel Cell Fundamentals[M]. New York: John Wiley & Sons, 2006: 8.
    [2]
    MURRAY E P, TSAI T, BARNETT S A. A direct-methane fuel cell with a ceria-based anode[J]. Nature, 1999, 400(6745): 649-651.
    [3]
    SANGTONGKITCHAROEN W, ASSABUMRUNGRAT S, PAVARAJARNV, et al. Comparison of carbon formation boundary in different modes of solid oxide fuel cells fueled by methane[J]. Journal of Power Sources, 2005, 142(1): 75-80.
    [4]
    PETERS R, DAHL R, KLTTGEN U, et al. Internal reforming of methane in solid oxide fuel cell systems[J]. Journal of Power Sources, 2002, 106(1): 238-244.
    [5]
    MBODJI M, COMMENGE J M, FALK L, et al. Steam methane reforming reaction process intensification by using a millistructured reactor: Experimental setup and model validation for global kinetic reaction rate estimation[J]. Chemical Engineering Journal, 2012, 207: 871-884.
    [6]
    VIPARELLI P, VILLA P, BASILE F, et al. Catalyst based on BaZrO3 with different elements incorporated in the structure: Ⅱ. BaZr(1-x) RhxO3 systems for the production of syngas by partial oxidation of methane[J]. Applied Catalysis A: General, 2005, 280(2): 225-232.
    [7]
    AHMED K, FOGER K. Kinetics of internal steam reforming of methane on Ni/YSZ-based anodes for solid oxide fuel cells[J]. Catalysis Today, 2000, 63(2): 479-487.
    [8]
    BRUS G. Experimental and numerical studies on chemically reacting gas flow in the porous structure of a solid oxide fuel cells internal fuel reformer[J]. International Journal of Hydrogen Energy, 2012, 37(22): 17 225-17 234.
    [9]
    DEGRD R, JOHNSEN E, KAROLIUSSEN H. Methane reforming on Ni/zirconia SOFC anodes[R]. Pennington, NJ: Electrochemical Society, 1995.
    [10]
    LEE A L, ZABRANSKY R F, HUBER W J. Internal reforming development for solid oxide fuel cells[J]. Industrial & Engineering Chemistry Research, 1990, 29(5): 766-773.
    [11]
    MOGENSEND. Methane steam reforming kinetics over Ni-YSZ anode materials for Solid Oxide Fuel Cells[D]. Technical University of Denmark: Topsoe Fuel Cell A/S, 2011.
    [12]
    LIU J, BARNETT S A. Operation of anode-supported solid oxide fuel cells on methane and natural gas[J]. Solid State Ionics, 2003, 158(1):11-16.
    [13]
    WANG B, ZHU J, LINZ. A theoretical framework for multiphysics modeling of methane fueled solid oxide fuel cell and analysis of low steam methane reforming kinetics[J]. Applied Energy, 2016, 176: 1-11.
    [14]
    ZEPPIERI M, VILLA P L, VERDONEN, et al. Kinetic of methane steam reforming reaction over nickel-and rhodium-based catalysts[J]. Applied Catalysis A: General, 2010, 387(1): 147-154.
    [15]
    BEBELIS S, ZERITIS A, TIROPANIC, et al. Intrinsic kinetics of the internal steam reforming of CH4 over a Ni-YSZ-cermet catalyst-electrode[J]. Industrial & Engineering Chemistry Research, 2000, 39(12): 4 920-4 927.
    [16]
    BODER M, DITTMEYER R. Catalytic modification of conventional SOFC anodes with a view to reducing their activity for direct internal reforming of natural gas[J]. Journal of Power Sources, 2006, 155(1): 13-22.
    [17]
    ACHENBACH E, RIENSCHE E. Methane/steam reforming kinetics for solid oxide fuel cells[J]. Journal of Power Sources, 1994, 52(2): 283-288.
    [18]
    KING D L, STROHM JJ, WANG X, et al. Effect of nickel microstructure on methane steam-reforming activity of Ni-YSZ cermet anode catalyst[J]. Journal of Catalysis, 2008, 258(2): 356-365.
    [19]
    WANG B, JIANG Z, LIN Z. Multi-physics modeling of solid oxide fuel cell fueled by methane and analysis of carbon deposition[J]. Chinese Journal of Chemical Physics, 2015, 28(3): 299-307.
    [20]
    KRATZER P, HAMMER B, NO J K. A theoretical study of CH4 dissociation on pure and gold-alloyed Ni (111) surfaces[J]. The Journal of Chemical Physics, 1996, 105(13): 5 595-5 604.
    [21]
    YANG H, WHITTENJ L. Dissociative chemisorption of CH4 on Ni(111)[J]. The Journal of Chemical Physics, 1992, 96(7): 5 529-5 537.
    [22]
    STEWART C N, EHRLICH G. Dynamics of activated chemisorption: Methane on rhodium[J]. The Journal of Chemical Physics, 1975, 62(12): 4 672-4 682.
    [23]
    LEMONIDOU A A, VASALOS I A. Carbon dioxide reforming of methane over 5 wt.% Ni/CaO-Al2O3 catalyst[J]. Applied Catalysis A: General, 2002, 228(1): 227-235.
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