Methane steam reforming kinetics over Ni-YSZ anodematerials for Solid Oxide FuelCells

Methane steam reforming kinetics over Ni-YSZ anodematerials for Solid Oxide FuelCells Solid Oxide Fuel Cells (SOFC) is a technology with great potential. Its high efficiency makes it a relevant alternative to existing technologies for utilizing fossil fuels and its fuel versatility makes it invaluable in the transition from a fossil fuel based energy system to on based on renewable energy. The overall efficiency of a fuel cell system operating on natural gas can be significantly improved by having part of the steam reforming take place inside the SOFC stack. In order to avoid large temperature gradients as a result of the highly endothermal steam reforming reaction, the amount of internal reforming has to be carefully controlled. The objective of this thesis is to make such a careful control possible by examining the rate of internal steam reforming in SOFCs. The catalytic steam reforming activity of Ni-YSZ anode material was tested both in a packed bed reactor to determine intrinsic kinetics, and in a stack configuration to determine the rate observed under realistic SOFC conditions. The kinetic expressions obtained from respectively the packed bed measurements and the stack measurements are shown in Equations 3 and 4. Furthermore, a simple model was derived, which can accurately predict the steam reforming rate in a stack from the rate expression obtained from the packed bed experiments. During the experiments a previously unreported long term dynamic behavior of the catalyst was observed. After startup, the initial high reactivity was slowly reduced by a factor 5-10 over a period of several days or several weeks depending on operating temperature. It was also found that prolonged exposure to a H2O/H2 mixture without CH4 resulted in a reactivation of the catalytic activity up to the initial high level. It was attempted to account for this behavior through characterization with SEM, TEM, XRD and EXAFS.

[1]  A. Hagen,et al.  Ni/YSZ electrode degradation studied by impedance spectroscopy — Effect of p(H2O) , 2011 .

[2]  J. F. B. Rasmussen,et al.  The Effect of H2S on the Performance of SOFCs using Methane Containing Fuel , 2010 .

[3]  Kevin Kendall,et al.  Numerical modelling of methane-powered micro-tubular, single-chamber solid oxide fuel cell , 2010 .

[4]  I. Chorkendorff,et al.  Noble metal catalysts for methane steam reforming , 2010 .

[5]  Mogens Bjerg Mogensen,et al.  Continuum mechanics simulations of NiO/Ni–YSZ composites during reduction and re-oxidation , 2010 .

[6]  Alex C. Hoffmann,et al.  Effects of heat sources on the performance of a planar solid oxide fuel cell , 2010 .

[7]  I. S. Nashawi,et al.  Forecasting World Crude Oil Production Using Multicyclic Hubbert Model , 2010 .

[8]  Jens R. Rostrup-Nielsen,et al.  Steady-state kinetics and mechanism of methane reforming with steam and carbon dioxide over Ni catalyst , 2010 .

[9]  S. Dahl,et al.  Support effects and catalytic trends for water gas shift activity of transition metals , 2010 .

[10]  Mikko Pihlatie,et al.  Testing and improving the redox stability of Ni-based solid oxide fuel cells , 2009 .

[11]  Mogens Bjerg Mogensen,et al.  Redox stability of SOFC: Thermal analysis of Ni-YSZ composites , 2009 .

[12]  Charles F. Keller,et al.  Global warming: a review of this mostly settled issue , 2009 .

[13]  M. Mogensen,et al.  Mechanical properties of NiO/Ni–YSZ composites depending on temperature, porosity and redox cycling , 2009 .

[14]  W. Green,et al.  Computational Investigation of Thermochemistry and Kinetics of Steam Methane Reforming on Ni(111) under Realistic Conditions , 2009 .

[15]  S. Jensen,et al.  Solid Oxide Electrolysis Cells: Microstructure and Degradation of the Ni/Yttria-Stabilized Zirconia Electrode , 2008 .

[16]  J. Nørskov,et al.  First principles calculations and experimental insight into methane steam reforming over transition metal catalysts , 2008 .

[17]  Samuel Stucki,et al.  Charge, mass and heat transfer interactions in solid oxide fuel cells operated with different fuel gases-A sensitivity analysis , 2008 .

[18]  Robert T. Rozmiarek,et al.  Effect of nickel microstructure on methane steam-reforming activity of Ni–YSZ cermet anode catalyst , 2008 .

[19]  K. Thydén,et al.  Microstructural characterization of SOFC Ni–YSZ anode composites by low-voltage scanning electron microscopy , 2008 .

[20]  Shinji Kimijima,et al.  Performance analysis of the SOFC–MGT hybrid system with gasified biomass fuel , 2007 .

[21]  Matias Halinen,et al.  Dynamic Model of 5kW SOFC CHP Test Station , 2007 .

[22]  Ayodeji Jeje,et al.  3D modeling of anode-supported planar SOFC with internal reforming of methane , 2007 .

[23]  Mogens Bjerg Mogensen,et al.  Detailed Characterization of Anode-Supported SOFCs by Impedance Spectroscopy , 2007 .

[24]  Vinod M. Janardhanan,et al.  Non-commercial Research and Educational Use including without Limitation Use in Instruction at Your Institution, Sending It to Specific Colleagues That You Know, and Providing a Copy to Your Institution's Administrator. All Other Uses, Reproduction and Distribution, including without Limitation Comm , 2022 .

[25]  E. Ivers-Tiffée,et al.  Internal Reforming of Methane at Ni/YSZ and Ni/CGO SOFC Cermet Anodes , 2006 .

[26]  R. Dittmeyer,et al.  Catalytic modification of conventional SOFC anodes with a view to reducing their activity for direct internal reforming of natural gas , 2006 .

[27]  A. Hagen,et al.  Break Down of Losses in Thin Electrolyte SOFCs , 2006 .

[28]  J. Sehested,et al.  Four challenges for nickel steam-reforming catalysts , 2006 .

[29]  O. Deutschmann,et al.  Methane reforming kinetics within a Ni–YSZ SOFC anode support , 2005 .

[30]  J. Nørskov,et al.  Methane activation on Ni(111) : Effects of poisons and step defects , 2005 .

[31]  Nigel M. Sammes,et al.  SOFC mathematic model for systems simulations-Part 2: definition of an analytical model , 2005 .

[32]  S. Campanari,et al.  Comparison of Finite Volume SOFC Models for the Simulation of a Planar Cell Geometry , 2005 .

[33]  Nigel M. Sammes,et al.  SOFC mathematic model for systems simulations. Part one: from a micro-detailed to macro-black-box model , 2005 .

[34]  E. Iglesia,et al.  Isotopic and kinetic assessment of the mechanism of reactions of CH4 with CO2 or H2O to form synthesis gas and carbon on nickel catalysts , 2004 .

[35]  J. Nørskov,et al.  Atomic-scale imaging of carbon nanofibre growth , 2004, Nature.

[36]  H. Ho,et al.  Multi-level modeling of SOFC–gas turbine hybrid system , 2003 .

[37]  J. Nørskov,et al.  Steam Reforming and Graphite Formation on Ni Catalysts , 2002 .

[38]  R. Peters,et al.  Internal reforming of methane in solid oxide fuel cell systems , 2002 .

[39]  I. Yasuda,et al.  3-D model calculation for planar SOFC , 2001 .

[40]  K. Ahmed,et al.  Kinetics of internal steam reforming of methane on Ni/YSZ-based anodes for solid oxide fuel cells , 2000 .

[41]  S. Neophytides,et al.  Intrinsic Kinetics of the Internal Steam Reforming of CH4 over a Ni−YSZ−Cermet Catalyst−Electrode , 2000 .

[42]  S. Sunde.  Simulations of Composite Electrodes in Fuel Cells , 2000 .

[43]  J. Grunwaldt,et al.  In Situ Investigations of Structural Changes in Cu/ZnO Catalysts , 2000 .

[44]  Werner Lehnert,et al.  Modelling of gas transport phenomena in SOFC anodes , 2000 .

[45]  S. Primdahl.  nickel/yttria-stabilised zirconia cermet anodes for solid oxide fuel cells , 1999 .

[46]  T. Ressler.  WinXAS: a program for X-ray absorption spectroscopy data analysis under MS-Windows. , 1998, Journal of synchrotron radiation.

[47]  A. Jensen,et al.  Catalytic and gas–solid reactions involving HCN over limestone , 1997 .

[48]  J. Nørskov,et al.  Kinetic Implications of Dynamical Changes in Catalyst Morphology during Methanol Synthesis over Cu/ZnO Catalysts , 1997 .

[49]  L. M. Aparicio.  Transient Isotopic Studies and Microkinetic Modeling of Methane Reforming over Nickel Catalysts , 1997 .

[50]  R. Oedegaard,et al.  Methane reforming on Ni/zirconia SOFC anodes , 1995 .

[51]  Ankudinov,et al.  Multiple-scattering calculations of x-ray-absorption spectra. , 1995, Physical review. B, Condensed matter.

[52]  E. Riensche,et al.  Methane/steam reforming kinetics for solid oxide fuel cells , 1994 .

[53]  Masashi Mori,et al.  Production cost estimation of solid oxide fuel cells , 1994 .

[54]  N. Giordano,et al.  Thermodynamic analysis of methane fueled solid oxide fuel cell system , 1992 .

[55]  H. Girault.  Basic principles of membrane technology , 1992 .

[56]  R. Zabransky,et al.  Internal reforming development for solid oxide fuel cells , 1990 .

[57]  E. Ruckenstein,et al.  Mechanism of redispersion of supported metal catalysts in oxidative atmospheres , 1985 .

[58]  R. Whittaker,et al.  Steam reforming catalysts , 1973 .

[59]  K. Kobe.  The properties of gases and liquids , 1959 .

[60]  M. Pihlatie.  Stability of Ni-YSZ composites for solid oxide fuel cells during reduction and re-oxidation , 2010 .

[61]  E. Ivers-Tiffée,et al.  Kinetics of (reversible) internal reforming of methane in solid oxide fuel cells under stationary and APU conditions , 2010 .

[62]  Shahriar Shafiee,et al.  When will fossil fuel reserves be diminished , 2009 .

[63]  B. Maribo-Mogensen,et al.  Internal Steam Reforming in Solid Oxide Fuel Cells , 2008 .

[64]  D. Mogensen.  Mathematical Modelling of Solid Oxide Fuel Cells , 2007 .

[65]  N. Houbak,et al.  A ZeroDimensional Model of a 2nd Generation Planar SOFC Using Calibrated Parameters , 2006 .

[66]  Jacob Brouwer,et al.  A thermodynamic analysis of electricity and hydrogen co-production using a solid oxide fuel cell , 2005 .

[67]  J. Niemantsverdriet,et al.  Concepts of modern catalysis and kinetics , 2005 .

[68]  G. S. Samuelsen,et al.  A thermodynamic analysis of tubular solid oxide fuel cell based hybrid systems , 2003 .

[69]  Jens Pålsson,et al.  Thermodynamic Modelling and Performance of Combined Solid Oxide Fuel Cell and Gas Turbine Systems , 2002 .

[70]  Jens R. Rostrup-Nielsen,et al.  Hydrogen and Synthesis gas by Steam- and CO2 reforming , 2002 .

[71]  Nobuyoshi Nakagawa,et al.  Catalytic activity of Ni–YSZ–CeO2 anode for the steam reforming of methane in a direct internal-reforming solid oxide fuel cell , 2001 .

[72]  P. V. Hendriksen,et al.  Model studies of internal steam reforming in SOFC stacks , 1997 .

[73]  S. Sunde.  A Mathematical Model for Internal Reforming at Composite Anodes for Solid Oxide Fuel Cells , 1997 .

[74]  Oslo.  Second European solid oxide fuel cell forum, 6-10 May 1996, Oslo, Norway , 1996 .

[75]  F. R. Foulkes,et al.  Fuel Cell Handbook , 1989 .

[76]  D. Newsome.  The Water-Gas Shift Reaction , 1980 .