能源化学(英文版)

能源化学(英文) ›› 2011, Vol. 20 ›› Issue (6): 568-576.DOI: 10.1016/S1003-9953(10)60235-6

• Articles • 上一篇    下一篇

 Thermodynamic analysis of mixed and dry reforming of methane for solar thermal applications

Y. Sun1*, T. Ritchie1, S. S. Hla2, S. McEvoy1, W. Stein1, J. H. Edwards3   

  1. 1. CSIRO Energy Technology, P. O. Box 330, Newcastle, NSW 2300, Australia; 2. CSIRO Energy Technology, P. O. Box 883, Pullenvale, QLD 4069, Australia;

     3. CSIRO Energy Technology, P. O. Box 136, North Ryde, NSW 2113, Australia

  • 收稿日期:2011-04-06 修回日期:2011-05-13 出版日期:2011-11-20 发布日期:2011-11-18
  • 通讯作者: Yanping Sun

 Thermodynamic analysis of mixed and dry reforming of methane for solar thermal applications

Y. Sun1*, T. Ritchie1, S. S. Hla2, S. McEvoy1, W. Stein1, J. H. Edwards3     

  1. 1. CSIRO Energy Technology, P. O. Box 330, Newcastle, NSW 2300, Australia; 2. CSIRO Energy Technology, P. O. Box 883, Pullenvale, QLD 4069, Australia;

     3. CSIRO Energy Technology, P. O. Box 136, North Ryde, NSW 2113, Australia

     

     

  • Received:2011-04-06 Revised:2011-05-13 Online:2011-11-20 Published:2011-11-18

摘要： Thermodynamic analysis of the reforming of methane with carbon dioxide alone ("dry reforming") and with carbon dioxide and steam together ("mixed reforming") is performed as part of a project which investigates the suitability of these endothermic reactions for the storage of solar thermal energy. The Gibbs free energy minimization method was employed to identify thermodynamically optimal operating conditions for dry reforming as well as mixed reforming with a desired H2/CO molar ratio of 2. The non-stoichiometric equilibrium model was developed using FactSage software to conduct the thermodynamic calculations for carbon formation, H2/CO ratio, CH4 conversion and H2 yield as a function of reaction temperature, pressure and reactant molar ratios. Thermodynamic calculations demonstrate that in the mixed reforming process, optimal operating conditions in a carbon-free zone are under H2O/CH4/CO2 = 1.0/1.0/0.5, p = 1 to 10 bar andT = 800 to 850 ℃ for the production of syngas with a H2/CO molar ratio of 2. Under the optimal conditions, the maximum H2 yield of 88.0% is achieved at 1 bar and 850 ℃ with a maximum CH4 conversion of 99.3%. In the dry reforming process, a carbon formation regime is always present at a CO2/CH4 molar ratio of 1 forT = 700-1000 ℃ andp = 1-30 bar, whereas a carbon-free regime can be obtained at a CO2/CH4 molar ratio greater than 1.5 andT≥800 ℃.

关键词: mixed steam reforming of CH4 with CO2, CO2 reforming, syngas, solar thermal application

Abstract: Thermodynamic analysis of the reforming of methane with carbon dioxide alone (``dry reforming") and with carbon dioxide and steam together (``mixed reforming") is performed as part of a project which investigates the suitability of these endothermic reactions for the storage of solar thermal energy. The Gibbs free energy minimization method was employed to identify thermodynamically optimal operating conditions for dry reforming as well as mixed reforming with a desired H2/CO molar ratio of 2. The non-stoichiometric equilibrium model was developed using FactSage software to conduct the thermodynamic calculations for carbon formation, H2/CO ratio, CH4 conversion and H2 yield as a function of reaction temperature, pressure and reactant molar ratios. Thermodynamic calculations demonstrate that in the mixed reforming process, optimal operating conditions in a carbon-free zone are under H2O/CH4/CO2 = 1.0/1.0/0.5, p = 1 to 10 bar andT = 800 to 850 ℃ for the production of syngas with a H2/CO molar ratio of 2. Under the optimal conditions, the maximum H2 yield of 88.0% is achieved at 1 bar and 850 ℃ with a maximum CH4 conversion of 99.3%. In the dry reforming process, a carbon formation regime is always present at a CO2/CH4 molar ratio of 1 forT = 700-1000 ℃ andp = 1-30 bar, whereas a carbon-free regime can be obtained at a CO2/CH4 molar ratio greater than 1.5 andT≥800 ℃.

Key words: mixed steam reforming of CH4 with CO2, CO2 reforming, syngas, solar thermal application