!SURFACE MECHANISM OF CH4 REFORMING AND OXIDATION OVER NI !*********************************************************************** !**** !**** CH4 ON Ni - SURFACE MECHANISM !**** !**** Version 2.0 2011 !**** !**** L. Maier, B. Schaedel, K. Herrera Delgado, S. Tischer !**** O. Deutschmann !**** Karlsruhe Institute of Technology, Germany !**** Contact: mail@detchem.com (O. Deutschmann) !**** !**** temp. range 500-2000K !**** !**** Ref: L. Maier, B. Schädel, K. Herrera Delgado, !**** S. Tischer, O. Deutschmann. !**** Steam Reforming of Methane over Nickel: Development !**** of a Multi-Step Surface Reaction Mechanism. !**** Topics in Catalysis 54 (2011) 845-858. !**** www.detchem.com/mechanisms !**** !**** Kinetic data: !**** k = A * T**b * exp (-Ea/RT) A b Ea !**** (cm,mol,s) - J/mol !**** !**** !**** Surface site density: 2.66E-9 mol/cm**2 !**** !**** !**** (SURFACE CHEMKIN format) !**** !*********************************************************************** SITE /NI_surface/ SDEN /2.66E-09/ NI(s) /1/ H2O(s) /1/ H(s) /1/ OH(s) /1/ CO(s) /1/ C(s) /1/ CH3(s) /1/ CH2(s) /1/ CH(s) /1/ CH4(s) /1/ O(s) /1/ CO2(s) /1/ HCO(s) /1/ END THERMO ALL 300.0 1000.0 5000.0 CH4 (adjust) C 1H 4 0 0 300.00 5000.00 1000.00 1 1.68347883E+00 1.02372356E-02-3.87512864E-06 6.78558487E-10-4.50342312E-14 2 -1.00807871E+04 9.62339497E+00 7.78741479E-01 1.74766835E-02-2.78340904E-05 3 3.04970804E-08-1.22393068E-11-9.82522852E+03 1.37221947E+01 4 H2 (adjust) H 2 0 0 0 300.00 5000.00 1000.00 1 3.06670950E+00 5.74737550E-04 1.39383190E-08-2.54835180E-11 2.90985740E-15 2 -8.65474120E+02-1.77984240E+00 3.35535140E+00 5.01361440E-04-2.30069080E-07 3 -4.79053240E-10 4.85225850E-13-1.01916260E+03-3.54772280E+00 4 H2O (adjust) H 2O 1 0 0 300.00 5000.00 1000.00 1 2.61104720E+00 3.15631300E-03-9.29854380E-07 1.33315380E-10-7.46893510E-15 2 -2.98681670E+04 7.20912680E+00 4.16772340E+00-1.81149700E-03 5.94712880E-06 3 -4.86920210E-09 1.52919910E-12-3.02899690E+04-7.31354740E-01 4 CO (adjust) C 1O 1 0 0 300.00 5000.00 1000.00 1 3.02507806E+00 1.44268852E-03-5.63082779E-07 1.01858133E-10-6.91095156E-15 2 -1.42683496E+04 6.10821772E+00 3.26245165E+00 1.51194085E-03-3.88175522E-06 3 5.58194424E-09-2.47495123E-12-1.43105391E+04 4.84889698E+00 4 CO2 (adjust) C 1O 2 0 0 300.00 5000.00 1000.00 1 4.45362282E+00 3.14016873E-03-1.27841054E-06 2.39399667E-10-1.66903319E-14 2 -4.89669609E+04-9.55395877E-01 2.27572465E+00 9.92207229E-03-1.04091132E-05 3 6.86668678E-09-2.11728009E-12-4.83731406E+04 1.01884880E+01 4 O2 (adjust) O 2 0 0 0 300.00 5000.00 1000.00 1 3.61221390E+00 7.48531660E-04-1.98206470E-07 3.37490080E-11-2.39073740E-15 2 -1.19781510E+03 3.67033070E+00 3.78371350E+00-3.02336340E-03 9.94927510E-06 3 -9.81891010E-09 3.30318250E-12-1.06381070E+03 3.64163450E+00 4 AR (adjust) AR 1 0 0 0 300.00 5000.00 1000.00 1 2.50000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 -7.45375020E+02 4.36600060E+00 2.50000000E+00 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00-7.45374980E+02 4.36600060E+00 4 N2 (adjust) N 2 0 0 0 300.00 5000.00 1000.00 1 2.85328990E+00 1.60221280E-03-6.29368930E-07 1.14410220E-10-7.80574650E-15 2 -8.90080930E+02 6.39648970E+00 3.70441770E+00-1.42187530E-03 2.86703920E-06 3 -1.20288850E-09-1.39546770E-14-1.06407950E+03 2.23362850E+00 4 NI(s) (adjust) NI 1 0 0 0 300.00 3000.00 1000.00 1 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 2 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 3 0.00000000E+00 0.00000000E+00 0.00000000E+00 0.00000000E+00 4 H2O(s) (adjust) H 2O 1NI 1 0 500.00 2000.00 2000.00 1 3.50421382E+00 6.68594839E-04 1.76268743E-06-1.17030152E-09 2.26185355E-13 2 -3.79129166E+04-1.05582534E+01 3.50421382E+00 6.68594839E-04 1.76268743E-06 3 -1.17030152E-09 2.26185355E-13-3.79129166E+04-1.05582534E+01 4 H(s) (adjust) H 1NI 1 0 0 500.00 2000.00 2000.00 1 1.38522354E+00-3.60291509E-05 1.01482878E-06-6.39234047E-10 1.26064639E-13 2 -5.45886573E+03-5.04262898E+00 1.38522354E+00-3.60291509E-05 1.01482878E-06 3 -6.39234047E-10 1.26064639E-13-5.45886573E+03-5.04262898E+00 4 OH(s) (adjust) H 1O 1NI 1 0 500.00 2000.00 2000.00 1 2.08905501E+00 1.71443903E-03-4.27838552E-07 9.11211411E-12 1.13760370E-14 2 -2.67334298E+04-3.86138841E+00 2.08905501E+00 1.71443903E-03-4.27838552E-07 3 9.11211411E-12 1.13760370E-14-2.67334298E+04-3.86138841E+00 4 CO(s) (adjust) C 1O 1NI 1 0 500.00 2000.00 2000.00 1 1.04958397E+00 5.37825549E-03-3.51895909E-06 1.06323431E-09-1.12689240E-13 2 -2.73744388E+04 7.60559022E+00 1.04958397E+00 5.37825549E-03-3.51895909E-06 3 1.06323431E-09-1.12689240E-13-2.73744388E+04 7.60559022E+00 4 C(s) (adjust) C 1NI 1 0 0 500.00 2000.00 2000.00 1 -3.49330914E+00 5.23524687E-03-3.03308918E-06 6.55611035E-10-1.40966550E-14 2 -2.23124726E+03 7.68421239E+00-3.49330914E+00 5.23524687E-03-3.03308918E-06 3 6.55611035E-10-1.40966550E-14-2.23124726E+03 7.68421239E+00 4 CH3(s) (adjust) C 1H 3NI 1 0 500.00 2000.00 2000.00 1 -6.10760599E-01 8.61612510E-03-2.17714930E-06-6.63815294E-10 3.13819319E-13 2 -8.89792082E+03-2.00828704E+00-6.10760599E-01 8.61612510E-03-2.17714930E-06 3 -6.63815294E-10 3.13819319E-13-8.89792082E+03-2.00828704E+00 4 CH2(s) (adjust) C 1H 2NI 1 0 500.00 2000.00 2000.00 1 -1.56917589E+00 7.30948876E-03-2.33683999E-06-2.63575385E-10 2.08877321E-13 2 1.94307500E+03 4.44265982E+00-1.56917589E+00 7.30948876E-03-2.33683999E-06 3 -2.63575385E-10 2.08877321E-13 1.94307500E+03 4.44265982E+00 4 CH(s) (adjust) C 1H 1NI 1 0 500.00 2000.00 2000.00 1 -2.52762352E+00 6.00297402E-03-2.49669461E-06 1.36758705E-10 1.03915796E-13 2 9.56681068E+03 7.44010148E+00-2.52762352E+00 6.00297402E-03-2.49669461E-06 3 1.36758705E-10 1.03915796E-13 9.56681068E+03 7.44010148E+00 4 CH4(s) (adjust) C 1H 4NI 1 0 500.00 2000.00 2000.00 1 3.47651462E-01 9.92277358E-03-2.01747493E-06-1.06404583E-09 4.18759375E-13 2 -1.38997273E+04-4.61646253E+00 3.47651462E-01 9.92277358E-03-2.01747493E-06 3 -1.06404583E-09 4.18759375E-13-1.38997273E+04-4.61646253E+00 4 O(s) (adjust) O 1NI 1 0 0 500.00 2000.00 2000.00 1 9.33885773E-01 1.49287485E-03-1.51153811E-06 7.60133452E-10-1.42499395E-13 2 -2.88011883E+04-3.47247502E+00 9.33885773E-01 1.49287485E-03-1.51153811E-06 3 7.60133452E-10-1.42499395E-13-2.88011883E+04-3.47247502E+00 4 CO2(s) (adjust) C 1O 2NI 1 0 500.00 2000.00 2000.00 1 2.15782085E+00 8.85798101E-03-7.33295570E-06 3.01455469E-09-4.83617407E-13 2 -5.17211366E+04-3.96778204E-01 2.15782085E+00 8.85798101E-03-7.33295570E-06 3 3.01455469E-09-4.83617407E-13-5.17211366E+04-3.96778204E-01 4 HCO(s) (adjust) C 1H 1O 1NI 1 500.00 2000.00 2000.00 1 1.42054865E+00 6.41898600E-03-3.25611216E-06 6.60406470E-10-1.25958802E-14 2 -1.72299589E+04-1.34060408E+00 1.42054865E+00 6.41898600E-03-3.25611216E-06 3 6.60406470E-10-1.25958802E-14-1.72299589E+04-1.34060408E+00 4 END REACTIONS KJOULES/MOLE H2 + 2NI(s) => 2H(s) 1.000E-002 0.00 0.0 STICK 2H(s) => H2 + 2NI(s) 2.545E+019 0.00 81.2 O2 + 2NI(s) => 2O(s) 1.000E-002 0.00 0.0 STICK 2O(s) => O2 + 2NI(s) 4.283E+023 0.00 474.9 CH4 + NI(s) => CH4(s) 8.000E-003 0.00 0.0 STICK CH4(s) => CH4 + NI(s) 8.705E+015 0.00 37.5 H2O + NI(s) => H2O(s) 1.000E-001 0.00 0.0 STICK H2O(s) => H2O + NI(s) 3.732E+012 0.00 60.8 CO2 + NI(s) => CO2(s) 1.000E-005 0.00 0.0 STICK CO2(s) => CO2 + NI(s) 6.447E+007 0.00 26.0 CO + NI(s) => CO(s) 5.000E-001 0.00 0.0 STICK CO(s) => CO + NI(s) 3.563E+011 0.00 111.3 COV /CO(s) 0.000E+000 0.00 -50.0/ H(s) + O(s) => NI(s) + OH(s) 5.000E+022 0.00 97.9 NI(s) + OH(s) => H(s) + O(s) 1.781E+021 0.00 36.1 H(s) + OH(s) => NI(s) + H2O(s) 3.000E+020 0.00 42.7 NI(s) + H2O(s) => H(s) + OH(s) 2.271E+021 0.00 91.8 2OH(s) => H2O(s) + O(s) 3.000E+021 0.00 100.0 H2O(s) + O(s) => 2OH(s) 6.373E+023 0.00 210.9 C(s) + O(s) => NI(s) + CO(s) 5.200E+023 0.00 148.1 NI(s) + CO(s) => C(s) + O(s) 1.354E+022 -3.00 116.1 COV /CO(s) 0.000E+000 0.00 -50.0/ CO(s) + O(s) => NI(s) + CO2(s) 2.000E+019 0.00 123.6 COV /CO(s) 0.000E+000 0.00 -50.0/ NI(s) + CO2(s) => CO(s) + O(s) 4.653E+023 -1.00 89.3 NI(s) + HCO(s) => H(s) + CO(s) 3.700E+021 0.00 0.0 COV /CO(s) 0.000E+000 0.00 50.0/ H(s) + CO(s) => NI(s) + HCO(s) 4.019E+020 -1.00 132.2 NI(s) + HCO(s) => CH(s) + O(s) 3.700E+024 -3.00 95.8 CH(s) + O(s) => NI(s) + HCO(s) 4.604E+020 0.00 110.0 NI(s) + CH4(s) => H(s) + CH3(s) 3.700E+021 0.00 57.7 H(s) + CH3(s) => NI(s) + CH4(s) 6.034E+021 0.00 61.6 NI(s) + CH3(s) => H(s) + CH2(s) 3.700E+024 0.00 100.0 H(s) + CH2(s) => NI(s) + CH3(s) 1.293E+023 0.00 55.3 NI(s) + CH2(s) => H(s) + CH(s) 3.700E+024 0.00 97.1 H(s) + CH(s) => NI(s) + CH2(s) 4.089E+024 0.00 79.2 NI(s) + CH(s) => H(s) + C(s) 3.700E+021 0.00 18.8 H(s) + C(s) => NI(s) + CH(s) 4.562E+022 0.00 161.1 CH4(s) + O(s) => OH(s) + CH3(s) 1.700E+024 0.00 88.3 OH(s) + CH3(s) => CH4(s) + O(s) 9.876E+022 0.00 30.4 CH3(s) + O(s) => OH(s) + CH2(s) 3.700E+024 0.00 130.1 OH(s) + CH2(s) => CH3(s) + O(s) 4.607E+021 0.00 23.6 CH2(s) + O(s) => OH(s) + CH(s) 3.700E+024 0.00 126.8 OH(s) + CH(s) => CH2(s) + O(s) 1.457E+023 0.00 47.1 CH(s) + O(s) => OH(s) + C(s) 3.700E+021 0.00 48.1 OH(s) + C(s) => CH(s) + O(s) 1.625E+021 0.00 128.6 END