From d1029224fbcfc4c33369d344edb2d1353b051134 Mon Sep 17 00:00:00 2001 From: Dave Goodwin Date: Sun, 5 Nov 2006 15:54:12 +0000 Subject: [PATCH] added mechanism for partial oxidation of methane on platinum from the Deutschmann group --- data/inputs/methane_pox_on_pt.cti | 291 ++++++++++++++++++++++++++++++ 1 file changed, 291 insertions(+) create mode 100644 data/inputs/methane_pox_on_pt.cti diff --git a/data/inputs/methane_pox_on_pt.cti b/data/inputs/methane_pox_on_pt.cti new file mode 100644 index 000000000..b418f3017 --- /dev/null +++ b/data/inputs/methane_pox_on_pt.cti @@ -0,0 +1,291 @@ +# +# SURFACE MECHANISM OF POX of CH4 on PT wire gauze +# +#*********************************************************************** +#**** * +#**** CH4-O2 SURFACE MECHANISM ON PT * +#**** * +#**** Version 1.0 Spring 2005 * +#**** * +#**** Raul Quiceno, Olaf Deutschmann, IWR, Heidelberg University, * +#**** Germany * +#**** Contact: mail@detchem.com (O. Deutschmann) * +#**** * +#**** Reference: * +#**** R. Quiceno, J. Perez-Ramyrez, J. Warnatz, O. Deutschmann. * +#**** Appl. Catal. A: General (2006) * +#**** www.detchem.com/mechanisms * +#**** * +#**** * +#**** The kinetic data of the backward reactions of * +#**** reactions in Section 3 are calculated * +#**** from thermodynamics (k_b = k_f /K) * +#**** * +#**** Surface site density: 2.72E-9 mol/cm**2 * +#**** * +#---------------------------------------------------------------------- + +units(length = "cm", time = "s", quantity = "mol", act_energy = "J/mol") + + +# +# Define a gas mixture. This contains only major species, and no +# gas-phase reactions. +# +ideal_gas(name = "gas", + elements = "O H C N Ar", + species = """H2 O2 H2O CH4 CO CO2 AR N2""", + transport = 'Mix', + options = ['skip_undeclared_elements', + 'skip_undeclared_species'], + initial_state = state(temperature = 300.0, pressure = OneAtm, + mole_fractions = 'CH4:0.095, O2:0.21, AR:0.79') + ) + + +# +# The platinum surface. +ideal_interface(name = "Pt_surf", + elements = " Pt H O C ", + species = """ PT(S) H(S) + H2O(S) OH(S) CO(S) CO2(S) CH3(S) + CH2(S) CH(S) C(S) O(S) """, + phases = "gas", + site_density = 2.72e-9, + reactions = "all", + options = ['skip_undeclared_elements', + 'skip_undeclared_species'], + initial_state = state(temperature = 900.0, + coverages = 'O(S):0.00, PT(S):0.01, H(S):0.99') + ) + + + +#------------------------------------------------------------------------------- +# Species data +#------------------------------------------------------------------------------- + +species(name = "CH4", + atoms = " C:1 H:4 ", + thermo = ( + NASA( [ 300.00, 1000.00], [ 7.787414790E-01, 1.747668350E-02, + -2.783409040E-05, 3.049708040E-08, -1.223930680E-11, + -9.825228520E+03, 1.372219470E+01] ), + NASA( [ 1000.00, 5000.00], [ 1.683478830E+00, 1.023723560E-02, + -3.875128640E-06, 6.785584870E-10, -4.503423120E-14, + -1.008078710E+04, 9.623394970E+00] ) + ) + ) + +species(name = "O2", + atoms = " O:2 ", + thermo = ( + NASA( [ 300.00, 1000.00], [ 3.783713500E+00, -3.023363400E-03, + 9.949275100E-06, -9.818910100E-09, 3.303182500E-12, + -1.063810700E+03, 3.641634500E+00] ), + NASA( [ 1000.00, 5000.00], [ 3.612213900E+00, 7.485316600E-04, + -1.982064700E-07, 3.374900800E-11, -2.390737400E-15, + -1.197815100E+03, 3.670330700E+00] ) + ) + ) + +species(name = "CO", + atoms = " C:1 O:1 ", + thermo = ( + NASA( [ 300.00, 1000.00], [ 3.262451650E+00, 1.511940850E-03, + -3.881755220E-06, 5.581944240E-09, -2.474951230E-12, + -1.431053910E+04, 4.848896980E+00] ), + NASA( [ 1000.00, 5000.00], [ 3.025078060E+00, 1.442688520E-03, + -5.630827790E-07, 1.018581330E-10, -6.910951560E-15, + -1.426834960E+04, 6.108217720E+00] ) + ) + ) + +species(name = "CO2", + atoms = " C:1 O:2 ", + thermo = ( + NASA( [ 300.00, 1000.00], [ 2.275724650E+00, 9.922072290E-03, + -1.040911320E-05, 6.866686780E-09, -2.117280090E-12, + -4.837314060E+04, 1.018848800E+01] ), + NASA( [ 1000.00, 5000.00], [ 4.453622820E+00, 3.140168730E-03, + -1.278410540E-06, 2.393996670E-10, -1.669033190E-14, + -4.896696090E+04, -9.553958770E-01] ) + ) + ) + +species(name = "H2", + atoms = " H:2 ", + thermo = ( + NASA( [ 300.00, 1000.00], [ 3.355351400E+00, 5.013614400E-04, + -2.300690800E-07, -4.790532400E-10, 4.852258500E-13, + -1.019162600E+03, -3.547722800E+00] ), + NASA( [ 1000.00, 5000.00], [ 3.066709500E+00, 5.747375500E-04, + 1.393831900E-08, -2.548351800E-11, 2.909857400E-15, + -8.654741200E+02, -1.779842400E+00] ) + ) + ) + +species(name = "H2O", + atoms = " H:2 O:1 ", + thermo = ( + NASA( [ 300.00, 1000.00], [ 4.167723400E+00, -1.811497000E-03, + 5.947128800E-06, -4.869202100E-09, 1.529199100E-12, + -3.028996900E+04, -7.313547400E-01] ), + NASA( [ 1000.00, 5000.00], [ 2.611047200E+00, 3.156313000E-03, + -9.298543800E-07, 1.333153800E-10, -7.468935100E-15, + -2.986816700E+04, 7.209126800E+00] ) + ) + ) + +species(name = "AR", + atoms = " Ar:1 ", + thermo = ( + NASA( [ 300.00, 1000.00], [ 2.500000000E+00, 0.000000000E+00, + 0.000000000E+00, 0.000000000E+00, 0.000000000E+00, + -7.453749800E+02, 4.366000600E+00] ), + NASA( [ 1000.00, 5000.00], [ 2.500000000E+00, 0.000000000E+00, + 0.000000000E+00, 0.000000000E+00, 0.000000000E+00, + -7.453750200E+02, 4.366000600E+00] ) + ) + ) + + +#------------------------------------------------------------------------------- +# Reaction data +#------------------------------------------------------------------------------- + +# Adsorption reactions + +surface_reaction("H2 + 2 PT(S) => 2 H(S)", + stick(0.046, 0, 0, + coverage = ['PT(S)',0.0, -1.0, 0.0])) + +surface_reaction( "O2 + 2 PT(S) => 2 O(S)", + Arrhenius(1.89000E+21, -0.5, 0)) + +surface_reaction( "CH4 + 2 PT(S) => CH3(S) + H(S)", + stick(0.0009, 0.0, 72000.0)) + +surface_reaction( "CH4 + PT(S) + O(S) => CH3(S) + OH(S)", + Arrhenius(5.0e18, 0.7, 42000.0, + coverage = ['O(S)', 0.0, 0.0, 8000])) + +surface_reaction( "CH4 + PT(S) + OH(S) => CH3(S) + H2O(S)", + stick(1.0, 0.0, 10000.0)) + +surface_reaction( "H2O + PT(S) => H2O(S)", + stick(7.50000E-01, 0, 0)) + +surface_reaction( "CO2 + PT(S) => CO2(S)", + stick(0.005, 0, 0)) + +surface_reaction( "CO + PT(S) => CO(S)", + stick(0.84, 0, 0)) + + +# Desorption reactions + +surface_reaction( "2 H(S) => H2 + 2 PT(S)", + Arrhenius(3.70000E+21, 0, 67400, + coverage = ['H(S)', 0.0, 0.0, -10000.0])) + +surface_reaction( "2 O(S) => O2 + 2 PT(S)", + Arrhenius(3.70000E+21, 0, 235500, + coverage = ['O(S)', 0.0, 0.0, -188300.0]) ) + +surface_reaction( "H2O(S) => H2O + PT(S)", [4.50000E+12, 0, 41800]) + +surface_reaction( "CO(S) => CO + PT(S)", + Arrhenius(1.00000E+15, 0, 146000, + coverage = ['CO(S)', 0.0, 0.0, -33000.0])) + +surface_reaction( "CO2(S) => CO2 + PT(S)", [1.00000E+13, 0, 27100]) + + +# surface reactions + +surface_reaction( "C(S) + O(S) => CO(S) + PT(S)", [3.70000E+19, 0, 0]) + +surface_reaction( "CO(S) + PT(S) => C(S) + O(S)", + Arrhenius(3.70000E+19, 0, 236500, + coverage = ['CO(S)', 0.0, 0.0, -33000])) + +# error in paper. This reaction is consistent with the version in the +# file on the DETCHEM mechanisms web site, but differs from the +# version in the Applied Catalysis paper. +surface_reaction( "CO(S) + O(S) => CO2(S) + PT(S)", + Arrhenius(3.70000E+21, 0, 117600, + coverage = ['CO(S)', 0.0, 0.0, -33000])) + +# minor diff w paper +surface_reaction( "CO2(S) + PT(S) => CO(S) + O(S)", + Arrhenius(3.70000E+19, 0, 173300, + coverage = ['O(S)', 0.0, 0.0, 94100])) + +surface_reaction( "CO(S) + OH(S) => CO2(S) + H(S)", + Arrhenius(1.0000E+19, 0, 38700, + coverage = ['CO(S)', 0.0, 0.0, -30000])) + +surface_reaction( "CO2(S) + H(S) => CO(S) + OH(S)", + Arrhenius(1.0000E+19, 0, 8400)) + +surface_reaction( "CH3(S) + PT(S) => CH2(S) + H(S)", + Arrhenius(1.2600E+22, 0, 70300)) + +surface_reaction( "CH2(S) + H(S) => CH3(S) + PT(S)", + Arrhenius(3.0900E+22, 0, 0, + coverage = ['H(S)', 0.0, 0.0, -2800])) + +surface_reaction( "CH2(S) + PT(S) => CH(S) + H(S)", + Arrhenius(7.3100E+22, 0, 58900, + coverage = ['C(S)', 0.0, 0.0, 50000])) +surface_reaction( "CH(S) + H(S) => CH2(S) + PT(S)", + Arrhenius(3.0900E+22, 0, 0, + coverage = ['H(S)', 0.0, 0.0, -2800])) + + +surface_reaction( "CH(S) + PT(S) => C(S) + H(S)", + Arrhenius(3.0900E+22, 0, 0, + coverage = ['H(S)', 0.0, 0.0, -2800])) + +surface_reaction( "C(S) + H(S) => CH(S) + PT(S)", + Arrhenius(1.2500E+22, 0, 138000)) + +surface_reaction( "H(S) + O(S) => OH(S) + PT(S)", + Arrhenius(1.2800E+21, 0, 11200)) + +surface_reaction( "OH(S) + PT(S) => H(S) + O(S)", + Arrhenius(7.39e19, 0, 77300, + coverage = ['O(S)', 0.0, 0.0, -73200])) + +surface_reaction( "H2O(S) + PT(S) => H(S) + OH(S)", + Arrhenius(1.15e19, 0, 101400, + coverage = ['O(S)', 0.0, 0.0, 167300])) + +surface_reaction( "2 OH(S) => H2O(S) + O(S)", + Arrhenius(7.4e20, 0, 74000)) + +surface_reaction( "H2O(S) + O(S) => 2 OH(S)", + Arrhenius(1.0e20, 0, 43100, + coverage = ['O(S)', 0.0, 0.0, 240600])) + +surface_reaction( "H2 + C(S) => CH2(S)", + stick(0.04, 0, 29700, + coverage = ['C(S)', 0.0, 0.0, 4600])) + +surface_reaction( "CH2(S) => C(S) + H2", + Arrhenius(7.69e13, 0, 25100, + coverage = ['C(S)', 0.0, 0.0, 50000])) + +surface_reaction( "H(S) + OH(S) => H2O(S) + PT(S)", + Arrhenius(2.04e21, 0, 66220)) + +surface_reaction( "CH3(S) + H(S) => CH4 + 2 PT(S)", + Arrhenius(3.3e21, 0, 50000, + coverage = ['H(S)', 0.0, 0.0, -2800])) + +surface_reaction( "CH3(S) + H2O(S) => CH4 + OH(S) + PT(S)", + Arrhenius(3.7e21, 0, 110600)) + +surface_reaction( "CH3(S) + OH(S) => CH4 + O(S) + PT(S)", + Arrhenius(3.7e21, 0, 87900))