! --------------------------------------------------------------------------------------------------------------------------------------- # ! --------------------------------------------------------------------------------------------------------------------------------------- # ! Reduced mechanism for CH4 and TiCL4 oxidation - Reaction file ! Original reactions taken from: ! - West, R. H. et al., First-principles thermochemistry for the production of TiO2 from TiCl4. J. Phys. Chem. A 2007a, 111, 3560–3565. ! - West, R. H. et al., A detailed kinetic model for combustion synthesis of titania from TiCl4. Combust. Flame 2009, 156, 1764–1770. ! - Bowman, C. et al. GRI-Mech2.11,http://www.me.berkeley. edu/gri_mech/ ! - Shah, J. J. and Fox, R. O. Computational fluid dynamics simulation of chemical reactors: Application of in situ adaptive tabulation ! to methane thermochlorination chemistry. Ind. Eng. Chem. Res. 1999, 38, 4200–4212. ! Detailed on the reduction procedure can be found in Mehta, Fox, Pepiot, IECR 2015 (in review) ! --------------------------------------------------------------------------------------------------------------------------------------- # ! --------------------------------------------------------------------------------------------------------------------------------------- # ELEMENTS N AR H O CL TI C END SPECIES N2 AR H H2 H2O O OH CL2 CLO CL TICL3 TIOCL2 H2O2 O2 TIO2CL3 HO2 TICL2 CH HCO CH2 CH2O CH2(S) CH3OH CO CH3 CH4 CH3O C2H6 C2H5 C2H4 HCL CO2 C2H2 C2H3 CCL4 CCL3 CHCL3 CHCL2 CH2CL2 CH2CL CH3CL TICL4 TIOCL3 TI2O2CL6 TI2O2CL4 TIO2CL2 TI2O3CL3 TI3O4CL4 TI2O3CL2 TI5O6CL8 TIO2(RU) END REACTIONS 2H+M=>H2+M 1.000e+18 -1.000 0.00 AR/0.63/ H2/0.00/ H2O/0.00/ CH4/2.00/ C2H6/3.00/ CO2/0.00/ 2H+H2O=>H2+H2O 6.000e+19 -1.250 0.00 O+H2<=>H+OH 5.000e+04 2.670 6290.63 REV / 2.974e+04 2.635 4404.88 / O+CL2<=>CLO+CL 4.460e+12 0.000 3279.16 REV / 7.504e+12 -0.117 4780.11 / TICL3+O=>TIOCL2+CL 1.000e+13 0.000 0.00 2OH(+M)<=>H2O2(+M) 7.400e+13 -0.370 0.00 AR/0.70/ H2/2.00/ H2O/6.00/ CO/1.50/ CH4/2.00/ C2H6/3.00/ CO2/2.00/ LOW / 2.300e+18 -0.900 -1700.05 / TROE/ 0.7346 94.00 1756.00 5182.00 / REV / 8.285e+23 -1.921 50478.01 / 2OH<=>O+H2O 3.570e+04 2.400 -2109.94 REV / 6.657e+05 2.330 15272.47 / H+OH+M=>H2O+M 2.200e+22 -2.000 0.00 AR/0.38/ H2/0.73/ H2O/3.65/ CH4/2.00/ C2H6/3.00/ OH+H2<=>H+H2O 2.160e+08 1.510 3429.73 REV / 2.395e+09 1.405 18926.86 / TICL3+O2(+M)<=>TIO2CL3(+M) 1.925e+35 -6.577 9890.06 LOW / 1.060e+36 -6.319 0.00 / TROE/ 0.1183 26.93 100000.00 5219.00 / REV / 1.076e+46 -8.769 67304.02 / CL+O2<=>CLO+O 8.790e+14 0.000 55043.02 REV / 2.639e+14 -0.073 -4825.53 / H+2O2=>HO2+O2 3.000e+20 -1.720 0.00 TICL2+O2=>TIOCL2+O 1.000e+13 0.000 0.00 H+O2<=>O+OH 8.300e+13 0.000 14412.05 REV / 1.646e+11 0.437 -2944.55 / H+O2+M<=>HO2+M 2.800e+18 -0.860 0.00 N2/0.00/ AR/0.00/ H2O/0.00/ O2/0.00/ CO/0.75/ C2H6/1.50/ CO2/1.50/ REV / 4.033e+18 -0.872 48924.47 / H+O2+AR=>HO2+AR 7.000e+17 -0.800 0.00 H+O2+H2O<=>HO2+H2O 9.380e+18 -0.760 0.00 REV / 1.351e+19 -0.772 48924.47 / H+O2+N2<=>HO2+N2 3.750e+20 -1.720 0.00 REV / 5.402e+20 -1.732 48924.47 / 2HO2=>O2+H2O2 4.200e+14 0.000 12000.48 DUPLICATE H+HO2=>O+H2O 3.970e+12 0.000 670.89 OH+HO2<=>O2+H2O 2.900e+13 0.000 -500.00 REV / 5.218e+13 0.257 69598.47 / H+HO2<=>O2+H2 2.800e+13 0.000 1068.12 REV / 4.543e+12 0.362 55664.44 / O+HO2=>OH+O2 2.000e+13 0.000 0.00 H+HO2=>2OH 1.340e+14 0.000 635.04 2HO2=>O2+H2O2 1.300e+11 0.000 -1630.02 DUPLICATE OH+H2O2=>HO2+H2O 1.750e+12 0.000 320.03 DUPLICATE OH+H2O2<=>HO2+H2O 5.800e+14 0.000 9560.23 REV / 2.181e+13 0.502 41037.28 / DUPLICATE H+H2O2<=>HO2+H2 1.210e+07 2.000 5200.76 REV / 4.103e+04 2.607 21175.91 / O+H2O2=>OH+HO2 9.630e+06 2.000 4000.96 CH+O2=>O+HCO 3.300e+13 0.000 0.00 CH+H2<=>H+CH2 1.107e+08 1.790 1669.93 REV / 1.802e+09 1.498 -1035.37 / CH+H2O=>H+CH2O 1.713e+13 0.000 -755.02 CH2(S)+H2O(+M)<=>CH3OH(+M) 2.000e+13 0.000 0.00 H2/2.00/ H2O/6.00/ CO/1.50/ CH4/2.00/ C2H6/3.00/ CO2/2.00/ LOW / 2.700e+38 -6.300 3099.90 / TROE/ 0.1507 134.00 2383.00 7265.00 / REV / 2.340e+45 -7.610 97657.74 / CH2(S)+AR<=>CH2+AR 9.000e+12 0.000 599.90 REV / 6.562e+12 -0.062 9514.82 / CH2(S)+O2=>H+OH+CO 2.800e+13 0.000 0.00 CH2(S)+O2=>CO+H2O 1.200e+13 0.000 0.00 CH2(S)+H2O<=>CH2+H2O 3.000e+13 0.000 0.00 REV / 2.187e+13 -0.062 8914.91 / CH2(S)+H2<=>CH3+H 7.000e+13 0.000 0.00 REV / 2.256e+16 -0.582 16324.09 / CH2(S)+N2<=>CH2+N2 1.500e+13 0.000 599.90 REV / 1.094e+13 -0.062 9514.82 / CH2+O2=>OH+HCO 1.320e+13 0.000 1500.00 OH+CH2=>H+CH2O 2.000e+13 0.000 0.00 CH2+H2<=>H+CH3 5.000e+05 2.000 7229.92 REV / 2.210e+08 1.481 14639.10 / O+CH2=>H+HCO 8.000e+13 0.000 0.00 OH+CH2<=>CH+H2O 1.130e+07 2.000 2999.52 REV / 7.698e+06 2.188 21202.20 / H+CH2(+M)=>CH3(+M) 2.500e+16 -0.800 0.00 AR/0.70/ H2/2.00/ H2O/6.00/ CO/1.50/ CH4/2.00/ C2H6/3.00/ CO2/2.00/ LOW / 3.200e+27 -3.140 1229.92 / TROE/ 0.68 78.00 1995.00 5590.00 / H+CH3(+M)<=>CH4(+M) 1.270e+16 -0.630 382.89 AR/0.70/ H2/2.00/ H2O/6.00/ CO/1.50/ CH4/2.00/ C2H6/3.00/ CO2/2.00/ LOW / 2.477e+33 -4.760 2440.25 / TROE/ 0.783 74.00 2941.00 6964.00 / REV / 1.009e+36 -4.921 108126.20 / HO2+CH3=>OH+CH3O 2.000e+13 0.000 0.00 HO2+CH3<=>O2+CH4 1.000e+12 0.000 0.00 REV / 2.827e+14 -0.149 56763.86 / CH4+HO2=>H2O2+CH3 1.447e+05 2.565 23322.18 2CH3(+M)<=>C2H6(+M) 2.120e+16 -0.970 619.98 AR/0.70/ H2/2.00/ H2O/6.00/ CO/1.50/ CH4/2.00/ C2H6/3.00/ CO2/2.00/ LOW / 1.770e+50 -9.670 6218.93 / TROE/ 0.5325 151.00 1038.00 4970.00 / REV / 3.363e+58 -11.055 98207.46 / CH3+O2<=>O+CH3O 2.675e+13 0.000 28800.19 REV / 4.477e+15 -0.476 1385.99 / O+CH3=>H+CH2O 8.430e+13 0.000 0.00 OH+CH3<=>CH2+H2O 5.600e+07 1.600 5420.65 REV / 1.405e+06 2.015 13508.60 / CH3+O2=>OH+CH2O 3.600e+10 0.000 8938.81 2CH3<=>H+C2H5 4.990e+12 0.100 10599.90 REV / 7.631e+17 -1.076 1795.65 / OH+CH3(+M)=>CH3OH(+M) 6.300e+13 0.000 0.00 H2/2.00/ H2O/6.00/ CO/1.50/ CH4/2.00/ C2H6/3.00/ CO2/2.00/ LOW / 2.700e+38 -6.300 3099.90 / TROE/ 0.2105 83.50 5398.00 8370.00 / OH+CH3<=>CH2(S)+H2O 2.501e+13 0.000 0.00 REV / 8.606e+11 0.477 -827.20 / CH2+CH3=>H+C2H4 4.000e+13 0.000 0.00 OH+CH4<=>CH3+H2O 1.000e+08 1.600 3119.02 REV / 6.366e+05 2.007 16450.76 / CH+CH4=>H+C2H4 6.000e+13 0.000 0.00 O+CH4<=>OH+CH3 1.020e+09 1.500 8599.43 REV / 3.482e+05 1.977 4548.28 / H+CH4<=>CH3+H2 6.600e+08 1.620 10841.30 REV / 3.788e+05 2.132 8673.52 / CH2+CH4<=>2CH3 2.460e+06 2.000 8269.60 REV / 6.242e+05 1.992 13513.38 / CH4+CL<=>CH3+HCL 1.000e+13 0.000 2109.94 REV / 2.670e+09 0.542 -993.79 / CH2(S)+CH4<=>2CH3 1.600e+13 0.000 -570.03 REV / 2.960e+12 -0.070 13589.87 / O+CO+M=>CO2+M 6.020e+14 0.000 2999.52 AR/0.50/ H2/2.00/ H2O/6.00/ O2/6.00/ CO/1.50/ CH4/2.00/ C2H6/3.00/ CO2/3.50/ CH2(S)+CO<=>CH2+CO 9.000e+12 0.000 0.00 REV / 6.562e+12 -0.062 8914.91 / OH+CO<=>H+CO2 4.760e+07 1.228 70.03 REV / 2.627e+14 -0.051 26242.83 / O+HCO=>H+CO2 3.000e+13 0.000 0.00 HCO+M<=>H+CO+M 1.870e+17 -1.000 17000.48 H2/2.00/ H2O/0.00/ CO/1.50/ CH4/2.00/ C2H6/3.00/ CO2/2.00/ REV / 3.531e+16 -0.767 1279.64 / O+HCO=>OH+CO 3.000e+13 0.000 0.00 HCO+H2O<=>H+CO+H2O 2.244e+18 -1.000 17000.48 REV / 4.237e+17 -0.767 1279.64 / OH+HCO=>H2O+CO 5.000e+13 0.000 0.00 HCO+O2=>HO2+CO 7.600e+12 0.000 400.10 H+HCO=>H2+CO 7.340e+13 0.000 0.00 CH3+HCO=>CH4+CO 2.648e+13 0.000 0.00 O2+CH2O=>HO2+HCO 1.000e+14 0.000 40009.56 CH3O(+M)=>CH2O+H(+M) 4.770e+13 0.132 25119.50 H2/2.00/ H2O/6.00/ CO/1.50/ CH4/2.00/ C2H6/3.00/ CO2/2.00/ LOW / 1.943e+32 -5.122 28083.17 / TROE/ 0.758 94.00 1555.00 4200.00 / HO2+CH2O=>HCO+H2O2 1.000e+12 0.000 7999.52 O+CH2O=>OH+HCO 3.900e+13 0.000 3539.67 CH3+CH2O=>HCO+CH4 3.320e+03 2.810 5860.42 H+CH2O=>HCO+H2 2.300e+10 1.050 3274.38 OH+CH2O=>HCO+H2O 3.430e+09 1.180 -446.94 H+CH3O=>H2+CH2O 2.000e+13 0.000 0.00 H+CH3O=>CH2(S)+H2O 1.600e+13 0.000 0.00 H+CH3O=>OH+CH3 3.200e+13 0.000 0.00 CH3O+O2=>HO2+CH2O 4.280e-13 7.600 -3530.11 OH+CH3OH<=>CH3O+H2O 6.300e+06 2.000 1500.00 REV / 4.622e+06 2.165 16723.23 / O+CH3OH=>OH+CH3O 1.300e+05 2.500 5000.00 H+CH3OH<=>CH3O+H2 4.200e+06 2.100 4870.94 REV / 2.779e+05 2.370 4596.08 / CH3+CH3OH<=>CH3O+CH4 1.000e+07 1.500 9940.25 REV / 1.153e+09 1.259 11830.78 / CH2(S)+CO2<=>CH2+CO2 7.000e+12 0.000 0.00 REV / 5.104e+12 -0.062 8914.91 / CH2(S)+CO2=>CO+CH2O 1.400e+13 0.000 0.00 H+C2H2(+M)<=>C2H3(+M) 5.600e+12 0.000 2399.62 AR/0.70/ H2/2.00/ H2O/6.00/ CO/1.50/ CH4/2.00/ C2H6/3.00/ CO2/2.00/ LOW / 3.800e+40 -7.270 7220.36 / TROE/ 0.7507 98.50 1302.00 4167.00 / REV / 8.420e+39 -7.098 42304.02 / OH+C2H2=>CH3+CO 4.830e-04 4.000 -2000.00 O+C2H2=>CO+CH2 1.020e+07 2.000 1900.10 C2H3+O2=>HCO+CH2O 3.980e+12 0.000 -239.96 H+C2H3=>H2+C2H2 3.000e+13 0.000 0.00 H+C2H4<=>C2H3+H2 1.325e+06 2.530 12239.48 REV / 5.572e+02 3.016 4249.52 / H+C2H4(+M)<=>C2H5(+M) 1.080e+12 0.454 1820.03 AR/0.70/ H2/2.00/ H2O/6.00/ CO/1.50/ CH4/2.00/ C2H6/3.00/ CO2/2.00/ LOW / 1.200e+42 -7.620 6969.41 / TROE/ 0.9753 210.00 984.00 4374.00 / REV / 2.242e+42 -7.741 43140.54 / O+C2H4=>CH3+HCO 1.920e+07 1.830 219.89 OH+C2H4<=>C2H3+H2O 3.600e+06 2.000 2500.00 REV / 1.679e+04 2.381 10009.56 / CH3+C2H4<=>C2H3+CH4 2.270e+05 2.000 9199.33 REV / 1.663e+05 1.974 3377.15 / C2H4(+M)<=>H2+C2H2(+M) 8.000e+12 0.440 88766.73 AR/0.70/ H2/2.00/ H2O/6.00/ CO/1.50/ CH4/2.00/ C2H6/3.00/ CO2/2.00/ LOW / 7.000e+50 -9.310 99856.60 / TROE/ 0.7345 180.00 1035.00 5417.00 / REV / 1.328e+48 -8.996 56787.76 / O+C2H5=>CH3+CH2O 1.320e+14 0.000 0.00 H+C2H5(+M)<=>C2H6(+M) 5.210e+17 -0.990 1580.07 AR/0.70/ H2/2.00/ H2O/6.00/ CO/1.50/ CH4/2.00/ C2H6/3.00/ CO2/2.00/ LOW / 1.990e+41 -7.080 6684.99 / TROE/ 0.8422 125.00 2219.00 6882.00 / REV / 2.472e+44 -7.289 107456.98 / C2H5+O2=>HO2+C2H4 8.400e+11 0.000 3874.28 H+C2H6<=>C2H5+H2 1.150e+08 1.900 7531.07 REV / 2.163e+04 2.459 10258.13 / OH+C2H6=>C2H5+H2O 3.540e+06 2.120 869.98 CH3+C2H6=>C2H5+CH4 6.140e+06 1.740 10449.33 O+C2H6=>OH+C2H5 8.980e+07 1.920 5690.73 2CL+M<=>CL2+M 2.230e+14 0.000 -1798.28 REV / 2.789e+15 -0.078 55807.84 / CL2<=>2CL 1.849e+12 0.000 57982.79 REV / 1.478e+11 0.078 369.98 / CCL4<=>CCL3+CL 1.000e+16 0.000 70936.90 REV / 1.699e+09 1.193 641.25 / CCL4+CL<=>CCL3+CL2 1.000e+14 0.000 12179.73 REV / 2.125e+08 1.115 -498.80 / CHCL3+CL<=>CCL3+HCL 1.000e+13 0.000 460.09 REV / 6.975e+09 0.585 7844.17 / CHCL3+CL<=>CHCL2+CL2 1.000e+14 0.000 18879.06 REV / 1.550e+09 0.860 -608.03 / CHCL3<=>CHCL2+CL 1.000e+16 0.000 77629.06 REV / 1.239e+10 0.938 532.03 / CH2CL2<=>CH2CL+CL 1.000e+16 0.000 81142.45 REV / 1.143e+11 0.741 444.79 / CL2+CH2CL=>CL+CH2CL2 1.429e+10 0.663 -695.27 CH2CL2+CL<=>CHCL2+HCL 1.000e+13 0.000 460.09 REV / 5.369e+09 0.427 4856.60 / CL2+CH3=>CL+CH3CL 1.608e+11 0.505 -1109.46 CH3CL<=>CH3+CL 1.000e+16 0.000 84369.02 REV / 1.285e+12 0.583 30.59 / CH3CL+CL<=>CH2CL+HCL 1.000e+13 0.000 460.09 REV / 1.384e+10 0.281 2691.20 / TICL4+M<=>TICL3+CL+M 5.400e+18 0.000 80234.23 REV / 1.171e+12 1.167 -12660.13 / 2TICL3<=>TICL2+TICL4 9.600e+12 0.000 8358.03 REV / 6.660e+15 -0.388 392.45 / TICL3+CL2<=>TICL4+CL 1.000e+13 0.000 0.00 REV / 3.686e+18 -1.090 35277.25 / TICL3+M<=>TICL2+CL+M 7.700e+18 0.000 92423.52 REV / 1.159e+15 0.780 -8446.46 / TICL3+CLO<=>TICL4+O 1.000e+13 0.000 0.00 REV / 2.191e+18 -0.972 33795.41 / O2+TICL3=>O+TIOCL3 1.208e+09 1.230 24928.30 TIOCL3+O<=>TIO2CL3 1.000e+13 0.000 0.00 REV / 1.226e+19 -1.220 92232.31 / CL+TIO2CL3=>CLO+TIOCL3 5.825e+17 -1.025 33126.20 2TIOCL3<=>TI2O2CL6 1.000e+13 0.000 0.00 REV / 1.039e+27 -2.888 55162.52 / TIOCL2+CL<=>TIOCL3 1.000e+13 0.000 0.00 REV / 4.873e+18 -1.432 39149.14 / 2TIOCL2<=>TI2O2CL4 1.000e+13 0.000 0.00 REV / 6.313e+28 -3.054 86663.48 / TIO2CL2+CL<=>TICL3+O2 1.000e+13 0.000 0.00 REV / 2.501e+07 1.153 13522.94 / TIO2CL2+TICL3=>TI2O2CL4+CL 1.000e+13 0.000 0.00 TIO2CL2+CL<=>TIO2CL3 1.000e+13 0.000 0.00 REV / 2.538e+17 -1.298 80831.74 / TIO2CL2+TIOCL2<=>TI2O3CL3+CL 1.000e+13 0.000 0.00 REV / 3.818e+20 -1.717 34416.83 / CL2+TIO2CL2<=>CL+TIO2CL3 1.000e+13 0.000 0.00 REV / 2.029e+16 -1.220 23217.02 / TIO2CL2+CL<=>TIOCL2+CLO 1.000e+13 0.000 0.00 REV / 8.942e+06 1.160 8549.24 / TIO2CL2+O<=>TIOCL2+O2 1.000e+13 0.000 0.00 REV / 2.979e+07 1.233 68427.34 / TIO2CL3+TICL3<=>TI2O2CL6 1.000e+13 0.000 0.00 REV / 4.916e+26 -3.019 56955.07 / TI2O3CL3+TIOCL2<=>TI3O4CL4+CL 1.000e+13 0.000 0.00 REV / 1.211e+23 -1.727 40487.57 / TI2O3CL2+CL<=>TI2O3CL3 1.000e+13 0.000 0.00 REV / 3.202e+17 -1.333 49856.60 / TI2O2CL6+TI3O4CL4=>TI5O6CL8+CL2 1.000e+13 0.000 0.00 TI2O2CL4+TI3O4CL4=>TI5O6CL8 1.000e+13 0.000 0.00 TI5O6CL8+2O2=>5TIO2(RU)+4CL2 1.000e+25 0.000 0.00 TICL4+O2=>TIO2(RU)+2CL2 8.260e+04 0.000 20269.60 TICL3+O2=>TIO2(RU)+CL2+CL 8.260e+04 0.000 20269.60 TIO2CL3=>TIO2(RU)+CL2+CL 8.260e+04 0.000 20269.60 TI2O2CL4+O2=>2TIO2(RU)+2CL2 8.260e+04 0.000 20269.60 TI3O4CL4+O2=>3TIO2(RU)+2CL2 8.260e+04 0.000 20269.60 TI2O2CL6+O2=>2TIO2(RU)+3CL2 8.260e+04 0.000 20269.60 TICL2+O2=>TIO2(RU)+CL2 8.260e+04 0.000 20269.60 TIO2CL2=>TIO2(RU)+CL2 8.260e+04 0.000 20269.60 END