Gas-phase Kinetic Study of Pyrolysis in the System of CH4+C2H5OH+Ar

doi:10.15541/jim20240158

Abstract

Abstract:

Preparation of carbon-carbon composites through the chemical vapor infiltration (CVI) process, utilizing CH₄ and C₂H₅OH as precursors, can effectively improve the deposition rate and produce highly structured pyrolytic carbon. Understanding the reaction mechanism is essential for computational fluid dynamics (CFD) studies. Chemical reaction mechanisms typically involve numerous free radicals and reactions, and manually constructing such mechanisms based on experimental data alone risks omitting critical species and reactions. Hence, in this research, a thorough gas-phase pyrolysis kinetic mechanism for the CH₄+C₂H₅OH+Ar system was developed using the reaction mechanism generator (RMG). This mechanism included 31 core species and 214 core reactions, accurately predicting the evolution of major species' formation and consumption. The simulation results were consistent with experimental observations. Through a detailed analysis of the kinetics and sensitivity of reactants and critical products, reactions influencing the formation and consumption of crucial species were identified. Reaction pathway analysis further clarified relationships among different species, identifying core species within the mechanism. By simplifying the detailed mechanism based on sensitivity and rection pathway analysis at 1373 K and 10 kPa, a gas-phase kinetic mechanism was derived, composed of 18 species and 44 reactions. This streamlined model substantially boosts computational efficiency while retaining key species, providing a more convenient foundation for further CFD studies and applications.

Key words: carbon/carbon composite, gas-phase dynamic, mechanism analysis, mechanism simplification

CLC Number:

TB332

MA Yongjie, LIU Yongsheng, GUAN Kang, ZENG Qingfeng. Gas-phase Kinetic Study of Pyrolysis in the System of CH₄+C₂H₅OH+Ar[J]. Journal of Inorganic Materials, 2024, 39(11): 1235-1244.

Figures/Tables 11

References 28

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No.	Reaction	*A	n	E/(kJ·mol^-1)
1	C₂H₄+M<=>H+C₂H₃+M	3.98×10¹⁷	0	411.144
2	H+C₂H₄<=>H₂+C₂H₃	1.32×10⁷	2.5	47.168
3	H+H+M<=>H₂+M	1.0	0	0
4	CH₄+M<=>H+CH₃+M	1.0×10¹⁷	0	359.232
5	CH₃+C₂H₄<=>CH₄+C₂H₃	5.0×10¹²	0	54.428
6	H₂+CH₃<=>H+CH₄	2.75×10⁴	2.5	39.435
7	2CH₃+M<=>C₂H₆+M	3.08×10⁴¹	-7.0	11.568
8	CH₃+CH₄<=>H+C₂H₆	8.0×10¹³	2.0	167.472
9	C₂H₅<=>H+C₂H₄	2.04×10¹⁵	0	144.713
10	C₂H₆<=>H+C₂H₅	2.08×10³⁸	-7.1	445.928
11	2CH₃<=>H+C₂H₅	3.01×10¹³	0	56.576
12	CH₃+CH₄<=>H₂+C₂H₅	1.0×10¹³	0	96.296
13	H+C₂H₅<=>H₂+C₂H₄	2.0×10¹²	0	0
14	2C₂H₄<=>C₂H₃+C₂H₅	1.82×10¹⁴	0	270.183
15	C₂H₃+C₂H₆<=>C₂H₄+C₂H₅	1.08×10^-3	4.5	14.653
16	H+C₂H₆<=>H₂+C₂H₅	5.4×10²	3.5	21.813
17	CH₃+C₂H₆<=>CH₄+C₂H₅	5.5×10^-1	4.0	37.757
18	H+C₃H₆<=>CH₃+C₂H₄	3.4×10¹³	0	14.650
19	C₃H₆<=>CH₃+C₂H₃	2.5×10¹⁴	0	417.378
20	C₂H₄+M<=>H₂+C₂H₂+M	8.0×10¹²	0.4	371.641
21	H+C₂H₃<=>H₂+C₂H₂	3.0×10¹³	0	0
22	C₃H₆<=>CH₄+C₂H₂	1.8×10¹²	0	293.076
23	C₂H₃+M<=>H+C₂H₂+M	7.94×10¹⁴	0	130.088
24	2H+H₂<=>2H₂	9.0×10¹⁶	-0.6	0
25	CH₃+C₂H₃<=>CH₄+C₂H₂	2.0×10¹³	0	0
26	2H+H₂O<=>H₂+H₂O	6.0×10¹⁹	-1.25	0
27	H₂O+C₂H₄(+M)<=>C₂H₅OH(+M)	1.0×100	0	0
28	2C₂H₅<=>C₂H₄+C₂H₆	6.9×10¹³	-0.35	0
29	2C₂H₃<=>C₂H₂+C₂H₄	2.9597×10¹³	-0.312	0
30	CH₃+C₂H₅<=>CH₄+C₂H₄	6.57×10¹⁴	-0.68	0
31	C₂H₃+C₂H₅<=>C₂H₂+C₂H₆	2.1064×10¹³	-0.251	0
32	CH₃+CH₂OH(+M)<=>C₂H₅OH(+M)	1.0	0	0
33	CH₃+CH₂OH(+M)<=>H₂O+C₂H₄(+M)	1.0	0	0
34	C₂H₅OH(+M)<=>H₂+CH₃CHO(+M)	7.24×10¹¹	0.095	381.028
35	HCO+CH₃(+M) <=>CH₃CHO(+M)	1.0	0	0
36	H+HCO<=>H₂+CO	7.34×10¹³	0	0
37	HCO+CH₃<=>CO+CH₄	2.648×10¹³	0	0
38	H₂O+HCO<=>H+H₂O+CO	1.5×10¹⁸	-1.0	71.176
39	H+CH₃CHO<=>H₂+CO+CH₃	2.05×10⁹	1.16	10.069
40	CH₃+CH₃CHO<=>CO+CH₃+CH₄	2.72×10⁶	1.77	24.786
41	HCO+M<=>CO+H+M	1.87×10¹⁷	-1.0	71.176
42	CH₃CHO(+M)<=>CO+CH₄(+M)	1.0	0	0
43	HCO+C₂H₃<=>CO+C₂H₄	9.033×10¹³	0	0
44	HCO+C₂H₅<=>CO+C₂H₆	4.3×10¹³	0	0

No.	Reaction	*A	n	E/(kJ·mol^-1)
1	C₂H₄+M<=>H+C₂H₃+M	3.98×10¹⁷	0	411.144
2	H+C₂H₄<=>H₂+C₂H₃	1.32×10⁷	2.5	47.168
3	H+H+M<=>H₂+M	1.0	0	0
4	CH₄+M<=>H+CH₃+M	1.0×10¹⁷	0	359.232
5	CH₃+C₂H₄<=>CH₄+C₂H₃	5.0×10¹²	0	54.428
6	H₂+CH₃<=>H+CH₄	2.75×10⁴	2.5	39.435
7	2CH₃+M<=>C₂H₆+M	3.08×10⁴¹	-7.0	11.568
8	CH₃+CH₄<=>H+C₂H₆	8.0×10¹³	2.0	167.472
9	C₂H₅<=>H+C₂H₄	2.04×10¹⁵	0	144.713
10	C₂H₆<=>H+C₂H₅	2.08×10³⁸	-7.1	445.928
11	2CH₃<=>H+C₂H₅	3.01×10¹³	0	56.576
12	CH₃+CH₄<=>H₂+C₂H₅	1.0×10¹³	0	96.296
13	H+C₂H₅<=>H₂+C₂H₄	2.0×10¹²	0	0
14	2C₂H₄<=>C₂H₃+C₂H₅	1.82×10¹⁴	0	270.183
15	C₂H₃+C₂H₆<=>C₂H₄+C₂H₅	1.08×10^-3	4.5	14.653
16	H+C₂H₆<=>H₂+C₂H₅	5.4×10²	3.5	21.813
17	CH₃+C₂H₆<=>CH₄+C₂H₅	5.5×10^-1	4.0	37.757
18	H+C₃H₆<=>CH₃+C₂H₄	3.4×10¹³	0	14.650
19	C₃H₆<=>CH₃+C₂H₃	2.5×10¹⁴	0	417.378
20	C₂H₄+M<=>H₂+C₂H₂+M	8.0×10¹²	0.4	371.641
21	H+C₂H₃<=>H₂+C₂H₂	3.0×10¹³	0	0
22	C₃H₆<=>CH₄+C₂H₂	1.8×10¹²	0	293.076
23	C₂H₃+M<=>H+C₂H₂+M	7.94×10¹⁴	0	130.088
24	2H+H₂<=>2H₂	9.0×10¹⁶	-0.6	0
25	CH₃+C₂H₃<=>CH₄+C₂H₂	2.0×10¹³	0	0
26	2H+H₂O<=>H₂+H₂O	6.0×10¹⁹	-1.25	0
27	H₂O+C₂H₄(+M)<=>C₂H₅OH(+M)	1.0×100	0	0
28	2C₂H₅<=>C₂H₄+C₂H₆	6.9×10¹³	-0.35	0
29	2C₂H₃<=>C₂H₂+C₂H₄	2.9597×10¹³	-0.312	0
30	CH₃+C₂H₅<=>CH₄+C₂H₄	6.57×10¹⁴	-0.68	0
31	C₂H₃+C₂H₅<=>C₂H₂+C₂H₆	2.1064×10¹³	-0.251	0
32	CH₃+CH₂OH(+M)<=>C₂H₅OH(+M)	1.0	0	0
33	CH₃+CH₂OH(+M)<=>H₂O+C₂H₄(+M)	1.0	0	0
34	C₂H₅OH(+M)<=>H₂+CH₃CHO(+M)	7.24×10¹¹	0.095	381.028
35	HCO+CH₃(+M) <=>CH₃CHO(+M)	1.0	0	0
36	H+HCO<=>H₂+CO	7.34×10¹³	0	0
37	HCO+CH₃<=>CO+CH₄	2.648×10¹³	0	0
38	H₂O+HCO<=>H+H₂O+CO	1.5×10¹⁸	-1.0	71.176
39	H+CH₃CHO<=>H₂+CO+CH₃	2.05×10⁹	1.16	10.069
40	CH₃+CH₃CHO<=>CO+CH₃+CH₄	2.72×10⁶	1.77	24.786
41	HCO+M<=>CO+H+M	1.87×10¹⁷	-1.0	71.176
42	CH₃CHO(+M)<=>CO+CH₄(+M)	1.0	0	0
43	HCO+C₂H₃<=>CO+C₂H₄	9.033×10¹³	0	0
44	HCO+C₂H₅<=>CO+C₂H₆	4.3×10¹³	0	0

Gas-phase Kinetic Study of Pyrolysis in the System of CH₄+C₂H₅OH+Ar

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