甲烷在O2/CO2气氛下的框架和总包简化机理

doi:10.7503/cjcu20170458

摘要/Abstract

摘要：

构建了适用于甲烷在O₂/CO₂气氛下燃烧的框架机理和总包简化机理. 首先使用直接关系图法将甲烷详细氧化机理GRI Mech 3.0初步简化成了包含24组分和126步反应的框架机理; 然后, 在框架机理的基础上使用准稳态假设法得到了17组分14步反应的总包机理. 最后, 对框架机理和总包机理在不同火焰类型中的计算结果进行验证. 结果表明, 发展的框架机理和总包机理适用于多种反应器, 与详细机理的计算结果基本相同.

关键词: 甲烷, 框架机理, 总包机理, 富氧燃烧

Abstract:

A skeletal and a reduced mechanism of methane at O₂/CO₂ atmosphere were developed. A skeletal mechanism with 24 species and 126 reactions was obtained from detail mechanism GRI Mech 3.0 via directed relation graph method. Then, a reduced mechanism was developed from the skeletal mechanism with quasi steady state approximation, which consist of 17 species and 14 reaction steps. The predictions of different kinds of flames using the skeletal and the reduced mechanism are almost identical with that using the detailed mechanism.

Key words: Methane, Skeletal mechanism, Reduced mechanism, Oxy-combustion

中图分类号:

O641

TrendMD:

胡贤忠, 于庆波, 李延明. 甲烷在O₂/CO₂气氛下的框架和总包简化机理. 高等学校化学学报, 2018, 39(1): 95.

HU Xianzhong, YU Qingbo, LI Yanming. Skeletal and Reduced Mechanisms of Methane at O₂/CO₂ Atmosphere^†. Chem. J. Chinese Universities, 2018, 39(1): 95.

图/表 9

Table 1 Parameters of sample points

Model	Temperature/K	Pressure/Pa	Molar ratio of CH₄/O₂	Molar ratio of O₂/CO₂	Number of sample points
PSR	300, 400, 500, 600	1.0×101325	0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70	0.21/0.79, 0.25/0.75, 0.29/0.71, 0.33/0.67	144
PREMIX	300, 500, 700, 900	1.0×101325	0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70	0.21/0.79, 0.25/0.75, 0.29/0.71, 0.33/0.67	144
PFR	1000, 1200, 1400, 1600, 1800, 2000	0.8×101325, 1.0×101325, 1.2×101325	0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70	0.21/0.79, 0.25/0.75, 0.29/0.71, 0.33/0.67	648
0D	1000, 1200, 1400, 1600, 1800, 2000	1.0×101325, 1.5×101325, 2.0×101325	0.30, 0.35, 0.40, 0.45, 0.50, 0.55, 0.60, 0.65, 0.70	0.21/0.79, 0.25/0.75, 0.29/0.71, 0.33/0.67	648

Fig.1 Number of species of skeletal mechanism generated by DRG and the averaged error as a function of threshold values

Table 2 Order of quasi-steady-state components in four reactor models

Rank	PREMIX	Rank	PSR	Rank	PFR	Rank	0D
1	C	1	CH₃O	1	C	1	CH
2	CH₂(S)	2	CH₂(S)	2	CH	2	C
3	CH	3	CH	3	HCCO	3	HCCO
4	CH₂OH	4	C	4	CH₂OH	4	CH₂(S)
5	HCCO	5	HCCO	5	CH₂(S)	5	CH₂OH
6	HCO	6	CH₂OH	6	CH₂	6	CH₂
7	CH₂	7	HCO	7	HCO	7	CH₃O
8	CH₃O	8	H₂O₂	8	CH₃O	8	HCO
9	CH₂CO	9	CH₂	9	H	9	CH₂CO
10	HO₂	10	CH₂CO	10	CH₂CO	10	C₂H₄

Table 3 14-step global reaction mechanisms

No.	Global reaction	No.	Global reaction
1	2O $?$ O₂	8	CH₃+O $?$ CH₂O+H
2	H+O $?$ OH	9	CH₄+O $?$ CH₃+OH
3	H₂+O $?$ H+OH	10	CO+O $?$ CO₂
4	HO₂+O $?$ O₂+OH	11	CH₂O+O $?$ HCO+OH
5	H₂O₂+O $?$ HO₂+OH	12	C₂H₄+O $?$ CH₃+HCO
6	CH₃+OH+O $?$ CO+H₂+H₂O	13	CH₂CO+OH+O $?$ 2CO+H+H₂O
7	CH₃+OH+O $?$ H+H₂O+HCO	14	2CH₃ $?$ C₂H₆

Table 3 14-step global reaction mechanisms

No.	Global reaction	No.	Global reaction
1	2O $?$ O₂	8	CH₃+O $?$ CH₂O+H
2	H+O $?$ OH	9	CH₄+O $?$ CH₃+OH
3	H₂+O $?$ H+OH	10	CO+O $?$ CO₂
4	HO₂+O $?$ O₂+OH	11	CH₂O+O $?$ HCO+OH
5	H₂O₂+O $?$ HO₂+OH	12	C₂H₄+O $?$ CH₃+HCO
6	CH₃+OH+O $?$ CO+H₂+H₂O	13	CH₂CO+OH+O $?$ 2CO+H+H₂O
7	CH₃+OH+O $?$ H+H₂O+HCO	14	2CH₃ $?$ C₂H₆

Fig.2 Laminar flame speeds of CH4 as a function of equivalence ratios with 24 species skeletal mechanism, 14 steps global reduced mechanism, detailed mechanism and experimental measurementsT=300 K, p=101315 Pa.

Fig.3 Predictions of CH4/O2/CO2 flame structure with 24 species skeletal mechanism, 14 steps global reduced mechanism and detailed mechanism

Fig.4 Predictions of ignition time of CH4/O2/CO2 mixtures with 24 species skeletal mechanism, 14 steps global reduced mechanism and detailed mechanismn(O2)/n(CO2)=0.24/0.76, T=300 K, p=101325 Pa. (A) n(CH4)/n(O2)=0.4; (B) n(CH4)/n(O2)=0.5;(C) n(CH4)/n(O2)=0.6.

Fig.5 Predictions of flame temperature versus pressure of CH4/O2/CO2 mixtures with 24 species skeletal mechanism, 14 steps global reduced mechanism and detailed mechanism(A) n(CH4)/n(O2)=0.35, n(O2)/n(CO2)=0.31/0.69; (B) n(CH4)/n(O2)=0.50, n(O2)/n(CO2)=0.26/0.74;(C) n(CH4)/n(O2)=0.60, n(O2)/n(CO2)=0.35/0.65.

Fig.6 Predictions of flame structure of CH4/O2/CO2 mixtures with 24 species skeletal mechanism, 14 steps global reduced mechanism and detailed mechanism(A) CH4 and H2O; (B) CO; (C) OH. n(CH4)/n(O2)=0.50, n(O2)/n(CO2)=0.24/0.76, T=1200 K, p=101325 Pa.

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甲烷在O₂/CO₂气氛下的框架和总包简化机理

Skeletal and Reduced Mechanisms of Methane at O₂/CO₂ Atmosphere^†

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