燃烧反应机理构建的极小反应网络方法 氢氧燃烧

doi:10.7503/cjcu20190568

摘要/Abstract

摘要：

基于化学同时平衡原理, 提出复杂反应体系的极小反应网络方法(MRN), 在指定中间物种数目条件下, 构建反应步数最小的详细燃烧反应机理. 确定了8个物种的氢氧燃烧的6个独立反应, 对缺乏动力学参数的独立反应进行组合替代, 反应速率常数采用Arrhenius双参数形式. 采用构建的9步反应氢氧燃烧机理(MRN-C0)进行了点火延迟时间和层流火焰速度的模拟.

关键词: 燃烧反应机理, 化学平衡, 反应网络, 基元反应

Abstract:

In the construction of detailed combustion mechanisms, the reaction networks become more and more complicated so far, thus the numbers of species and reactions increase seriously. On the other hand, the too large size of the reaction mechanism will make the combustion numerical simulation difficult in practice. In this work, the minimized reaction network method(MRN) based on the principle of chemical simultaneous equilibrium was proposed in order to construct detailed combustion mechanism with minimum number of reaction steps for the given chemical species and applied to hydrogen-oxygen combustion at first. Six independent reactions were determined for an eight-species system. This minimized mechanism in principle is enough to describe the combustion process. However, some global reactions need to be replaced by other reaction steps owing to the lack of the rate constants. In this way, a nine-step detailed mechanism of hydrogen combustion(MRN-C0) was developed. In dealing with the kinetic parameters, the two-parameter Arrhenius equation was adopted to replace the so-called modified Arrhenius equation. Such a treatment guarantees the physics of the activation energy and pre-exponential factor. The reliability of this new method, MRN, has been verified through the numerical simulations of ignition delay time and laminar flame with the nine-step hydrogen combustion mechanism.

Key words: Combustion reaction mechanism, Chemical equilibrium, Reaction network, Elementary reaction

中图分类号:

O643

TrendMD:

李象远, 申屠江涛, 李宜蔚, 李娟琴, 王静波. 燃烧反应机理构建的极小反应网络方法氢氧燃烧. 高等学校化学学报, 2020, 41(4): 772.

LI Xiangyuan, SHENTU Jiangtao, LI Yiwei, LI Juanqin, WANG Jingbo. Combustion Mechanism Construction Based on Minimized Reaction Network: Hydrogen-Oxygen Combustion ^†. Chem. J. Chinese Universities, 2020, 41(4): 772.

图/表 7

参考文献 34

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Step	Reaction	Stoichiometric coefficient
Step	Reaction	O	H₂O	H	HO₂	H₂O₂	OH	H₂	O₂
1	H₂?H+H	0	0	2	0	0	0	-1	0
2	H₂+O₂?HO₂+H	0	0	1	1	0	0	-1	-1
3	H₂O₂?OH+OH	0	0	0	0	-1	2	0	0
4	O+H₂O?OH+OH	-1	-1	0	0	0	2	0	0
5	H₂+O?H+OH	-1	0	1	0	0	1	-1	0
6	H₂+OH?H+H₂O	0	1	1	0	0	-1	-1	0
7	O₂+H?O+OH	1	0	-1	0	0	1	0	-1
8	O+H?OH	-1	0	-1	0	0	1	0	0
9	H₂O₂+H?H₂O+OH	0	1	-1	0	-1	1	0	0
10	H₂+HO₂?H₂O₂+H	0	0	1	-1	1	0	-1	0
11	OH+HO₂?H₂O₂+O	1	0	0	-1	1	-1	0	0
12	HO₂+H?OH+OH	0	0	-1	-1	0	2	0	0
13	H+O₂?HO₂	0	0	-1	1	0	0	0	-1
14	HO₂+O?OH+O₂	-1	0	0	-1	0	1	0	1
15	H+OH?H₂O	0	1	-1	0	0	-1	0	0
16	O₂?O+O	2	0	0	0	0	0	0	-1
17	H₂O₂+OH?H₂O+HO₂	0	1	0	1	-1	-1	0	0
18	OH+HO₂?H₂O+O₂	0	1	0	-1	0	-1	0	1
19	H₂O₂+O₂?HO₂+HO₂	0	0	0	2	-1	0	0	-1

Step	Reaction	Stoichiometric coefficient
Step	Reaction	O	H₂O	H	HO₂	H₂O₂	OH	H₂	O₂
1	H₂?H+H	0	0	2	0	0	0	-1	0
2	H₂+O₂?HO₂+H	0	0	1	1	0	0	-1	-1
3	H₂O₂?OH+OH	0	0	0	0	-1	2	0	0
4	O+H₂O?OH+OH	-1	-1	0	0	0	2	0	0
5	H₂+O?H+OH	-1	0	1	0	0	1	-1	0
6	H₂+OH?H+H₂O	0	1	1	0	0	-1	-1	0
7	O₂+H?O+OH	1	0	-1	0	0	1	0	-1
8	O+H?OH	-1	0	-1	0	0	1	0	0
9	H₂O₂+H?H₂O+OH	0	1	-1	0	-1	1	0	0
10	H₂+HO₂?H₂O₂+H	0	0	1	-1	1	0	-1	0
11	OH+HO₂?H₂O₂+O	1	0	0	-1	1	-1	0	0
12	HO₂+H?OH+OH	0	0	-1	-1	0	2	0	0
13	H+O₂?HO₂	0	0	-1	1	0	0	0	-1
14	HO₂+O?OH+O₂	-1	0	0	-1	0	1	0	1
15	H+OH?H₂O	0	1	-1	0	0	-1	0	0
16	O₂?O+O	2	0	0	0	0	0	0	-1
17	H₂O₂+OH?H₂O+HO₂	0	1	0	1	-1	-1	0	0
18	OH+HO₂?H₂O+O₂	0	1	0	-1	0	-1	0	1
19	H₂O₂+O₂?HO₂+HO₂	0	0	0	2	-1	0	0	-1

Reaction	O	H₂O	H	HO₂	H₂O₂	OH	H₂	O₂
Ⅰ	1	0	0	0	0	0	0	-1/2
Ⅱ	0	1	0	0	0	0	-1	-1/2
Ⅲ	0	0	1	0	0	0	-1/2	0
Ⅳ	0	0	0	1	0	0	-1/2	-1
Ⅴ	0	0	0	0	1	0	-1	-1
Ⅵ	0	0	0	0	0	1	-1/2	-1/2

Reaction	O	H₂O	H	HO₂	H₂O₂	OH	H₂	O₂
Ⅰ	1	0	0	0	0	0	0	-1/2
Ⅱ	0	1	0	0	0	0	-1	-1/2
Ⅲ	0	0	1	0	0	0	-1/2	0
Ⅳ	0	0	0	1	0	0	-1/2	-1
Ⅴ	0	0	0	0	1	0	-1	-1
Ⅵ	0	0	0	0	0	1	-1/2	-1/2

No.	Reaction	A/(cm³, mol, s)	E_a/(J·mol^-1)
R1	H₂+O₂?HO₂+H	1.763×10¹⁴	241671
R2	H₂+M?H+H+M	3.327×10¹⁴	426661
	Third-body efficiency	H₂/2.5/H₂O/12/He/0.83/
R3	H+O₂?O+OH	1.04×10¹⁴	66880
R4	H₂+O?H+OH	6.83×10¹³	43405
R5	H+O₂(+M) ? HO₂(+M)	1.137×10¹⁴	0
	Low pressure limit	2.28×10¹⁵	0
	Third-body efficiency	H₂/1.3/He/0.64/H₂O/10/Ar/0.5/
R6	HO₂+H?OH+OH	7.709×10¹³	8360
R7	H₂+HO₂?H₂O₂+H	3.01×10¹³	109002
R8	H₂O₂(+M) ? OH+OH(+M)	2.206×10¹⁵	209974
	Low pressure limit	4.173×10¹⁶	187916
	Third-body efficiency	H₂O/7.65/N₂/1.5/O₂/1.2/He/0.65/H₂O₂/7.7/H₂/3.7/
R9	H₂+OH?H+H₂O	4.38×10¹³	29218