C<sub>1</sub>~C<sub>4</sub>烷烃混合气体热爆燃的简化机理与分析

吴松林; 杜扬; 李国庆; 张培理

doi:10.11883/1001-1455(2015)05-0641-10

C₁~C₄烷烃混合气体热爆燃的简化机理与分析

doi: 10.11883/1001-1455(2015)05-0641-10

吴松林^{1, 2,},
杜扬¹,
李国庆¹,
张培理¹

1.
后勤工程学院供油系，重庆 401311
2.
后勤工程学院基础部，重庆 401311

基金项目: 国家自然科学基金项目(51276195);重庆市基础与前沿计划研究项目(cstc2013jcyjA00006)

详细信息

作者简介:
吴松林(1973—), 男, 博士研究生, 副教授, wusonglin100@163.com

中图分类号: O381
计量
- 文章访问数: 2541
- HTML全文浏览量: 307
- PDF下载量: 406
- 被引次数: 0
出版历程
- 收稿日期: 2014-04-08
- 修回日期: 2014-05-18
- 刊出日期: 2015-10-10

Reduced mechanism and analysis for thermal deflagration of C₁-C₄ alkane mixture

1.
Department of Petroleum Supply Engineering, Logistical Engineering University, Chongqing 401311, China
2.
Department of Fundamental Studies, Logistical Engineering University, Chongqing 401311, China

摘要

摘要: 为了探索油气在受限空间热爆燃发生的化学反应机理，以CHEMICAL4.1为平台，分析了C₁~C₄烷烃混合气体热爆燃过程的系统温度、主要组分浓度和中间产物生成率的变化规律。通过敏感性分析、生成速率分析和路径分析等方法，简化了C₁~C₄烷烃混合气体的详细机理，得到了一个包含37种组分、80个基元反应组成的简化机理，并进行了对比验证。在反应机理上印证了气体热爆燃过程存在缓慢氧化、快速氧化和反应平衡3个阶段。发现与超氧化氢和过氧化氢有关的基元反应是热爆燃发生的关键反应，而大量产生的氢基和羟基最终导致了热爆燃的发生。
- 爆炸力学 /
- 简化机理 /
- 敏感性分析 /
- C₁~C₄烷烃 /
- 油气 /
- 生成速率分析
Abstract: For studying the chemical mechanism of thermal deflagration of gasoline-air mixture in the confined space, the temperature of the system, the concentration of main components and the generation rate of production in the deflagration process of C₁-C₄ alkane were simulated with CHEMICAL4.1 as a platform. Based on the analysis for the simulated data of the chemical mechanism, three results were obtained as follows. (1)By sensitivity analysis, rate-of-production analysis, path analysis and so on, the detailed oxidation mechanism of C₁-C₄ alkane was studied, and drew a reduced mechanism which consisted of 37 species and 80 reactions. The comparison of the two mechanisms was presented. (2) There existed three distinct stages in the thermal deflagration process based on the analysis for the mechanism, namely slow oxidation, rapid oxidation and reaction equilibrium. (3) In the whole chain reaction process, the reactions generating hydroperoxyl and hydrogen peroxide were the key reactions because the hydrogen and hydroxyl groups were largely generated from them so that they induced the deflagration happen finally.
- mechanics of explosion /
- reduced mechanism /
- sensitivity analysis /
- C₁-C₄ alkane /
- gasoline-air mixture /
- rate-of-production analysis

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图 1 简化机理的研究思路

Figure 1. Research ideas for simplifing reaction mechanism

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图 2 温度随时间的变化曲线

Figure 2. Temperature varied with time in the system

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3(a) 主要烷烃的摩尔分数随时间的变化曲线

3(a). Mole fractions of main alkanes varied with time

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3(b) 主要产物的摩尔分数随时间的变化曲线

3(b). Mole fractions of main products varied with time

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3(c) 主要烃基的摩尔分数随时间的变化曲线

3(c). Mole fractions of main hydrocarbon varied with time

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3(d) 甲醛和氢基的摩尔分数随时间的变化曲线

3(d). Mole fractions of formaldehyde and hydrogen radical varied with time

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3(e) 其他基团的摩尔分数随时间的变化曲线

3(e). Mole fractions of other groups varied with time

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图 4 基元反应的温度敏感度直方图

Figure 4. Histograms of temperature sensitivity for basic reactions

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图 5 主要基团的总生成速率随时间的变化曲线

Figure 5. Generation rates of main groups varied with time

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6(a) 基元反应对氢基生成速率的影响

6(a). Effect of basic reactions on generation rates of hydrogen

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6(b) 基元反应对甲醛生成速率的影响

6(b). Effect of basic reactions on generation rates of formaldehyde

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图 7 骨干机理的反应路径

Figure 7. The reaction path of skeleton mechanism

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图 8 两种化学反应机理下计算得到的温度的比较

Figure 8. Comparison of temperature simulated under two chemical reaction mechanisms

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图 9 两种化学反应机理下计算得到的主要反应物和产物摩尔分数的比较

Figure 9. Comparison of mole fractions simulated under two chemical reaction mechanisms for main reactants and products

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表 1 C₁~C₄简化机理的反应方程

Table 1. Reaction equations for reduced mechanism of C₁~ C₄

反应编号	反应方程
R2^*	O+OH=O₂+H
R10	H+HO₂=OH+OH
R11^*	H+HO₂=H₂+O₂
R12	H+HO₂=O+H₂O
R14	OH+OH=O+H₂O
R16	H+H+H₂=H₂+H₂
R20	O+O+M=O₂+M
R21^*	HO₂+HO₂=H₂O₂+O₂
R23^*	OH+OH(+M)=H₂O₂(+M)
R24	H₂O₂+H=HO₂+H₂
R26	H₂O₂+O=OH+HO₂
R28^*	CH₃+CH₃(+M)=C₂H₆(+M)
R29	CH₃+H(+M)=CH₄(+M)
R30^*	CH₄+H=CH₃+H₂
R32	CH₄+O=CH₃+OH
R34^*	CH₃+HO₂=CH₃O+OH
R38^*	CH₃+O₂=CH₂O+OH
R55	CH₃O+M=CH₂O+H+M
R76	CH₂+O=CO+H+H
R77	CH₂+O=CO+H₂
R100	CH+O₂=HCO+O
R101	CH+O=CO+H
R102	CH+OH=HCO+H
R107	CH+CH₂O=CH₂CO+H
R112	C+O₂=CO+O
R113	C+OH=CO+H
R115	C+CH₂=C₂H+H
R116^*	CH₂O+H=HCO+H₂
R120^*	HCO+O₂=HO₂+CO
R121^*	HCO+M=H+CO+M
R123	HCO+H=CO+H₂
R124	HCO+O=CO+OH
R126	CO+OH=CO₂+H
R127	CO+O+M=CO₂+M
R130^*	C₂H₆+CH₃=C₂H₅+CH₄
R131^*	C₂H₆+H=C₂H₅+H₂
R140^*	C₂H₅+O₂=C₂H₄+HO₂
R141	C₂H₄+H=C₂H₃+H₂
R142^*	C₂H₄+OH=C₂H₃+H₂O
R143	C₂H₄+O=CH₃+HCO
R145^*	C₂H₄+CH₃=C₂H₃+CH₄
R146^*	C₂H₄+H(+M)=C₂H₅(+M)
R151^*	C₂H₃+O₂=CH₂O+HCO
R152^*	C₂H₃+O₂=CH₂HCO+O
R157^*	C₂H₃+O₂=C₂H₂+HO₂
R158^*	C₂H₃+CH₃=C₃H₆
R166	C₂H₂+OH=CH₂CO+H
R168	C₂H₂+OH=CH₃+CO
R183	CH₂HCO+H=CH₂CO+H₂
R184	CH₂HCO+O=CH₂O+HCO
R187	CH₂HCO+CH₃=>C₂H₅+CO+H
R200^*	CH₂CO+H=HCCO+H₂
R215	HCCO+O=CH+CO₂
R229	C₃H₈+O₂=i-C₃H₇+HO₂
R230	C₃H₈+O₂=n-C₃H₇+HO₂
R231	C₃H₈+HO₂=n-C₃H₇+H₂O₂
R233^*	C₃H₈+OH=n-C₃H₇+H₂O
R238^*	C₃H₈+H=n-C₃H₇+H₂
R247	n-C₃H₇+M=C₂H₄+CH₃+M
R248	n-C₃H₇+O₂=C₃H₆+HO₂
R249^*	i-C₃H₇+O₂=C₃H₆+HO₂
R250^*	C₃H₆+H(+M)=i-C₃H7(+M)
R251	i-C₃H₇+H=C₂H₅+CH₃
R252	n-C₃H₇+H=C₂H₅+CH₃
R257	C₃H₆+HO₂=a-C₃H₅+H₂O₂
R263	C₃H₆+O=C₂H₅+HCO
R264	C₃H₆+O=a-C₃H₅+OH
R268^*	C₃H₆+H=a-C₃H₅+H₂
R273	C₃H₆+O₂=a-C₃H₅+HO₂
R284	CH₂CHCHO+O=CH₂CHCO+OH
R290	CH₂CHCO+O=C₂H₃+CO₂
R295^*	a-C₃H₅+HO₂=CH₂CHCHO+H+OH
R354^*	C₄H₁₀=C₂H₅+C₂H₅
R355^*	C₄H₁₀=n-C₃H7+CH₃
R359	C₄H₁₀+O₂=s-C₄H₉+HO₂
R361	C₄H₁₀+a-C₃H₅=s-C₄H₉+C₃H₆
R364^*	C₄H₁₀+H=s-C₄H₉+H₂
R367^*	C₄H₁₀+OH=s-C₄H₉+H₂O
R369	C₄H₁₀+O=s-C₄H₉+OH
R372	s-C₄H₉+M=C₃H₆+CH₃+M

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表 2 C₁~C₄简化机理反应速率方程的参数

Table 2. Parmeters of reaction rate equations for reduced mechanism of C₁-C₄

反应编号	A	b	E_a/(J·mol^-1)
R2^*	2.02×10¹⁴	-0.4	0.0
R10	1.50×10¹⁴	0.0	1 000.0
R11	8.45×10¹¹	0.7	1 241.0
R12	3.01×10¹³	0.0	1 721.0
R14	3.57×10⁴	2.4	-2 112.0
R16	9.20×10¹⁶	-0.6	0.0
R20	1.89×10¹³	0.0	-1 788.0
R21^*	4.20×10¹⁴	0.0	11 982.0
R23^*	1.24×10¹⁴	-0.4	0.0
R24	1.98×10⁶	2.0	2 435.0
R26	9.55×10⁶	2.0	3 970.0
R28^*	9.22×10¹⁶	-1.2	636.0
R29	2.14×10¹⁵	-0.4	0.0
R30^*	2.20×10⁴	3.0	8 750.0
R32	6.92×10⁸	1.6	8 485.0
R34^*	7.00×10¹²	0.0	0.0
R38^*	2.51×10¹¹	0.0	14 640.0
R55	5.45×10¹³	0.0	13 497.0
R76	5.00×10¹³	0.0	0.0
R77	3.00×10¹³	0.0	0.0
R100	3.30×10¹³	0.0	0.0
R101	5.70×10¹³	0.0	0.0
R102	3.00×10¹³	0.0	0.0
R107	9.46×10¹³	0.0	-515.0
R112	2.00×10¹³	0.0	0.0
R113	5.00×10¹³	0.0	0.0
R115	5.00×10¹³	0.0	0.0
R116^*	2.19×10⁸	1.8	3 000.0
R120^*	7.58×10¹²	0.0	410.0
R121^*	1.86×10¹⁷	-1.0	17 000.0
R123	1.19×10¹³	0.2	0.0
R124	3.00×10¹³	0.0	0.0
R126	9.42×10³	2.2	-2 351.0
R127	6.17×10¹⁴	0.0	3 000.0
R130^*	5.50×10^-1	4.0	8 300.0
R131^*	5.40×10²	3.5	5 210.0
R140^*	3.00×10²⁰	-2.9	6 760.0
R141	3.36×10^-7	6.0	1 692.0
R142^*	2.02×10¹³	0.0	5 936.0
R143	1.02×10⁷	1.9	179.0
R145^*	6.62	3.7	9 500.0
R146^*	1.08×10¹²	0.5	1 822.0
R151^*	1.70×10²⁹	-5.3	6 500.0
R152^*	3.50×10¹⁴	-0.6	5 260.0
R157^*	2.12×10^-6	6.0	9 484.0
R158^*	4.46×10⁵⁶	-13.0	13 865.0
R166	2.18×10^-4	4.5	-1 000.0
R168	4.83×10^-4	4.0	-2 000.0
R183	4.00×10¹³	0.0	0.0
R184	1.00×10¹⁴	0.0	0.0
R187	4.90×10¹⁴	-0.5	0.0
R200^*	2.00×10¹⁴	0.0	8 000.0
R215	2.95×10¹³	0.0	1 113.0
R229	4.00×10¹³	0.0	48 610.0
R230	4.00×10¹³	0.0	51 360.0
R231	4.76×10⁴	2.5	16 492.0
R233^*	3.16×10⁷	1.8	934.0
R238^*	1.33×10⁶	2.5	6 756.0
R247	1.23×10¹³	-0.1	30 202.0
R248	3.58×10⁹	0.0	-3 532.0
R249^*	6.10×10²⁰	-2.9	7 910.0
R250^*	5.70×10⁹	1.2	874.0
R251	5.00×10¹³	0.0	0.0
252	1.00×10¹⁴	0.0	0.0
R257	9.64×10³	2.6	13 910.0
R263	1.58×10⁷	1.8	-1 216.0
R264	5.24×10¹¹	0.7	5 884.0
R268^*	1.73×10⁵	2.5	2 492.0
R273	2.00×10¹³	0.0	44 000.0
R284	7.24×10¹²	0.0	1 970.0
R290	1.00×10¹⁴	0.0	0.0
R295^*	1.00×10¹³	0.0	0.0
R354^*	2.00×10¹⁶	0.0	81 300.0
R355^*	1.74×10¹⁷	0.0	85 700.0
R359	4.00×10¹³	0.0	47 600.0
R361	3.16×10¹¹	0.0	16 400.0
R364^*	5.68×10⁵	2.4	3 765.0
R367^*	7.23×10⁷	1.6	-247.0
R369	5.62×10¹³	0.0	5 200.0
R372	2.14×10¹²	0.7	30 856.0

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