惰性气体影响乙烯爆炸极限参数及动力学特性

doi:10.16085/j.issn.1000-6613.2021-2432

摘要/Abstract

摘要：

为研究惰性气体对乙烯爆炸极限参数及动力学特性的影响，使用标准可燃气体爆炸极限装置和CHEMKIN软件，对比分析了N₂和CO₂对乙烯的爆炸极限、临界氧浓度和爆炸三角形的影响，通过模拟得到乙烯爆炸过程中温度、压力、·H、·O、·OH浓度变化，并进行了敏感性分析。结果表明，N₂和CO₂都使乙烯爆炸极限缩小，爆炸危险度减小，达到爆炸临界点时，N₂添加量为60.1%，CO₂添加量为43.3%，此时CO₂惰化的临界氧浓度为11.1%，N₂惰化的临界氧体积分数为7.7%。通过分析爆炸三角形，CO₂惰化下的乙烯爆炸区和窒息比相比N₂惰化下的明显减小。此外，N₂和CO₂均使乙烯的点火延迟时间增加，且爆炸后的温度和压力及自由基浓度均有所减小，通过对两种惰化条件下的乙烯爆炸过程中关键自由基变化的敏感性分析，发现R38、R46、R112、R119、R285、R294对·H、·O、·OH的生成起促进作用，R25、R173对·H、·O、·OH的生成起抑制作用，在降低敏感性系数方面，CO₂抑制作用大于N₂抑制作用，也从一定程度说明CO₂的惰化效果优于N₂的惰化效果。

关键词: 安全, 乙烯, 氮气, 二氧化碳, 爆炸极限, 动力学, 敏感性分析

Abstract:

To study the effect of inert gases on the explosion limits and chemical kinetics of ethylene, a standard test device was employed to analyze effects of N₂ and CO₂ on the explosion limit, critical oxygen concentration, and explosion triangle of ethylene. The sensitivity was analyzed after the simulation on the gas explosion include the temperature, pressure, concentration of ·H, ·O, ·OH by CHEMKIN software.The results showed that both N₂ and CO₂ narrowed the ethylene explosion limit and reduced the explosion hazard, reaching the explosion critical point with 60.1% N₂ addition and 43.3% CO₂ addition, when the critical oxygen concentration for CO₂ inerting was 11.1% and for N₂ inerting was 7.7%. By analyzing the explosion triangle, the explosion zone and asphyxiation ratio of ethylene under CO₂ inerting were significantly reduced compared with those under N₂ inerting. In addition, both N₂ and CO₂ increased the ignition delay time of ethylene and decreased the temperature and pressure and radical concentration after the explosion, the sensitivity analysis of key radical changes during ethylene explosion under two inert conditions revealed that R38, R46, R112, R119, R285, and R294 promoted the generation of ·H, ·O, ·OH, and R25 and R173 inhibited the generation of ·H, ·O, ·OH. In terms of sensitivity reduction coefficient, the inhibition effect of CO₂ was larger than that of N₂, which also indicated that the inerting effect of CO₂ was better than that of N₂ to a certain extent. This can provide some theoretical basis for the safe use of ethylene in petrochemical industry and the prevention and control of explosion accidents.

Key words: safety, ethylene, nitrogen, carbon dioxide, explosion limit, kinetics, sensitivity analysis

中图分类号:

X937

罗振敏, 刘璐, 苏彬, 宋方智. 惰性气体影响乙烯爆炸极限参数及动力学特性[J]. 化工进展, 2022, 41(9): 4653-4661.

LUO Zhenmin, LIU Lu, SU Bin, SONG Fangzhi. Effect of inert gas on ethylene explosion limit parameters and kinetic characteristics[J]. Chemical Industry and Engineering Progress, 2022, 41(9): 4653-4661.

图/表 11

图1 气体爆炸极限测试装置

表1 乙烯爆炸部分关键反应步

反应步	方程式	指前因子
R25	$O + C 2 H 4 ⇌ C H 3 + H C O$	1.25×10⁷
R38	$H + O 2 ⇌ O + O H$	2.65×10¹⁶
R46	$H + H O 2 ⇌ 2 O H$	8.40×10¹³
R112	$O H + C 2 H 4 ⇌ C 2 H 3 + H 2 O$	3.60×10⁶
R119	$H O 2 + C H 3 ⇌ O H + C H 3 O$	3.78×10¹³
R173	$C 2 H 3 + O 2 ⇌ H C O + C H 2 O$	4.58×10¹⁶
R285	$O + C 2 H 4 ⇌ H + C H 2 C H O$	6.70×10⁶
R294	$C 2 H 3 + O 2 ⇌ O + C H 2 C H O$	3.03×10¹¹

表1 乙烯爆炸部分关键反应步

反应步	方程式	指前因子
R25	$O + C 2 H 4 ⇌ C H 3 + H C O$	1.25×10⁷
R38	$H + O 2 ⇌ O + O H$	2.65×10¹⁶
R46	$H + H O 2 ⇌ 2 O H$	8.40×10¹³
R112	$O H + C 2 H 4 ⇌ C 2 H 3 + H 2 O$	3.60×10⁶
R119	$H O 2 + C H 3 ⇌ O H + C H 3 O$	3.78×10¹³
R173	$C 2 H 3 + O 2 ⇌ H C O + C H 2 O$	4.58×10¹⁶
R285	$O + C 2 H 4 ⇌ H + C H 2 C H O$	6.70×10⁶
R294	$C 2 H 3 + O 2 ⇌ O + C H 2 C H O$	3.03×10¹¹

表2 数值计算初始参数单位：%（体积分数）

序号	C₂H₄	N₂	O₂	N₂	CO₂
工况1	4	76	20
工况2	4	52	14	30
工况3	4	52	14		30

图2 氮气和二氧化碳对空气中乙烯爆炸极限及危险度的影响

图3 惰性气体对乙烯爆炸极限对应氧浓度的影响

图4 N2、CO2惰化下乙烯爆炸三角形

图5 温度、压力变化

图6 乙烯爆炸过程中关键自由基浓度变化规律

图7 爆炸过程·H敏感性系数

图8 爆炸过程·O敏感性系数

图9 爆炸过程·OH敏感性系数

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