硝酸-苯乙烯混合体系的热失控特性与机制

doi:10.16265/j.cnki.issn1003-3033.2019.11.006

中国安全科学学报 ›› 2019, Vol. 29 ›› Issue (11): 32-38.doi: 10.16265/j.cnki.issn1003-3033.2019.11.006

硝酸-苯乙烯混合体系的热失控特性与机制

朱云峰¹ 高级工程师, 钱亚男¹ 工程师, 徐伟^**1 教授级高工, 蒋军成² 教授, 石宁¹ 教授级高工, 王志荣² 教授

1 中国石油化工股份有限公司青岛安全工程研究化学品安全控制国家重点实验室,山东青岛266071;
2 南京工业大学安全科学与工程学院,江苏南京211816

收稿日期:2019-08-18 修回日期:2019-10-13 发布日期:2020-10-30
通讯作者: ** 徐伟(1981—)男,山东寿光人,博士,教授级高工,主要从事化工过程安全研究。E-mail: xuw.qday@sinopec.com。
作者简介:朱云峰 (1986—),男,山东寿光人,博士,高级工程师,主要从事反应失控机制、多相流安全泄放等方面的研究。E-mail: zhuyf.qday@sinopec.com。
基金资助:
“十三五”国家重点研发计划项目(2017YFC0804707)。

Thermal runaway characteristics and mechanism of nitric acid-styrene hybrid system

ZHU Yunfeng¹, QIAN Ya'nan¹, XU Wei, ¹ JIANG Juncheng², SHI Ning¹, WANG Zhirong²

1 State Key Laboratory of Safety and Control for Chemicals,SINOPEC Research Institute of Safety Engineering, Qingdao Shandong 266071,China;
2 College of Safety Science and Engineering, Nanjing Technology University, Nanjing Jiangsu 211816, China

Received:2019-08-18 Revised:2019-10-13 Published:2020-10-30

摘要/Abstract

摘要： 硝酸氧化是粗苯乙烯脱色精制的关键技术,采用C600热扫描仪、VSP2绝热量热仪、ReactIR原位红外光谱(FTIR)仪等测试装备,结合ReaxFF分子动力学模拟方法,研究反应体系的热稳定性、绝热失控特性、失控动力学与失控引发机制。结果表明:苯乙烯自聚失控自加速起始温度(θ₀)为132 ℃,绝热温升(Δθ_ad)为209 ℃,最高失控压力(P_max)为1.2 MPa,表观活化能(Ea)为131.3 kJ/mol,反应级数(n)为3.6。体系中含有硝酸时失控过程分为2段,第1阶段为苯乙烯侧链氧化反应,θ₀为51 ℃,Δθ_ad为70 ℃,Ea为71.3 kJ/mol,n为0.3;第2阶段为苯乙烯自聚失控,θ₀为131 ℃,Δθ_ad为152 ℃,P_max为2.1 MPa。在工业生产过程中应严格控制脱色反应硝酸的配比、降低反应温度,避免硝化、氧化等副反应的发生。

关键词: 硝酸, 苯乙烯, 反应失控, 绝热温升(Δθ_ad), 红外光谱(FTIR), 分子动力学模拟

Abstract: Nitric acid oxidation is the key technology for the decolorization and refining of crude styrene. In order to investigate the thermal stability, adiabatic runaway characteristics, thermal runaway dynamics and runaway initiation mechanism of the reaction system, C600 thermal scanner, VSP2 adiabatic calorimeter, ReactIR in-situ FTIR spectrometer, combined with ReaxFF molecular dynamics simulation method were used to carry out experiments. The results show that θ₀ of styrene self-polymerization runaway is 132 ℃, the Δθ_ad is 209 ℃, the P_max is 1.2 MPa, the Ea is 131.3 kJ/mol, and the reaciton order is 3.6. The runaway process containing nitric acid is divided into two stages. The first stage is the styrene side chain oxidation reaction, and the θ₀ is 51 ℃, the Δθ_ad is 70 ℃, the Ea is 71.3 kJ/mol, and the reaciton order is 0.3. The second stage is styrene self-polymerization runaway, and the θ₀ is 131 ℃, Δθ_ad is 152 ℃, and P_maxis 2.1 MPa. In the industrial production process, it is necessary to strictly control the proportion of nitric acid in decolorization reaction, lower the reaction temperature, and prevent side reactions such as nitrification and oxidation.

Key words: nitric acid, styrene, reaction runaway, adiabatic temperature rise(Δθ_ad), fourier transform infrared(FTIR), molecular dynamics simulation

中图分类号:

X937

朱云峰, 钱亚男, 徐伟, 蒋军成, 石宁, 王志荣. 硝酸-苯乙烯混合体系的热失控特性与机制[J]. 中国安全科学学报, 2019, 29(11): 32-38.

ZHU Yunfeng, QIAN Ya'nan, XU Wei, JIANG Juncheng, SHI Ning, WANG Zhirong. Thermal runaway characteristics and mechanism of nitric acid-styrene hybrid system[J]. China Safety Science Journal, 2019, 29(11): 32-38.

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硝酸-苯乙烯混合体系的热失控特性与机制

Thermal runaway characteristics and mechanism of nitric acid-styrene hybrid system

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