铁锈对环氧乙烷水溶液失控反应的影响

doi:10.12034/j.issn.1009-606X.20180166

过程工程学报 ›› 2018, Vol. 18 ›› Issue (S1): 138-145.DOI: 10.12034/j.issn.1009-606X.20180166CSTR: 32067.14.jproeng.180166

铁锈对环氧乙烷水溶液失控反应的影响

刘静如*，金满平，赵磊，张帆*，徐伟，石宁

中国石化安全工程研究院化学品安全控制国家重点实验室，山东青岛 266071

收稿日期:2018-05-11 修回日期:2018-09-07 出版日期:2018-11-22 发布日期:2018-11-19
通讯作者: 刘静如 liujr.qday@sinopec.com
基金资助:
国家重点研发计划——典型危险化学品储运过程火灾爆炸防控工程示范

Effect of rust on runaway reaction of ethylene oxide aqueous solution

Jingru LIU^*, Manping JIN, Lei ZHAO, Fan ZHANG^*, Wei XU, Ning SHI

SINOPEC Research Institute of Safety Engineering, State Key Laboratory of Safety and Control for Chemicals, Qingdao, Shandong 266071, China

Received:2018-05-11 Revised:2018-09-07 Online:2018-11-22 Published:2018-11-19
Contact: Jing-Ru LIU liujr.qday@sinopec.com

摘要/Abstract

摘要： 采用绝热量热仪对环氧乙烷(EO)水溶液?铁锈/Fe2O3体系进行了绝热量热实验，得到了铁锈、Fe2O3固体与EO水溶液接触时的起始放热温度、最高放热温度和压力、绝热温升、失控反应过程温度、压力等参数. 结果表明，在实验条件下EO水溶液与现场铁锈接触时失控反应特征不明显，未出现温度、压力剧升现象；发生失控反应的起始放热温度、最高反应温度、最高压力等随EO浓度降低而减小，达到最大反应速率的时间在30 min内，30wt% EO水溶液?Fe2O3体系的起始放热温度接近100℃，纯EO?Fe2O3体系的起始放热温度为150℃. Fe2O3固体比现场铁锈对EO及其水溶液失控反应的催化诱导作用更明显，且随EO浓度升高，失控后果更严重.

关键词: 环氧乙烷, 失控反应, 绝热量热, 热稳定性, 过程安全

Abstract: Exothermic reaction of ethylene oxide (EO) contacting with rust is believed to be responsible for explosion accidents of EO distillation tower. In order to systematically study the influence of iron rust/Fe2O3 on the thermodynamic parameters of runaway reaction of EO aqueous solution, the adiabatic calorimetry tests of EO aqueous solution?rust/Fe2O3 system were carried out by adiabatic calorimeter Venting Size Package-2 (VSP-2). The thermodynamic parameters such as the initial exothermic temperature, the maximum exothermic temperature and pressure, time to maximum reaction rate, the adiabatic temperature rise, the variation of temperature and pressure during runaway reaction process were obtained for EO aqueous solution?rust/Fe2O3 system. The results showed that under the experimental conditions the runaway reaction characteristics of EO aqueous solution?rust system were not obvious. There were no distinct temperature and pressure rise during reaction, and the maximum temperature and pressure of the system were lower than 200℃ and 1.0 MPa respectively. For Fe2O3 contacting with EO aqueous solutions, the initial exothermic temperature, the maximum reaction temperature and pressure decreased with increase of EO aqueous solution concentrations, and the time to maximum reaction rate was less than 30 minutes. The initial exothermic temperature of 30wt% EO aqueous solution?Fe2O3 system was close to 100℃. The initial exothermic temperature of pure EO?Fe2O3 system was about 150℃ and the adiabatic temperature rised close to 180℃. The addition of polymer in the Fe2O3?EO aqueous solution system had no obvious effect on the catalytic induction of the runaway reaction, and the severity of the runaway reaction was lower than that of the Fe2O3?EO aqueous solution system. Therefore, the catalytic induction of Fe2O3 solids on the runaway reaction of EO and its aqueous solution was more obvious compared to the on-site rust, and with the increase of EO mass fraction, the consequences of runaway reactions were more serious. The study on runaway reaction behavior of EO with rust would be useful for EO distillation process design and explosion accident prevention.

Key words: ethylene oxide, runaway reaction, adiabatic calorimetry, thermal stability, process safety

刘静如金满平赵磊张帆徐伟石宁. 铁锈对环氧乙烷水溶液失控反应的影响[J]. 过程工程学报, 2018, 18(S1): 138-145.

Jingru LIU Manping JIN Lei ZHAO Fan ZHANG Wei XU Ning SHI. Effect of rust on runaway reaction of ethylene oxide aqueous solution[J]. Chin. J. Process Eng., 2018, 18(S1): 138-145.

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铁锈对环氧乙烷水溶液失控反应的影响

Effect of rust on runaway reaction of ethylene oxide aqueous solution

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