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肉桂醛氧化过程的特性与危害

Characteristics and hazards of the cinnamaldehyde oxidation process.

作者信息

Yu Chang, Li Yuan-Lin, Liang Min, Dai Su-Yi, Ma Li, Li Wei-Guang, Lai Fang, Liu Xiong-Min

机构信息

School of Chemistry and Chemical Engineering, Guangxi University Nanning 530004 Guangxi China

出版信息

RSC Adv. 2020 May 20;10(32):19124-19133. doi: 10.1039/c9ra10820c. eCollection 2020 May 14.

Abstract

Pressure and temperature behavior of the cinnamaldehyde oxidation process was determined using a custom-designed mini closed pressure vessel test (MCPVT), which is a new method to investigate the stability and hazard assesment of the cinnamaldehyde oxidation reaction. The oxidation products were analyzed by gas chromatography-mass spectrometry (GC-MS). The results showed that cinnamaldehyde was stable under nitrogen atmosphere but very unstable under oxygen atmosphere. The initial oxidation products were analyzed by iodimetry and the cinnamaldehyde peroxide value could reach 139.44 mmol kg when the oxidation temperature was 308 K. The oxidation kinetics of cinnamaldehyde were studied by using the pressure time (-) curves obtained from the MCPVT process. The reaction is a second-order reaction, the kinetic equation is ln  = -2233.66 × (1/) + 11.19, and the activation energy is 18.57 kJ mol at 308-338 K. The explosion of the cinnamaldehyde oxidation reaction was observed by MCPVT, in which the onset temperature was 373 K. The main products of cinnamaldehyde oxidation are acetaldehyde, benzaldehyde, phenylacetaldehyde, acetophenone, 2-hydroxyphenyl acetone, cinnamaldehyde epoxide, benzoic acid, and cinnamic acid. Oxidation is a three-step process: (1) cinnamaldehyde reacts with oxygen to form peroxides; (2) complex oxidation reactions are caused by the thermal decomposition of peroxides; (3) rapid oxidation and thermal decomposition lead to explosion hazard.

摘要

采用定制设计的微型密闭压力容器试验(MCPVT)测定了肉桂醛氧化过程的压力和温度行为,这是一种研究肉桂醛氧化反应稳定性和危险性评估的新方法。通过气相色谱-质谱联用仪(GC-MS)分析氧化产物。结果表明,肉桂醛在氮气气氛下稳定,但在氧气气氛下非常不稳定。采用碘量法分析了初始氧化产物,当氧化温度为308 K时,肉桂醛的过氧化值可达139.44 mmol/kg。利用MCPVT过程获得的压力-时间(-)曲线研究了肉桂醛的氧化动力学。该反应为二级反应,动力学方程为ln  = -2233.66 × (1/) + 11.19,在308 - 338 K时活化能 为18.

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