相转移催化作用下大豆油的环氧化反应的安全特性研究  

Thermal Hazard Investigation of the Epoxidation Reaction of Soybean Oil

作　　者：张风炎 董永路 林树东[1,2,3] 桂雪峰 胡继文 ZHANG Fengyan;DONG Yonglu;LIN Shudong;GUI Xuefeng;HU Jiwen(Guangzhou Institute of Chemistry,Chinese Academy of Sciences,CAS Engineering Laboratory for Special Fine Chemicals,Guangzhou 510650,China;Management Committee of Shaoguan NanXiong Hi-Teac Industry Development Zone,CASH GCC Shaoguan Research Institute of Advanced Materials,Nanxiong 512400,China;University of Chinese Academy of Sciences,Beijing 100049,China)

机构地区：[1]中国科学院广州化学研究所,中国科学院新型特种精细化学品工程实验室,广东省电子有机聚合物材料重点实验室,广东广州510650 [2]国科广化韶关新材料研究院,国科广化精细化工孵化器(南雄)有限公司,广东南雄512400 [3]中国科学院大学,北京100049

出　　处：《纤维素科学与技术》2023年第3期33-38,I0002,共7页Journal of Cellulose Science and Technology

基　　金：韶关科技计划工程(210906134536798)。

摘　　要：针对在自制相转移催化剂([(C18H37)2(CH3)2N]3{PO4[W(O)(O2)2]4})作用下大豆油(SBO)的环氧化反应过程的热危险性进行了研究。首先,通过DSC研究了双氧水在本体系中的热力学及稳定特性,结果表明该催化剂能够提升H2O2的热稳定性,强化其氧化能力。其次,采用原位红外技术监测了SBO环氧化反应的全过程,通过建立环氧化反应动力学进一步研究潜在的危害性。动力学的决定系数(0.9886~0.9974)表明SBO环氧化反应为一级反应。计算得到的SBO环氧化反应的表观活化能为15.43 kJ/mol,表明该反应体系对温度敏感,易受到温度变化的影响。另外,ΔG(31.38~32.50 kJ/mol)和ΔH(12.67 kJ/mol)为正值以及ΔS(-56.18 kJ/mol)为负值,表明使用催化剂的SBO环氧化反应是遵循非自发的、吸热的过程。因此,研究结果表明低温反应和间歇进料的方式能够最有效地降低其热失控风险。In this study,the thermal hazard of the epoxidation reaction of soybean oil(SBO)with hydrogen peroxide in the presence of a phase transfer catalyst([(C_(18)H_(37))_(2)(CH_(3))_(2)N]_(3){PO_(4)[W(O)(O_(2))_(2)]_(4)})was investigated.Firstly,the thermal decomposition characteristics of H_(2)O_(2)in the system were studied using DSC,and the results showed that the catalyst enhances the thermal stability of H_(2)O_(2)and strengthens its oxidation capacity.Secondly,the reaction process of SBO epoxidation was monitored by in situ infrared technology,and the potential hazards were further investigated by the kinetics of the epoxidation reaction.The determination coefficients of the kinetics(0.9886~0.9974)indicated that the SBO epoxidation reaction follows a first-order reaction.The calculated apparent activation energy for the SBO epoxidation reaction was 15.43 kJ/mol,indicating that the reaction system is temperature sensitive to temperature variations.Moreover,the positive values ofΔG(31.38~32.50 kJ/mol)andΔH(12.67 kJ/mol),and the negative value ofΔS(-56.18 kJ/mol)indicated that the SBO epoxidation reaction followed a non-spontaneous and endothermic process.Therefore,the results of the study indicate that the low-temperature reaction and intermittent feeding approach can most effectively reduce the risk of its thermal runaway.

关 键 词：环氧化 热危险 热分解 原位红外 动力学 速率常数 活化能 

分 类 号：TQ032.4[化学工程]