论文总字数：19237字

摘 要

反应热失控是导致化学事故的重要原因之一。随着世界化工特别是精细化工的迅速发展，各种安全事故也频繁发生。因此，有必要对反应过程的放热行为进行研究。本研究结合氟胞嘧啶生产过程，采用全自动反应量热仪对其中的氯化反应和胺化反应两个高危工艺的放热现象进行了研究。使用差示扫描量热仪对原料的热危险性进行了研究，利用热重分析仪对胺化产物在空气和氮气气氛下的热解行为进行了分析。基于动态升温实验，利用Friedman法和Starink法计算了胺化产物在分解过程中的表观活化能。此外，还进行了绝热实验，研究了胺化产物在绝热条件下的热失控现象。结果表明在反应的初始阶段，产生了大量的热。结合绝热实验发现，胺化反应能达到的最高温度高于胺化产物的初始分解温度，一旦反应失控，极易引起二次反应。胺化产物在氮气气氛下的热解分为三个阶段，在空气气氛下的热解分为两个阶段。在两种气氛下，产物分解初期的表观活化能都比较高，随着分解的进行表观活化能均逐渐降低。

关键词:全自动反应量热仪 放热现象 氯化反应 胺化反应 热失控

Risk assessment of chlorination and amination in the production of fluorocytosine and thermal risk analysis of the product

Abstract

Reaction thermal runaway is one of the most important reasons leading to chemical accidents. With the rapid progress of the chemical industry in the world, especially the fine chemical industry, various safety accidents also occur hourly. Therefore, it is necessary to study the exothermic behavior of the reaction process. In this study , the exothermic phenomena of the two high-risk processes of chlorination and amination were analyzed by automatic reaction calorimeter combined with the production process of fluorocytosine. We use differential scanning calorimeter to analyze the thermal hazard of raw materials and use thermogravimetric analyzer to analyze the pyrolysis behavior of amine products in air and nitrogen atmosphere. Based on the dynamic heating experiment，the apparent activation energies of amines during decomposition were calculated by Friedman method and Starink method. Moreover, an adiabatic experiment was conducted to study the thermal runaway of amines under adiabatic conditions. The results show that a lot of heat is generated during the initial phase of the reaction. Combined with adiabatic experiments , the highest temperature that amine reaction can reach is higher than the initial decomposition temperature of amine products. Once the reaction is out of control, it is easy to cause a second reaction. The pyrolysis of amine products in nitrogen atmosphere is divided into three stages, and the pyrolysis in air atmosphere is divided into two stages. In the two atmospheres, the apparent activation energy of the product at the initial stage of decomposition is relatively high, but decreases gradually with the decomposition.

Key Words: reaction calorimeter; exothermic phenomena; chlorination reaction; amination reaction; thermal runaway

目录

摘 要 I

ABSTRACT II

第一章 绪论 1

1.1 研究背景及意义 1

1.2国内外研究现状 1

1.2.1 热危险性 1

1.2.2 热分析技术 2

1.3热分析动力学基本原理和方法 3

1.4 本论文的工作 3

1.3.1论文的研究内容 3

1.3.2论文的技术路线 3

1.3.3论文的章节安排 4

第二章 实验部分 5

2.1实验仪器 5

2.1.1全自动反应量热仪(RC1e) 5

2.1.2热重分析仪(TG) 5

2.1.3差示扫描量热仪（DSC） 5

2.1.4 Phi-Tec绝热量热仪 6

2.2 实验原料 6

2.3 实验主要反应 6

2.3.1氯化反应 6

2.3.2氨化反应 7

2.4本章总结 7

第三章 量热计算 8

3.1反应过程的绝热温升(ΔTad,r) 8

3.2合成反应最高温度(MTSR) 8

3.3 热惰性因子（φ） 8

3.4 表观活化能(Ea) 9

第四章 数据处理与分析 10

4.1 RC1e分析 10

4.2 非等温分析 12

4.2.1 DSC实验 12

4.2.2 TG实验 14

4.3绝热分析 17

4.4表观活化能分析 18

4.5 本章总结 19

第五章 论文总结 20

参考文献 21

附件1 23

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