臺灣博碩士論文加值系統

在傳統的職業安全上，對於化學物質因熱不穩定性所造成的熱分解反應，以及反應後所產生的氣態產物所造成的風險危害上，吾人對於其風險危害的分析著重在其引起的高溫、高壓以及進一步所造成的爆炸事故。
但是，熱分解反應所產生的氣態產物是否會有其他潛在的風險？然而這些風險是在傳統職業安全上的反應性危害分析時較少被考慮到的，傳統上對於這些具有熱不穩定性的化學品吾人在風險危害評估上往往是著重於在熱分解反應後所產生的氣體是否累積具有足夠多的能量造成存放該化學品的密閉容器發生過壓爆炸。
在本篇論文裡，我們討論了在傳統上認為是低蒸氣壓而忽略其易燃性危害的離子液體其中的 [C6mim][Cl] ，以及 2016 年台中興太化學製藥造成 2 死的爆炸事故中的肇事化學品 DMPAT ，在對這兩種化學品進行熱不穩定性分析後，發現其因受熱導致的分解反應後所產生的氣相產物反而增加了可燃性危害的風險。
對 [C6mim][Cl] 而言，本研究發現對此化學品的液相預先加熱處理後， [C6mim][Cl] 的閃火點會隨著預先熱處理的溫度提高而降低，進而增加易燃性危害的風險，甚而在 DMPAT 中，其氣態產物的自燃點低於 PHI-TEC II 測試的最終溫度，這些結果表示，在熱不穩定性所造成之熱反應的性風險危害中，除了傳統上分析的因為其高溫、高壓的氣態產物所產生的爆炸後果還需要進一步分析、評估反應物中的氣態產物所衍生出的易燃性或是如 DMPAT 所衍生出的自燃性風險。
因此化學物質因其反應性原因而額外產生的風險危害是值得在風險危害評估中進行討論的。

For hazard risk analysis, we focus on explosion accident, that with high temperature and high pressure which caused by chemicals thermal decomposition, in traditional occupational safety. There were a question about those product gas from thermal decomposition. Were they have no potential hazards? Those were not to be consider in traditional occupational safety hazard risk analysis.
In this thesis, we discussed [C6mim][Cl] ,one of iron liquid, which be considered with low vapor pressure, and without flammability hazard. Then we chosen DMPAT which cause an runaway reaction explosion accident in Taichung. Both of those chemicals were be consider about flammability hazard. But in this thesis, we find that [C6mim][Cl]’s flash point decrease with preheat step temperature increase. And in DMPAT, we find not only cause runaway reaction explosion but also produce some flammable gas, which have auto-ignition temperature who lower then final reaction temperature. That’s mean when that time after reaction, those gas can be ignition by high temperature.
In that two case, we know that, chemicals thermal decomposition is not be consider explosion by high temperature and high pressure. It’s need to be analysis those produce gas to avoid increase flammability hazard or additional hazard like DMPAT add auto-ignition hazard.

摘要 I
Abstract II
致謝 III
目錄 IV
圖次 V
表次 VI
第一章. 前言 1
第二章. 文獻回顧 4
2.1 閃火點 4
2.2 離子液體的熱解研究 4
2.3 興太 DMPAT爆炸事故 4
第三章. 研究材料與方法 6
3.1 材料與方法 9
3.1.1 [C6mim][Cl]/DMPAT預先熱處理過程 9
3.1.2 閃火點測試 12
3.1.3 TGA/DSC 13
3.1.4 傅立葉轉換紅外光譜測試 14
3.1.5 TGA-FTIR 測試 16
3.1.6 Pyrolysis-gas chromatography-mass 18
3.1.7 PHI-TEC II失控反應測試 22
第四章. 結果與討論 23
4.1 [C6mim][Cl] 的熱分解反應與其衍生的危害 23
4.1.1 閃火點測試結果[2] 23
4.1.2 [C6mim][Cl] TGA-FTIR 的氣態產物分析 27
4.1.3 [C6mim][Cl] 經熱處理後的 ATR 測試結果 44
4.2 DMPAT 熱分解反應性結果與其衍生的危害 46
4.2.1 PHI-TEC II 測試結果 46
4.2.2 DMPAT 的 TGA/DSC 測試結果 48
4.2.3 DMPAT 熱分解的氣態產物分析 52
4.2.4 DMPAT 的結晶結果的 ATR 分析 67
第五章. 結論 69
5.1 [C6mim][Cl] 的熱解行為討論 69
5.2 DMPAT 熱爆炸行為討論 70
5.3 化學物質熱反應性所形成的可燃性危害與反應性危害 71
第六章. 參考文獻 72

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