臺灣博碩士論文加值系統

摘要
含抑制劑苯乙烯單體為化學工業重要原料之一，在常溫下有極微弱之自發性放熱聚合反應，於製造、儲存或處置時若未加於抑制，可能使溫度持續昇高，其結果為劇烈的熱爆炸、火災或毒性物質大量外洩等重大工安事故，比較其它熱危害分析熱卡計如排放設計儀器（VSP2）無法偵測到此微小放熱聚合反應之熱量。 本研究使用微差掃描熱卡計 (DSC) 進行熱掃描，可獲得聚合反應的放熱起始溫度與聚合熱，再使用多頻道微量熱卡計 (TAM) 進行接近室溫下的恆溫放熱行為量測，以提供完整的含抑制劑苯乙烯單體動力學、熱力學資料庫以及提供後續反應機制推估之參考。
本研究延續本製程與防災實驗室先前一系列研究苯乙烯單體之方法，針對含抑制劑苯乙烯單體進行低溫放熱行為分析及模擬失控反應研究，研究結果發現，含抑制劑苯乙烯單體其恆溫動力學於高溫部份 (120℃以上) 屬n階反應，而於50℃至85℃低溫部分則屬自催化反應。本研究得到含10 ppm抑制劑苯乙烯單體在低溫部份之反應階數為0.5級，活化能為53.420 kJ/mole，頻率因子為1.117×103 (1/sec)，反應速率常數即為1.117×103 exp (-53,420/8.314×T)，含抑制劑苯乙烯單體起始溫度與抑制劑濃度成線性正比關係，且到達最大反應速率時間對數值與溫度成線性關係。此外，上述參數可提供給製程工廠應用於低溫下含抑制劑苯乙烯單體儲存與運輸災害之預防。

ABSTRACT
Inhibited Styrene Monomer (SM) is one of the important raw materials used in the petrochemical industry. Under ambient conditions, it demonstrates extremely weak exothermic behaviors.Compared with other calorimeters used for hazard analysis, such as Vent Sizing Package2, (VSP2) which cannot detect such weak exothermic phenomena, in this research, the exothermic polymerization is characterized by an isothermal microcalorimeter, Thermal Activity Monitor (TAM) and Differential Scanning Calorimeter (DSC). Thermograms showed that SM with 10 ppm inhibitor of 4-t-butylcatechol (TBC) in the temperature range above 120℃ follows n-th order reaction. However, from 50℃ to 85℃, it follows an autocatalytic reaction. In addition, reaction order, rate constant and activation energy are verified to be 0.5, 53.419 kJ/mol and 1.117×103 exp (-53,419/8.314×T), respectively. From the experimental the exothermal onset temperature is linearly proportion to the inhibitor concentration. Meanwhile the logarithm time reach maximum reaction rate is linearly proportion to the inhibitor concentration, as well. Finally, the acquired parameters can be provided to proactively the accidents at low temperature conditions during storage and transportation.

目錄
目次 頁次
中文摘要 i
英文摘要 ii
致謝 iii
目錄 iv
表目錄 vi
圖目錄 vii
符號說明 viii
第一章､緒論1
1.1 研究緣起1
1.2 研究目的3
1.3 研究內容4
1.4 預期成果4
第二章､文獻回顧6
2.1 文獻資料6
第三章､苯乙烯單體與抑制劑9
3.1 苯乙烯單體9
3.1.1 苯乙烯單體特性9
3.1.2 苯乙烯單體危害與安全處置儲存 9
3.1.3 聚合反應機制 11
3.1.4 苯乙烯單體製造流程12
3.2抑制劑/第三丁基鄰苯二酚特性化學反應機制14
3.3 苯乙烯單體安全管理、運輸相關規定16
第四章､實驗方法及理論應用17
4.1 實驗設備17
4.2 儀器測試原理18
4.2.1 微差掃描熱卡計18
4.2.2 多頻道微量熱卡計20
4.3 操作流程22
4.3.1微差掃描熱卡計實驗22
4.3.2多頻道微量熱卡計實驗23
4.4 恆溫分解動力學 24
4.4.1 n階反應機制 25
4.4.2 自催化反應機制26
4.5 熱動力參數應用技術29
第五章､結果與討論 39
5.1 昇溫與恆溫熱危害分析39
5.1.1 DSC 昇溫熱聚合掃描39
5.1.2 TAM 恆溫熱聚合掃描43
5.2 反應動力學探討 45
5.2.1 反應階數求法 45
5.2.2 反應速率常數 46
5.2.3 活化能計算 49
5.2.4 頻率因子計算 50
5.2.5 動力學總體探討 51
5.3 自加速反應分解溫度計算 53
第六章､結論與建議 56
6.1 結論 56
6.2 建議 57
參考文獻 58

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