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標題: 有機過氧化物-過氧化丁酮失控反應熱危害探討暨反應物不相容性研究
Thermal Runaway Hazard and Incompatible Reaction Analysis for Organic Peroxide - Methyl Ethyl Ketone Peroxide
作者: 張榮興
Chang, Ron-Hsin
關鍵字: Methyl Ethyl Ketone Peroxide;不相容性反應;Thermal Instability;Incompatibility;Runaway Behaviors;Differential Scanning Calorimetry;Vent Sizing Package2;過氧化丁酮;動力學參數;反應到達最大放熱速率所需要的時間;失控反應
出版社: 化學工程學系所
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有機過氧化物因其自身反應機制之複雜,常因熱分解或火災造成嚴重之意外事故。然而除物質自身可能導致失控之意外,製造、運輸及儲存過程中,亦潛藏著物質間不相容性反應之危害。過氧化丁酮 (Methyl Ethyl Ketone Peroxide, MEKPO) 在橡膠工業中常見之硬化劑及起始劑,為反應性之有機過氧化物,其具有不穩定特性,歷年來在台灣、韓國、日本和大陸造成許多重大火災及爆炸事故。
本研究針對 MEKPO 之反應進行熱危害評估,透過危差掃描熱卡計進行 MEKPO 及其不相容性反應物質之昇溫掃描,再藉由模擬軟體來模擬並評估其動力學參數。結果指出 MEKPO 在與上述任何一種不相容物混合時具有高度危害。由其熱譜圖中發現,MEKPO 之放熱起始溫度約為 100℃ 上下,在與微量之不相容性物質反應,造成其放熱起始溫度之降低,而整體熱譜圖亦從原有二只明顯之放熱波峰依不同之不相容物產生明顯之改變,顯示不相容性反應所造成之物質不穩定之情狀。軟體模擬所獲得反應到達最大放熱速率所需要的時間 (Time to Maximum Rate, TMR),當 MEKPO 與不相容性物質混合時,明顯可發現 TMR 的減少,尤其當 MEKPO 與鐵鏽混合時,其減少的幅度更為明顯,亦即當鐵鏽存在於製程或儲槽中,將快速誘發失控反應的發生。
後續以緊急排放處理儀 (Vent Sizing Package2, VSP2) 進行 MEKPO 及其不相容反應之絕熱昇溫測試,研究結果發現 MEKPO 在與微量金屬鐵離子、酸根離子及鹼根離子反應過程中,皆促使反應溫度降低,增加失控反應危害發生之機率,其中鐵離子及鹼根離子,在混合之同時亦產生壓力及溫度上昇之情形,而又以鐵離子之影響最為明顯,因此在製程及儲運條件下,須嚴防此類不相容性物質與MEKPO混合,避免造成難以挽回之危害。

Methyl ethyl ketone peroxide (MEKPO) is extensively employed in the chemical industries. In the past four decades, several thermal explosions hazard with its thermal instability and incompatibility caused fires and explosions have been induced by MEKPO in East Asia. In this study, the thermal decomposition and runaway behaviors of MEKPO with about 1 mass % incompatibilities such as H2SO4, HCl, NaOH, KOH, Fe2O3, FeCl3, and FeSO4 were analyzed by differential scanning calorimetry (DSC) with the following kinetics evaluation to identify the root-cause of the runaway reactions and kinetics-based curve fitting to assess hazardous phenomena via utilized curve fitting to optimize the kinetic parameters. And used Vent Sizing Package2 (VSP2), the adiabatic calorimetry to obtain the thermokinetic data and analyzed the hazardous phenomena.
From the thermal curves of pure MEKPO and ones with incompatible substances, all the onset temperatures were advanced, especially with alkaline or iron ion material. In some tests, the incompatible reactions under low temperature conditions were found. To confirm the incompatible reaction hazard phenomena, we thoroughly investigated MEKPO with different incompatibilities by VSP2. From the tests, various onset temperatures, heat of decompositions, adiabatic temperature rises, and self-heat rates could be clearly compared. From the simple calculated kinetics, all the activation energies of incompatible tests were corroborated to be lower than the MEKPO alone in a deeper degree.
其他識別: U0005-1010200717393100
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