異丙苯過氧化氫與氫氧化鈉之反應性危害分析

Reaction Hazard Analysis for Cumene Hydroperoxide with Sodium Hydroxide

10.7005/JOSH.200809.0246

陳燕琳(Yen-Lin Chen)；周穎濱(Ying-Pin Chou)；侯宏誼(Hung-Yi Hou)；徐啟銘(Chi-Min Shu)

異丙苯過氧化氫 ； 氫氧化鈉 ； 微差掃描熱卡計 ； 多頻道微量熱卡計 ； 動力學參數 ； Cumene hydroperoxide CHP ； Sodium hydroxide NaOH ； Differential scanning calorimetry DSC ； Thermal activity monitor TAM ； Kinetic parameters

勞工安全衛生研究季刊

16卷3期（2008 / 09 / 01）

246 - 254

繁體中文

異丙苯過氧化氫(cumene hydroperoxide, CHP)在製程工業上用途相當廣泛，但近四十年來已發生許多意外事故。其主要用途為丙烯－丁二烯－苯二烯共聚物(acrylonitrile butadiene styrene, ABS)聚合反應的起始劑(initiator)，及酚(phenol)與過氧化氫二異丙苯(dicumyl peroxide, DCPO)的生產製造。氫氧化鈉(sodium hydroxide, NaOH)用於異丙苯(cumene)氧化生成CHP的製程階段中，其功用為調整pH值，避免製程中pH值過低。 本研究針對CHP與其不相容物質NaOH運用微差掃描熱卡計(differential scanning calorimetry, DSC)進行其熱危害特性分析，觀察其反應性危害(reactive hazards)。由熱譜圖(thermal curve)可以得到反應之放熱起始溫度(exothermic onset temperature, T0)、最大放熱溫度(exothermic maximum temperature, T(下標 max))與分解反應熱(heat of decomposition, △H(下標 d))等動力學參數，並配合多頻道微量熱卡計(thermal activity monitor, TAM)進行恆溫實驗，觀察於恆溫狀態下之放熱行為，實驗結果指出，CHP與NaOH混合會導致放熱起始溫度提前，並出現兩只放熱波峰，使其反應機制複雜化，且於恆溫實驗下亦有類似之現象，會導致放熱提前，綜合文獻與實驗結果，評估製程及儲運中NaOH對於CHP可能造成之影響。

In Taiwan, organic peroxides have caused many severe explosions and fires, most of which were ignited by thermal instabilities, chemical pollutants, and even mechanical shock. Cumene hydroperoxide (CHP) is used in polymerization reactions for producing phenol and dicumyl peroxide (DCPO). This study analyzed the thermal hazard of CHP with sodium hydroxide (NaOH) by differential scanning calorimetry (DSC) and a thermal activity monitor (TAM). After obtaining the thermal curves from DSC, curve fitting was employed to obtain the thermokinetic parameters, such as the exothermic onset temperature (T0), peak temperature (T(subscript max)), and enthalpy (△H(subscript d)). Depending on the operating conditions, NaOH is either incompatible with or a catalyst for CHP. When CHP is mixed with NaOH, the onset temperature is reached earlier and the reactions become more complex than in the pure case.

1. (2006).NFPA 43B, National Fire Protection Association, Quincy,.
2. (1998).The Isothermal Calorimetric Manual for Thermometric AB.Jarfalla, Sweden:
3. H Y Hou,C M Shu,Y S Duh(2001).Exothermic Decomposition of Cumene Hydroperoxide at Low Temperature Conditions.AIChE Journal,47,1893-1896.
4. H Y Hou,T S Liao,W H Ling,Y S Duh,C M Shu.(2006).Thermal Hazard Studies for Dicumyl Peroxide by DSC and TAM.J Therm Anal Calorim,83,167-171.
5. H Y Hou,Y S Duh,W H Lin,K H Hu,C M Shu.(2006).Reactive Incompatibility of Cumene Hydroperoxide Mixed with Alkaline Solutions.J Therm Anal Calorim,85,145-150.
6. Takayuki Ando,Yasuhiro Fujumeta,Shigeru Morisaki(1987).DSC Data for Reactive Chemical Substances (1).Safety Document of the Japan Research Institute of Industrial Safety.
7. Y S Duh,C S Kao,C Lee,S W Yu(1997).Runaway Hazard Assessment of Cumene Hyproperoxide from the Cumene Oxidation Process.Trans Inst Chem Eng,75,73-80.
8. Y S Duh,C S Kao,H H Hwang,W L Lee(1998).Thermal Decomposition Kinetics of Cumene Hydroperoxide.Trans Inst Chem Eng,76,271-276.
9. Y S Duh,T C Ho,J R Chen.(1998).Case Studies of Incidents in Runaway Reactions and Emergency Relief.AIChE Loss Prevention Symposium,6,1-9.
10. Y W Wang,C M Shu,Y S Duh,C S Kao(2001).Thermal Runaway Hazards of Cumene Hydroperoxide with Contaminants.Ing Eng Chem Res,40,1125-1132.
11. Y W Wang,Y S Duh,C M Shu(2006).Evaluation of Adiabatic Runaway Reaction and Ventsizing for Emergency Relief from DSC.J Therm Anal Calorim,85,225-234.