臺灣博碩士論文加值系統

過氧化二苯甲醯 (Benzoyl Peroxide, BPO) 為有機過氧化物的一種，其中含有不穩定的氧原子，工業上之作用為提供自由基，作為聚合反應之起始劑。過氧化物中含有不穩定的過氧基 (-O-O-)，所以爆炸時毋須外界大氣中氧助燃，即可形成分解爆炸反應。
本文藉由微差掃描熱卡計 (Differential Scanning Calorimetry, DSC) 的使用，求取過氧化二苯甲醯之化學反應動力數據及探討其在儲運上的熱危害與防止對策。過氧化二苯甲醯依反應濃度及操作條件之不同，熱分解起始溫度約為101~105℃，分解熱約為800~1,100 J/g，反應階數為0.9階，活化能約為163 kJ/mol，反應速率常數約為6.67×10-6 sec-1。假設此系統為標準試驗容器，其內側表面積 (a)、熱傳係數 (U) 及內容物重量 (m) 皆為固定值，則不可回復溫度約為69.7及73.7℃，自加速分解溫度約為63.7及67.6℃ (25 kg PE瓶及55 gal容器) ，最後將BPO溶於甲苯中發現其為n階反應。
利用上述安全參數，結合熱力、動力學及熱失控數據結果用以預測過氧
化物的熱失控如溫度控制、應用緊急排放設計與不相容物控制等製程條件控制，而實際運用於工廠化學災害之預防。

Benzoyl peroxide (BPO) has been used as initiator or medicine. In Taiwan and Japen, several severe fire and explosion incidents had occurred due to its thermal reactivity and explosive properties.
In this study, the thermal decomposition of BPO was characterized by the isothermal microcalorimeter, TAM (Thermal Activity Monitor). It could investigate the thermal hazards while storing BPO and determine its thermokinetic data on isothermal condition. Thermograms show that in the temperature range from 70℃ to 90℃, follows the autocatalytic reaction. In addition, the reaction order, activation energy and rate constant are verified be 0.9, 163 KJ/mol and 4.38×1018 exp (-163, 230/8.314×T), respectively. Finally, the practical suggestions can be provided to prevent the specific plant from accidents, especially at low temperature conditions during storage and transportation.

目次 頁次
中文摘要 ----------------------------------------------------- -------- i
英文摘要 -------------------------------------------------------------- ii
誌謝 -------------------------------------------------------------- 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-------------------------------------------- 3
1.4 預期成果------------------------------------------- 3
1.5 研究流程-------------------------------------------- 4
第二章、 文獻回顧------------------------------------- --- -------- 5
2.1 過氧化二苯甲醯 (BPO) 介紹------------------------------------- 5
2.2 BPO之相關法規----------------------------------------------- 11
第三章、 理論及應用--------------------------------------------------- 16
3.1 恆溫分解動力學---------------------------------------------- 16
3.1.1 n階反應機制---------------------------------------- 17
3.1.2 自催化反應機制------------------------------------ 18
3.2 熱動力參數應用技術---------------------------------------- 20
第四章、 實驗方法----------------------------------------------------- 24
4.1 實驗設備------------------------------------------------ 24
4.2 儀器測試原理-------------------------------------------------- 24
4.2.1 微差掃描熱卡計 (DSC) ------------------------------ 24
4.2.2 多頻道微量熱卡計 (TAM)----------------- -- 27
4.3 實驗設計------------------------------------------------------ 30
4.3.1 本質安全實驗－DSC昇溫掃描測試--------------------- 30
4.3.2 TAM恆溫反應熱危害分析實驗----------------------- 31
第五章、 結果與討論------------------------------------------------ 38
5.1 BPO之昇溫熱分解掃瞄---------------------------------------- 38
5.2 恆溫熱分解探討------------------------------------------------ 41
5.3 恆溫熱分解反應熱動力學探討------------------------------ 43
5.3.1 反應速率常速之計算--------------------------------- 44
5.3.2 活化能之計算--------------------------------------- 46
5.3.3 頻率因子計算--------------------------------------- 47
5.4 安全參數之推算------------------------------------------------ 48
5.5 BPO溶於甲苯之反應探討----------------------------- --- 49
第六章、 結論與建議--------------- ---------------------------------- 52
6.1 結論---------------------------------------------------------- 52
6.2 建議------------------------------------------------------- 53
參考文獻 ------------------------------------------------------------- 55
附錄一 物質安全資料表--------------------------------------------- 61
附錄二 DSC昇溫掃描熱譜圖-------------------------------- ---- 64
附錄三 恆溫掃描餘熱實驗後樣品圖---------------------------------- 67
附錄四 過氧化二苯甲醯進出口資料--------------------------------- 70

1.化綠十字，2004，“化學品安全資料簡表”，1月。
2.行政院勞工委員會，1994，“危險性工作場所審查暨檢查辦法”，5月。
3.行政院勞工委員會，1998，“防火、防爆對策技術手冊”，頁43，4月。
4.杜逸興，高振山，1996，“失控反應危害評估與應用”，化工技術月刊，1
月。
5.吳鴻鈞，2001 “過氧化物儲存不當，遇熱可能產生爆炸，導致勞工受傷
或死亡”， 勞工安全衛生研究所工安警訊，9月。
6.侯宏誼，2000，異丙苯過氧化氫低溫放熱行為之研究，雲林科技大學環
境與安全研究所，碩士論文。
7.施多喜，1988，“有機過氧化物MEKPO及BPO之防災”，刑事科學，29
期，頁9-23。
8.陳聖一，1996，“爆炸性物質危害事故之探討”，火藥技術，12卷，2期，頁65-84，九月。
9.陳美玲，杜逸興，柏雅玲，1994，有機過氧化物之熱危害評估，工研院
工安衛中心，六月。
10.福山郁生，1992， “有機過酸化物的事故例”，Explosion，2卷，頁119。
11.賴耿陽，1993，塑膠大全，台灣復文興業股份有限公司，台北。
12.林文煌，2005，異丙苯過氧化氫與不相容物氫氧化鈉反應性研究，雲林科技大學環境與安全衛生研究所，碩士論文。
13.AIChE, 1995, Guidelines for Chemical Reactivity Evaluation and Application to Process Design, CCPS, New York, pp. 13-16.
14.Ambrovic P. and Lazar M., 1969, European Polymer Journal. Supplement, p. 361.
15.C. H. Bamford and C. F. H. Tipper, 1977, Chemical Kinetics-Decomposition and Isomerisation of Organic Compounds, Vol. 5, Elsevier Publishing Company, New York, USA.
16.CAM 49, 1956, Transportation of Explosives and Other Dangerous Articles, December, USA.
17.Chen-Shan Kao and Kwan-Hua Hu, 2002, “Acrylic Reactor Runaway and Explosion Accident Analysis”, Journal of Loss Prevention in the Process Industries, Vol. 15, pp. 213-222.
18.Denis Zeimet, and David N. Ballard, 2000, Hazardous Material Behavior and Emergency Response Operations, Des Plaines, Illinois, USA.
19.David N. Waters and John L. Paddy, 1988, “Equations for Isothermal Differential Scanning Calorimetric Curves”, Analytical Chemistry, Vol. 60, No. 1, pp. 53-57.
20.D. Al Doori, R. Huggett, J. F. Bates and S. C. Brooks, 1988, “A Comparison of Denture Base Acrylic Resins Polymerised by Microwave Irradiation and by Conventional Water Bath Curing Systems”, Dental Materials, Vol. 4, No. 1, pp. 25-32.
21.D. H. Fine and Peter Gray, 1967, “Explosive Decomposition of Solid Benzoyl Peroxide”, Combustion and Flame, Vol. 11, pp. 71-78.
22.Dong Yang, Hiroshi Koseki and Kazutoshi Hasegawa, 2003, “Predicting the Self-accelerating Decomposition Temperature (SADT) of Organic Peroxides Based on Non-isothermal Decomposition Behavior”, Journal of Loss Prevention in the Process Industries, Vol. 16, pp. 411-416.
23.Eugene Meyer, 1977, Chemistry of Hazardous Materials, Prentice-Hall Inc, USA.
24.Fisher, H. G. and D. D. Goetz, 1991, “Determination of Self-accelerating Decomposition Temperatures using the Accelerating Rate Calorimeter”, Journal of Loss Prevention in the Process Industries, Vol. 4, pp. 305-316.
25.F. Zaman, A. E. Beezer, J. C. Mitchell, Q. Clarkson, J. Elliot, A.F. Davis and R. J. Willson, 2001, “The Stability of Benzoyl Peroxide by Isothermal Microcalorimetry”, International Journal of Pharmaceutics, Vol. 277, pp. 133-137.
26.George Odian, 1991, Principles of Polymerization, 3rd ed., Wiley Interscience, New York, USA.
27.H. Scott Fogler, 2001, Elements of Chemical Reaction Engineering, 3rd ed., Prentice-Hall, Inc, USA.
28.Herman F. Mark, 1985, Encyclopedia of Polymer Science and Engineering-Polyesters Unsaturated, Vol. 12, Johm Wiley and Sons, New York, USA.
29.Houng-Yi Hou, Chi-Min Shu and Yih-Shing, Duh, 2001 “Exothermic Decomposition of Cumene Hydroperoxide at Low Temperature Conditions”, AIChE Journal, Vol. 47, No. 8, pp. 1893-1896.
30.Jacqueline I. Kroschwitz and Mary Howe-Grant, 1996, Encyclopedia of Chemical Technology, Vol. 18, 4th ed., John Wiley and Sons, Inc., Canada.
31.Joseph C. Leung and Charles F. Askonas, 2002, “Free-Radical Polymerization Runaway Behavior and Kinetic Modeling”, DIERS Las Vegas Meeting, Los Vegas, Nevada, USA.
32.Jinhua Sun, Yongfu Li and Kazutoshi Hasegawa, 2001, “A Study of Self-accelerating Decomposition Temperature (SADT) using Reaction Calorimetry”, Journal of Loss Prevention in the Process Industries, Vol. 14, pp. 331-336.
33.Li, Y. F., and Hasegawa, K., 1998, “On the Thermal Decomposition Mechanism of Self-reaction Materials and the Evaluating Method for their SADTs”, 5th International Symposium Loss Prevention, pp. 555-569.
34.Mettler Toledo, 2005, “STARe Thermal Analysis”, Sweden.
35.M. W. Whitmore and G. P. Baker, 1999, “Investigation of the Use of a Closed Pressure Vessel Test for Estimating Condensed Phase Explosive Properties of Organic Compounds”, Journal of Loss Prevention in the Process Industries, Vol. 12, pp. 207-216.
36.M. Takebayashi, T. Shingaki and Y. Ito, 1953, “The Catalytic Action of Organic Peroxides on the Polymerization of Ethenoid Compounds. II. The Activity of Substituted Benzoyl Peroxide on the Polymerization of Vinyl Acetate”, Bulletin of the Chemical Society of Japan, Vol. 26, pp. 475-478.
37.N. N. Semenov, 1958, Some Problems of Chemical Kinetics and Reactivity, Vol. 1, Pergamon Press Ltd, New York, USA.
38.NFPA 432, 2002, “Code for the Storage of Organic Peroxide Formulations”, National Fire Protection Association, Quincy, MA, USA.
39.NFPA 704, 2001, “Standard System for the Identification of the Hazards of Materials for Emergency Response”, National Fire Protection Association, Quincy, MA, USA.
40.Nippon Oil and Fats Co., Ltd, 1996, Organic Peroxides, 4th ed., Tokyo.
41.O. J. Walker and G. L. E. Wild, 1937, “The Thermal and Photochemical Decomposition of Acetyl Peroxide”, Journal of Chemical Society, pp. 1132-1136.
42.Plaats, G. van der, 1992, “The Practice of Thermal Analysis”, Mettler Toledo.
43.P. C. Bowers, 1984, Self-heating: Evaluating and Controlling the Hazards, Elsevier Science Publishers B. V., New York, USA.
44.Sima. Chervin and Glenn T. Bodman, 1997, “Mechanism and Kinetics of Decomposition from Isothermal DSC Data: Development and Application”, Process Safety Progress, Vol. 16, No. 2, pp. 94-100.
45.Sanjeev R. Saraf, William J. Rogers, M. Sam Mannan, Glenn T. Bodman and Sima Chervin, “Correlating Explosive Properties to DSC Parameters”, The 31st Annual Conference of the North American Thermal Analysis Society (NATAS), Albuquerque, USA, September 22-24, 2003.
46.Sanjeev R. Saraf, William J. Rogers and M. Sam Mannan, 2003, “Using Screening Test Data to Recognize Reactive Chemical Hazards”, Journal of Hazardous Materials, Vol. 104, pp. 255-267.
47.The Isothermal Calorimetric Manual for Thermometric AB, Jarfalla, Sweden.
48.T. R. Cuadrado, J. Borrajo and R. J. J. Williams, 1983, “On the Curing Kinetics of Unsaturated Polyesters with Styrene”, Journal of Applied Polymer Science, Vol. 28, pp. 485-499.
49.Urben, P. G., 1999, Bretherick’s Handbook of Reactive Chemical Hazards, Vol. 1, 6th ed., Madras, India.
50.United Nations, 2003, UN Recommendations on the Transport of Dangerous Goods, 13th ed., Vol. 1.
51.Whitmore, M. W. and Wilberforce, J. K., 1993, “Use of the Accelerating Rate Calorimeter and the Thermal Activity Monitor to Estimate Stability Temperature”, Journal of Loss Prevention in the Process Industries, Vol. 6, pp. 95-101.
52.W. E. Cass, 1946, “Kinetics of the Decomposition of Benzoyl Peroxide in Various Solvents”, Journal of the American Chemical Society, Vol. 68, pp. 1967-1976.
53.X. R. Li and H. Koseki, “Interpretation of Decomposition Mechanisms of Unstable Substances Near the SADT by an Isothermal Method”, 11th International Symposium Loss Prevention 2004, Czech Republic, Praha, 31 May - 3 June 2004, pp. 2278-2285.
54.X. R. Li and H. Koseki, 2005, “SADT Prediction of Autocatalytic Material using Isothermal Calorimetry Analysis”.
55.Yu, Y. H., and Hasegawa, K., 1996, “Derivation of the Self-accelerating Decomposition Temperature for Self-reactive Substances using Isothermal Calorimetry”, Journal of Hazardous Materials, Vol. 45, pp. 193-205.