臺灣博碩士論文加值系統

本研究主要針對過氧化丁酮與無機酸（硝酸、鹽酸、硫酸、磷酸）及其它不相容性物質之混合失控反應及不相容反應機制進行研究與分析探討。過氧化丁酮廣泛應用於工業上，由於其具有高放熱及不穩定之特性，因此於近幾十年間已造成多次火災及爆炸事故。本研究主要採用微差掃描熱卡計、緊急洩壓排放處理儀及恆溫卡計，進行分析及研究過氧化丁酮之失控反應行為，並藉由模擬分析技術進行評估動力學參數，如活化能、頻率因子、反應階數、反應熱及安全參數等。結果顯示，此些無機酸及不相容性物質易增加過氧化丁酮之危險性，最後將藉由本研究所得之安全資訊提供於業界及實際製程，以期避免事故再度發生。

The thermal stability of solutions of methyl ethyl ketone peroxide (MEKPO) dissolved in dimethyl phthalate (DMP), with the presence of inorganic acids (HCl, HNO3, H3PO4, and H2SO4) and the other incompatible materials as contaminants had been studied. MEKPO is extensively employed in the chemical industries. Several severe fires and explosions have been induced by MEKPO in East Asia during the last four decades. Therefore, this study was conducted with a view to realize its essentially hazardous characteristics. In this study, we used differential scanning calorimetry (DSC), thermal activity monitor III (TAMIII), and vent sizing package 2 (VSP2) 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. Inorganic acids and other contaminants were mixed with MEKPO and studied under various perturbed situations. All the results indicated that when MEKPO is mixed with contaminants, it dramatically increases the degree of hazard in the initial stage, especially affected by HNO3. To lessen the degree of hazard, hazardous information must be provided to the manufacturing process.

CATALOG
Abstract in Chinese……………………………………………………………………… i
Abstract in English……………………………………………………………………… ii
Acknowledgements………………………………………………………………………… iv
Table Captions………………………………………………………………………….. vii
Figure Captions………………………………………………………………………… ix
1. Introduction……………………………………………………………….. 1
2. Experimental………………………………………………………………… 5
2.1 Standard Procedure for Preparation of MEKPO 10, 15, and 31 mass%............... 5
2.2 Standard Procedure for Preparation of HNO3 (2, 6 N), H3PO4 (6 N), H2SO4
(0.5 M and 6 N) and NaNO3 (6 M)……………………………………………… 5
2.3 Other Contaminants………………………………………………………… 5
2.4 Differential Scanning Calorimetry (DSC)……………………………. 5
2.5 Vent Sizing Package 2 (VSP2)………………………………………….. 6
2.6 Thermal Activity Monitor III (TAMIII)………………………………… 7
3. Utility of Safety Parameters………………………………………………………… 9
3.1 Time to Maximum Rate (TMR)…………………………………………… 9
3.2 Temperature of No Return (TNR)……………………………………….. 10
3.3 Self-Accelerating Decomposition Temperature (SADT)………………. 10
4. Results and Discussion…………………………………………………… 12
4.1 Discussion on MEKPO 15 mass%, HNO3 (2 and 6 N), and NaNO3 (6 M)
by DSC………………………………………………………………………….. 12
4.2 Discussion on MEKPO (10 mass%, 50 mL), H2SO4 (6 N, 5 mL), HNO3
(6 N, 5 mL), and H3PO4 (6 N, 5 mL) by VSP2…………………………………. 17
4.3 Discussion on MEKPO (31 mass%) with H2SO4 (0.5 M), KOH (1.0 M),
or Fe2O3 (solid) by DSC………………………………………………………… 19
4.4 Discussion on MEKPO (31 mass%) with Acetone 99 mass% by DSC…… 20
4.5 Discussion on MEKPO (31 mass%) with Acetone 99 mass% by TAMIII. 22
4.6 Discussion on MEKPO 31 mass%, HNO3 (6 N), and NaNO3 (6 M) by TAMIII. 23
4.7 Discussion on MEKPO 31 mass%, H3PO4 (6 N), and H2SO4 (6 N) by TAMIII.. 23
5. Conclusions…………………………………………………………………. 25
6. Nomenclature……………………………………………………………….. 27
7. Literature Cited……………………………………………………………………... 28
8. Tables……………………………………………………………………….. 34
9. Figures………………………………………………………………………. 52
10. Autobiography………………………………………………………………. 86

Literature Cited
Akzo Nobel Chemicals, Inc. Curing Agents for Thermoset Resins. 1996, 1.
Andreozzi, R., Caprio, V., Crescitelli, S., Russo, G. The Thermal Stability of Tert-Butyl Hydroperoxide-Acid Mixtures. J. Hazard. Mater. 1988, 17, 305.
Barnes, I.; Bastian, V.; Becker, K. H.; Tong, Z. Kinetics and Products of the Reactions of NO3 with Monoalkenes, Dialkenes, and Monoterpenes. J. Phys.Chem. 1990, 94, 2413.
Black, E. D., Hayon, E. J. Phys. Chem. 1970, 74, 3199.
Broszkiewicz, R. K. The Radiation-Induced Formation of NO3 in Aqueous Solutions. Int. J. Appl. Radiat. Isotopes. 1967, 18, 25.
Cha, J. H., Kim, K. S., Choi, S., Yeon, S. H., Lee, H., Kim, H. S., Kim, H. Thermal and Electrochemical Properties of Morpholinium Salts with Bromide Anion. Korean J. Chem. Eng., 2005, 22, 945.
Chang, R. H., Tseng, J. M., Jehng, J. M., Shu, C. M., Hou, H. Y. Thermokinetic Model Simulations for Methyl Ethyl Ketone Peroxide Contaminated with H2SO4 or NaOH by DSC and VSP2. J. Therm. Anal. Cal., 2006, 83, 57.
Chervin, S., Bodman, G. T. Phenomenon of Autocatalysis in Decomposition of Energetic Chemicals. Thermochim. Acta. 2002, 392, 371.
Cho, C. K., Chang, K. S., Cale, T. S. Thermal Runaway Prevention in Catalytic Packed Bed Reactor by Solid Temperature Measurement and Control. Korean J. Chem. Eng., 1993, 10, 195.
Christoforatou, E. L., Balakotaiah, V. Runaway Limits for Adiabatic Packed-bed Catalytic Reactors. AIChE J. 1998, 44, 394.
Clayden, J. Greeve, N., Warren, S., Wothers, P. Organic Chemistry, Oxford, UK, 2001, 1020.
Code for the Storage of Organic Peroxide Formulations, NFPA 43B; National Fire Protection Association, Quincy, MA, USA, 2002.
Connell, P. S., Howard, C. J. Kinetics Study of the Reaction HO + HNO3. Int. J. Chem. Kinet. 1985, 17, 17.
Daniel Swern, Organic Peroxides. John Wiley & Sons, Inc. 1970.
Daniels, M. Pulse Radiolysis of the Aqueous Nitrate System. Formation of NO3 in Concentrated Solutions and the Mechanism of “Direct Action”1. J. Phys. Chem. 1966, 70, 3022.
Daniels, M. Radiation Chemistry of the Aqueous Nitrate System.1 ш. Pulse Electron Radiolysis of Concentrated Sodium Nitrate Solutions. J. Phys. Chem. 1969, 73, 3710.
Duh, Y. S., Hsu, C. C., Kao, C. S., Yu, S. W. Applications of Reaction Calorimetry in Reaction Kinetics and Thermal Hazard Evaluation. Thermochim. Acta., 1996, 285, 67.
Fisher, H. G., Goetz, D. D. Determination of Salf-Accelerating Decomposition Temperature Using the Accelerating Rate Calorimeter. J. Loss Prev. Process Ind. 1991, 4, 305.
Fraunfelder, F. T., Coster, D. J., Drew, R., Fraunfelder, F. W. Ocular Injury by Methyl Ethyl Ketone Peroxide. American Journal of Ophthalmology. 1990, 110, 635.
Fu, Z. M., Li, X. R., Koseki, H., Mok, Y. S. Evaluation on Thermal Hazard of Methyl Ethyl Ketone Peroxide by Using Adiabatic Method. J. Loss Prev. Process Ind. 2003, 16, 389.
Gunjan, T., Purnendu, B. Development and Experimental Validation of the Model of a Tall, Continuous-Flow, Countercurrent, Bubble-Type Ozone Contactor. Ind. Eng. Chem. Res. 2006, 45, 109.
Grolmes, M. A. Pressure Relief Requirements of Organic Peroxides and Other Related Compounds, International Symposium on Runaway Reactions, Pressure Relief Design, and Effluent Handling, New Orleans, LA,USA, March, 1998.
Hai, Z., Zhiming, X., Pengjiang, G.; Rongzu, H., Shengli, G., Binke, N., Yan, F., Qizhen, S., Rong, L. Estimation of the Critical Rate of Temperature Rise for Thermal Explosion of First-Order Autocatalytic Decomposition Reaction Systems Using Non-Isothermal DSC. J. Hazard. Mater. 2002, 94, 205.
Hou, H. Y., Liao, T. S., Duh, Y. S., Shu, C. M. Thermal Hazard Studies for Dicumyl Peroxide by DSC and TAM. J. Therm. Anal. Cal., 2006, 83, 167.
Hou, H. Y., Shu, C. M., Duh, Y. S. Exothermic Decomposition of Cumene Hydroperoxide at Low Temperature Conditions. AIChE J. 2001, 47, 1893.
Iizuka, Y., Surianarayanan, M. Comprehensive Kinetic Model for Adiabatic Decomposition of Di-tert-butyl Peroxide Using BatchCAD. Ind. Eng. Chem. Res. 2003, 42, 2987.
Jiang, P. Y., Katsumura, Y., Domae, M., Ishikawa, K., Nagaishi, R., Ishigure, K., Yoshida, Y. J. Chem. Soc., Faraday Trans. 1992, 88, 3319.
Katsumura, Y.; Jiang, P. Y.; Nagaishi, R.; Oishi, T.; Ishigure, K.; Yoshida, Y. Pulse Radiolysis Study of Aqueous Nitric Acid Solutions: Formation Mechanism, Yield, and Reactivity of NO3 Radical. J. Phys. Chem. 1991, 95, 4435.
Kim, K. S., Ko, J. W. Real-Time Risk Monitoring System for Chemical Plants. Korean J. Chem. Eng., 2005, 22, 26.
Kossoy, A. A. Inherently Safer and Assessment of Reaction Hazards Technology Workshop, Yunlin, ROC, 2002.
Kossoy, A. A., Akhmetshin, Y. Identification of Kinetic Models for the Assessment of Reaction Hazards. Process Safety Progress, 2007, DOI: 10.1002/prs.10189.
Kossoy, A. A., Koludarova, E. Specific Features of Kinetics Evaluation in Calorimetric Studies of Runaway Reactions. J. Loss Prev. Process Ind. 1995, 8, 229.
Kossoy, A. A., Hofelich, T. Methodology and Software for Assessing Reactivity Ratings of Chemical Systems. Pro. Safety. Prog. 2003, 22, 235.
Kossoy, A. A., Benin, A. I., Akhmetshin, Y. G. An Advanced Approach to Reactivity Rating. J. Hazard. Mater. 2005, 118, 1.
Kotoyori, T. The Self-Accelerating Decomposition Temperature (SADT) of Solids of the Quasi-Autocatalytic Decomposition Type. J. Hazard. Mater. 1999, 64, 1.
Kozlowska-Milner, E.; Bmzkiewicz, R. K. Radiar. Phys. Chem. 1978, 11, 253.
Kwon, B. G., Lee, J. H. Anal. Chem. 2004, 76, 6359.
Leila, B. D., Fierz, H. Autocatalytic Decomposition Reactions, Hazards and Detection. J. Hazard. Mater. 2002, 93, 137.
Leung, J. C., Greed, M. J., Fisher, H. G. Round-Robin Vent Sizing Package Results, International Symposium on Runaway Reactions, Cambridge, MA, USA, March, 1989.
Li, X. R., Sun, J. H., Koseki, H., Hasegawa, K. Experimental Determination of the Minimum Onset Temperature of Runaway Reaction from a Radioactive Salt Disposal in Asphalt. J. Hazard. Mater., 2005, A120, 51.
Li, X., Koseki, H., Iwata, Y., Mok, Y. S. Decomposition of Methyl Ethyl Ketone Peroxide and Mixtures with Sulfuric Acid. J. Loss Prev. Process Ind. 2004, 17, 23.
Liaw, H. J., Chen, C. J., Yur, C. C. The multiple runaway-reaction behavior prediction of MEK–oxidation reactions. J. Loss Prev. Process Ind., 2001, 14, 371.
Lide, D.R. CRC Handbook of Chemistry and Physics, 86th ed., CRC Press. 2006, 9, 55.
Long, G. T., Brems, B. A., Wight, C. A. Autocatalytic Thermal Decomposition Kinetics of TNT. Thermochim. Acta. 2002, 388, 175.
Maruthamuthu, P., Neta, P. J. Phys. Chem. 1978, 82, 710.
Martin, J. L. Kinetic Analysis of an Asymmetrical DSC Peak in the Curing of an Unsaturated Polyester Resin Catalysed with MEKP and Cobalt Octoate. Polymer. 1999, 40, 3451.
Milas, N. A.; Golubovic, A. Studies in Organic Peroxides. XXV. Preparation, Separation and Identification of Peroxides Derived from Methyl Ethyl Ketone and Hydrogen Peroxide. J. American Chem. Soci., 1959, 81, 5824.
Minamoto, K. Allergic Contact Dermatitis due to Methyl Ethyl Ketone Peroxide, Cobalt Naphthenate and Acrylates in the Manufacture of Fibreglass-Reinforced Plastics. Contact Dermatitis. 2002, 46, 58.
Neta, P.; Huic, R. E. Rate Constants for Reactions of NO3 Radicals in Aqueous Solutions. J. Phys. Chem. 1986, 90, 4644.
Neta, P.; Huie, R. E.; Ross, A. E. J. Phys. Chem. Ref. Data. 1988, 17, 1116.
Ning, B., Hu, R., Zhang, H., Xia, Z., Guo, P., Liu, R., Lu, G., Jiang, J. Estimation of the Critical Rate of Temperature Rise for Thermal Explosion of Autocatalytic Decomposing Reaction of Nitrocellulose Using Non-isothermal DSC. Thermochim. Acta., 2004, 416, 47.
OSHA, Methyl Ethyl Ketone Peroxide Organic Method # 77, Occupational Safety and Health Administration, USA, 1989.
Park, K. S., Kim, J. Y. Classification and Trend Analysis of Fuel Gas Accidents in Korea between 1996 and 1999. Korean J. Chem. Eng., 2001, 18, 285.
Pfaffli, P. Determination of Airborne Methyl Ethyl Ketone Peroxide. Fresenius’ J. Anal. Chem. 1992, 342, 183.
Pihcv, A. K.; Sibirskaya, G. K.; Sbirsbov, E. M.; Glazunov, P. Ya.; Spitsyu, V. I. Lbkl. Akad. Nauk SSSR. 1974, 215, 645.
Rcdlich, O.; Duerst, R. N.; Merbach, A. J. Chem. Phys. 1968, 49, 2986.
Recommendations on the Transport of Dangerous Goods, 6th ed.; United Nations Publications: Geneva, Switzerland, 1989, 263.
Recommendations on the Transport of Dangerous Goods, Tests and Criterion, 1st ed.; United Nations Publications: Geneva, Switzerland; 1986, 168.
Saraf, S. R., Rogers, W. J., Mannan, M. S. Application of Transition State Theory for Thermal Stability Prediction. Ind. Eng. Chem. Res. 2003, 42, 1341.
Sevim, F., Demir, F., Bilen, M. and Okur, H. Kinetic Analysis of Thermal Decomposition of Boric Acid from Thermogravimetric Data. Korean J. Chem. Eng., 2006, 23, 736.
Shastri, L. V.; Huie, R. E. Inr. J. Chem. Klnet. 1990, 22, 505.
STARe Software with Solaris Operating System, Operating Instructions; Mettler Toledo: Sweden, 2004.
Townsend, D. I., Tou, J. C. Thermal Hazard Evaluation by an Accelerating Rate Calorimeter. Thermochim. Acta. 1980, 37, 1.
Product Information of TAMIII Thermostat, www.thermometric.com, 2007.
Tseng, J. M., Chang, R. H., Shu, C. M. Thermal Hazard Evaluation for Methyl Ethyl Ketone Peroxide Mixed With Inorganic Acids. J. Therm. Anal. Cal., 2006, 85, 189.
Tseng, J. M., Shu, C. M., Yu, Y. C. Thermal Hazard Simulations for Methyl Ethyl Ketone Peroxide Induced by Contaminants. Korean J. Chem. Eng. 2005, 22, 797.
Wang, Y. W., Shu, C. M., Duh, Y. S., Kao, C. S. Thermal Runaway Hazards of Cumene Hydroperoxide with Contaminants. Ind. Eng. Chem. Res., 2001, 40, 1125.
Yeh, P. Y., Shu, C. M., Duh, Y. S. Thermal Hazard Analysis of Methyl Ethyl Ketone Peroxide. Ind. Eng. Chem. Res. 2003, 42, 1.
“VSP2 Manual and Methodology,” Fauske & Associates, Inc., USA, 1996.