臺灣博碩士論文加值系統

離子液體 (Ionic Liquids, ILs)具有極低的蒸氣壓、高熱穩定性和催化功能，故有綠色溶劑之稱，在工業上已證明可取代揮發性有機溶劑，並廣泛應用於其他領域上。早期離子液體被視為完全沒有蒸氣壓，不具易燃性，但最近有研究證實離子液體具有可燃性，可被歸類於閃火點大於93℃以上的液體Class ⅢB。
本研究主要是使用熱重量分析儀 (thermogravimetric analysis, TGA)、傅立葉轉換紅外線光譜儀 (fourier transform infrared spectroscopy, FTIR)來研究1-ethyl-3methylimidazolium ethyl sulfate ([Emim][EtSO4])、1-hexyl-3-methylimidazolium chloride ([C6mim][Cl])及1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide ([Bmim][NTf2])這三種離子液體的分解產物與閃火點間的關係。利用TGA-FTIR對離子液體氣相分解產物進行分析進而探討離子液體分解產物對閃火點的關係。
研究結果發現離子液體在閃火點附近的分解產物，經過TGA-FTIR紅外線光譜分析後發現該氣體為易燃性氣體，例如:甲醇、乙醇、乙烯、氯甲烷等。了解離子液體易燃性的成因有助於火災、爆炸的風險評估與發展離子液體化學品處置、使用的本質安全設計。

Ionic Liquids have a high degree of thermal stability, catalyst and extremely low vapor pressure. It as a green solvent and proven to be replaced by volatile organic solvents in industry. Recently, research has been verified that ionic liquids is flammable and be classified in a flash point greater than 93℃ above the liquid Class III B. The reason for ionic liquids combustible is different from the traditional organic solvents defined liquids. The flash point for traditional organic solvent are relative to their vapor pressures, but the cause of flash point for ionic liquid is combustible to vapor pressures.The flash point of ionic point is caused by decomposition.
This study is used the Thermogravimetric analysis (TGA) and fourier transform infrared spectroscopy (FTIR) to measure 1-ethyl-3methylimidazolium ethyl sulfate ([Emim][EtSO4])、1-hexyl-3-methylimidazolium chloride ([C6mim][Cl]) and 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide
([Bmim][NTf2]). Analysis of decomposition products of ionic liquid flash point by TGA/FTIR is helpful for investigation of the ionic lipqid’s flash point.
In this study found that ionic liquid near the flash point will decompose the flammable gas like methanol, ethen, chloromethane etc. Realizing the cause for flammability of ionic liquid is helpful for fire, explosion hazard, process safety design and harzard reduction.

摘要 i
Abstract ii
誌謝 iii
目錄 iv
表目錄 vi
圖目錄 vii
第一章 緒論 1
第一節 研究背景 1
第二節 研究目的 3
第二章 文獻回顧 4
第一節 名詞定義 4
2-1-1閃火點 4
2-1-2離子液體 5
2-1-3燃燒界限 6
第二節 離子液體的易燃性與穩定性 7
第三章 研究材料與方法 14
第一節 研究方法 14
第二節 研究材料 15
第三節 研究儀器設備 16
3-3-1 HFP 360-Pensky Martens 閃火點測試儀 16
3-3-2 HFP 360-Pensky Martens 測試方法 20
3-3-3熱重量分析儀 Thermogravimetric Analysis (TGA) 21
3-3-4熱重量分析儀測試方法 23
3-3-5差示掃描量熱儀 Differential Scanning Calorimetry (DSC) 25
3-3-6差示掃描量熱儀測試方法 27
3-3-7傅立葉轉換紅外線光譜儀 28
3-3-8傅立葉轉換紅外線光譜儀測試方法 30
3-3-9離子液體氣相分解產物的TGA-FTIR測試方法 31
第四章 結果與討論 32
第一節 熱重損失圖與閃火點位置之分析 32
第二節 離子液體之氣相分析 36
4-2-1 TGA/FTIR動態升溫數據分析 36
4-2-2 TGA/FTIR恆溫數據分析 47
4-2-3 TGA/FTIR動態升溫與恆溫數據比對 56
第三節 TGA/FTIR閃火點下之體積百分濃度(%)公式推導 75
第五章 結論 76
參考文獻 77

1.陳永祥 張裕昌 李雲嫦 趙奕姼，對環境友善的綠色化學，科學發展2005，396，37-61
2.A. Marciniak, Influence of cation and anion structure of the ionic liquid on extraction processes based on activity coefficients at infinite dilution. A review, Fluid Phase Equilibr., 2010;294:213-233.
3.P. Kubisa, Ionic liquids as solvents for polymerization processes–Progress and challenges, Progress in Polymer Sci., 2009;34: 1333-1347.
4.S. Seki, Y. Ohno, Y. Kobayashi, H. Miyashiro, A. Usami, Y. Mita, H. Tokuda, M. Watanabe, K. Hayamizu, S. Tsuzuki, M. Hattori, N. Terada, Imidazolium-based room temperature ionic liquid for lithium secondary battery, J. Electrochem. Soc., 2007;154:A173-A177.
5.H. Olivier-Bourbigou, L. Magna, and D. Morvan, Ionic liquids and catalysis: recent progress from knowledge to applications, Applied Catalysis A: General, 2010;373:1-56.
6.J. F. Brennecke, E. J. Maginn , Ionic liquids: Innovative fluids for chemical processing, AIChE J., 2001;47:2384-2389.
7.A. E. Visser, R. P. Swatloski, R. D. Rogers, Traditional extractants in nontraditional solvents: Groups 1 and 2 extraction by crown ethers in room-temperature ionic liquids, Green Chem., 2000;39:3596-3604.
8.D. M. Fox, W. H. Awad, J. W. Gilman, P. H. Maupin, H. C. De Long, P. C. Trulove, Flammability, thermal stability, and phase change characteristics of several trialkylimidazolium salts, Green Chem., 2003;5:724-727.
9.D. M. Fox, J. W. Gilman, A. B. Morgan, J. R. Shields, P. H. Maupin, R. E. Lyon, H. C. De Long, P. C. Trulove, Flammability and thermal analysis characterization of imidazolium-based ionic liquids, Ind. Eng. Chem. Res., 2008;47:6327-6332.
10.M. Smiglak, M. Reichert, J. D. Holbrey, J. S. Wilkes, L. Sun, L. Sun, J. S. Thrasher, K. Kirichenko, S. Singh, A. K. Katrizky, R. D. Rogers, Combustible ionic liquids by design: is laboratory safety another ionic liquid myth, Chem. Commun., 2006;2554-2556.
11.http://nfpa.org/faq.asp?categoryID=920
12.CCPS/AIChE, Guidelines for engineering design for process safety, AIChe, New York, 1993.
13.H.-J. Liaw, C.-C. Chen, Y. -C. Chen, J.-R. Chen, S.-K. Huang, S.- N.Liu, Relationship between flash point of ionic liquids and their thermal decomposition, Green Chem., 2012,14(7):2001-2008.
14.A. Arce, H. Rodríguez, A. Soto, Use of a green and cheap ionic liquid to purify gasoline octane boosters, Green Chem., 2007;9:247-253.
15.J. Eβer, P. Wasserscheid, A. Jess, Deep desulphurization on oil refinery streams by extraction with ionic liquids. Green Chem. 2004;6:316-322.
16.J. S. Torrecilla, A. Fernández, J. García, F. Rodríguez, Determination of 1-ethyl-3-methylimidazolium ethylsulfate ionic liquid and toluene concentration in aqueous solutions by artificial neural network/uv spectroscopy, Ind. Eng. Chem. Res., 2007;46:3787-3793.
17.N. Calvar, B. González, E. Gomez, A. Domínguez, Study of the behaviour of the azeotropic mixture ethanol–water with imidazolium-based ionic liquids, Fluid Phase Equilib., 2007;259;51-56.
18.J. A. Laszlo, D. L. Compton, Comparison of peroxidase activities of hemin, cytochrome c and microperoxidase-11 in molecular solvents and imidazolium-based ionic liquids, J. Mol. Catal. Part B: Enzymatic, 2002;18:109-120.
19.F. P. Lees, Loss prevention in the process industries (2nded.)Burrerworth-Heinemann, Oxford(1996) Vol.1
20.Crowl, D. A., & Louvar, J. F. Chemical process safety: fundamentals with applications. Englewood Cliffs, NJ: Prentice-Hall. (1990).
21.H.-J. Liaw, Y.-H. Lee, C.-L. Tang, H.-H. Hsu, J.-H. Liu, A mathematical model for predicting the flash point of binary solutions, J. Loss Prevent. Proc. 2002;15: 429-438.
22.H.-J. Liaw, T.-P Lee, J.-S. Tasi, W.-H. Hsiao, M.-H. Chen, T.-T. Hsu, Binary liquid solutions exhibiting minimum flash point behavior, J. Loss Prevent. ,2003;16:173-186.
23.張星辰等。離子液體-從理論基礎到研究進展。北京；化學工業出版社。2009。
24.http://www.sigmaaldrich.com/sigma-aldrich/technical-documents/articles/chemfiles/ionic-liquids0.html#Use
25.鄒友全。離子液體-性質、製備與應用。中國石化出版社。2006.
26.中華民國工業安全衛生學會，勞工安全管理師 2001.
27.L. P. N. Rebelo, J. N. Canongia Lopes, J. M. S. S. Esperanca, E. Filipe, On the critical temperature, normal boiling point, and vapor pressure of ionic liquids, J. Phys.Chem. B, 2005;109:6040-6043.
28.M. J. Earle, J. M. S. S. Esperanca, M. A. Gilea, J. N. Canongia Lopes, L. P. N. Rebelo, J. W. Magee, K. R. Seddon, J. A. Widegren, The distillation and volatility of ionic liquids, Nature, 2006;439:831-834.
29.Y. U. Paulechka, D. H. Zaitsau, G. J. Kabo, A. A. Strechan, Vapor pressure and thermal stability of ionic liquid 1-butyl-3-methylimidazolium bis(trifluoromethylsulfonyl)amide, Thermochemica Acta, 2005;439:158-160.
30.D. H. Zaitsau, G. J. Kabo, A. A. Strechan, Y. U. Paulechka, A. Tschersich, S. P. Verevkin, A. Heintz, Experimental vapor pressures of 1-alkyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imides and a correlation scheme for estimation of vaporization enthalpies of ionic liquids, J. Phys. Chem. A, 2006;110:7303-7306.
31.T. J. Wooster, K. M. Johanson, K. J. Fraser, D. R. MacFarlane, J. L. Scott, Thermal degradation of cyano containing ionic liquids. Green Chem., 2006;6:691-696.
32.A. Seeberger, A. K. Andresen, A. Jess, Prediction of long-term stability of ionic liquids at elevated temperatures by means of non-isothermal thermogravimetrical analysis, Phys. Chem. Chem. Phys., 2009;11:9375-9381.
33.F. Heym, B. Etzold, C. Kern, A. Jess, An improved method to measure the rate of vaporisation and thermal decomposition of high boiling organic and ionic liquids by thermogravimetrical analysis, Phys. Chem. Chem. Phys., 2010;12:12089-12100.
34.F. Heym, B. Etzold, C. Kern and A. Jess, Analysis of evaporation and thermal decomposition of ionic liquids by thermogravimetrical analysis at ambient pressure and high vacuum, Green Chem., 2011;13:1453-1466.
35.M. Kosmulski, J. Gustafsson, J. B. Rosenholm, Thermal stability of low temperature ionic liquids revisited, Thermochim. Acta, 2004;412:47-53.
36.M. E. Van Valkenburg, R. L. Vaughn, M. Williams, J. S. Wilkes, Thermochemistry of ionic liquid heat-transfer fluids, Thermochim. Acta, 2005;425:181-188.
37.D. M, Fox, J. W. Gilman, H. C. De Long, P. C. Trulove, TGA decomposition kinetics of 1-butyl-2,3-dimethylimidazolium tetrafluoroborate and the thermal effects of contaminants, J. Chem. Thermodyn., 2005;37: 900-905.
38.W. H. Awad, J. W. Gilman, M. Nyden, R. H., Jr. Harris, T. E. Sutto, J. Callahan, P. C. Trulove, H. C. De Long, D. M. Fox, Thermal degradation studies of alkyl-imidazolium salts and their application in nanocomposite, Thermochim. Acta, 2004;409:3-11.
39.R. E. Del Sesto, T. M. McCleskey., C. Macombe, K. C. Ott, A. T. Koppisch, G. A. Baker, A. K. Burrell, Limited thermal stability of imidazolium and pyrrolidinium ionic liquids, Thermochim. Acta, 2009;491:118-120.
40.D. A. Crowl, J. F. Louvar, Chemical process safety: Fundamentals with applications; Prentice Hall PTR: NJ, 2002.
41.R. Hagiwara, J. S. Lee, Ionic liquids for electrochemical devices, Electrochem., 2007;75:23-34.
42.S. Keskin, D. Kayrak-Talay, U. Akman, O. Hortacsu, A review of ionic liquids towards supercritical fluid applications, J. Supercrit. Fluids, 2007;43:150-180.
43.S. Mannan, Lee`s Loss Prevention in the Process Industries, 3rd ed., 1. Elsevier Butterworth-Heinemann: Oxford, U. K., 2005.
44.R. E. Lyon, Plastics, and Elastomers, in handbook of materials in fire protection, Chapter 3, C. A. Harper, Ed., McGraw-Hill : New York, 2003.
45.D. M. Fox, W. H. Awad, J. W. Gilman, P. H. Maupin, P. C. Trulove, H. C. De Long, Thermal and kinetic studies of trialkylimidazolium salts, in Ionic Liq. IIIA: Fundam., Progress, Challenges, Opportunities, Prop. Struct., 2005;901:193-206.
46.ASTM D 93, Standard test methods for flash-point by Pensky-Martens closed cup tester, American Society for Testing and Materials, West Conshohocken, PA, 2008.
47.S. Shane, Q. Hee, Hazardous waste analysis. Rockville, MD: Government Institutes. 1999.
48.American Society For Testing and Materials , Standard Test Method for Compositional Analysis by Thermogravimetry, 2008
49.W. Wm. Wendlandt “Thermal analysis”,Ch1.
50.http://finechem.dlut.edu.cn/intruments0.htm
51.American Society For Testing and Materials , Standard Test Method for Assignment of the Glass Transition Temperatures by Differential Scanning Calorimetry, 2008.
52.徐章家，杜逸興，"微差掃瞄熱卡計與加速熱卡計在化學反應危害評估之應用"，化學災害研討會，第一屆，1994.
53.A. Fernández, J. S. Torrecilla, J. García, F. Rodríguez, Thermophysical properties of 1-ethyl-3-methylimidazolium ethylsulfate and 1-butyl-3-methylimidazolium methylsulfate ionic liquids, J. Chem. Eng. Data, 2007;52:1979-1983.
54.I. Harvey, J. Arellano, J. G. Guarino, F. U. Paredes,S. D. Arco, Thermal stability and moisture uptake of 1-alkyl-3-methylimidazolium bromide, J. Therm. Anal. Calorim., 2011;103:725-730.
55.J. D. Holbrey, W. M. Reichert, R. P. Swatloski, G. A. Broker, W. R. Pitner, K. R. Seddon, R. D. Rogers, Efficient, halide free synthesis of new, low cost ionic liquids: 1,3-dialkylimidazolium salts containing methyl- and ethyl-sulfate anions, Green Chem. 2002;4:407-413.
56.A. Fernández, J. S. Torrecilla, J. García, F. Rodríguez, Thermophysical properties of 1-ethyl-3-methylimidazolium ethylsulfate and 1-butyl-3-methylimidazolium methylsulfate ionic liquids, J. Chem. Eng. Data, 2007;52:1979-1983.
57.L_ea Chancelier, Alpha-Oumar Diallo, Catherine Santini, Guy Marlair, Thibaut Gutel, et al..Targeting adequate thermal stability and _re safety in selecting ionic liquid-based electrolytesfor energy storage. Physical Chemistry Chemical Physics, Royal Society of Chemistry, 2014:1967-1976.