臺灣博碩士論文加值系統

極低共熔溶液 (deep eutectic solvent, DES) 用途廣泛，可作為二氧化碳吸收劑，改善溫室效應之影響，其結構與離子液體 (room temperature ionic liquid, RTIL) 相似，相較於離子溶液，極低共熔溶劑原料較為便宜而且配製方法簡單，能兼具經濟及環保效益，其具有低揮發性、低毒性的特質，本研究主要量測雙成分極低共熔系統不同比例之熔點，系統分別為:
(1) choline chloride + urea
(2) choline chloride + malonic acid
(3) N,N-diethylethanolammonium chloride + ethylene glycol
(4) N,N-diethylethanolammonium chloride + dithylene glycol
(5) N,N-diethylethanolammonium chloride + triethylene glycol
(6) N,N-diethylethanolammonium chloride + urea
(7) N,N-diethylethanolammonium chloride + malonic acid
(8) N,N-diethylethanolammonium chloride + acetic acid
使用示差掃描熱分析儀 (differential scanning calorimeter, DSC) 量測樣品熔點，量測溫度範圍為90°C至150°C，所量測之結果使用TA Universal Analysis軟體分析DSC熱曲線，實驗求得之熔點數據以Wilson模型回歸計算參數，求得回歸參數值。觀察熔點的變化趨勢是否符合曲線，所建立之完整固液相平衡數據資料，可供相關設計參考，作為熱力學之基礎數據的計算依據。

Deep eutectic solvents (DESs) are emerging environmentally benign alternatives to volatile organic compounds for a wide range of applications. They are also proposed as low-cost alternatives to traditional ionic liquids, and have great potential for bulk applications. They can be prepared with relative ease from the huge number of available ammonium salts and hydrogen bond donors. In this study, the following DESs were investigated:
(1) choline chloride + urea
(2) choline chloride + malonic acid
(3) N,N-diethylethanolammonium chloride + ethylene glycol
(4) N,N-diethylethanolammonium chloride + dithylene glycol
(5) N,N-diethylethanolammonium chloride + triethylene glycol
(6) N,N-diethylethanolammonium chloride + urea
(7) N,N-diethylethanolammonium chloride + malonic acid
(8) N,N-diethylethanolammonium chloride + acetic acid
The melting points of the mixtures (at different mole ratios) were measured using a differential scanning calorimeter. The phase diagram of each DES was developed, and the eutectic compositions were determined. Results showed that all the DESs investigated exhibited large depression in melting point (up to 160 K). The experimental data were well correlated by the Wilson activity coefficient model.

目錄
摘要 I
Abstract II
致謝 III
目錄 IV
表目錄 VIII
圖目錄 XII
第 1 章 緒論 1
1-1 前言 1
1-2 研究動機 4
1-3 研究目的 5
第 2 章 文獻回顧 6
2-1 離子液體簡介 6
2-2 極低共熔溶液 9
2-3 計算模式 13
2-3-1 固液平衡理論 13
2-3-2 Wilson模型 17
第 3 章 DSC量測原理 19
3-1 DSC簡介 19
3-2 DSC種類 19
3-3 DSC量測熔點 22
第 4 章 實驗 25
4-1 實驗藥品 25
4-2 實驗裝置 28
4-3 實驗步驟 29
4-3-1 DSC爐子清潔 29
4-3-2 DSC爐子校正 29
4-4 樣品製備 30
4-5 填充樣品盤 31
第 5 章 結果與討論 32
5-1 文獻驗證 32
5-1-1 choline chloride (1) + urea (2) mixtures 33
5-1-2 choline chloride (1) + malonic acid (2) mixtures 41
5-2 低共熔溶劑雙成分熔點量測 46
5-2-1 N,N-diethylethanolammonium chloride (1) + ethylene glycol (2) mixtures 46
5-2-2 N,N-diethylethanolammonium chloride (1) + diethylene glycol (2) mixtures 50
5-2-3 N,N-diethylethanolammonium chloride (1) + triethylene glycol (2) mixtures 54
5-2-1 N,N-diethylethanolammonium chloride (1) + urea (2) mixtures 58
5-2-2 N,N-diethylethanolammonium chloride (1) + malonic acid (2) mixtures 62
5-2-3 N,N-diethylethanolammonium chloride (1) + acetic acid (2) mixtures 66
5-3 結論 70
參考文獻 72
 
表目錄
Table 2 1 離子液體常見的陽離子結構式 7
Table 2 2 離子液體常見的陰離子結構式 8
Table 2 3 已知的極低共熔溶液(以Choline chloride及N,N-diethylethanolammonium chloride兩種鹵化鹽為基礎) 11
Table 4 1 chemical use in this study 26
Table 5 1 Melting points of choline chloride (1) + urea (2) mixtures 36
Table 5 2 Property of choline chloride (1) + urea (2) mixtures 38
Table 5 3 Wilson parameters of choline chloride (1) + urea (2) mixtures 38
Table 5 4 Melting points of choline chloride (1) + malonic acid (2) mixture 43
Table 5 5 Property of choline chloride (1) + malonic acid (2) mixtures 45
Table 5 6 Wilson parameters of choline chloride (1) + malonic acid (2) mixtures 45
Table 5 7 Melting points of N,N-diethylethanolammonium chloride (1) + ethylene glycol (2) mixture 47
Table 5 8 Property of N ,N-diethylethanolammonium chloride (1) + ethylene glycol (2) mixtures 49
Table 5 9 Wilson parameters of N ,N-diethylethanolammonium chloride (1) + ethylene glycol (2) mixtures 49
Table 5 10 Melting points of N,N-diethylethanolammonium chloride (1) + diethylene glycol (2) mixture 51
Table 5 11 Property of N ,N-diethylethanolammonium chloride (1) + diethylene glycol (2) mixtures 53
Table 5 12 Wilson parameters of N ,N-diethylethanolammonium chloride (1) + diethylene glycol (2) mixtures 53
Table 5 13 Melting points of N,N-diethylethanolammonium chloride (1) + triethylene glycol (2) mixture 55
Table 5 14 Property of N ,N-diethylethanolammonium chloride (1) + triethylene glycol (2) mixtures 57
Table 5 15 Wilson parameters of N ,N-diethylethanolammonium chloride (1) + triethylene glycol (2) mixtures 57
Table 5 16 Melting points of N,N-diethylethanolammonium chloride (1) + urea (2) mixture 59
Table 5 17 Property of N ,N-diethylethanolammonium chloride (1) + urea (2) mixtures 61
Table 5 18 Wilson parameters of N ,N-diethylethanolammonium chloride (1) + urea (2) mixtures 61
Table 5 19 Melting points of N,N-diethylethanolammonium chloride (1) + malonic acid (2) mixture 63
Table 5 20 Property of N ,N-diethylethanolammonium chloride (1) + malonic acid (2) mixtures 65
Table 5 21 Wilson parameters of N ,N-diethylethanolammonium chloride (1) + malonic acid (2) mixtures 65
Table 5 22 Melting points of N,N-diethylethanolammonium chloride (1) + acetic acid (2) mixture 67
Table 5 23 Property of N ,N-diethylethanolammonium chloride (1) + acetic acid (2) mixtures 69
Table 5 24 Wilson parameters of N ,N-diethylethanolammonium chloride (1) + acetic acid (2) mixtures 69
Table 5 25 本研究所求得極低共熔系統之eutectic point 70
 
圖目錄
Figure 2 1 Sketch of an eutectic phase diagram (Bromberg, 1980) 9
Figure 2 2 Freezing point of choline chloride/urea mixtures as a function of composition (Abbott et al., 2003). 10
Figure 3 1 Schematric of power compecsated DSC (Hatakeyama and Quinn, 1994.) 20
Figure 3 2 Schematic of heat flux DSC(Hatakeyama and Quinn, 1994.) 21
Figure 3 3 DSC curve in the region of phase transition and the characteristic temperature (Haines, 2002). 23
Figure 3 4 Melting endotherm peak 24
Figure 5 1 Melting points of choline chloride (1) + urea (2) mixtures 37
Figure 5 2 DSC curve for choline chloride (1) + urea(2) eutectic (Morrison et al., 2009) 39
Figure 5 3 DSC curve for choline chloride (1) + urea (2) eutectic in this study 40
Figure 5 4 Melting points of choline chloride (1) + malonic acid (2) mixtures 44
Figure 5 5 Melting points of N,N-diethylethanolammonium chloride (1) + ethylene glycol (2) mixture 48
Figure 5 6 Melting points of N,N-diethylethanolammonium chloride (1) + diethylene glycol (2) mixture 52
Figure 5 7 Melting points of N,N-diethylethanolammonium chloride (1) + triethylene glycol (2) mixture 56
Figure 5 8 Melting points of N,N-diethylethanolammonium chloride (1) + urea (2) mixture 60
Figure 5 9 Melting points of N,N-diethylethanolammonium chloride (1) + malonic acid (2) mixture 64
Figure 5 10 Melting points of N,N-diethylethanolammonium chloride (1) + acetic acid (2) mixture 68

參考文獻
Abbott, A. P.; Boothby, D.; Capper, G.; Davies, D. L.; Rasheed, R. K. Deep eutectic solvents formed between choline chloride and carboxylic acids: versatile alternatives to ionic liquids. J. Am. Chem. Soc. 2004, 126, 9142-9147.
Abbott, A. P.; Capper, G.; Davies, D. L.; Rasheed, R. K.; Tambyrajah, V. Novel solvent properties of choline chloride/urea mixtures. Chem. Commun. 2003, (1), 70-71.
Astarita, G.; Savage, D. W.; Bisio, A. Gas treating with chemical solvents. John Wiley &; Sons 1983, 70-71.
Bromberg, J. P. Physical Chemistry. Allyn &; Bacon 1980.
Haines, P. J. Principles of Thermal Analysis and Calorimetry. Royal Society of Chemistry 2002.
Hatakeyama, T.; Quinn, F. X. Thermal Analysis: Fundamentals and Applications to Polymer Science. John Wiley &; Sons 1994.
IPCC. Intergovernmental panel on climate change special report on carbon dioxide capture and storage. Cambridge, Cambridge University Press. 2005.
Jadhav, P. D.; Rayalu, S. S.; Biniwale, R. B.; Devotta, S. CO2 emission and its mitigation by adsorption on zeolites and activated carbon. Current Science Association 2007, 92, 724-726.
Kathrina, R. S.; Rhoda, B. L.; Meng-Hui, L. Densities, refractive indices, and viscosities of N,N-diethylethanol ammonium chloride–glycerol or –ethylene glycol deep eutectic solvents and their aqueous solutions. J. Chem. Thermodyn. 2013, 65, 65-72.
Kohl, L. A.; Riesenfeld, F. C. GasPurification. 4th ed. Houston 1985.
Lewis, G. N. The osmotic pressure of concentrated solutions, and the laws of the perfect solution. J. Am. Chem. Soc. 1908, 30, 668-683.
Lin, C.-M.; Leron, R. B. ; Caparanga, A. R.; Li, M.-H. Henry's constant of carbon dioxide-aqueous deep eutectic solvent (choline chloride/ethylene glycol, choline chloride/glycerol, choline chloride/malonic acid) systems. J. Chem. Thermodyn. 2014, 68, 216-220.
Morrison, H. G.; Sun, C. C.; Neervannan, S. Characterization of thermal behavior of deep eutectic solvents and their potential as drug solubilization vehicles. International Journal of Pharmaceutics 2009, 378, 136-139.
NIST. National institute of standard and technology chemistry webbook. http://webbook.nist.gov/chemistry/. 2011.
Schladt, M. J.; Filburn, T. P.; Helble, J. J. Supported amine sorbents under temperature swing absorption for carbon dioxide and moisture capture. Ind. Eng. Chem. Res. 2007, 46, 1590-1597.
Seddon, K. R. Room-temperature ionic liquids : Neoteric solvents for clean catalysis. Kinet. Catal 1995, 37, 693-697.
Sen, M.; Paolucci, S. Using carbon dioxide and ionic liquids for absorption refrigeration. 7th IIR Gustav Lorentzen Conference on Natural Working Fluids 2006, Trondheim, Norway,.
Wilson, G. M. Vapor-liquid equilibrium. XI: A new expression for the excess free energy of mixing. J. Am. Chem. Soc. 1964, 86, 127-130.
Yan, S.; Fang, M.; Zhang, W.; Luo, Z.; Cen, K. Technique analysis and research progress of CO2 separation from flue gas be chemical absorption. Huagong Jinzhan 2006, 25, 1018-1024.
李夣輝 自排放氣中回收二氧化碳之技術. 化工技術 2004, 12, 171-185.
陳道達 熱分析; 1992.