臺灣博碩士論文加值系統

本篇研究探討在不同壓力的環境下，木質素（Lignin）對於離子液體1-Butyl-3-methylimidazolium trifluoromethanesulfonate ([Bmim][TFS]) 與1-Hexyl-3-methylimidazolium trifluoromethansulfonate ([Hmim][TFS])的作用力關係。
起初我們由紅外光譜觀察到在不同比例混合成的木質素與離子液體溶液陰陽離子皆無明顯的變化，但當我們改變壓力條件時可以觀察到顯著的變化。
首先陰離子部分我們看到純的離子液體[Bmim][TFS]每根峰的訊號位置皆會隨著壓力增加而呈現藍位移的趨勢，這是由於壓力使得共價鍵間的距離縮短使頻率增加所導致的緣故；而〖 ν〗_as (CF_3 ) 在壓力增加的環境下會使得波峰裂解為二。當我們加入不同濃度的木質素後，隨著壓力逐漸升高，各個峰值位置的變化趨勢會因濃度的不同而有不同的曲線關係， 而和純離子液體比較，〖 ν〗_as (CF_3 ) 也會因木質素的濃度增加，在高壓的環境中降低裂解的程度，推測是木質素會和其產生作用力導致無法產生裂解。
最後我們也嘗試改變離子液體陽離子端的脂肪族碳鏈數目，結果顯示當碳鏈數目增加時，同時也會抑制陰陽離子的裂解情形，推測是長碳鏈阻隔了原本的排列情形，使得在高壓的環境下無法發生裂解。

一、 序論 1
1.1.木質素 1
1.1.1.木質素鍵結形式 2
1.1.2.木質素的分離與性質 2
1.1.3.鹼催化降解 5
1.1.4.酸催化降解 6
1.1.5.以離子液體作為媒介的酸催化 8
1.2.離子液體 10
1.2.1.前言 10
1.2.2.離子鹽類 11
1.2.3.離子液體 12
1.2.4.質子型離子液體 13
1.2.5.非質子型離子液體 14
1.2.6.其他形式離子液體 14
1.2.7.離子液體性質 15
1.2.8.晶體晶格結構 16
1.2.9.離子對與自由離子 16
1.2.10.氫鍵網絡 17
1.2.11.壓力 18
二、實驗
2.1.紅外光譜 20
2.1.1.原理 20
2.1.2.傅立葉轉換紅外光譜 22
2.2.壓力校正 23
2.3.藥品與儀器 25
2.3.1.藥品 25
2.3.2.儀器 26
2.4.方法 27
2.5.實驗步驟 27
2.5.1.藥品配置 27
2.5.2常壓部分 28
2.5.3.高壓部分 28
三、結果討論 29
3.1.陰離子部分 29
3.1.1.陰離子常壓討論 29
3.1.2.陰離子高壓討論 31
3.1.3.陰離子趨勢討論 34
3.2.陽離子部分 35
3.2.1.陽離子常壓討論 35
3.2.2.陽離子高壓討論 37
3.2.3.陽離子趨勢討論 39
3.3.改變碳鏈數目討論 42
四、結論 44
五、參考文獻 45

圖目錄
圖1.1、木質素單體結構與標記位置 2
圖1.2、1,5,7-Triazabicyclo[4.4.0]dec-5-ene (TBD) 6
圖1.3、GG與VG結構通式，其中GG:R=H、VG:R=CH3 7
圖1.4、由phenolic所反應的鹼催化裂解α-aryl ether bond機制 7
圖1.5、酸催化水解木質素β-Phenyl Ether Linkages機制 8
圖1.6、VG與GG的β-O-4鍵裂解反應式 8
圖1.7、酸性離子液體中，GG和VG的降解過程 9
圖1.8、離子液體 [C2mim]Cl分子模型圖 17
圖1.9、分子構形結構轉變示意圖 19
圖2.1、分子振動方式示意圖 21
圖2.2、分子的四種彎曲振動示意圖 21
圖2.3、FTIR組成簡圖 23
圖2.4、壓力對螺絲轉動距離趨勢圖 25
圖3.1、不同比例[Bmim][TFS]/Lignin混合液之常壓光譜圖 29
圖3.2、離子液體[Bmim][TFS]陰離子加入0%wt(左上)、5%wt(左下)、20%wt(右下)木質素壓力變化光譜圖 30
圖3.3、不同濃度[Bmim][TFS]/Lignin混合液之陰離子在不同壓力下位移關係圖 33
圖3.4、不同比例[Bmim][TFS]/Lignin混合液陽離子之常壓光譜圖 35
圖3.5、離子液體[Bmim][TFS]陽離子加入0%wt(左上)、5%wt(右上)、20%wt(左下)木質素壓力變化光譜圖 37
圖3.6、不同濃度[Bmim][TFS]/Lignin混合液之陰離子在不同壓力下位移關係圖 39
圖3.7、不同比例[Hmim][TFS]/Lignin混合液陰陽離子之常壓光譜圖 40
圖3.8、純離子液體[Hmim][TFS]陰陽離子隨壓力變化光譜圖 41
圖3.9、離子液體[Hmim][TFS]陰陽離子加入20%wt木質素壓力變化光譜圖 41
圖3.10、不同濃度[Hmim][TFS]/Lignin混合液之陰離子在不同壓力下位移關係圖 42

表目錄
表2.1、氘氧根與氫氧根在不同相之最小平方係數 24

1.Jingyu Wang; Yong Qian; Yonghong Deng; Di Liu; Hao Li; Xueqing Qiu. Probing the interactions between lignin and inorganic oxides using atomic force microscopy. Applied Surface Science 2016, 390, 617–622.
2.Zakzeski, J.; Bruijnincx, P. C. A.; Jongerius, A. L.; Weckhuysen, B. M. The catalytic valorization of lignin for the production of renewable chemicals. Chem. Rev. 2010, 110, 3552−3599.
3.Ragauskas, A. J.; Beckham, G. T.; Biddy, M. J.; Chandra, R.; Chen, F.; Davis, M. F.; Davison, B. H.; Dixon, R. A.; Gilna, P.; Keller, M.; Langan, P.; Naskar, A. K.; Saddler, J. N.; Tschaplinski, T. J.; Tuskan, G. A.; Wyman, C. E. Lignin valorization: improving lignin processing in the biorefinery. Science 2014, 344, 709.
4.Xu, C. P.; Arancon, R. A. D.; Labidi, J.; Luque, R. Lignin depolymerisation strategies: towards valuable chemicals and fuels. Chem. Soc. Rev. 2014, 43, 7485−7500.
5.Pandey, M. P.; Kim, C. S. Lignin depolymerization and conversion: A review of thermochemical methods. Chem. Eng. Technol. 2011, 34, 29−41.
6.Abdulkhani, A.; Karimi, A.; Mirshokraie, A.; Hamzeh, Y.; Marlin, N.; Mortha, G. Isolation and chemical structure characterization of enzymatic lignin from populus deltoideswood. J. Appl. Polym. Sci. 2010, 118, 469−479.
7.Guerra, A.; Filpponen, I.; Lucia, L. A.; Argyropoulos, D. S. Comparative evaluation of three lignin isolation protocols for various wood species. J. Agric. Food Chem. 2006, 54, 9696−9705.
8.Yang, Q.; Wu, S. B.; Lou, R.; Lv, G. J. Structural characterization of lignin from wheat straw. Wood Sci. Technol. 2011, 45, 419−431.
9.Lopez, M.; Huerta-Pujol, O.; Martinez-Farre, F. X.; Soliva, M. Approaching compost stability from Klason lignin modified method: Chemical stability degree for OM and N quality assessment. Resour. Conserv. Recycl. 2010, 55, 171−181.
10.Xiao, B.; Sun, X. F.; Sun, R. C. Chemical, structural, and thermal characterizations of alkali-soluble lignins and hemicelluloses, and cellulose from maize stems, rye straw, and rice straw. Polym. Degrad. Stab. 2001, 74, 307−319.
11.Pu, Y. Q.; Jiang, N.; Ragauskas, A. J. Ionic liquid as a green solvent for lignin. J. Wood Chem. Technol. 2007, 27, 23−33.
12.Hossain, M. M.; Aldous, L. Ionic liquids forlignin processing: dissolution, isolation, and conversion. Aust. J. Chem. 2012, 65, 1465− 1477.
13.Jia, S.; Cox, B. J.; Guo, X.; Zhang, Z. C.; Ekerdt, J. G. Decomposition of a phenolic lignin model compound over organic Nbases in an ionic liquid. Holzforschung 2010, 64, 577−580.
14.Jia, S.; Cox, B. J.; Guo, X.; Zhang, Z. C.; Ekerdt, J. G. Cleaving the β-O-4 bonds of lignin model compounds in an acidic ionic liquid, 1-H-3-Methylimidazolium Chloride: an optional strategy for the degradation of lignin. ChemSusChem 2010, 3, 1078−1084.
15.Jia, S.; Cox, B. J.; Guo, X.; Zhang, Z. C.; Ekerdt, J. G. Decomposition of a phenolic lignin model compound over organic Nbases in an ionic liquid. Holzforschung 2010, 64, 577−580.
16.Jia, S. Y.; Cox, B. J.; Guo, X. W.; Zhang, Z. C.; Ekerdt, J. G. hydrolytic cleavage of beta-O-4 ether bonds of lignin model compounds in an ionic liquid with metal chlorides. Ind. Eng. Chem. Res. 2011, 50, 849−855.
17.Cox, B. J.; Jia, S.; Zhang, Z. C.; Ekerdt, J. G. Catalytic degradation of lignin model compounds in acidic imidazolium based ionic liquids: Hammett acidity and anion effects. Polym. Degrad. Stab. 2011, 96, 426−431.
18.Ghassan M.J. Al Kaisya; Mohamad Ibrahim Abdul Mutaliba; Mohamad Azmi Bustama; Jean-Marc Levequeb; Nawshad Muhammadc. Liquid-Liquid extraction of aromatics and sulfur compounds from base oil using ionic liquids. Chem. Eng. 2016,4, 4786–4793
19.Murray, S. M.; O’Brien, R. A.; Mattson, K. M.; Ceccarelli, C.; Sykora, R. E.; West, K. N.; Davis, J. H. Angew. Chem., Int. Ed. 2010, 49, 2755−2758.
20.Mirjafari,A.;Pham,L.N.;McCabe,J.R.;Mobarrez,N.;Salter,E. A.;Wierzbicki,A.;West,K.N.;Sykora,R.E.;Davis,J.H.RSCAdv.2013, 3, 337−340.
21.Xu, W.; Angell, C. A. Solvent-free electrolytes with aqueous solution-like conductivities. Science 2003, 302, 422-425.
22.Feng,Su.;Cheng,Peng. ;Guan-Lin,Li. ;Li,Xu. ;Yun-Jun,Yan. Biodiesel production from woody oil catalyzed by Candida rugosa lipase in ionic liquid. Renewable Energy 2016,90, 329-335.
23.Greaves,T.L.;Drummond,C.J. Solvent nanostructure, the solvophobic effect and amphiphile self-assembly in ionic liquids. Chem. Soc. Rev. 2013,42,1096− 1120.
24.Welton, T. Room-temperature ionic liquids. solvents for synthesis and catalysischem. Rev. 1999, 99, 2071
25.Izgorodina, E. I.; MacFarlane, D. R. J. Phys. Chem. B 2011, 115, 14659−14667.
26.Evans, D. F.; Chen, S.-H.; Schriver, G. W.; Arnett, E. M. J. Am. Thermodynamics of solution of nonpolar gases in a fused salt. Hydrophobic bonding behavior in a nonaqueous system. Chem. Soc. 1981, 103, 481−482.
27.Fumino,K.;Wulf,A.;Ludwig,R.Angew.Chem.,Int.Ed.2009,48, 3184.
28.Faria, L. F. O.; Penna, T. C.; Ribeiro, M. C. C. J. Phys. Chem. B 2013, 117, 10905−10912.
29.Chang, H.-C.; Hung, T.-C.; Wang, H.-S.; Chen, T.-Y. Local structures of ionic liquids in the presence of gold under high pressures. AIP Adv. 2013, 3, 032147.
30.Chunbo Leng, J. Duncan Kish, Jason E. Roberts, Iman Dwebi, Nara Chon, and Yong Liu . Temperature-dependent henry’s law constants of atmospheric amines. J.Phys.Chem. A 2015, 119, 8884-8891.
31.Banwell ,C. N.; McCash,E. M. Fundamentals of molecular spectroscopy, 4th ed, McGraw, 2005.
32.P.T.T.Wong; D.J.Moffatt. The uncoupled O-H or O-D stretch in water as an internal pressure gauge for high-pressure infrared spectroscopy of aqueous systems. Applied Spectroscopy 1987, 41(6):1070-1072.
33.Ashif H. Tamboli; Harshad A. Bandal; Hern Kim. Solvent free synthesis of cyclic ureas and urethanes by carbonylation method in the basic dicationic ionic liquid catalysts. Chem. Eng. 2016, 306, 826–831.
34.Gianmarco Griffini, Valeria Passoni, Raffaella Suriano, Marinella Levi, and Stefano Turri. Polyurethane coatings based on chemically unmodified fractionated lignin. Chem. Eng. 2015, 3, 1145−1154.