臺灣博碩士論文加值系統

本文旨在利用超臨界流體層析儀進行正己烷及環己烷在5A級分子篩的滯留行為的探討。本研究以5A級分子篩作為固定相(Stationary phase)，超臨界二氧化碳為移動相，調查溫度與壓力對於正己烷及環己烷的滯留行為的影響。研究結果發現，在40℃，2.0 g CO2/min的操作條件下，將壓力由1000 psi增加至1500 psi及2000 psi時，正己烷與環己烷的滯留時間皆隨著壓力增加而延長；在2000 psi，2.0 g CO2/min，將溫度由40℃增加至50℃及60℃時，正己烷與環己烷的滯留時間皆隨著溫度增加而縮短，但是兩者的滯留時間差異不大。由以上結果顯示，正己烷及環己烷在分子篩的滯留行為相似，因此無法有效利用超臨界二氧化碳配合5A級分子篩進行分離。根據實驗結果，本研究利用層析模擬的微分式初步估算環己烷在分子篩中的吸附常數及軸擴散係數，可作為未來環己烷相關分離程序之參考。

This study uses supercritical fluid chromatography (SFC) to investigate the retention behavior of n-Hexane and cyclohexane on the molecular sieves. The isotherms and dispersion coefficients of the cyclohexane in the bed of molecular sieves are obtained by curve fitting from the spectrum of SFC. The studied pressures are 1000, 1500, and 2000 psi, the investigated temperatures are 40, 50, and 60 ℃, and the flow rate of carbon dioxide is 2.0 g/min. The experimental results showed that both the temperature and pressure can affect the isotherms, but the retention behaviors of n-hexane and cyclohexane on the molecular sieves have no significant difference. This study provides a fast and simple method to investigate the isotherms of organic compound on solids. In addition, the collected isotherms will also provide useful information for the future application of the separation of cyclohexane.

中文摘要…………………………………………………………………………...I
英文摘要…………………………………………………………………….…II
第一章 緒論………………………………………………..……………....……1
第二章 文獻回顧………………………………………………………………..3
2.1、異構化製程概述……………………………….……………….…3
2.2、吸附分離原理……………………………………………………..5
2.2.1、吸附種類………………………………………………………..5
2.3、超臨界流體層析技術發展…………………………………….. ..9
2.3.1、超臨界流體概論……………………………….………………9
2.3.2、超臨界流體特性……………………………………………….10
2.3.3、層析法原理…………………………………………………….16
2.3.4、超臨界流體層析……………………………………………….17
2.3.5、各種層析法之比較…………………………………………….19
2.3.6、超臨界二氧化碳之優點………………………………………..20
2.3.7、超臨界流體技術之運用………………………………………..21
2.3.8、超臨界流體發展趨勢………………………………………….23
第三章 實驗方法………………….….……………………………..…………25
3.1、儀器設備………………………………………………..………...25
3.2、實驗藥品………………………………………………..………...27
第四章 實驗結果與討論………………………………………..…………..…28
4.1、以超臨界流體層析調查正己烷及環己烷在固定相滯留行為...28
4.2、層析模擬………………………………………………………….29
第五章 結論………………………………………………….…….…………32
第六章 參考文獻………………………………………….…………………33

1.梁明在、蔡佩芬，張仲讓、梁茹茜，第5屆2006年超臨界流體技術應用與發展研討會論文集,P37~42
2.江建忠，利用超臨界流體技術製備生質柴油之研究，國立清華大學化學工程學系碩士論文，2007。
3.洪英哲，超臨界流體轉酯化反應製備生質柴油，國立清華大學化學工程學系碩士論文，2009。
4.UOP Process Technology Training Manual ,“SafeCat System And Total Isomerization Process”,Chinese Petroleum Corporation Kaoshiung Refinery Taiwan,November,1993。
5.單元操作/Warren L.McCabe,JulianC.Smith Peter Harriott原著；李尚凡等譯
6.黃文龍、宏正宗,"吸附劑在石化工業之應用”,石油季刊,Vol.40,No.4，pp49~57,2004。
7.McHugh,M.A.,and Ktuknis V.J.,Supercritical Fluid Extraction:Principe and Practice,2nded.,Butterworth-Heinemann,Boston(1994)
8.Caude,M.; Thie`baut, D. Practical”Supercritical Fluid Chromatography and Extraction”; Harwood Academic Publishers: Amsterdam, 1999
9.Darr, J. A.; Poliakoff, M. Chem. Rev. 1999, 99, 495–541
10.Brunner, G., “Supercritical Fluids: Technology and Application to Food Processing,” Journal of Food Engineering, Vol.67,pp.21-33(2005)
11.Ajznberg,N., Trabelsi, F.,and Recasens, F.,”What`s New in Industrial polymerization with Supercritical Solvent?A Short Review,”Chemical Engineering and Technology,Vol.23,pp.829-839(2000)
12.Saito Muneo,Yosio Yamauchi and Tsuneo Okuyama,”Franctionation by packed-column SFC principles and application”,1994 3~77.
13.Filippi Richard P de,”CO2 as a Solvent:Application to fats,oils and other matericals”,Chemistry and Industry,1982,19,390.
14.Hildebrand, J. H. and R. L. Scott,”Regular solutions (prentice-hall,Englewood cliffs, N. J.)”,1962
15.Lou, X.; Janssen, H.; Cramers, C. A. J.”Chromatog”r. A 1997, 785, 57–64
16.Chang C. J., k. L. Chiu, Y. L. Chen and C. Y. Chang,”Separation of catechins from green tea using carbon dioxide extraction”,Food Chemistry, 2000, 68, 109~113.
17.王煌忠、張慶源等，”超臨界二氧化碳萃取茶葉精油及濃縮研究”,興大工程學刊,1999，第十卷,第三期,1~9.
18.Chemical Technology in January 2011
19.張學明、杜子邦、黃功勛,”超臨界流體技術於生醫材料中之應用”,化工技術,15(11),pp154~166,2007
20.桂椿雄，「超臨界流體萃取法之簡介」，化學，第56卷，第4期，第42-47頁(1998)
21.Dziezak,J.D.,”Innovative Separation Process Finding Its Way into the Food Industry”,Food Technology,June,66(1986)
22.Chen,S.H.,”A Rough-Hard-Sphere Theory for Diffusion in Supercritical Carbon Dioxide”,Chem.Eng.Sci.,38,655(1983)
23.Tsekhanskaya,Y.V.,”Diffusion of Naphthalene in Carbon Dioxide Near the Liquid-Gas Critical Point”,Russ.J.of Chem.,45,744(1971)
24.Francis, A.,”Solvent Extraction with Liquid Carbon Dioxide,”Industrial and Engineering Chemistry,Vol.47, No. 2, pp.230-233(1955)
25.Peng,D.Y.,and Robinson,D.B.,”New Two-Constant Equation of State,”Industrial and Engineering Chemistry,Fundamentals, Vol.15,pp.59-64(1976)
26.Kevin, M., Scholsky,”Polymeriztion Reactions at High Pressure and Supercritical Condition,”Journal of Supercritical Fluids, Vol.6,No.2,pp.103-127(1993)
27.林文發，「超臨界流體在高分子的應用」，化工，第41卷，第4期，第48-56頁(1994)
28.戴昌毅、張傑明、許修禎，「超臨界流體與醇類溶劑汽液平衡之新量測技術」，化工，第43卷，第5期，第128-143頁(1996)
29.談駿嵩，「超臨界流體在中之吸附與脫附」，化工，第41卷，第4期(1994)
30.Roselius, W., Vitzthum, O., and Hubert, P.,”Method of Extracting Coffee Oil Containing Aroma Constituents from Roasted Coffee,” U. S. Patent 4,328,255(1982)
31.Hung,T.V.&Unger,M.A.(1994)Food Australia 46(5):235.
32.陳重文(1996)以超臨界二氧化碳萃取法降低豬油中之膽固醇。台大食科所博士論文
33.Phillipson,B.E.,Rothrock.D.W.,Conner,W.E.,Harris,W.S.,and Illingworth,D.R.(1985)New England J.Med.312:1210.
34.Kinsella,J.E.(1986)Food Technology 40:89.
35.Chun-Hao Chen、Jer-Yi Liao、Ming-Tsai Liang，”Application ofSupercritical Fluid Extractive Technology in Chinese Herbal Medicine”, 2003 Conference and Exhibition on the Supercritical fluid technology,P3.3
36.Ting-Chia Huang and Ming-Chi Wei,”A Study on Extraction of Herbs by Supercritical Carbon Dioxide”, 2003 Conference and Exhibition on the Supercritical fluid technology,P3.4
37.陳延平、蘇至善、陳彥銘、陳宗勳、連培榮，”以超臨界流體技術進行藥物微粒與生醫材料之製備”， 第5屆2006年超臨界流體技術應用與發展研討會論文集,P57~64
38.Marr,R.,and Gamse,T.,”Use of Supercritical Fluid for Different Processes Including New Developments – a Review,”Chemical Engineerring and Processing,Vol.39,pp19-28(2000).
39.Hawthorne S. B.,and Miller D.J.,”Direct Comparison of Soxhlet and Low- and High-Temperature Supercritical CO2 Extraction Efficiencies of Organics from Environment Solids,”Analytical Chemistry,Vol. 66, No.22, pp.4005-4012(1994)
40.周信佑，「超臨界二氧化碳流體萃取含有有機農藥廢水及土壤之研究」，碩士論文，逢甲大學土木及水利工程研究所，台中(1999)。
41.盧漢諭，「以超臨界二氧化碳流體萃取法移除廢水與土壤之毒性物質研究」，碩士論文，逢甲大學土木及水利工程研究所，台中(1999)。
42.陳政群、陳明德、黃家銘、梁明在、張仲讓、蔡長成、林順益，”超臨界水氧化技術處理石化廠廢水液評估之研究”， 第5屆2006年超臨界流體技術應用與發展研討會論文集,P83~90。