臺灣博碩士論文加值系統

萃取精油的方式有很多，最常見的方法是以有機溶劑萃取，但這些有機溶劑在分離過程時產生的揮發性化合物會造成人體與環境的危害，並且增加燃燒與爆炸的風險，除此之外，有機溶劑會殘留於萃取物中，進一步的分離過程會增加實驗的成本。超臨界流體萃取(SFE)近年來是精油萃取的一種熱門方式，特別是以二氧化碳作為溶劑，其無毒、不易燃燒、容易取得、可循環利用…等多種優勢，大幅降低實驗的風險與成本。而超臨界相的二氧化碳是一種非極性溶劑，其高擴散度和低黏度的特性很適合萃取低分子量的化合物，達成超臨界的條件也相對容易，使用的能源相對較少。
本次實驗以超臨界二氧化碳烘箱設備萃取澳洲茶樹(Melaleuca alternifolia)之葉子部位(以下簡稱茶樹)，透過壓力、以及溫度的改變，探討精油產率的變化。首先，以索氏萃取法得出茶樹粗脂肪率作為超臨界流體萃取(SFE)的產率參考，實驗採用三水準兩因子3^2設計，壓力設定2000psi、3000psi與4000psi，溫度設定40℃、50℃與60℃，以動靜態相平衡設備進行半流動式萃取，所得的產率再比對粗脂肪率是否差異過多。實驗結果以雙因子變異數分析與二階線性迴歸分析，探討最佳產率的實驗條件以及各項因子與因子間交互作用的顯著性，並對兩因子能得到的最大產率進行預估。

There are many ways to extract essential oils. The most common method is extraction with organic solvents, but, the volatile compounds generated by these organic solvents during the separation process will cause harm to human body and the environment, and increase the risk of combustion and explosion, in addition, organic solvents will remain in the extract, and further separation processes will increase the cost of the experiment. Supercritical fluid extraction (SFE) has been a popular method for essential oil extraction in recent years, especially using carbon dioxide as a solvent, which has many advantages such as non-toxic, non-flammable, easy to obtain, recyclable, etc., which greatly reduces the risk and cost of experiments. The carbon dioxide in the supercritical phase is a non-polar solvent. Its high diffusivity and low viscosity are very suitable for the extraction of low molecular weight compounds. It is relatively easy to achieve supercritical conditions and uses relatively little energy.
The experiment uses supercritical carbon dioxide oven equipment to extract Australian tea tree, and the yield of essential oils were investigated through the changes of pressure and temperature. First, the crude fat rate of tea tree was obtained by Soxhlet extraction method as a reference for the yield of SFE, The experiment adopts a three-level two-factor design, the pressure is set to 2000psi, 3000psi and 4000psi, and the temperature is set to 40℃, 50℃ and 60℃. Semi-flow extraction is carried out with dynamic and static phase equilibrium equipment, and the yield obtained is compared to whether the crude fat rate is too different. The experimental results were analyzed by ANOVA and second-order regression to examine the experimental conditions of the best yield and the significance of the interaction between various factors, and to predict the maximum yield that can be obtained by the two factors.

摘要 I
Abstract III
目錄 IV
表目錄 VII
圖目錄 VIII
第一章 緒論 1
1-1前言 1
1-2茶樹簡介 2
1-3研究背景與實驗目的 4
第二章 文獻回顧 5
2-1超臨界流體 5
2-1-1超臨界流體起源 6
2-1-2超臨界流體的種類 7
2-1-3物化性質 8
2-1-4超臨界之應用 10
2-1-5超臨界設備 13
2-2超臨界萃取的方式 14
2-2-1超臨界萃取之原理 15
2-2-2超臨界萃取與傳統萃取差異 19
2-2-3超臨界萃取優缺點 20
2-3索氏萃取法 21
2-3-1索氏萃取法之原理 21
2-3-2索氏萃取法的優缺點 21
第三章 實驗設計法與數據分析 22
3-1實驗設計法 22
3-1-1三水準兩因子32設計 24
3-2實驗數據分析 27
3-2-1二階線性迴歸 28
第四章 實驗 29
4-1實驗材料與設備 29
4-1-1實驗材料 29
4-1-2實驗設備 33
4-2實驗步驟 44
4-2-1索氏萃取法實驗程序 45
4-2-2超臨界二氧化碳萃取實驗程序 46
第五章 結果與討論 49
5-1索氏萃取實驗數據 49
5-2 32設計實驗數據總整理 50
5-3 32設計實驗線性迴歸分析與變異數分析 52
5-3-1二階線性迴歸分析 52
5-3-2變異數分析 53
5-4 32設計實驗迴歸分析圖 54
5-4-1固定壓力(X1)水準，溫度對產率的迴歸線圖 54
5-4-2固定溫度(X2)水準，壓力對產率的迴歸線圖 55
5-4-3反應曲面含等高線圖 57
第六章 結論 60
參考文獻 61

[1]潘懷宗、劉晉魁、周良穎、謝秉甫、李沐勳 利用超臨界二氧化碳萃取肉桂中之精油成份:並與水蒸氣蒸餾法進行比較 中醫藥雜誌 第5卷 3期 頁199-207 1994
[2]Bevan, C. D.; Marshall, P. S. The Use of Supercritical Fluids in the Isolation of Natural Products. Natural Product Reports 1994, 32, 451–466.A.B. Author, Title of Book, ABC Press, Taichung, Taiwan, pp. 300-307, 2005.
[3]Phelps, C. L.; Smart, N. G.; Wai, C. M. Past, Present and Possible Future Applications of Supercritical Fluid Extraction Technology. Journal of Chemical Education1996,73,1163-1168
[4]Supercritical fluids in separation and purification: A review, Sampatrao D.Manjare, KabirDhingra, Materials Science for Energy Technologies, Volume 2, Issue 3, December 2019, Pages 463-484
[5]L.Lodia,V.O.C.Conchaab,R.A Souzaa,L.C.Medinac,R.M.Filhod M.R.W.Maciel, An Experimental study of a pilot plant DE asphalting process in subcritical and supercritical conditions, Pet. Sci. Technol.,32 (22) (2014), pp. 2659-2665
[6]S.H. Joo, S.M. Shin, Extraction of cobalt from spent cmb catalyst using supercritical CO2, Arch. Metall. Mater., 60 (2015), p. 1535
[7]L. Zhiyi, L. Xuewu, C. Shuhua, Z. Xiaodong, X. Yuanjing, W. Yong, X. Feng, An experimental and simulating study of supercritical CO2 extraction for pepper oil, Chem. Eng. Process., 45 (2006), pp. 264-267
[8]S.V.A. Martin, M.J. Cocero, T. Gamse, Supercritical carbon dioxide fractionation of lavandin essential oil: experiments and modelling, J. Supercrit. Fluids, 45 (2008), pp. 181-188
[9]Holmes Peter. Aromatica: a clinical guide to essentail oil theraprutics, p 435, 73 Collier Street, London: Jessica Kingsley Publishers Ltd, 2016.
[10]Y-Y Gao 1, M A Di Pascuale, W Li, A Baradaran-Rafii, A Elizondo, C-L Kuo, V K Raju, S C G Tseng, In vitro and in vivo killing of ocular Demodex by tea tree oil, Br J Ophthalmol, 2005 Nov;89(11):1468-73
[11]Carson, C. F., L. Ashton, L. Dry, D. W. Smith, and T. V. Riley.2001. Melaleuca alternifolia (tea tree) oil gel (6%) for the treatment of recurrent herpes labialis. J. Antimicrob. Chemother.48:450-451
[12]Cox, S. D., C. M. Mann, and J. L. Markham.2001. Interactions between components of the essential oil of Melaleuca alternifolia. J. Appl. Microbiol.91:492-497.
[13]Hammer, K. A., L. Dry, M. Johnson, E. M. Michalak, C. F. Carson, and T. V. Riley.2003. Susceptibility of oral bacteria to Melaleuca alternifolia (tea tree) oil in vitro. Oral Microbiol. Immunol.18:389-392.
[14]May, J., C. H. Chan, A. King, L. Williams, and G. L. French.2000. Time-kill studies of tea tree oils on clinical isolates. J. Antimicrob. Chemother.45:639-643.
[15]Messager, S., K. A. Hammer, C. F. Carson, and T. V. Riley.2005. Assessment of the antibacterial activity of tea tree oil using the European EN 1276 and EN 12054 standard suspension tests. J. Hosp. Infect.59:113-125
[16]Messager, S., K. A. Hammer, C. F. Carson, and T. V. Riley.2005. Effectiveness of hand-cleansing formulations containing tea tree oil assessed ex vivo on human skin and in vivo with volunteers using European standard EN 1499. J. Hosp. Infect.59:220-228.
[17]Gustafson, J. E., Y. C. Liew, S. Chew, J. Markham, H. C. Bell, S. G. Wyllie, and J. R. Warmington.1998. Effects of tea tree oil on Escherichia coli. Lett. Appl. Microbiol.26:194-198.
[18]C. F. Carson, K. A. Hammer, T. V. Riley ASM Melaleuca alternifolia (Tea Tree) Oil: a Review of Antimicrobial and Other Medicinal Properties Journals Clinical Microbiology Reviews Vol. 19, No. 1
[19]Annarica Calcabrini, Annarita Stringaro, Laura Toccacieli, Stefania Meschini, Manuela Marra, Marisa Colone, Giuseppe Arancia, Agnese Molinari, GiuseppeSalvatore, Francesca Mondello, Journal of Investigative Dermatology, Volume 122, Issue 2, February 2004, Pages 349-360.
[20]Holmes Peter. Aromatica: a clinical guide to essentail oil theraprutics, p 437, 73 Collier Street, London: Jessica Kingsley Publishers Ltd, 2016.
[21]Herrero, M.; Cifuentes, A.; Ibañez, E. Sub- and supercritical fluid extraction of functional ingredients from different natural sources: Plants, food-by-products, algae and microalgae: A review. Food Chem 2006, 98, 136–148.
[22]Farid Chemat, Maryline Abert-Vian, Anne Sylvie Fabiano-Tixier, Jochen Strube, Lukas Uhlenbrock, Veronika Gunjevic, Giancarlo Cravotto, Green extraction of natural products. Origins, current status, and future challenges, TrAC Trends in Analytical Chemistry, Volume 118, September 2019, Pages 248-263.
[23]M. Cvjetko Bubalo, S. Vidovic, I. Radojcic Redovnikovic, S.Jokic, New perspective in extraction of olant biologically active compounds by green solvents, Food Bioprod. Process. 109 (2018) 52-73, 2018.
[24]Fiori, L. Supercritical extraction of sunflower seed oil: Experimental data and model validation, Journal of Supercritical Fluids, Volume 50, Issue 3, October 2009, Pages 218-224
[25]Corso, M.P., Fagundes-Klen, M.R., Silva, E.A., Cardozo Filho, L., Santos, J.N., Freitas, L.S., Dariva, C, Extraction of sesame seed (Sesamun indicum L.) oil using compressed propane and supercritical carbon dioxide, Journal of Supercritical Fluids, Volume 52, Issue 1, February 2010, Pages 56-61
[26]Z. Knez, E. Markocic, M. Leitgeb, M. Primozic, M. Knez Hrncic, M. Skerget, Industrial applications of supercritical fluids: a review, Energy 77 (2014) 235-243.
[27]M. Mukhopadhyay, 2000, Natural Extracts Using Supercritical Carbon Dioxide, CRC Press LLC.
[28]J. B. Hannay and J. Hogarth, Membrane interface for online Supercritical fluid extraction flow-injection analysis, A29,p324,Proc,Roy. Soc. London Ser., 1897
[29]Akgerman, Supercritical fluid extraction of contaminants from environmental matrices, Waste Management, Vol.13,Issue 5-7,pp.403-415, 1993
[30]連培榮、孫傳家 超臨界流體萃取的應用 食品科技與安全專題報導 2009年9月
[31]楊顯整 超臨界綠色技術之概述 綠基會通訊專題報導 2009年7月
[32]P. Pellerin, Supercritical fluid extraction of natural raw materials for the flavor and perfume industry, Perfumer & Flavorist, Vol. 16, No. 4, pp. 37-39 , 1991
[33]Steven Lim, Keat-Teong Lee, Influences of different co-solvents in simultaneous supercritical extraction and transesterification of Jatropha curcas L. seeds for the production of biodiesel, Chemical Engineering Journal, Volume 221, 1 April 2013, Pages 436-445
[34]U. Salgan, H. Kormaz, A green separation process for recovery of healthy oil from pumpkin seed, J. Supercrit. Fluids, 58 (2011), pp. 239-248
[35]M. A. McHugh, V. J. Krukonis, Supercritical fluid extraction : Principles and Practice, Butterworth Publishers,1986
[36]Supercritical Fluid Extraction, Density Considerations, Wikipedia, 2007 11
[37]Supercritical fluid, Wikipedia
[38]L. T. Tayor, Supercritical fluid extraction, John Wiley & Sons,1996
[39]丁耀柏 以超臨界流體去除晶圓上之光阻 國立清華大學化學工程研究所 碩士論文，2005
[40]邵明偉 超臨界發泡射出成形聚烯烴高分子奈米複材機械/熱/發泡性質之探討 清雲科技大學 機械工程系所 碩士論文 2008
[41]葛歡慶、輝國鈞、李菁 中藥現代化與超臨界二氧化碳流體新技術的應用 第二屆全國超臨界流體技術學術及應用研討會論文集 1998
[42]劉家宏 利用超臨界二氧化碳萃取與純化茶葉中之兒茶素 長庚大學 化學工程與材料工程研究所，碩士論文
[43]高而仕 超臨界二氧化碳萃取洛神花多酚成分及其抗氧化活性之研究美容科技學刊 第8卷 三期 頁106-127 2011
[44]廖盛焜、李勝騰、張原儒 超臨界流體染色技術 科學發展 470期 P29，2012
[45]林奘民 超臨界二氧化碳在聚酯、聚丙烯纖維染色之研究 長庚大學 化學工程研究所 碩士論文 2002
[46]郭峻銘 超臨界流體萃取法於下水汙泥中直鏈烷基苯磺酸分析之研究 國立交通大學 環境工程所研究所 碩士論文 2003
[47]鄭光煒 化工熱力學在超臨界技術之研究 國立台灣大學工程學刊 第84期 頁45-57 2002
[48]P. C. Simoes, Multicomponent Phase Equilibria of an Extra-Virgin Olive Oil in Supercritical Carbon Dioxide, Journal of Supercritical Fluids, Vol. 9, Issue 2, pp. 75-81, 1996
[49]Y. Takeshita, Y. Sato, Measuremeant of copper compound solubility in supercritical carbon dioxide and correlation using a solution model, Journal of Supercritical Fluids, Vol.24, Issue 2,pp.91-101.2002
[50]U. Kopcak, R. S. Mohamed, Caffeine solubility in supercritical carbon dioxide/co-solvent mixtures, Journal of Supercritical Fluids, Vol. 34, Issue 2, pp. 209-214, 2005
[51]陳登科 超臨界二氧化碳萃取蛹蟲草蟲草素之探討 朝陽科技大學應用化學系 碩士論文 2004
[52]張傑明、張慶源、巫錫銘，超臨界溶媒技術萃取天然物之應用，化工技術，10 (6)，頁172-178，1998
[53]簡智翔 共溶劑對β-胡蘿蔔素於超臨界二氧化碳溶解度影響之研究 國立中央大學 化學工程與材料工程研究所 碩士論文 2004
[54]H. Brogle, CO2 as a solvent: its properties and applications, Chem. and Ind., 19, p.385, 1982
[55]Kajimoto, Solvation in Supercritical Fluids: Its Effects on Energy Transfer and Chemical Reactions, Journal of Chemical Reviews, Vol.99, pp.355-389, 1999
[56]E. Stahl, E. Schuetz, H. K. Mangold, Extraction of seed oils with liquid and supercritical carbon dioxide, Journal of Agricultural and Food Chemistry, Vol. 28, pp. 1153-1157, 1980
[57]T. H. Pang, E. McLaughlln, Supercritical extraction of aromatic hydrocarbon solids and tar sand bitumens, Journal of Industrial and Engineering Chemistry Process Design and Development, Vol. 24, Issue 4, pp. 1027-1032, 1985
[58]J. M. DeSimone, Practical Approaches to Green Solvents, Journal of Science, Vol. 297, No. 5582¸pp. 799-803, 2002
[59]陳俊達 超臨界二氧化碳萃取紫蘇油之研究 國立高雄應用科技大學 化學工程與材料工程研究所 碩士論文 2009
[60]潘懷宗、劉晉魁、周良穎、謝秉甫、李沐勳,利用超臨界二氧化碳萃取肉桂中之精油成份:並與水蒸氣蒸餾法進行比較,中醫藥雜誌,第5卷, 3期, 頁199-207,1994
[61]S. Burt, Essential oils: their antibacterial properties and potential applications in foods─a review, International, Journal of Food Microbiology, Vol.94, Issue 3, pp.223-253, 2004
[62]T. Baysal, D. A. J. Starmans Supercritial carbon dioxide extraction of carvone and limonene from caraway seed, Journal of Supercritical Fluids, Vol.14, Issue3,p.223-234, 1999
[63]M. V. Palmer and S. S. T. Ting, Application for supercritical fluid technology in food processing, Food Chemistry, Vol. 52, Issue 4, pp. 345-352, 1995
[64]葉玉雯 比較索氏萃取法與超臨界萃取法對含萘及五氯酚土壤萃取之研究 中興大學 環境工程學研究所 碩士論文 1999
[65]M.D Luque de Castro, L.E Garcia-Ayuso, Soxhlet extraction of solid materials: an outdated technique with a promising innovative future, Analytica Chimica Acta, Vol. 369, Issue 1-2, pp.1-10, 1998
[66]R. A. Fisher, Design of Experiments, Br Med J. 1936 Mar 14; 1(3923): 554.
[67]Douglas C. Montgomery, Design and Analysis of Experiments譯者:黎正中、陳源樹 實驗設計與分析 高立圖書有限公司 2001 第五版