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按一下以編輯母片標題樣式,按一下以編輯母片,第二層,第三層,第四層,第五層,*,超臨界流體技術,及其應用,Introduction to,Supercritical Fluid Technology :,Principles and Applications,林華經,引光生物科技有限公司,中華民國,98,年,11,月,30,日,從咖啡談起,您喝咖啡嗎,?,您喝過無咖啡因咖啡嗎,?,您喜歡喝無咖啡因咖啡嗎,?,無咖啡因咖啡,:,超臨界流體技術最早商業化應用的產品,何謂超臨界流體,當物質所處的壓力、溫度同時都大於其臨界壓力及臨界溫度時，則進入所謂的超臨界態,此物質則稱之為超臨界流體,二氧化碳的相圖,Temperature,SupercriticalFluid,Solid,Liquid,Triple Point,Critical Point,31.3,o,C, 1072 psi,Pressure,Gas,超臨界流體的特性,不是氣體，又有點像氣體,不是液體，又有點像液體,同時具備氣體及液體的雙重特性,二氧化碳的物理性質,狀態,氣態,超臨界態,液態,密度,0.62.0,x 10,-3,0.2 0.9,0.8 1.0,黏度,0.53.5,x 10,-4,2.09.9,x 10,-4,0.32.4,x 10,-2,擴散係數,0.01 1.0,0.53.3,x 10,-4,0.52.0,x 10,-5,超臨界流體的優點,幾乎無表面張力,低黏度,高擴散係數,高密度,高溶解能力,溶解能力可調,常見的超臨界流體之臨界性質,T,c,(,C),P,c,(,atm,),c,(,g,mL,-1,),CO,2,31.3,72.9,0.47,N,2,O,36.5,72.5,0.45,SF,2,45.5,37.1,0.74,NH,3,132.5,112.5,0.24,H,2,O,374,227,0.34,n,-C,4,H,10,152,37.5,0.23,n,-C,6,H,12,197,33.3,0.23,Xe,16.6,58.4,1.10,CCl,2,F,2,112,40.7,0.56,CHF,3,25.9,46.9,0.52,Source,: “SFE and Its use in Chromatographic Sample Preparation” Ed. S. Westwood. Chapter 1,使用超臨界二氧化碳的優點,低臨界點,操作安全,取得容易,環保,於常溫常壓下為氣體,超臨界流體之重要發展史,1822,Cagniard,de la Tour,發現物質的超臨界狀態,1861 Core,描述,Naphthalene,溶解在二氧化碳中的現象,1869 Andrews,量測二氧化碳的臨界點,1879,Hanny,首先研究超臨界流體的溶解度,1939,Horwarth,申請利用超臨界二氧化碳流體來濃縮果汁的第一份專利,1954 Francis,蒐集,464,個物質的相圖，並描述,261,種有機化合物在液態二,氧化碳中的溶解度,1963,Zosel,申請利用超臨界二氧化碳來萃取,68,種不同物質的專利,1963-1972,蘇聯,Krasnodar,研究學會利用超臨界流體來萃取,80,餘種不同植物,能源危機與環保政策對傳統有機溶劑的管制漸趨嚴格，使得超臨,界二氧化碳的研究與利用被大量開發,超臨界流體技術之應用,超臨界流體萃取,Supercritical Fluid Extraction,超臨界流體層析,Supercritical Fluid Chromatography,超臨界流體清洗,Supercritical Fluid Cleaning,超臨界流體乾燥,Supercritical Fluid Drying,超臨界流體反應,Supercritical Fluid Reaction,超臨界流體發泡,Supercritical Fluid Foaming,超臨界流體造粒,Supercritical Fluid Particle Formation,超臨界水氧化,Supercritical Water Oxidation,其他,Others,超臨界流體萃取,Supercritical Fluid Extraction,(SFE),Restrictor,CO,2,sample cell,in heated,chamber,CO,2,Trap,Solid or,Liquid,Modifier,Pump,SFE,示意圖,CO,2,Pump,(high pressure),Liquid Carbon Dioxide (requires a dip tube),SFE,萃取機制,SC-CO,2,+ dissolved,analyte,to the trap,High Pressure,Liquid,CO,2,SC-CO,2,diffuses matrix,dissolves and resolves,analyte,from the matrix,Heat,二氧化碳洩壓過程,Trapping Solid,High Surface Area,Adequate Amount,Trapping Liquid,High Surface Tension,Analyte,is Soluble,Low Volatility,Pressurized,Cryogenically Cooled,Gaseous,CO,2,Gaseous,CO,2,CO,2,is changing,from a SF (2 ml/min),to an expanded gas,(1 L/min),Analyte,no longer,soluble,Mechanical movement,of,analyte,due to the,rapid expansion requires,the use of trapping,material,SFE ,萃取技巧,Pressure,Increase pressure increases density = increase in,solubilizing,power.,Temperature,Increase temperature may decreases density = decrease in,solubilizing,power (,ie,CO2 at 100 bar),Extraction Time,Flow Rate,Fluid Composition,Co-solvents/modifiers,Reactant Additive,Static vs. Dynamic Extraction,SFE ,萃取技巧,Role of Modifiers in SFE,Changes in Solvent Polarity,Interaction with Matrix,Interaction with,Analyte,Methods of Addition,Directly into extraction cell (spiking),On line modifier addition (uses a second pump),超臨界流體萃取應用,Applications of,Supercritical Fluid Extraction,超臨界流體萃取應用,食品,製藥,天然物萃取,動物飼料,化學分析,環保分析,刑事案件,超臨界流體萃取應用在食品上的優點,無有機溶劑殘留的問題,可萃取易熱分解及高揮發性之成分,無殘留萃取後的裂解物,超臨界流體萃取在食品上的應用,咖啡豆及茶葉的咖啡因去除,啤酒苦味花的萃取,植物精油萃取,香辛料的萃取與保存,天然色素的萃取,小麥胚芽的萃取,淡味菸草的製造,高價值魚油的精製,中草藥及天然物的萃取,環保分析應用,Matrices,Soil,Tissue,Clay,Sandy Loam,Sludge,River Sediment,Marine Sediment,Fly Ash,Incinerator Ash,Target,Analytes,TPH,PAH,PCBs,Pesticides,Dibenzofurans,Dioxins,環保分析官方法規,US EPA 3560 - TPH in Soil:,Supercritical Fluid Extraction of Total Recoverable Petroleum Hydrocarbons,US EPA 3561 - PAH in Soil:,Supercritical Fluid Extraction of,Polyaromatic,Hydrocarbons,US EPA 3562 - PCB and OCP:,Supercritical Fluid Extraction of Polychlorinated Biphenyls (PCBs) and,Organochlorine,US EPA 3545:,Pressurized Fluid Extraction (PFE),USDOE STD-3013-99:,Determination of Residual Water in Impure Plutonium Oxides,AOAC draft,:,SFE-GC/MS determination of pesticide residues in non-fatty fruits and vegetables,超臨界流體層析,Supercritical Fluid Chromatography,SFC is a separation technique similar to HPLC and GC where the mobile phase or carrier gas is replaced by a supercritical fluid,Limitations of GC and HPLC,GC Sample Limitations :,Volatility,Thermal stability,Low molecular weight,HPLC Analytical Limitations :,No universal detector,Low efficiency,Low resolution,SFC Overcomes Limitations of GC and HPLC,Extends molecular weight range of GC,Lower operating temperature than GC,Faster separation time than HPLC,Higher separation efficiency than HPLC,Universal detector can be used, FID,Both packed (HPLC-type) and GC-type columns can be used,SFE / SFC,示意圖,SFC Applications,Industrial :,Synthetic,oligomers, polymers / additives,Surfactants (,polyglycols,),Oligo,/ polysaccharides, sucrose polyesters,Pesticides,Isocyanates,Dyes,Waxes,SFC Applications,Biochemical :,Steroids,Prostaglandins,Fatty acids / lipids,Antibiotics,Drugs of abuse,SFC Applications,Fossil Fuels :,Fractionation of petroleum and coal-derived,fluids,Hydrocarbon group analysis,Simulated distillation,超臨界流體清洗,原理,:,以超臨界二氧化碳將不要的東西,(,雜質,),自目標物,(,待清洗物,),中帶出,超臨界流體清洗應用,超臨界二氧化碳乾洗,金屬零件去除油汙,晶圓清洗及去光阻,生醫材料清洗及去熱敏原,台灣義美食品洗米技術應用,超臨界流體乾燥,原理,:,以超臨界二氧化碳將殘餘水份,(,或溶劑,),自目標物,(,待乾燥物,),中帶出,超臨界流體乾燥應用,化學,(,有機合成,),製藥最後乾燥,金屬零件乾燥,半導體元件乾燥,氣凝膠及半通透膜乾燥,生醫材料乾燥,矽晶粉之回收,超臨界流體反應,原理,:,以超臨界二氧化碳將反應物帶入目標物,(,如多孔性觸媒載體,),中進行反應,超臨界流體反應之應用,多孔性觸媒之製備,奈米複合材料之製備,高分子複合材料之改質,膨脹流體中觸媒催化之氫化及烷化反應,超臨界流體發泡,原理,:,以超臨界二氧化碳取代傳統之化學發泡劑,來製造高分子發泡產品,超臨界流體發泡應用,運動器材,衣著、鞋底,3C,家電外殼、電子產品零件,汽車內裝及外殼零件,包裝材料,家俱、家庭飾品及裝潢材料,透光隔熱材料,超臨界流體造粒,原理,:,依據物質在超臨界二氧化碳中的溶解度高低,溶解度高者,:,採超臨界溶液快速膨脹法,(RESS),Rapid Expansion of Supercritical Solution,溶解度低者,:,採壓縮反溶劑沉澱法,(PCA),Precipitation by Compressed Anti-solvent,超臨界流體造粒應用,藥物吸收,藥物釋放控制,奈米粒子製備,奈米複合材料製備,超臨界水氧化技術,原理,:,水於超臨界,(,及次臨界,),態時酸性增強，具有,強氧化力及強腐蝕性,超臨界水氧化技術之應用,高毒性有害事業廢棄物之處理,高毒性有機廢液之處理,高效能氧化技術,廢棄彈藥之處理,廢棄生化武器之處理,核廢料之處理,超臨界流體技術之其他應用,超臨界二氧化碳地質封存,超臨界二氧化碳滅菌,超臨界二氧化碳高分子加工,超臨界二氧化碳超重力法吸附及脫附,超臨界甲醇轉酯化法製備生質柴油,超臨界水發電,Thanks For Your Attention !,林華經,引光生物科技有限公司,台北市中山區吉林路,150,號,4F-5,TEL : (02) 2541-2572,FAX : (02) 2541-6579,
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