超臨界流體技術(shù)及其應(yīng)用課件

超臨界流體技術(shù)及其應(yīng)用IntroductiontoSupercriticalFluidTechnology:PrinciplesandApplications林華經(jīng)引光生物科技有限公司中華民國(guó)98年11月30日超臨界流體技術(shù)及其應(yīng)用Introductionto1從咖啡談起您喝咖啡嗎?您喝過(guò)無(wú)咖啡因咖啡嗎?您喜歡喝無(wú)咖啡因咖啡嗎?無(wú)咖啡因咖啡:超臨界流體技術(shù)最早商業(yè)化應(yīng)用的產(chǎn)品從咖啡談起2何謂超臨界流體當(dāng)物質(zhì)所處的壓力、溫度同時(shí)都大於其臨界壓力及臨界溫度時(shí)，則進(jìn)入所謂的超臨界態(tài)

此物質(zhì)則稱之為超臨界流體何謂超臨界流體當(dāng)物質(zhì)所處的壓力、溫度同時(shí)都大於其臨界壓力及臨3二氧化碳的相圖TemperatureSupercritical

FluidSolidLiquidTriplePointCriticalPoint31.3oC,1072psiPressureGas二氧化碳的相圖TemperatureSupercritica4超臨界流體的特性不是氣體，又有點(diǎn)像氣體不是液體，又有點(diǎn)像液體同時(shí)具備氣體及液體的雙重特性超臨界流體的特性不是氣體，又有點(diǎn)像氣體5二氧化碳的物理性質(zhì)狀態(tài)氣態(tài)超臨界態(tài)液態(tài)密度0.6–2.0x10-30.2–0.90.8–1.0黏度0.5–3.5x10-42.0–9.9x10-40.3–2.4x10-2擴(kuò)散係數(shù)0.01–1.00.5–3.3x10-40.5–2.0x10-5二氧化碳的物理性質(zhì)狀態(tài)氣態(tài)超臨界態(tài)液態(tài)密度0.6–2.0x6超臨界流體的優(yōu)點(diǎn)幾乎無(wú)表面張力低黏度高擴(kuò)散係數(shù)高密度高溶解能力溶解能力可調(diào)超臨界流體的優(yōu)點(diǎn)幾乎無(wú)表面張力7常見(jiàn)的超臨界流體之臨界性質(zhì)Tc(°C)Pc(atm)c(gmL-1)CO231.372.90.47N2O36.572.50.45SF245.537.10.74NH3132.5112.50.24H2O3742270.34n-C4H1015237.50.23n-C6H1219733.30.23Xe16.658.41.10CCl2F211240.70.56CHF325.946.90.52Source:“SFEandItsuseinChromatographicSamplePreparation”Ed.S.Westwood.Chapter1常見(jiàn)的超臨界流體之臨界性質(zhì)Tc(°C)Pc(atm)c8使用超臨界二氧化碳的優(yōu)點(diǎn)低臨界點(diǎn)操作安全取得容易環(huán)保於常溫常壓下為氣體使用超臨界二氧化碳的優(yōu)點(diǎn)低臨界點(diǎn)9超臨界流體之重要發(fā)展史

1822CagniarddelaTour發(fā)現(xiàn)物質(zhì)的超臨界狀態(tài)1861Core描述Naphthalene溶解在二氧化碳中的現(xiàn)象1869Andrews量測(cè)二氧化碳的臨界點(diǎn)1879Hanny首先研究超臨界流體的溶解度1939Horwarth申請(qǐng)利用超臨界二氧化碳流體來(lái)濃縮果汁的第一份專利1954Francis蒐集464個(gè)物質(zhì)的相圖，並描述261種有機(jī)化合物在液態(tài)二氧化碳中的溶解度1963Zosel申請(qǐng)利用超臨界二氧化碳來(lái)萃取68種不同物質(zhì)的專利1963-1972蘇聯(lián)Krasnodar研究學(xué)會(huì)利用超臨界流體來(lái)萃取80餘種不同植物能源危機(jī)與環(huán)保政策對(duì)傳統(tǒng)有機(jī)溶劑的管制漸趨嚴(yán)格，使得超臨界二氧化碳的研究與利用被大量開(kāi)發(fā)超臨界流體之重要發(fā)展史10超臨界流體技術(shù)之應(yīng)用超臨界流體萃取SupercriticalFluidExtraction超臨界流體層析SupercriticalFluidChromatography超臨界流體清洗SupercriticalFluidCleaning超臨界流體乾燥SupercriticalFluidDrying超臨界流體反應(yīng)SupercriticalFluidReaction超臨界流體發(fā)泡SupercriticalFluidFoaming超臨界流體造粒SupercriticalFluidParticleFormation超臨界水氧化SupercriticalWaterOxidation其他Others超臨界流體技術(shù)之應(yīng)用超臨界流體萃取Supercriti11超臨界流體萃取

SupercriticalFluidExtraction(SFE)

超臨界流體萃取

12RestrictorCO2samplecellinheatedchamberCO2TrapSolidorLiquidModifierPumpSFE示意圖CO2Pump(highpressure)LiquidCarbonDioxide(requiresadiptube)RestrictorCO2samplecellCO2Tra13SFE萃取機(jī)制SC-CO2+dissolvedanalytetothetrapHighPressureLiquidCO2SC-CO2diffusesmatrix,dissolvesandresolvesanalytefromthematrixHeatSFE萃取機(jī)制SC-CO2+dissolvedana14二氧化碳洩壓過(guò)程TrappingSolidHighSurfaceAreaAdequateAmountTrappingLiquidHighSurfaceTensionAnalyteisSolubleLowVolatilityPressurizedCryogenicallyCooledGaseousCO2GaseousCO2CO2ischangingfromaSF(2ml/min)toanexpandedgas(1L/min)AnalytenolongersolubleMechanicalmovementofanalyteduetotherapidexpansionrequirestheuseoftrappingmaterial二氧化碳洩壓過(guò)程TrappingSolidGaseousG15SFE–萃取技巧PressureIncreasepressureincreasesdensity=increaseinsolubilizingpower.TemperatureIncreasetemperaturemaydecreasesdensity=decreaseinsolubilizingpower(ieCO2at100bar)ExtractionTimeFlowRateFluidCompositionCo-solvents/modifiersReactantAdditiveStaticvs.DynamicExtractionSFE–萃取技巧Pressure16SFE–萃取技巧RoleofModifiersinSFEChangesinSolventPolarityInteractionwithMatrixInteractionwithAnalyteMethodsofAdditionDirectlyintoextractioncell(spiking)Onlinemodifieraddition(usesasecondpump)SFE–萃取技巧RoleofModifiersin17超臨界流體萃取應(yīng)用ApplicationsofSupercriticalFluidExtraction超臨界流體萃取應(yīng)用Applicationsof18超臨界流體萃取應(yīng)用食品製藥天然物萃取動(dòng)物飼料化學(xué)分析環(huán)保分析刑事案件超臨界流體萃取應(yīng)用食品19超臨界流體萃取應(yīng)用在食品上的優(yōu)點(diǎn)無(wú)有機(jī)溶劑殘留的問(wèn)題可萃取易熱分解及高揮發(fā)性之成分無(wú)殘留萃取後的裂解物

超臨界流體萃取應(yīng)用在食品上的優(yōu)點(diǎn)無(wú)有機(jī)溶劑殘留的問(wèn)題20超臨界流體萃取在食品上的應(yīng)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(jià)值魚(yú)油的精製中草藥及天然物的萃取

超臨界流體萃取在食品上的應(yīng)用咖啡豆及茶葉的咖啡因去除21環(huán)保分析應(yīng)用MatricesSoilTissueClaySandyLoamSludgeRiverSedimentMarineSedimentFlyAshIncineratorAshTargetAnalytesTPHPAHPCBsPesticidesDibenzofuransDioxins環(huán)保分析應(yīng)用MatricesTargetAnalytes22環(huán)保分析官方法規(guī)USEPA3560-TPHinSoil:SupercriticalFluidExtractionofTotalRecoverablePetroleumHydrocarbons

USEPA3561-PAHinSoil:SupercriticalFluidExtractionofPolyaromaticHydrocarbons

USEPA3562-PCBandOCP:SupercriticalFluidExtractionofPolychlorinatedBiphenyls(PCBs)andOrganochlorine

USEPA3545:PressurizedFluidExtraction(PFE)USDOESTD-3013-99:DeterminationofResidualWaterinImpurePlutoniumOxidesAOACdraft:SFE-GC/MSdeterminationofpesticideresiduesinnon-fattyfruitsandvegetables

環(huán)保分析官方法規(guī)USEPA3560-TPHinS23超臨界流體層析

SupercriticalFluidChromatography

SFCisaseparationtechniquesimilartoHPLCandGCwherethemobilephaseorcarriergasisreplacedbyasupercriticalfluid超臨界流體層析

SupercriticalFluidC24LimitationsofGCandHPLCGCSampleLimitations:VolatilityThermalstabilityLowmolecularweightHPLCAnalyticalLimitations:NouniversaldetectorLowefficiencyLowresolution

LimitationsofGCandHPLCGCS25SFC

OvercomesLimitationsofGCandHPLCExtendsmolecularweightrangeofGCLoweroperatingtemperaturethanGCFasterseparationtimethanHPLCHigherseparationefficiencythanHPLCUniversaldetectorcanbeused,FIDBothpacked(HPLC-type)andGC-typecolumnscanbeusedSFC

OvercomesLimitationsof26SFE/SFC示意圖SFE/SFC示意圖27SFCApplicationsIndustrial:

Syntheticoligomers,polymers/additivesSurfactants(polyglycols)Oligo/polysaccharides,sucrosepolyestersPesticidesIsocyanatesDyesWaxesSFCApplicationsIndustrial:28SFCApplicationsBiochemical:SteroidsProstaglandinsFattyacids/lipidsAntibioticsDrugsofabuseSFCApplicationsBiochemical:29SFCApplicationsFossilFuels:Fractionationofpetroleumandcoal-derivedfluidsHydrocarbongroupanalysisSimulateddistillationSFCApplicationsFossilFuels:30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(zhì))自目標(biāo)物

(待清洗物)中帶出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(zhì))31超臨界流體清洗應(yīng)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(yī)材料清洗及去熱敏原臺(tái)灣義美食品洗米技術(shù)應(yīng)用超臨界流體清洗應(yīng)用超臨界二氧化碳乾洗32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(biāo)物

(待乾燥物)中帶出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)33超臨界流體乾燥應(yīng)用化學(xué)(有機(jī)合成)製藥最後乾燥金屬零件乾燥半導(dǎo)體元件乾燥氣凝膠及半通透膜乾燥生醫(yī)材料乾燥矽晶粉之回收超臨界流體乾燥應(yīng)用化學(xué)(有機(jī)合成)製藥最後乾燥34超臨界流體反應(yīng)原理:以超臨界二氧化碳將反應(yīng)物帶入目標(biāo)物

(如多孔性觸媒載體)中進(jìn)行反應(yīng)超臨界流體反應(yīng)原理:以超臨界二氧化碳將反應(yīng)物帶入目標(biāo)物35超臨界流體反應(yīng)之應(yīng)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(zhì)膨脹流體中觸媒催化之氫化及烷化反應(yīng)超臨界流體反應(yīng)之應(yīng)用多孔性觸媒之製備36超臨界流體發(fā)泡原理:以超臨界二氧化碳取代傳統(tǒng)之化學(xué)發(fā)泡劑來(lái)製造高分子發(fā)泡產(chǎn)品超臨界流體發(fā)泡原理:以超臨界二氧化碳取代傳統(tǒng)之化學(xué)發(fā)泡劑37超臨界流體發(fā)泡應(yīng)用運(yùn)動(dòng)器材衣著、鞋底3C家電外殼、電子產(chǎn)品零件汽車(chē)內(nèi)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發(fā)泡應(yīng)用運(yùn)動(dòng)器材38超臨界流體造粒原理:依據(jù)物質(zhì)在超臨界二氧化碳中的溶解度高低溶解度高者:採(cǎi)超臨界溶液快速膨脹法(RESS)

RapidExpansionofSupercriticalSolution溶解度低者:採(cǎi)壓縮反溶劑沉澱法(PCA)

PrecipitationbyCompressedAnti-solvent超臨界流體造粒原理:依據(jù)物質(zhì)在超臨界二氧化碳中的溶解度高39超臨界流體造粒應(yīng)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流體造粒應(yīng)用藥物吸收40超臨界水氧化技術(shù)原理:水於超臨界(及次臨界)態(tài)時(shí)酸性增強(qiáng)，具有強(qiáng)氧化力及強(qiáng)腐蝕性超臨界水氧化技術(shù)原理:水於超臨界(及次臨界)態(tài)時(shí)酸性增強(qiáng)41超臨界水氧化技術(shù)之應(yīng)用高毒性有害事業(yè)廢棄物之處理高毒性有機(jī)廢液之處理高效能氧化技術(shù)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水氧化技術(shù)之應(yīng)用高毒性有害事業(yè)廢棄物之處理42超臨界流體技術(shù)之其他應(yīng)用超臨界二氧化碳地質(zhì)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(zhuǎn)酯化法製備生質(zhì)柴油超臨界水發(fā)電超臨界流體技術(shù)之其他應(yīng)用超臨界二氧化碳地質(zhì)封存43ThanksForYourAttention!林華經(jīng)引光生物科技有限公司臺(tái)北市中山區(qū)吉林路150號(hào)4F-5TEL:(02)2541-2572FAX:(02)2541-6579ThanksForYourAttention!44超臨界流體技術(shù)及其應(yīng)用IntroductiontoSupercriticalFluidTechnology:PrinciplesandApplications林華經(jīng)引光生物科技有限公司中華民國(guó)98年11月30日超臨界流體技術(shù)及其應(yīng)用Introductionto45從咖啡談起您喝咖啡嗎?您喝過(guò)無(wú)咖啡因咖啡嗎?您喜歡喝無(wú)咖啡因咖啡嗎?無(wú)咖啡因咖啡:超臨界流體技術(shù)最早商業(yè)化應(yīng)用的產(chǎn)品從咖啡談起46何謂超臨界流體當(dāng)物質(zhì)所處的壓力、溫度同時(shí)都大於其臨界壓力及臨界溫度時(shí)，則進(jìn)入所謂的超臨界態(tài)

此物質(zhì)則稱之為超臨界流體何謂超臨界流體當(dāng)物質(zhì)所處的壓力、溫度同時(shí)都大於其臨界壓力及臨47二氧化碳的相圖TemperatureSupercritical

FluidSolidLiquidTriplePointCriticalPoint31.3oC,1072psiPressureGas二氧化碳的相圖TemperatureSupercritica48超臨界流體的特性不是氣體，又有點(diǎn)像氣體不是液體，又有點(diǎn)像液體同時(shí)具備氣體及液體的雙重特性超臨界流體的特性不是氣體，又有點(diǎn)像氣體49二氧化碳的物理性質(zhì)狀態(tài)氣態(tài)超臨界態(tài)液態(tài)密度0.6–2.0x10-30.2–0.90.8–1.0黏度0.5–3.5x10-42.0–9.9x10-40.3–2.4x10-2擴(kuò)散係數(shù)0.01–1.00.5–3.3x10-40.5–2.0x10-5二氧化碳的物理性質(zhì)狀態(tài)氣態(tài)超臨界態(tài)液態(tài)密度0.6–2.0x50超臨界流體的優(yōu)點(diǎn)幾乎無(wú)表面張力低黏度高擴(kuò)散係數(shù)高密度高溶解能力溶解能力可調(diào)超臨界流體的優(yōu)點(diǎn)幾乎無(wú)表面張力51常見(jiàn)的超臨界流體之臨界性質(zhì)Tc(°C)Pc(atm)c(gmL-1)CO231.372.90.47N2O36.572.50.45SF245.537.10.74NH3132.5112.50.24H2O3742270.34n-C4H1015237.50.23n-C6H1219733.30.23Xe16.658.41.10CCl2F211240.70.56CHF325.946.90.52Source:“SFEandItsuseinChromatographicSamplePreparation”Ed.S.Westwood.Chapter1常見(jiàn)的超臨界流體之臨界性質(zhì)Tc(°C)Pc(atm)c52使用超臨界二氧化碳的優(yōu)點(diǎn)低臨界點(diǎn)操作安全取得容易環(huán)保於常溫常壓下為氣體使用超臨界二氧化碳的優(yōu)點(diǎn)低臨界點(diǎn)53超臨界流體之重要發(fā)展史

1822CagniarddelaTour發(fā)現(xiàn)物質(zhì)的超臨界狀態(tài)1861Core描述Naphthalene溶解在二氧化碳中的現(xiàn)象1869Andrews量測(cè)二氧化碳的臨界點(diǎn)1879Hanny首先研究超臨界流體的溶解度1939Horwarth申請(qǐng)利用超臨界二氧化碳流體來(lái)濃縮果汁的第一份專利1954Francis蒐集464個(gè)物質(zhì)的相圖，並描述261種有機(jī)化合物在液態(tài)二氧化碳中的溶解度1963Zosel申請(qǐng)利用超臨界二氧化碳來(lái)萃取68種不同物質(zhì)的專利1963-1972蘇聯(lián)Krasnodar研究學(xué)會(huì)利用超臨界流體來(lái)萃取80餘種不同植物能源危機(jī)與環(huán)保政策對(duì)傳統(tǒng)有機(jī)溶劑的管制漸趨嚴(yán)格，使得超臨界二氧化碳的研究與利用被大量開(kāi)發(fā)超臨界流體之重要發(fā)展史54超臨界流體技術(shù)之應(yīng)用超臨界流體萃取SupercriticalFluidExtraction超臨界流體層析SupercriticalFluidChromatography超臨界流體清洗SupercriticalFluidCleaning超臨界流體乾燥SupercriticalFluidDrying超臨界流體反應(yīng)SupercriticalFluidReaction超臨界流體發(fā)泡SupercriticalFluidFoaming超臨界流體造粒SupercriticalFluidParticleFormation超臨界水氧化SupercriticalWaterOxidation其他Others超臨界流體技術(shù)之應(yīng)用超臨界流體萃取Supercriti55超臨界流體萃取

SupercriticalFluidExtraction(SFE)

超臨界流體萃取

56RestrictorCO2samplecellinheatedchamberCO2TrapSolidorLiquidModifierPumpSFE示意圖CO2Pump(highpressure)LiquidCarbonDioxide(requiresadiptube)RestrictorCO2samplecellCO2Tra57SFE萃取機(jī)制SC-CO2+dissolvedanalytetothetrapHighPressureLiquidCO2SC-CO2diffusesmatrix,dissolvesandresolvesanalytefromthematrixHeatSFE萃取機(jī)制SC-CO2+dissolvedana58二氧化碳洩壓過(guò)程TrappingSolidHighSurfaceAreaAdequateAmountTrappingLiquidHighSurfaceTensionAnalyteisSolubleLowVolatilityPressurizedCryogenicallyCooledGaseousCO2GaseousCO2CO2ischangingfromaSF(2ml/min)toanexpandedgas(1L/min)AnalytenolongersolubleMechanicalmovementofanalyteduetotherapidexpansionrequirestheuseoftrappingmaterial二氧化碳洩壓過(guò)程TrappingSolidGaseousG59SFE–萃取技巧PressureIncreasepressureincreasesdensity=increaseinsolubilizingpower.TemperatureIncreasetemperaturemaydecreasesdensity=decreaseinsolubilizingpower(ieCO2at100bar)ExtractionTimeFlowRateFluidCompositionCo-solvents/modifiersReactantAdditiveStaticvs.DynamicExtractionSFE–萃取技巧Pressure60SFE–萃取技巧RoleofModifiersinSFEChangesinSolventPolarityInteractionwithMatrixInteractionwithAnalyteMethodsofAdditionDirectlyintoextractioncell(spiking)Onlinemodifieraddition(usesasecondpump)SFE–萃取技巧RoleofModifiersin61超臨界流體萃取應(yīng)用ApplicationsofSupercriticalFluidExtraction超臨界流體萃取應(yīng)用Applicationsof62超臨界流體萃取應(yīng)用食品製藥天然物萃取動(dòng)物飼料化學(xué)分析環(huán)保分析刑事案件超臨界流體萃取應(yīng)用食品63超臨界流體萃取應(yīng)用在食品上的優(yōu)點(diǎn)無(wú)有機(jī)溶劑殘留的問(wèn)題可萃取易熱分解及高揮發(fā)性之成分無(wú)殘留萃取後的裂解物

超臨界流體萃取應(yīng)用在食品上的優(yōu)點(diǎn)無(wú)有機(jī)溶劑殘留的問(wèn)題64超臨界流體萃取在食品上的應(yīng)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(jià)值魚(yú)油的精製中草藥及天然物的萃取

超臨界流體萃取在食品上的應(yīng)用咖啡豆及茶葉的咖啡因去除65環(huán)保分析應(yīng)用MatricesSoilTissueClaySandyLoamSludgeRiverSedimentMarineSedimentFlyAshIncineratorAshTargetAnalytesTPHPAHPCBsPesticidesDibenzofuransDioxins環(huán)保分析應(yīng)用MatricesTargetAnalytes66環(huán)保分析官方法規(guī)USEPA3560-TPHinSoil:SupercriticalFluidExtractionofTotalRecoverablePetroleumHydrocarbons

USEPA3561-PAHinSoil:SupercriticalFluidExtractionofPolyaromaticHydrocarbons

USEPA3562-PCBandOCP:SupercriticalFluidExtractionofPolychlorinatedBiphenyls(PCBs)andOrganochlorine

USEPA3545:PressurizedFluidExtraction(PFE)USDOESTD-3013-99:DeterminationofResidualWaterinImpurePlutoniumOxidesAOACdraft:SFE-GC/MSdeterminationofpesticideresiduesinnon-fattyfruitsandvegetables

環(huán)保分析官方法規(guī)USEPA3560-TPHinS67超臨界流體層析

SupercriticalFluidChromatography

SFCisaseparationtechniquesimilartoHPLCandGCwherethemobilephaseorcarriergasisreplacedbyasupercriticalfluid超臨界流體層析

SupercriticalFluidC68LimitationsofGCandHPLCGCSampleLimitations:VolatilityThermalstabilityLowmolecularweightHPLCAnalyticalLimitations:NouniversaldetectorLowefficiencyLowresolution

LimitationsofGCandHPLCGCS69SFC

OvercomesLimitationsofGCandHPLCExtendsmolecularweightrangeofGCLoweroperatingtemperaturethanGCFasterseparationtimethanHPLCHigherseparationefficiencythanHPLCUniversaldetectorcanbeused,FIDBothpacked(HPLC-type)andGC-typecolumnscanbeusedSFC

OvercomesLimitationsof70SFE/SFC示意圖SFE/SFC示意圖71SFCApplicationsIndustrial:

Syntheticoligomers,polymers/additivesSurfactants(polyglycols)Oligo/polysaccharides,sucrosepolyestersPesticidesIsocyanatesDyesWaxesSFCApplicationsIndustrial:72SFCApplicationsBiochemical:SteroidsProstaglandinsFattyacids/lipidsAntibioticsDrugsofabuseSFCApplicationsBiochemical:73SFCApplicationsFossilFuels:Fractionationofpetroleumandcoal-derivedfluidsHydrocarbongroupanalysisSimulateddistillationSFCApplicationsFossilFuels: