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0 Tweet 3 Like 0 Variation of properties in the dense phase region; Part 1 – Pure Compounds In this tip of the month (TOTM) we will describe the dense phase of a pure compound, what it is, and how it impacts processes. We will illustrate how thermophysical properties change in the dense phase as well as in the neighboring phases. The application of dense phase in the oil and gas industry will be discussed briefly. In next month TOTM, we will discuss the dense phase behavior of multicomponent systems. When a pure compound, in gaseous or liquid state, is heated and compressed above the critical temperature and pressure, it becomes a dense, highly compressible fluid that demonstrates properties of both liquid and gas. For a pure compound, above critical pressure and critical temperature, the system is oftentimes referred to as a “dense fluid” or “super critical fluid” to distinguish it from normal vapor and liquid (see Figure 1 for carbon dioxide). Dense phase is a fourth (Solid, Liquid, Gas, Dense) phase that cannot be described by the senses. The word “fluid” refers to anything that will flow and applies equally well to gas and liquid. Pure compounds in the dense phase or supercritical fluid state normally have better dissolving ability than do the same substances in the liquid state. The dense phase has a viscosity similar to that of a gas, but a density closer to that of a liquid. Because of its unique properties, dense phase has become attractive for transportation of natural gas, enhanced oil recovery, food processing and pharmaceutical processing products. The low viscosity of dense phase, super critical carbon dioxide (compared with familiar liquid solvents), makes it attractive for enhanced oil recovery (EOR) since it can penetrate through porous media (reservoir formation). As carbon dioxide dissolves in oil, it reduces viscosity and oilwater interfacial tension, swells the oil and can provide highly efficient displacement if miscibility is achieved. Additionally, substances disperse throughout the dense phase rapidly, due to high diffusion coefficients. Carbon dioxide is of particular interest in densefluid technology because it is inexpensive, nonflammable, nontoxic, and odorless. Pipelines have been built to transport natural gas in the dense phase region due to its higher density, and this also provides the added benefit of no liquids formation in the pipeline. In the following section we will illustrate the variation of thermophysical properties in the dense phase and its neighboring phases. Methane properties have been calculated with HYSYS software for a series of temperatures and pressures. Table 1 presents, the pressures and temperatures and their paths used in this study. The calculated thermophysical properties are plotted as a function of pressure and temperature in Figures 2 to 9. The thermophysical property is shown on the lefthand side yaxis, temperature on the xaxis and pressure on the righthand side yaxis. Table 1. PressureTemperature combination and the paths chosen for methane Search for: Search English TOTM Home Spanish TOTM Home Archives July 2015 June 2015 May 2015 April 2015 March 2015 February 2015 January 2015 December 2014 November 2014 October 2014 September 2014 August 2014 July 2014 June 2014 May 2014 April 2014 March 2014 February 2014 January 2014 December 2013 November 2013 October 2013 September 2013 August 2013 July 2013 June 2013 May 2013 April 2013 March 2013 February 2013 January 2013 December 2012 November 2012 October 2012 September 2012 August 2012 July 2012 June 2012 May 2012 April 2012 March 2012 February 2012 Public Courses InHouse Courses Operator Training

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  • 7/21/2015 VariationofpropertiesinthedensephaseregionPart1PureCompounds|CampbellTipoftheMonth

    http://www.jmcampbell.com/tipofthemonth/2009/12/variationofpropertiesinthedensephaseregionpart1purecompounds/ 1/7

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    VariationofpropertiesinthedensephaseregionPart1PureCompounds

    Inthistipofthemonth(TOTM)wewilldescribethedensephaseofapurecompound,whatitis,andhowitimpactsprocesses.Wewillillustratehowthermophysicalpropertieschangeinthedensephaseaswellasintheneighboringphases.Theapplicationofdensephaseintheoilandgasindustrywillbediscussedbriefly.InnextmonthTOTM,wewilldiscussthedensephasebehaviorofmulticomponentsystems.

    Whenapurecompound,ingaseousorliquidstate,isheatedandcompressedabovethecriticaltemperatureandpressure,itbecomesadense,highlycompressiblefluidthatdemonstratespropertiesofbothliquidandgas.Forapurecompound,abovecriticalpressureandcriticaltemperature,thesystemisoftentimesreferredtoasadensefluidorsupercriticalfluidtodistinguishitfromnormalvaporandliquid(seeFigure1forcarbondioxide).Densephaseisafourth(Solid,Liquid,Gas,Dense)phasethatcannotbedescribedbythesenses.Thewordfluidreferstoanythingthatwillflowandappliesequallywelltogasandliquid.Purecompoundsinthedensephaseorsupercriticalfluidstatenormallyhavebetterdissolvingabilitythandothesamesubstancesintheliquidstate.Thedensephasehasaviscositysimilartothatofagas,butadensityclosertothatofaliquid.Becauseofitsuniqueproperties,densephasehasbecomeattractivefortransportationofnaturalgas,enhancedoilrecovery,foodprocessingandpharmaceuticalprocessingproducts.

    Thelowviscosityofdensephase,supercriticalcarbondioxide(comparedwithfamiliarliquidsolvents),makesitattractiveforenhancedoilrecovery(EOR)sinceitcanpenetratethroughporousmedia(reservoirformation).Ascarbondioxidedissolvesinoil,itreducesviscosityandoilwaterinterfacialtension,swellstheoilandcanprovidehighlyefficientdisplacementifmiscibilityisachieved.Additionally,substancesdispersethroughoutthedensephaserapidly,duetohighdiffusioncoefficients.Carbondioxideisofparticularinterestindensefluidtechnologybecauseitisinexpensive,nonflammable,nontoxic,andodorless.Pipelineshavebeenbuilttotransportnaturalgasinthedensephaseregionduetoitshigherdensity,andthisalsoprovidestheaddedbenefitofnoliquidsformationinthepipeline.

    Inthefollowingsectionwewillillustratethevariationofthermophysicalpropertiesinthedensephaseanditsneighboringphases.MethanepropertieshavebeencalculatedwithHYSYSsoftwareforaseriesoftemperaturesandpressures.Table1presents,thepressuresandtemperaturesandtheirpathsusedinthisstudy.

    ThecalculatedthermophysicalpropertiesareplottedasafunctionofpressureandtemperatureinFigures2to9.Thethermophysicalpropertyisshownonthelefthandsideyaxis,temperatureonthexaxisandpressureontherighthandsideyaxis.

    Table1.PressureTemperaturecombinationandthepathschosenformethane

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    Density:

    Figure2presentsthevariationofdensityindifferentphasesasafunctionofpressureandtemperature.IntheisobaricsubcoolingpathofAB,liquiddensityincreasesgradually.However,intheisothermalcompressionofBCpath,asmallincreaseofdensityisobserved.IntheisobaricCDpath,compressedliquiddensitydecreasesgraduallyastemperatureisincreasedwellintothedensephaseregion.However,asthetemperatureincreasesfurtherinthedensephase,densityreductionisaccelerated.ReductionofdensityisfurtheracceleratedduringisothermalexpansionofDE.IsobariccoolingofvaporalongEFpathcorrespondswithagradualincreaseindensity.Itcanbenotedthevaluesofdensephasedensityareclosetotheliquidphasedensityinsomeareasofthedensephaseregion,andisoverallsignificantlyhigherthanthevaporphasedensities.

    Viscosity:

    Figure3presentsthevariationofviscosityindifferentphasesasafunctionofpressureandtemperature.IntheisobaricsubcoolingpathofAB,liquidviscosityincreasesrapidly.However,intheisothermalcompressionofBCpath,averysmallchangeofviscosityisobserved.IntheisobaricCDpath,compressedliquidviscositydecreaseslinearlyandsharplyastemperatureisincreasedwellintothedensephaseregion.Asthetemperatureincreasesfurtherinthedensephase,viscosityreductionbecomesgradualandapproachesthegasphasevalues.ReductionofviscosityisquitesmallduringisothermalexpansionofDE.IsobariccoolingofvaporalongEFpathcorrespondswithnoappreciablechangeinviscosity.

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  • 7/21/2015 VariationofpropertiesinthedensephaseregionPart1PureCompounds|CampbellTipoftheMonth

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    CompressibilityFactor:

    Ingeneral,thecompressibilityfactorZ,calculatedbyanequationofstateisnotaccuratefortheliquidphase.Therefore,Figure4whichpresentscompressibilityfactorasafunctionofpressureandtemperatureshouldbeconsideredforqualitativestudyonly.IntheisobaricsubcoolingpathofAB,Zremainsalmostconstant.However,intheisothermalcompressionofBCpath,Zincreasesdrastically.IntheisobaricCDpath,Zincreasesgraduallyastemperatureisincreasedwellintothedensephaseregion.Asthetemperatureincreasesfurtherinthedensephase,theincreaseinZisaccelerated.TheincreaseinZisfurtheracceleratedduringisothermalexpansionofDE.IsobariccoolingofvaporalongFFpathcorrespondswithagradualdecreaseinZ.

    SurfaceTension:

    Figure5showsthatintheliquidphase,surfacetensionisastrongfunctionoftemperaturebutindependentofpressure.Abovethecriticaltemperature,surfacetensionisnotapplicableanditsvalueiszero.

    HeatCapacity:

    Generally,heatcapacityisapplicableinasinglephaseregionandshouldnotbeusedwhenthereisaphasechange.Figure6presentsthevariationofdensityindifferentphasesasafunctionofpressureandtemperature.IntheisobaricsubcoolingpathofAB,liquidheatcapacitydecreases.IntheisothermalcompressionofBCpath,asmalldecreaseofheatcapacityisobserved.IntheisobaricCDpath,compressedliquidheatcapacityincreasesgraduallyastemperatureisincreasedwellintothedensephaseregion.Asthetemperatureincreasesfurtherinthedensephase,heatcapacityreachesamaximumvalueandthenstartstodecrease.Thisisstrangebehaviorandsurprisinglyhighvaluesarecalculated.SimilarresultswereobtainedusingProMaxsoftware.ReductionofheatcapacityisfurthernoticedduringisothermalexpansionofDE.IsobariccoolingofvaporalongEFpathcorrespondswithagradualincreaseinheatcapacity.

    ThermalConductivity:

    Figure7presentsthevariationofthermalconductivityindifferentphasesasafunctionofpressureandtemperature.IntheisobaricsubcoolingpathofAB,liquidthermalconductivityincreases.IntheisothermalcompressionofBCpath,nochangeisobserved.IntheisobaricCDpath,compressedliquidthermalconductivitydecreasesgraduallyastemperatureisincreasedwellintothedensephaseregion.However,asthetemperatureincreasesfurtherinthedensephase,thermalconductivityreductionisaccelerated.ReductionofthermalconductivityisfurthernoticedduringisothermalexpansionofDE.IsobariccoolingofvaporalongEFpathcorrespondswithasmalldecreaseinthermalconductivity.

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  • 7/21/2015 VariationofpropertiesinthedensephaseregionPart1PureCompounds|CampbellTipoftheMonth

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    EnthalpyandEntropy:

    Figures8and9presentthevariationofenthalpyandentropyindifferentphasesasafunctionofpressureandtemperature.Asshowninthesefigures,theirqualitativevariationsaresimilar.IntheisobaricsubcoolingpathofAB,liquidenthalpyandentropydecrease.IntheisothermalcompressionofBCpath,nochangeisobserved.DuringtheisobaricCDpath,compressedliquidenthalpyandentropyvaluesincreasegraduallyastemperatureisincreasedwellintothedensephaseregion.However,asthetemperatureincreasesfurtherinthedensephase,theenthalpyandentropyincreasebecomeslarger.TheincreaseinenthalpyandentropyisfurthernoticedduringisothermalexpansionofDE.IsobariccoolingofvaporalongEFpathcorrespondswithadecreaseinenthalpyandentropy.

    Conclusions:

    Densephasebehaviorisuniqueandhasspecialfeatures.Thethermophysicalpropertiesinthisphasemayvaryabnormally.Careshouldbetakenwhenequationsofstateareusedtopredictthermophysicalpropertiesindensephase.Evaluationofequationsofstateshouldbeperformedinadvancetoassuretheiraccuracyinthisregion.Manysimulatorsoffertheoptiontouseliquidbasedalgorithms(e.g.COSTALD)forthisregion.AsshowninFigure1,thereisagradualchangeofphasetransitionfromgastodenseanddensetoliquidphasesorviceversa.Densephaseisahighlycompressiblefluidthatdemonstratespropertiesofbothliquidandgas.Thedensephasehasaviscositysimilartothatofagas,butadensityclosertothatofaliquid.Thisisafavorableconditionfortransportingnaturalgasindensephaseaswellascarbondioxideinjectionintocrudeoilreservoirforenhancedoilrecovery.

    Tolearnmoreaboutsimilarcasesandhowtominimizeoperationalproblems,wesuggestattendingourG40(Process/FacilityFundamentals),G4(GasConditioningandProcessing),PF81(CO2SurfaceFacilities),andPF4(OilProductionandProcessingFacilities)courses.

    JohnM.CampbellConsulting(JMCC)offersconsultingexpertiseonthissubjectandmanyothers.FormoreinformationabouttheservicesJMCCprovides,visitourwebsiteatwww.jmcampbellconsulting.com,[email protected].

    By:MarkBothamleyandMahmoodMoshfeghian

    Reference:

    1. ASPENone,EngineeringSuite,HYSYSVersion2006,AspenTechnology,Inc.,Cambridge,MassachusettsU.S.A.,2006.

  • 7/21/2015 VariationofpropertiesinthedensephaseregionPart1PureCompounds|CampbellTipoftheMonth

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    WrittenbyDr.MahmoodMoshfeghian

    Dr.MahmoodMoshfeghianisaninstructorandconsultantwithJohnMCampbellandCompany(JMC).HeistheauthorofmostofCampbellTipsoftheMonthanddevelopstechnicalsoftwareforJMC.Hehas35yearsteachingexperienceinuniversities(OklahomaStateUniversity,UniversityofShiraz,UniversityofSydneyandUniversityofQatar)aswellasforoilandgasindustries.Dr.MoshfeghianjoinedJMCin1990asaparttimeconsultantandthenasfulltimeinstructor/consultantin2005.PrevioustojoiningJMC,Dr.MoshfeghianwasaSeniorResearchScientistatKuwaitInstituteforScientificResearchandProfessorofChemicalEngineeringatShirazUniversity.Dr.MoshfeghianisaseniormemberofAIChEandhaspublishednumeroustechnicalpapersonthermodynamicproperties,andProcessEngineering.Dr.Moshfeghianhaspresentedinvitedpapersininternationalconferences.HeholdsaB.S.,anM.S.andaPh.D.inChemicalEngineering,allfromOklahomaStateUniversity.

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    4ResponsestoVariationofpropertiesinthedensephaseregionPart1PureCompounds

    1. TransportationofCO2inDensePhase|CampbellTipoftheMonthsays:January3,2012at8:35am

    []fluidtodistinguishitfromnormalvaporandliquid(seeFigure1forcarbondioxideinDecember2009TOTM[1]).Densephaseisafourth(Solid,Liquid,Gas,Dense)phasethatcannotbedescribedbythe[]

    Reply2. TransportedelCO2enlaFaseDensa|CampbellTipoftheMonthSpanishsays:

    January11,2012at2:57pm

    []M.,VariationofpropertiesinthedensephaseregionPart1Purecompounds,http://www.jmcampbell.com/tipofthemonth/2009/12/variationofpropertiesinthedensephaseregion,December[]

  • 7/21/2015 VariationofpropertiesinthedensephaseregionPart1PureCompounds|CampbellTipoftheMonth

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    Reply3. NonIsothermalTransportationofCO2intheDensePhase|CampbellTipoftheMonthsays:

    February1,2012at6:01am

    []fluidtodistinguishitfromnormalvaporandliquid(seeFigure1forcarbondioxideinDecember2009TOTM[]

    Reply4. TransporteNoIsotrmicodelCO2enlaFaseDensa|CampbellTipoftheMonthSpanishsays:

    February8,2012at12:05pm

    []Parauncompuestopuro,porencimadelapresinytemperaturacrtica,selerefierealsistemaconfrecuenciacomounodefasedensa,ofluidosupercrticoparadiferenciarlodeunvaporolquidonormal(vaselaFigura1paraeldixidodecarbonoenelPDMdeDiciembre2009[1]).[]

    Reply5. EffectofNitrogenImpuritiesonCO2DensePhaseTransportation|CampbellTipoftheMonthsays:

    March1,2012at8:30am

    []fluidtodistinguishitfromnormalvaporandliquid(seeFigure1forcarbondioxideinDecember2009TOTM[]

    Reply6. EffectofNitrogenImpuritiesonCO2DensePhaseTransportation|CampbellTipoftheMonthSpanish

    says:March12,2012at2:27pm

    []M.,VariationofpropertiesinthedesephaseregionPart1Purecompounds,TOTM,http://www.jmcampbell.com/tipofthemonth/2009/12/variationofpropertiesinthedensephaseregion,Dec[]

    Reply7. searchtoolssays:

    June22,2012at6:10am

    SubmitComment

    Reply8. TransportationofNaturalGasinDensePhase|CampbellTipoftheMonthsays:

    October23,2012at8:14am

    []orsupercriticalfluidtodistinguishitfromnormalvaporandliquid(seeFigure1inDecember2009TipOfTheMont(TOTM)[1]forcarbondioxideandinJanuary2010TOTM[2]foratypicalnaturalgas).Densephaseisa[]

    Reply9. TransportationofEthanebyPipelineintheDensePhase|CampbellTipoftheMonthsays:

    March1,2014at11:12am

    []fluidtodistinguishitfromnormalvaporandliquid(seeFigure1forcarbondioxideinDecember2009TOTM[]

    Reply10. TransportedelEtanoporGasoductoenlaFaseDensa|CampbellTipoftheMonthSpanishsays:

    March2,2014at1:22pm

    []M.,VariationofpropertiesinthedesephaseregionPart1Purecompounds,TOTM,http://www.jmcampbell.com/tipofthemonth/2009/12/variationofpropertiesinthedensephaseregion,Dec[]

    Reply11. retenciondeliquidoscausasyremediossays:

    July13,2014at10:35am

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    November17,2014at4:14am

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    Reply13.MuhammadShehreyarKhansays:

    January15,2015at4:10am

    Infirst&2nddiagramsAB&CDarereferredasisobaricprocessesalthoughpressureseemstochangefromapprox4.4MPa(g)to5.4MPa(g)incaseofAB(asindicatedbyblackline).

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