Select Thermodynamic Models For Process Simulation - A Practical Guide To A Three Steps Methodology

6/1/2015
SelectthermodynamicmodelsforprocesssimulationAPracticalGuidetoaThreeStepsMethodology
Selectthermodynamicmodelsforprocesssimulation
APracticalGuidetoaThreeStepsMethodology
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Casestudy1:Crystallizationoftracecomponentsinnaturalgas
liquefactionprocess(LIQUEFINTM)
Thecontinuousexpansionofliquefiednaturalgas(LNG)tradefornowmorethanthreedecadeshasbeenachievedthankstothepermanentsearchforcostreduction,
mainlyusingthesizeeffect.Topursuethisexpansionatthesamesustainedrateofupto10%percentperyear,someoperatorsarenowseriouslyconsideringtrains
withcapacitiesof6,7oreven8Mt/a.Inordertoreachsuchcapacities,withalwayshigherefficiencyandwithoutaddingcomplexityintheprocess,itisnecessaryto
departfromthetraditionalscheme.IFPandAxenshavedevelopedtheLIQUEFINTMprocesswiththeaimofproducinganLNGcheaperthanwithanyotherprocess,
atgoodconditionsofreliabilityandsafety,andfriendliertoenvironment.
Due to the increase of the world natural gas consumption, the distance between production and consumption sites is ever increasing. Pipeline transportation is not
economicalfortheselongdistancesandonlyliquidphasetransportationisfeasible.Asaconsequence,manyhighcapacitygasliquefactionplantsarepresentlyin
project.
Innaturalgasliquefactionprocesses,thegasfeediscooledtoverylowtemperatures(113Kor160C).Thepresenceoftracesofheavyhydrocarbonscomponents
intheliquefiednaturalgas(LNG)maythereforeresultincrystallization,andthereforepluggingtheinstallation.Thepresentworkinvestigatesthevapourliquidsolid
equilibriumandproposesawaytopredicttherisksofcrystallization.
Inafirstsection,theprocesswillbedescribedtoexplainthedifferentstepsinvolvedintheliquefactionofnaturalgas.Theoperatingconditionswillbespecifiedinthe
crucialpointsoftheprocessandaspecificemphasiswillbegivenontheriskofcrystallizationofheavyelementspresentinverylowproportions.
Inasecondsection,thethreebasicquestionstobeaskedtogiveacorrectanswertoathermodynamicproblemwillbeanalyzed:
Whatarethepropertiesgivenandtobecalculatedtoobtainthesolution?
Whatarethecomponentspresentinthemixture?
Whatarethephasespresentinthedifferentpartoftheprocess?
Inathirdpart,inthelightofthepreviousanswers,athermodynamicmodelwillbedeveloped.Here,acubicEoScoupledwithaHuronVidalmixingrulewillbeused.
Thechoiceofadequateexperimentaldatawillbediscussedaswellasthewaytoregressthem.
ThemodelwillbeappliedatthedifferentzonesoftheLIQUEFINTMprocessestablishedaspotentiallyriskyoperatingconditionsandsomerecommendationswillbe
givenforhowtooperatetheprocessandhowtoenhancethemodel.
1Processdescription
AllprocessesforLNGproductionsarebasedoncompression/expansionandheatexchangers.Someseparationvesselsand/ordistillationcolumnsarepresentinthe
process to satisfy commercial purities of products. An interesting comparison of different processes can be found in Martin et al. (2002 [1]) or in Mokhatab and
Economides(2006[2,3]).ThecasestudypresentedhereisbasedontheLIQUEFINTMprocesssoldbyAxens.
TheLIQUEFINTMprocessoperatesaccordingtothebasicflowschemepresentedinfigure61.Attheexitoftheprecooling,thegasisscrubbedfromitsheavyend
the top is further refrigerated in the precooling section and the condensate is used as scrubbing fluid. The vapour then enters the cryogenic section. The liquid
(bottom)ofthescrubberisintroducedtoademethanizertoremovetheheavycomponentsthatmayrepresentariskofcrystallization.Theheadofthedemethanizer
isintroducedinthecryogenicexchanger,reachingatemperatureof113K.
http://books.ifpenergiesnouvelles.fr/ebooks/thermodynamics/studies/06_Liquefin_2009_August.html
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Figure61:LIQUEFINTMgeneralscheme.
Thepresenceoftracesofheavycompounds(mainlyaromaticsandcyclohexane)inthenaturalgas,associatedtotheverylowtemperatureofthecryogenicprocess,
createadistinctriskofplugginginthelinesandtheheatexchangersasaresultofcrystallization.Thisisthereasonoftherequestedthermodynamicstudy.
2Thermodynamicanalysisoftheprocess
Accordingtothephilosophyproposedinthisbook(seechapter1),theanalysisiscentredonthreemainquestions:properties,componentsandphases.
2.1Properties
Themainriskintheprocess,fromathermodynamicpointofview,istheriskofplugging,i.e.toobserveasolidtocrystallizeinthelinesorintheexchangers.Froma
thermodynamicpointofview,thephenomenonunderconsiderationisafluidsolidequilibrium.Yet,thiscrystallizationisnotwantedand,therefore,thetruechangein
phasecompositionwhenlargeamountsofsolidsareformed(socalledflashcalculation,asintroducedinchapter2,section2.3.1.3)isnotneeded.Instead,theonset
of crystallization, or the phase split boundary is the true quantity that is required here. The problem of phase boundary calculation has been discussed in
section2.3.2.4.ofchapter2:themostgeneralapproachistoinvestigatethetangentplanecriterionusinganalgorithmasproposedbyMichelsen[4].Yet,aslongas
the precipitating phase can be considered as a pure component (which is the case in this work), it is sufficient to compare the fugacity (Gibbs energy) of that
component in the precipitating phase (solid) with the fugacity of this component in the fluid phase. Whenever the fugacity in the precipitating phase is lower, then
crystallizationwilloccur.Thealgorithmissummarizedinfigure62.
Figure62:Phaseborderevaluationbetweenliquidandsolid.
Itisconcludedthatinthisanalysis,aspecialattentionwillbegiventothefugacitycalculationofthecomponentsthatmaypotentiallycrystallize.
2.2Components
A typical feed for the process can be seen in table 61. All the components present in a natural gas are well known and belong to the type called "database
components"inchapter3,section1.2.1.Subsequently,thecrystallizationtemperatureofallcomponentscanbefoundindatabases.Thesearediscussedinsection
1.1.1.6ofchapter3,andintable62ofthatsection.
Table61:Typicalcompositionofanaturalgaswithahighbenzenecontent.
Feed
Component Composition(molar%)
N2
4.91
CH4
86.06
C2
5.45
C3
1.97
iC4
0.36
nC4
0.57
iC5
0.21
nC5
0.09
nC6
0.12
nC7
0.07
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nC8
0.04
nC9
0.01
CO2
0.01
Benzene
0.05
Cyclohexane
0.05
nCxstandsfornalkanewithxatomsofcarbon
Table62:Purecomponentscrystallizationdata(DIPPR,2008[12]).
TriplepointTemperature(K) TriplepointPressure(Pa) Enthalpyoffusion(J/kmol) Volumeoffusion(m3/kmol)

Cyclohexane
279.7
5.36E+03
2.74E+06
8.30E03
Benzene
278.7
4.76E+03
9.87E+06
1.04E02
nC9
219.7
4.31E01
1.55E+07
2.17E02
nC8
216.4
2.11E+00
2.07E+07
1.97E02
nC7
182.6
1.83E01
1.41E+07
1.39E02
nC6
177.8
9.02E01
1.31E+07
1.26E02
The crystallization temperature of a number of pure components, from cyclohexane to nC6 is lower than the process temperature (near 160 K). Nevertheless, the
presenceofothercomponentsinthemixtureactsasasolventandlowerstheriskofcrystallization.Thefugacitycalculationwillgivethedefinitiveanswer.
Inthiswork,focuswillbecentredonbenzene.Compositionmayvarywiththegasinexploitation,butforriskanalysis,itisgoodtotakeacompositionthatisrich
inbenzeneandotherheavycomponents.Someheaviercomponentslikedecanesorxylenesoralkylcyclohexanescanbepresentbutinsolowquantitiesthatthe
crystallizationrisksareneglected.CarbondioxidemayalsobeanissueasdiscussedbyEggemanandChafin(2005[5]).
Asseenintable61,theconcentrationofbenzeneinthefeedisverylow.Asaresult,thebehaviour(activity)ofthiscomponentisverydifferentfromthatofthepure
component (as discussed in chapter 3, section 4.1. In fact, it should be almost considered as an infinitely diluted component, and section 5.2.3 discussed how in
theseconditions,veryspecificdatashouldbeused(evenmixturedatashouldbeconsideredwithcaution).Theavailabilityofthedatawillhoweverleadtoconsider
severaltypesofinformationinthenextsection.
2.3Phases
Initially,thefeedisfoundasavapour,directlyproducedfromgasfield.Theobjectiveoftheprocessistocondensethisvapourtofacilitatetransportation.Thus,a
liquid is obtained as a result of the process. Due to the very low temperature of the cryogenic plant, some solid may appear as an anomalous behaviour. For this
reason,studyisconcernedwiththreephases:vapourliquidsolidequilibrium.
In chapter 4, fluidsolid equilibria of mixtures containing organic compounds was discussed in section 2.2.3.1. Pressuretemperature phase diagrams of
multicomponentmixturesmaybecomecomplexifsolidphasesareconsidered(Tiffinetal.1979[6]).Luksetal.(1981[7],1984[8])hasclassifiedthegasliquidsolid
phase diagrams into four types. Only the first type is of interest here, as it is the one encountered for the methane + benzene system. Its pressuretemperature
projection is sketched in figure 63. For the light component, the vapour pressure line, the solidus line and the sublimation line are easily recognized. For the light
component, only the vapour pressure line is drawn. The locus of critical points is visible as a doted line that connects the critical point of each of the pure
components.Inthisdiagram,thislineiscutbytwodashedlinesthatrepresentthreephasevapourliquidsolidequilibria(VLSE).
Themeaningofthesecurvesisbestunderstoodwheninvestigatingacutatconstantpressure.Anintermediatepressure(lineP1onfigure63),thatishigherthanthe
three phase points of either components, but lower than the critical point of both components (i.e., for the methane + benzene mixture, that yields that type of
diagram,between4.7kPaand4.6MPa)isanalyzed.Intheseconditions,thediagramsketchedonfigure64)isfound.
Figure63:PTvapourliquidsolidsketchforamethane+benzenemixture.
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At high temperature, the mixture is always in the vapour phase. In a mixture rich in benzene (dotted line), the vapourliquid equilibrium (VLE) region is first
encountereduponcooling(dewpointinfigure64).Aliquidphaseappears,thatisricherinbenzenethanthevapourphase.Iftheinitialmixturewassufficientlyrichin
benzene(doteddashedline),themixturemaybecomeentirelyliquid(reachitsbubblepoint)beforeformingasolid(pointA).Inthiswork,itisassumedthattheheavy
componentalwayscrystallizesasapurecomponent.Thismaynotalwaysbetrue,butitrepresentsthehighestriskofcrystallizingatagiventemperature.Coolingon
the mixture, a threephase line is reached before the mixture can become entirely liquid. This high temperature vapourliquidsolid three phase equilibrium line (HT
VLSE)formsthelimitbelowwhichtheliquidcrystallizesentirely:onlyavapourandasolidphasecoexistbelowthisline.Atstilllowertemperature,asecondthree
phase line is encountered, where the vapour condenses to form a liquid. The solid phase remains. This is the low temperature vapourliquidsolid three phase
equilibriumline(LTVLSE).
Now,considerthecaseofamixturewiththecompositionshownasadashedline,stillricherinmethane(whichisthecaseinnaturalgasliquefactionprocesses).In
thiscase,decreasingthetemperaturewillresultincrystallizingdirectlyfromthevapourphase(noHTVLSEisencountered).Sofar,whenthetemperatureisfurther
lowered,thevapourwillcondenseinaliquidphase,thathasahighercapacityofdissolvingthemeltand,asaresult,belowtheLTVLSEthreephaseline,nocrystal
isleft,butonlyaliquidandavapourphase:thisisthefarleftendoftheregularvapourliquidbiphasicequilibriumregion.Thevapourkeepscondensinguponfurther
coolinguntilthebubbletemperature,andeventually,atstilllowertemperature,benzenecrystals(SLE)willappearagain.
Figure64:Txy vapourliquidsolidsketchforamethane+benzenemixture.
3ProblemSolvingProcedure
3.1Evaluationofthemostappropriatemodel
Modelsforthecalculationofphaseequilibriumarebasedonthefugacities:phaseequilibriumisobservedwhenthefugacitiesofeachcomponentineachphaseare
equal.Afugacitymodelisneededforeachphaseunderconsideration(seefigure62).
3.1.1Fluidphasefugacity
As the mixture contains only hydrocarbons (see chapter 4, section 2.2), a wide choice of models is available for calculating these fugacities: activity coefficient
modelsaregenerallynotrecommendedforgases(notimpossible,butmorecomplextouse).Amongtheequationsofstate,thecubicequationsarethemostwell
known,andwillbeusedhere.Acubic,PengRobinson[9]equationofstateisselectedhereforcalculatingtheliquidandvapourfugacities(chapter3,section4.3.4).
Theparameterizationrequiresspecialcarefortworeasons:
1. Theequationisusedatverylowtemperature,inaregionwhereveryfewdataexistformodelvalidationand
2. Thecomponentofinterestisverydilutedinamajoritycomponentthatismethane.
Asaresult,specialattentionneedstobegiventothemixingrule.
3.1.1.1Selectionofthe(T)function
The first step in parameterizing a cubic equation of state is to make sure that the pure component vapour pressures are correctly modelled using the selected (T)
function. The usual model is that of Soave, which is very acceptable for alkanes, but considering that the benzene properties will be extrapolated at very low
temperatures,itwaspreferredtousetheTwuequation[10](seesection4.3.4.2,chapter3):
(61)
3.1.1.2Selectionofthemixingrule
Inordertobeabletoreachtheinfinitedilutionpropertiesofbenzene,itisimportanttohaveapowerfulmixingrule.Inthiswork,itwaschosentousethemixingrule
ofHuronVidal(1979[11]):
(62)
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with,forthePengRobinsonequation:
(63)
TheexcessGibbsenergyinequation(62)isexpressedusingamodifiedNRTL:
(64)
3.1.2Solidphasefugacity
Asolidphaseappearsif,foranyofthecomponents,thesolidfugacityislowerthanthefugacityoftheequilibriumphase.ThissolidfugacityfS0,iscalculatedusing
thegeneralthermodynamicrelationships(seechapter3,section4.4.1).:
(65)
ThisequationexpressesthechangeinGibbsenergybetweentheliquidandthesolidphase,atthesystempressureandtemperature.Onthelefthandside,fL0is the
fluidphasefugacityofthepurecomponentatthesystemtemperatureandpressure.Itiscalculatedusingthefluidstateequationofstate.
On the right hand side, the two first terms express the deviation due to the temperature difference between the fusion temperature and the system temperature.
Usually,onlythefirstterm,thatisproportionaltothefusionenthalpy(Hif)isused.However,verylargetemperaturedeviations(morethan100K)areconsidered,it
isimportanttoincludethesecondtermthattakesintoaccountthatthisfusionenthalpyvarieswithtemperature.Theproportionalityfactorisherec pif , the fusion
heatcapacitydifferencebetweensolidandliquid.Finally,thethirdtermofequation(65)isrequiredwhenthesystempressurediffersfromthatatwhichthefusion
properties are provided (which is usually atmospheric pressure). This last term is proportional to the volume of fusion, i . Both enthalpy of fusion and volume of
fusionareavailableindatabases(table62).
3.2Datarequiredanddataavailable
In order to construct a model it is essential to have experimental data, either for regressing parameters, or for validating the results. As it has been shown in the
previous point the selected equation(s) require(s) parameters. These parameters may be physical properties, available in data bases, or will be regressed from
experimentaldata.
3.2.1Purecomponentdata
3.2.1.1Characteristicparameters
Thechosenmodel(PengRobinson)requirestheuseofthecriticalparametersforeverypurecomponentofthemixture.Thankstothefactthatallcomponentsare
databasecomponents,theycanreadilybefoundintheDIPPRdatabase.
Thesolidfugacitymodelequation(65),inadditionrequiresfourmorepurecomponentproperties:Tif,Hif,c pifandi.ThetwofirstareavailabletoointheDIPPR
database, but c pif will have to be determined. As a first approximation, the last parameter will be neglected (this Poyntingtype correction affects the pressure
dependenceofthesolidfugacity,whichisgenerallysmall).
3.2.1.2Temperaturedependentdata
Inordertoparameterisethe(T)function(61),vapourpressuredataareneeded.Again,theDIPPRdatabaseprovidesanaccuratecorrelationofvapourpressurefor
allcomponentsofinterestinthiswork.
Finally,consideringthelowtemperatures,andthefactthatafluidsolidequilibriumisconsidered,purecomponentsublimationpressureswillbeuseful(seesection
1.1.2.3ofchapter3).ThisinformationisavailabletoointheDIPPRdatabase.
Table73:Dataforpurecomponents
Dataneeded
Dataavailable
Criticaltemperature
Inallcommondatabaseandprocesssimulators
Criticalpressure
Acentricfactor
Twuconstants
Somepublishedinoriginalpublication.
Availableinmostsimulatorsorfittedfromvapourpressure
Fusiontemperature
Inmostcommondatabaseandprocesssimulators
Fusionenthalpy
Inmostcommondatabaseandprocesssimulators
Heatcapacityoffusion Unavailable
3.2.2Mixturedata
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3.2.2.1Fluidsolidequilibriumdata
Sincethisworkdealswithcrystallizationoftracecomponentsfromagasmixture,itisessentialtofinddataofthesamekindthatcanvalidatetheapproach.Aftera
carefulliteraturesearch,followingtypesofdatacouldbeidentified(seetable64):
Table64:Availablefluidsolidequilibriumdataforthemethane+benzeneequilibrium
Reference
Pointsnumber Temperaturerange(K)
Datatype
Kuebler,G.P.McKinley,C.{Kuebler,19742391/id}
39
99200
lowtemperatureSLE
Neumann,A.etal.[13]
12
104185
lowtemperatureSLE
Luks,K.D.Hottovy,J.D.Kohn,J.P.[7]
23
165278
2SLVElines
Rijkers,M.P.W.Malais,M.Peters,C.J.DeSwaanArons,J.[14]
100
262298
lowandhightemperatureSLE+VSE+HTVLSEline
Neumann et al. (1972 [13]) have measured benzene and cyclohexane crystallization out of methane. As it can be seen on figure 6 5, the risk of crystallization of
benzeneisgreaterthanforcyclohexane,becauseatthesametemperature,alowercompositionofbenzenecanleadtosolidprecipitation.Yet,thetemperatureand
concentrationsdonotfitwiththoseoftheprocess.
The data of Neumann et al. don't provide pressure information. This is a clear drawback in using them. Nevertheless, it can be considered that pressure has a
negligibleeffectonphaseequilibriumofcondensedphases,asitisthecasehere.
Figure65:CrystallizationofCyclohexaneandbenzeneinmethane(dataofNeumannetal.1972[13]).
IthasbeenobservedthattheconditionsthatmaybeofinteresttoLNGprocessesarethosewherevapoursolidequilibrium(VSE)isencountered.Unfortunately,very
fewsuchdatahavebeenfound.OnlyRijkersetal.(1992[14])publishessuchdata,butforveryhighbenzeneconcentrations(10%benzene).
TheotherinformationfoundinliteratureisgivenbyLuksetal.[7].Theyprovidethreephasevapourliquidsoliddata.Twobranchesareobservedonfigure66,one
corresponding to the high temperature branch (HTVLSE) and the other corresponding to the low temperature branch (LTVLSE), information compatible with the
descriptionoffigure63.
Figure66:PressureTemperatureprojectionofthemethane+benzenethreephaselines,accordingtothedataofLuksetal.(1981)
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They provide as a function of temperature and pressure, the composition of the liquid phase. The graph of figure 66 clearly shows how the two three phase lines
changewithpressure.Thelowerthreephaselineendsatthemethanecriticalpoint.Asamatteroffact,fromthatpointonward,itbecomesimpossibletomakethe
differencebetweentheliquidandthevapourphase.Thehightemperaturethreephaselinecontinuesuntilmuchhigherpressuresbecausethecriticalpointslocusof
themethane+benzenemixturereacheshighpressures.
3.2.2.2Vapourliquidequilibriumdata
In order to determine parameters for the HuronVidal mixing rule, vapourliquid equilibria are generally used. Most often, bubble pressures are regressed, and
sometimesvapourcomposition,asdiscussedinchapter3,section3.
Methane (majority component) and benzene (crystallizing component) are the key components and will be focused on. Vapourliquid equilibrium data for these
mixtures exist, but at temperatures that are well above the process temperature. The lowest temperature data that were found originate from Rijkers et al. {Rijkers,
19921537/id},andcovereightdifferentisotherms,between270and330K.
3.3Parametersfitting
Inordertousethemodeldefinedabove,followingparametersneedtobedetermined:
Twu'sparametersfor(T)functiontousewiththePREoS.
BinaryinteractionparameterstousewiththeHuronVidalmixingrule.
Heatcapacityoffusiontouseinthesolidfugacitycalculation.
3.3.1Purecomponentparameters
The very first step is always to verify the pure component parameters of the equation of state. Use of validated critical parameters, and regression of the L, M, N
parametersofequation(61)foreachcomponentofthemixtureisaprerequisiteforthefurtheranalysis.Inthiswork,noemphasiswillbegiventothisfirststep.
3.3.2Binaryinteractioncoefficients
ThechoiceoftheHuronVidalmixingrule,thatisbasedonthemodifiedNRTLequation(64)resultsinthreeinteractionparametersatanygiventemperature:ji, ij
andji.Inaddition,theseparametersareafunctionoftemperature:
(66)
(67)
ThestrengthoftheHuronVidalmixingruleisthat,whennodataisavailable,anadequatechoiceoftheinteractionparametersisequivalenttoasimplecubicmixing
rulewith ij:takingij=0,itispossibletofind:
(68)
Ontheotherhand,whensufficientdataexist,itispossibletoregressthemallinordertoimprovetheaccuracyofthecalculations.Inthiswork,focuswillbecentred
onthemethane+benzenebinarymixture.
The binary interaction parameters (BIP) are generally fitted on vapourliquid equilibria. In the case of the methane + benzene mixture, these data are abundant, but
exist only at temperatures that are well above the process temperatures. The parameters available in the simulator that was used so far, were fitted on high
temperaturedata.Inthiswork,focuswillbeondataofRijkersetal.astheygoto250K,thelowestofallisothermsknownforthatmixture.Forcomparison,afirstset
ofBIPhasbeenobtainedwithdatathatdonotincludetheRijkersetal.dataset.
The deviation table 65 clearly shows that the first parameters were adapted to the high temperature conditions, but provide large deviations for the lower
temperatures.Thesecondsetwasadjustedonalldatausingfollowingobjectivefunction:
(69)
Rijkersetal.providenodataonthevapourcomposition,sothatthiscouldnotbeincludedintheregression.
Table65:Deviationtableforbinaryinteractionparametersets
Datasource(K)
parameters
Firstset Secondset
ij=0
270
15.05%
39.36%
46.0%
280
8.91%
32.20%
39.0%
290
6.40%
26.03%
33.0%
300
6.94%
21.28%
27.0%
310
8.53%
17.13%
23.0%
320
11.00%
14.11%
19.0%
330
11.18%
10.86%
16.0%
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340
12.30%
7.41%
15.0%
3.3.3Heatcapacityoffusion
Theparametersofthesolidfugacityfunction,equation(65),areallknownquantities(HifJ/molandifm3/mol)excepttheheatcapacityoffusionCpif.Asafirst
approximation,itispossibletoassumeitisnegligible.
Inordertovalidatethisapproach,thefirststepistoevaluatethepurecomponentfluidsolidequilibriumline,i.e.thesublimationline.Doingso,andassumingthatthe
vapourfugacityequalsthepartialpressure:
(610)
where
istherighthandsideofequation(65)withoutthePoyintingcorrectionterm(pressureislowandthistermisverysmall).
Figure67:Evaluationofthecorrectionterm(equation(610))asafunctionoftemperatureforbenzenecrystallization.
Figure67showstheresultofthiscalculation.Obviously,atthetriplepoint,allfugacitiesareequal(thisissobyconstructionofequation(65),butitisclearthatat
lowtemperature,thebenzenesublimationpressuredeviatesfromthesimplifiedmodel.Correctiontermcannotbeneglected.Itcanbeconcludedthatthesolidheat
capacityuponfreezing,Cpif,willneedtobefitted.Consideringtheexpressionsused,thecorrectiontermhasbeenchosenintheobjectivefunction:
(611)
Indeed,itisrathereasytocalculatetheexperimentalvalueofln(fi/fL0)byobservingthatwhencrystallizationoccurs,fi=fS0,wherefiisthefugacityofcomponenti
inthestablephase(calculatedusingtheequationofstateattheexperimentaltemperature,pressureandcomposition),whileiscalculatedusingthesameequationof
state,forpurebenzeneatintheliquidphaseatthesametemperatureandpressure.
Inadditiontothepurecomponentsublimationpressure,itispossibletoconsiderthemixtureLSEdatabyNeumannetal.,Itisessentialtoreproducecorrectlythese
latter data since the temperature and concentration conditions are close to the process conditions. Figure 6 8 shows the logarithm of the fugacity ratio for the two
typesofsolidequilibriumdata.Itisclearlyvisiblethatthetwocurvesarenotcolinear.ThereasonforthisismostprobablyduetotheimperfectionsoftheHuron
Vidal mixing rule that is used. When sublimation data are used, no mixing rule is needed, as all data concern the pure component. On the opposite, the low
temperature LSE data concern very small benzene concentrations in almost pure methane. Hence, in the latter case, the infinite dilution fugacity is used, which is
extrapolatedfromtheequationthathasbeenvalidatedonhightemperatureVLEdata.
Yet,inthepresentstudy,attentionhasbeenfocusedonthelowtemperatureandhighdilutionbehaviour.Doingsoforbenzene,ithasbeenfound,withafewtrialand
error,thevalueofCpif=200kJ/(kmol.K).
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Figure68:Correctionterm(equation(65))asafunctionoftemperatureforbenzenecrystallization.Thediamondsrefertosublimationdatathetrianglestobenzene
crystallizationinmethane.
3.4Modelvalidation
Firstatall,itisimportanttocheckthevalidityofthesolidificationmodel.Evolutionofbothfugacities(thebenzenesolidfugacityandthebenzenefluidfugacityinthe
mixturecalculatedwithEoS)iscomparedasafunctionoftemperature.Whenfugacitiesarethesame,afluidsolidequilibriumisexpected.Itcanbeappreciatedin
figure69thatthismodelpredictscorrectlythethreecasesshowninfigure64(thedashedlineatlowbenzenecomposition).
Figure69:Correctionterm(equation(65))asafunctionoftemperatureforbenzenecrystallization.Thediamondsrefertosublimationdatathetrianglestobenzene
crystallizationinmethane.
Themodelthatisthusdevelopedhasbeenfirstvalidatedbyextrapolationofpressureandtemperatureconditions,usingthedataofRijkersetal.(1992)asshownin
figure610.Thisplotshowstwodistincttypesofbehaviour.Athighertemperatures,andhighconcentrationsofbenzene,LSElinesareseen.Thedatapointsandthe
model (line) agree within 5 K. The model overpredicts crystallization temperatures which is acceptable for a safe design. At lower temperature, a vapoursolid
equilibriumlineisshown.Again,themodelqualitativelyagreeswiththedata.Thecrystallizationtemperatureincreaseswhilepressuredecreases.Atlowerpressures
(processconditions),itisexpectedtooverpredictthecrystallizationtemperature,againasaferesult.Unfortunately,nodatacouldbefoundshowingcrystallization
fromthevapourphaseatbenzeneconcentrationsthatareclosertotheprocessconditions(lessthan1%).
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Figure610:ModelvalidationonthebenzenecrystallizationdataoutofmethaneofRijkersetal.(1992).
4Applicationtoprocessanalysis
Asmentionedpreviously,fourdifferentpointshavebeenselectedforanalyzingtheriskofcrystallization.ThefeedtoLNGprocessisofcourseofmainimportance
duetothepresenceofthehighercontentinheavycomponents.Othercriticalflowsarethoseofthecryogenicsectionoftheexchangeratthelowertemperatureof
theprocess.Twodifferentflows,withsimilarcomposition,areanalysed:theheadofdemethanizerandtheLNGproductavailableatthetopofthevessel.Finally,the
bottomofthescrubberhasverydifferentcompositionandisanalyzedtoo.Thecompositionofthedifferentcurrentsissummarizedintable66.
Table66:Typicalmolarcompositionofthepointsanalyzedinprocess
Component
Feed
Headofdemethanizer
Composition(molar%) Composition(molar%)
N2
1.64
CH4
86
91.66
C2
5.71
C3
0.96
iC4
0.5
0.01
nC4
0.8
iC5
0.1
nC5
0.3
nC6
0.1
nC7
0.06
nC8
0.02
nC9
0.01
CO2
0.01
0.02
Benzene
0.05
10ppm
Cyclohexane
0.05
4.1Feedcrystallizationphasediagram
Using the feed composition given in table 61, figure 611 shows the crystallization of benzene at different temperaturepressure conditions. The vapourliquid (VL)
phaseenvelopeispredicted.Thereisaclearriskbelow90C,butpressurehasaneffectaswell:
When pressure is very low (atmospheric), solid appears much earlier (i.e. at higher temperature). This can be explained rather easily by observing that in these
conditions,theliquidphaseisratherconcentratedinbenzene.
Intheliquidregion,itisseenthatincreasingpressureresultsinahighersolubilityofthesolid.Thisisbecausethisliquidphaseremainssomewhatcompressibleasit
isessentiallycomposedofmethane,andthereforethetemperatureisclosetothecriticaltemperature.Hence,athigherpressure,theliquidisdenserwhichmeansit
isabettersolventforthebenzenecrystals.Notethatthephenomenonhadbeenoppositeiftheliquidhadbeenlesscompressible,asisthecasewithpurebenzene:
thehigherthepressure,thelargerthetendencytoformasolidphase.
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Figure611:Phasediagramofthefeed,givenintable61.LVmeansvapourliquidFmeansfluidphase.When'S'isincluded,benzeneiscrystallized.
4.2Demethanizerdiagram
A typical composition of the head of the demethanizer is shown in table 66. For this exercise, Benzene specification in the demethanizer and the LNG product
overheadhavebeenrelaxedto10ppminsteadofthegenerallyconsidered1ppm.
Thecorrespondingphasediagramsarepresentedinfigure66.
Figure612:Phasediagramoftheheadofthedemethanizerwith10ppmofbenzene(asshownintable66.
Thisfigure612againshowsthevapourliquidequilibriumzoneas'LV',andthesinglephaseregionas'F'.Threedifferentcrystallizationzonescanbeidentified:
Below115Kbenzenecrystallizesfromtheliquidphase.
Inthesamewayasinthefeed,benzenecrystallizationcanbeobservedatlowpressurewithinthevapourliquidzone.Inoppositionwithwhatisseeninfigure
611,thefluidisveryrichinmethane,andasaresultthevapourzone,belowthevapourliquidequilibrium,isvisible.Inthiszone,wherethefluidissingle
phasevapour,crystallizationalsooccurs,atratherhightemperatures(upto200K),eventhoughthebenzeneconcentrationisassmallas10ppmmolar.
ThislastcrystallizationzonecanbeexplainedwhenconsideringtheTxysketchof64.Itwasexplainedhow,atafixedpressure,afirstcrystallizationzonefromthe
vapour phase could be observed at moderate temperature. When temperature decreases, the crystals dissolve in the liquid that appears. The crystals reappear at
muchlowertemperature,outoftheliquidmethane.
Unfortunately,noexperimentaldataillustratingthisbehaviourcouldbefound.
5Conclusions
ThisworkwasexecutedinordertoevaluatetheriskofbenzenecrystallizationintheLIQUEFINTMgasliquefactionprocess.Theworkispresentedinthreestages:
Inordertounderstandthephysicalphenomenonofcrystallization,thephasediagramofthemethane+benzenebinarysystemisfirstinvestigatedindetail.It
isshownthattwoliquidsolidandonevapoursolidequilibriumzonesexist,inadditiontothewellknownvapourliquidequilibrium.
Inasecondstage,athermodynamicmodelisdeveloped,thatusesthePengRobinsonequationofstatewiththeHuronVidalMixingrule.Theparametersfor
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thismodelhavebeendeterminedbasedonhightemperatureVLEdata.Itisobviousthatthemodelisusedattemperaturesthatarewellbelowthetemperature
ofthedataused.Hence,carehasbeentakenthattheextrapolationtolowertemperaturesisasacceptableaspossible.Anadditionalparameter(fusionheat
capacity)isdeterminedusinglowtemperatureLSEdata.
Inafinalstage,themodelisusedtocalculatethephasediagramoftwotypicalcompositionsencounteredintheLIQUEFINTMprocess.Thefirstcomposition
isrichinheavyendcomponents.Asaresult,aliquidphaseisalwayspresent.Thisliquidmaybeconcentratedinbenzene,whichincreasesthecrystallization
riskathighertemperaturesandlowpressures.Thesecondcompositionisverypuremethane.Asaresult,asinglevapourphasemayexistathightemperature
andlowpressure.Eventhoughthebenzeneconcentrationisverysmallinthiscontext(10ppmmolar),acrystallizationriskfromthevapourphaseexists
whichjustifythechoiceforalowerbenzenespecificationinthedemethanizeroverhead.ThisphenomenonisofimportanceforthedesignoftheLNGprocess,
butnoexperimentaldatavalidatingthisbehaviourhasbeenfound.
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Select Thermodynamic Models For Process Simulation - A Practical Guide To A Three Steps Methodology

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TriplepointTemperature(K) TriplepointPressure(Pa) Enthalpyoffusion(J/kmol) Volumeoffusion(m3/kmol)

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