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ThermodynamicsandHYSYS 1
ThermodynamicsandHYSYS
2000AEATechnologyplc-AllRightsReserved.Chem2_5.pdf 1
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2 ThermodynamicsandHYSYS
WorkshopOneoftheminssetsof!"#"#isitsstrongthermodynmic
fo$ndtion.%otonlycnyo$$se&idevrietyofinternlproperty
pc'ges(yo$cn$set)$lrcp)ilitiestooverridespecificproperty
clc$ltionsformorecc$rcyovernrro&rnge.Or(yo$cn$sethe
f$nctionlityprovidedthro$ghO*Etointerct&ithe+ternlly
constr$ctedpropertypc'ges.
The)$ilt-inpropertypc'gesin!"#"#providecc$rte
thermodynmic(physiclndtrnsportpropertypredictionsfor
hydrocr)on(non-hydrocr)on(petrochemiclndchemiclfl$ids.
Thedt)seconsistsofne+cessof,500componentsndover,000
fitted)inrycoefficients.f li)rrycomponentcnnot)efo$nd
&ithinthedt)se(comprehensiveselectionofestimtionmethods
isvil)leforcretingf$lly definedhypotheticlcomponents.
!"#"#lsocontinsregressionpc'ge&ithinthet)$lrfet$re.
E+perimentlp$recomponentdt(&hich!"#"#providesforover
,000components(cn)e$sedsinp$ttotheregressionpc'ge.
Alterntively(yo$cns$pplementthee+istingdtors$pplysetof
yo$ro&ndt.Theregressionpc'ge&ill fittheinp$tdttooneof
then$mero$smthemticle+pressionsvil)lein!"#"#.This&ill
llo&yo$too)tinsim$ltionres$ltsforspecificthermophysicl
propertiesthtcloselymtchyo$re+perimentl dt.
!o&ever( thererecses&hen theprmetersclc$lted)y!"#"#
re notcc$rteeno$gh(orcses&henthemodels$sed)y!"#"#do
notpredictthecorrect)ehvio$rofsomeli/$id-li/$idmi+t$res
01eotropicmi+t$res.3orthosecsesitisrecommendedto$se
notherof!yprotech4sprod$cts(#T*.Thispo&erf$lsim$ltion
progrmprovidesnenvironmentfore+plortionofthermodynmic
model)ehvio$r(properdetermintionndt$ningofinterction
prmetersndphysiclproperties(s&ellslterntivedesignsfor
distilltionsystems.
2
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ThermodynamicsandHYSYS 3
6roper$seofthermodynmicpropertypc'geprmetersis'eyto
s$ccessf$lly sim$ltingnychemiclprocess.Effectsofpress$rend
tempert$recndrsticllylterthecc$rcyofsim$ltiongiven
missingprmetersorprmetersfittedfordifferentconditions.
!"#"#is$serfriendly)yllo&ing/$ic'vie&ingndchngingofthe
prtic$lrprmetersssocited&ithnyofthepropertypc'ges.n
ddition(yo$re)leto/$ic'lychec'theres$ltsofonesetof
prmetersndcomprethoseres$lts&ithnotherset.
nthismod$le(yo$&ill e+plorethethermodynmicpc'gesof!"#"#
ndtheproper$seoftheirthermodynmicprmeters.
LearningObjectivesOnceyo$hvecompletedthismod$le(yo$&ill)e)leto7
SelectanappropriatePropertyPackage
UnderstandthevalidityofeachActivityModel
Enternewinteractionparametersforapropertypackage
Checkmltiphase!ehaviorofastream
Understandtheimportanceofproperlyregressed!inarycoefficients
"
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4 ThermodynamicsandHYSYS
SelectingPropertyPackagesThepropertypc'gesvil)lein!"#"#llo&yo$topredict
propertiesofmi+t$resrngingfrom&ell definedlighthydrocr)on
systemstocomple+oilmi+t$resndhighlynon-idel non-electrolytic
chemiclsystems.!"#"#providesenhncede/$tionsofstte6R
nd6R#8forrigoro$stretmentofhydrocr)onsystems9semi-
empiricl ndvpo$rpress$remodelsforthehevierhydrocr)on
systems9stemcorreltionsforcc$rtestempropertypredictions9
ndctivitycoefficientmodelsforchemiclsystems.Allofthese
e/$tionshvetheiro&ninherentlimittionsndyo$reenco$rged
to)ecomemorefmilir&iththepplictionofeche/$tion.
Thefollo&ingt)lelistssometypicl systemsndrecommendedcorreltions7
Typeof#ystem Recommended6roperty6c'ge
TE: ehydrtion 6R
#o$r;ter 6R(#o$r6R
Cryogenic:s6rocessing 6R(6R#8
Air#eprtion 6R(6R#8
AtmCr$deTo&ers 6R(6R Options(:#
8c$$mTo&ers 6R(6R Options(:#,0(
Esso>
EthyleneTo&ers *ee>esler6loc'er
!igh!2#ystems 6R(?@or:#seeTA6limits
Reservoir#ystems 6R(6R Options
#tem#ystems #tem6c'ge(C#or:#
!ydrtenhi)ition 6R
Chemicl#ystems ActivityBodels(6R#8
!3Al'yltion 6R#8(%RT*Contct!yprotech
TE:ehydrtion&ith
Aromtics
6RContct!yprotech
#
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ThermodynamicsandHYSYS 5
E$ationsofState3oroil(gsndpetrochemiclpplictions(the6eng-Ro)insonEO#
6Risgenerllytherecommendedpropertypc'ge.!"#"#c$rrently
offerstheenhnced6eng-Ro)inson6Rnd#ove-Redlich->&ong
#R>e/$tionsofstte.nddition(!"#"#offersseverlmethods
&hichremodifictionsofthesepropertypc'ges(incl$ding6R#8(
?$d'evitch@offee?@nd>)dinner>.*ee>esler6loc'er
*>6isndpttionofthe*ee>eslere/$tionsformi+t$res(&hich
itself&smodifiedfromthe=;Re/$tion.Ofthese(the6eng-
Ro)insone/$tionofsttes$pportsthe&idestrngeofoperting
conditionsndthegretestvrietyofsystems.The6eng-Ro)insonnd
#ove-Redlich->&onge/$tionsofstteEO#genertellre/$ired
e/$ili)ri$mndthermodynmicpropertiesdirectly.Altho$ghtheformsoftheseEO#methodsrecommon&ithothercommercil
sim$ltors(theyhve)eensignificntlyenhnced)y!yprotechto
e+tendtheirrngeofpplic)ility.
%hePeng&'o!insonpropertypackageoptionsarePR(SourPR(andPRSV)
Soave&'edlich&*wonge$ationofstateoptionsaretheSRK(SourSRK(KDandZJ)
3ortheChemiclind$stryd$etothecommonocc$rrenceofhighly
non-idelsystems(the6R#8EO#my)econsidered.tist&o-fold
modifictionofthe6Re/$tionofsttethte+tendsthepplictionof
theoriginl6Rmethodforhighlynon-idelsystems.
+thasshowntomatchvaporpressrecrvesofprecomponentsandmi,tres(especiallyatlowvaporpressres)
+thas!eensccessfllye,tendedtohandlenon&idealsystemsgivingresltsasgoodasthoseo!tained!yactivitymodels)
Alimitedamontofnon&hydrocar!oninteractionparametersareavaila!le)
ActivityModels
Altho$ghe/$tionofsttemodelshveprovento)everyreli)lein
predictingpropertiesofmosthydrocr)on)sedfl$idsoverlrge
rngeofopertingconditions(theirpplictionhs)eenlimitedtoprimrily non-polr or slightlypolr components. 6olr or non-
idel chemiclsystemshve trditionlly)eenhndled$singd$l
model pproches.
ActivityBodelsrem$chmoreempiriclinnt$re&hencompredto
-
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6 ThermodynamicsandHYSYS
thepropertypredictionsinthehydrocr)onind$stry.3ore+mple(
theycnnot)e$sedsreli)lysthee/$tionsofstteforgenerli1ed
pplictionore+trpoltinginto$ntestedopertingconditions.Their
t$ningprmeterssho$ld)efittedginstrepresenttivesmpleof
e+perimentldtndtheirpplictionsho$ld)elimitedtomoderte
press$res.
3oreverycomponentiinthemi+t$re(theconditionof
thermodynmicse/$ili)ri$misgiven)ythee/$lity)et&eenthe
f$gcitiesoftheli/$idphsendvpo$rphse.Thisfet$regivesthe
fle+i)ilityto$seseprtethermodynmicmodelsfortheli/$idndgs
phses(sothef$gcitiesforechphsehvedifferentforms.nthis
pproch7
ane$ationofstateissedforpredictingthevaporfgacitycoefficients.normallyidealgasassmptionorthe'edlich*wong(Peng&'o!insonorS'*e$ationsofstate(althogha/iriale$ationofstateisavaila!leforspecificapplications0
anactivitycoefficientmodelissedfortheli$idphase)
Altho$ghthereisconsider)lereserch)eingcond$ctedtoe+tend
e/$tionofsttepplictionsintothechemicl ind$strye.g.(6R#8
e/$tion(thestteofthertofpropertypredictionsforchemicl
systemsisstill governedminly)yActivityBodels.
ActivityModelsproducethebestresultswhentheyareappliedintheoperatingregionforwhichtheinteractionparameterswereregressed.
Activitycoefficientsref$dgeDfctorsppliedtotheidelsol$tion
hypothesisRo$lt4s*&initssimplestformtollo&thedevelopment
ofmodels&hichct$llyrepresentreldt.Altho$ghtheyref$dgeDfctors(ctivitycoefficientshvene+ctthermodynmicmenings
thertioofthef$gcitycoefficientofcomponentinmi+t$ret6nd
T(ndthef$gcitycoefficientofthep$recomponenttthesme6nd
T.Consequently,morecautionshouldbeexercisedwhenselectingthese
modelsforyoursimulation.
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ThermodynamicsandHYSYS
Thefollo&ingt)le)rieflys$mmri1esrecommendedctivity
coefficientmodelsfordifferentpplictionsrefertothe)$lleted
referenceg$ide)elo&7
Appliction Brg$les vn*r ;ilson %RT* %FAC
=inry#ystems A A A A A
B$lticomponent
#ystems
*A *A A A A
A1eotropic#ystems A A A A A
*i/$id-*i/$id
E/$ili)ri
A A %AA A A
il$te#ystems G G A A A
#elf-Associting
#ystems
G G A A A
6olymers %A %A %A %A A
E+trpoltion G G : : :
!2Applica!le "#!23otApplica!le $24estiona!le %25ood &!26imitedApplication
7
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' ThermodynamicsandHYSYS
8verviewofModels
Margles
Oneoftheerliestctivitycoefficiente+pressions&sproposed)y
Brg$lesttheendofthe,Hthcent$ry.
%heMarglese$ationwasthefirst5i!!se,cessenergyrepresentationdeveloped)
%hee$ationdoesnothaveanytheoretical!asis(!tisseflfor$ickestimatesanddatainterpolation)
+nitssimplestform(ithas9stonead9sta!leparameterandcanrepresentmi,treswhichfeatresymmetricactivitycoefficientcrves)
TheMargulesequationshouldnotbeusedforextrapolationbeyondtherangeoverwhichtheenergyparameters havebeenfitted.
ThevanLaarequationperformspoorlyfordilutesystemsandCA!Trepresentmanycommonsystems,suchasalcohol"hydrocarbonmixtures, withacceptableaccuracy.
!"#"#hsne+tendedm$lticomponentBrg$lese/$tion&ith$pto
fo$rdI$st)leprmetersper)inry.Thefo$rdI$st)leprmeters
fortheBrg$lese/$tionin!"#"#retheiIndIitempert$re
independentndthe)iInd)Iitermstempert$redependent.
%hee$ationwillseparametervalesstoredin:;S;Soranysersppliedvaleforfrtherfittingthee$ationtoagivensetofdata)
+n:;S;S(thee$ationisempiricallye,tendedandthereforecationshold!ee,ercisedwhenhandlingmlticomponentmi,tres)
van6aar
The vn *r e/$tion &s the first :i))s e+cess energy
representtion &ithphysicl significnce. This e/$tion fits mny
systems /$ite &ell( prtic$lrly for **E component distri)$tions. t
cn)e$sedfor
systemsthte+hi)itpositiveornegtivedevitionsfromRo$lt4s*&.
#omeofthedvntgesnddisdvntgeforthismodel re7
5enerallyre$ireslessCPUtimethanotheractivitymodels)
+tcanrepresentlimitedmisci!ilityaswellasthreephasee$ili!rim)
+tcannotpredictma,imaorminimaintheactivitycoefficient
andtherefore(generallyperformspoorlyforsystemswithhalogenatedhydrocar!onsandalcohols)
+talsohasatendencytopredicttwoli$idphaseswhentheydonote,ist)
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ThermodynamicsandHYSYS (
Thevn*re/$tionimplementedin!"#"#hst&oprmeters&ith
linertempert$redependency(th$sm'ingitfo$rprmeter
model.n!"#"#( thee/$tionisempiricllye+tendedndthereforeits
$sesho$ld)evoided&henhndlingm$lticomponentmi+t$res.
=ilson
The;ilsone/$tion(proposed)y:rntB.;ilsonin,HJ(&sthe
firstctivitycoefficiente/$tiontht$sedtheloclcompositionmodel
toderivethe:i))sE+cessenergye+pression.toffers
thermodynmicllyconsistentpprochtopredictingm$lti-
component)ehvio$rfromregressed)inrye/$ili)ri$mdt.
The #ilson equationCA!T be used forproblems involving liquid"liquidequilibrium.
The additionalparameterinthe$TLequation,calledthealphaterm,ornon"randomnessparameter,
representsthe inverseofthecoordinationnumberofmolecule%i&surroundedbymolecules%'&.(ince liquidsusuallyhaveacoordinationnumberbetween)and*,youmightexpectthe alphaparameterbetween+.-and+.)).
Althoghthe=ilsone$ationismorecomple,andre$iresmoreCPUtimethaneitherthevan6aarorMarglese$ations(itcanrepresentalmostallnon&idealli$idsoltionssatisfactorilye,ceptelectrolytesandsoltionse,hi!itinglimitedmisci!ility.66Eor/66E0)
+tperformsane,cellent9o!ofpredictingternarye$ili!rimsingparametersregressedfrom!inarydataonly)
+twillgivesimilarresltstotheMarglesandvan6aare$ationsforweaknon&idealsystems(!tconsistentlyotperformsthemforincreasinglynon&idealsystems)
+tcannotpredictli$id&li$idphasesplittingandthereforesholdonly!esedonpro!lemswheredemi,ingisnotanisse)
O$re+periencesho&sthtthe;ilsone/$tioncn)ee+trpolted
&ith reson)le confidence to other operting regions &ith the
sme setofregressedenergyprmeters.
3'%6
The%RT*%on-Rndom-T&o-*i/$ide/$tion(proposed)yRenon
nd6r$snit1in,HK(isne+tensionoftheoriginl ;ilsone/$tion.t
$sessttisticlmechnicsndtheli/$idcell theorytorepresentthe
li/$idstr$ct$re.Theseconcepts(com)ined&ith;ilson4slocl
compositionmodel(prod$cene/$tioncp)leofrepresenting8*E(
**E(nd8**Ephse)ehvio$r.*i'ethe;ilsone/$tion(the%RT*
model isthermodynmiclly consistentndcn)eppliedtoternry
ndhigherordersystems$singprmetersregressedfrom)inrye/$ili)ri$mdt.The%RT*model hsncc$rcycompr)letothe
;ilsone/$tionfor8*Esystems.
%he3'%6com!inestheadvantagesofthe=ilsonandvan6aare$ations)
>
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1) ThermodynamicsandHYSYS
+tisnote,tremelyCPUintensive)
+tcanrepresent66E$itewell)
:owever(!ecaseofthemathematicalstrctreofthe3'%6e$ation(itcanprodceerroneosmltiplemisci!ilitygaps)
The%RT*e/$tionin!"#"#continsfivedI$st)leprmeters
0tempert$redependentndindependentforfittingper)inrypir.
U3+4UAC
The%FAC%verslFAsiChemicle/$tionproposed)y
A)rmsnd6r$snit1in,HL5$sessttisticlmechnicsndthe/$si-
chemicl theoryof:$ggenheimtorepresenttheli/$idstr$ct$re.The
e/$tioniscp)leofrepresenting**E(8*End8**E&ithcc$rcycompr)letothe%RT*e/$tion()$t&itho$ttheneedfornon-
rndomnessfctor(itist&oprmetermodel.
The%FACe/$tionissignificntlymoredetilednd
sophistictedthnnyoftheotherctivitymodels.
+tsmainadvantageisthatagoodrepresentationof!oth/6Eand66Ecan!eo!tainedforalargerangeofnon&electrolytemi,tressingonlytwoad9sta!leparametersper!inary)
%hefittedparameterssallye,hi!itasmallertemperatredependencewhichmakesthemmorevalidfore,trapolationprposes)
%heU3+4UACe$ationtili?estheconceptoflocal
compositionasproposed!y=ilson)Sincetheprimaryconcentrationvaria!leisasrfacefractionasopposedtoamolefraction(itisapplica!letosystemscontainingmoleclesofverydifferentsi?esandshape(schaspolymersoltions)
%heU3+4UACe$ationcan!eappliedtoawiderangeofmi,trescontaining:28(alcohols(nitriles(amines(esters(ketones(aldehydes(halogenatedhydrocar!onsandhydrocar!ons)
n its simplest form it is t&oprmeter model( &ith the sme
remr's s;ilson nd%RT*.%FACneeds vnder;ls re
ndvol$meprmeters(ndthosecnsometimes)ediffic$lttofind(
especilly for non-condens)le gses ltho$gh 66R hs fir
n$m)ervil)le.
E,tendedand5eneral3'%6
TheE+tendednd:enerl%RT*modelsrevritionsofthe%RT*
model(simple%RT*&ithcomple+tempert$redependencyforthe
iIndIiterms.Applyeithermodel tosystems7
1@
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ThermodynamicsandHYSYS 11
The general$TLmodel isparticularly susceptible toinaccuracies if the model isusedoutsideofthe intendedrange.
Care mustbetaentoensurethatyouare operatingwithintheboundsofthemodel.
ointeractionbetween/non"condensable/componentpairsista.enintoaccountinthe 0L1calculations.
withawide!oilingpointrange!etweencomponents
whereyore$iresimltaneossoltionof/6Eand66E(andtheree,istsawide!oilingrangeorconcentrationrange!etweencomponents
E+tremec$tionm$st)ee+ercised&hene+trpolting)eyondthe
tempert$rendpress$rernges$sedinregressionofprmeters.5$e
tothelrgern$m)erofprmeters$sedinfitting(incc$rteres$lts
cn)eo)tinedo$tsidetheoriginl)o$nds.
Chien&3ll
Chien-%$ll isnempiriclmodeldesignedtollo&yo$tomi+nd
mtchmodels&hich&erecreted$singdifferentmethodsnd
com)inedintom$lticomponente+pression.TheChien-%$llmodel
providesconsistentfrme&or'forpplyinge+istingctivitymodels
on)inry)y)inry)sis.nthismnner(Chien-%$ll llo&syo$to
selectthe)estctivitymodel forechpirinthecse.3ore+mple(
Chien-%$ll cnllo&the$sertohve)inrydefined$sing%RT*(
nother$singBrg$lesndnother$singvn*r(ndcom)inethem
toperformthreecomponentclc$ltion(mi+ingthreedifferent
thermodynmicmodels.
TheChien%$llmodelllo&sMsetsofcoefficientsforechcomponent
pir(ccessi)levitheA(=ndCcoefficientmtrices.
providesmoreinformtionon6roperty6c'ges(E/$tionsof#tte(ndActivity Bodels(ndthee/$tionsforech.
:enrys6aw
!enry4s*&cnnot)eselectede+plicitlyspropertymethodin
!"#"#.!o&ever(!"#"#&ill $se!enry4s*&&hennctivitymodel is
selectedndNnon-condens)leNcomponentsreincl$ded&ithinthe
componentlist.
!"#"#considersthefollo&ingcomponentsnon-condens)le7
Bethne(Ethne(Ethylene(Acetylene(!ydrogen(!eli$m(Argon(
%itrogen(O+ygen(%O(!2#( CO2(ndCO.
11
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12 ThermodynamicsandHYSYS
Thee+tended!enry4s*&e/$tionin!"#"#is$sedtomodeldil$te
sol$teAsolventinterctions.N%on-condens)leNcomponentsre
definedsthosecomponentsththvecriticltempert$res)elo&the
systemtempert$re.
ActivityModel/aporPhase8ptions
Therereseverlmethodsvil)leforclc$ltingthe8po$r6hsein
conI$nction&iththeselectedli/$idctivitymodel.Thechoice&ill
dependonspecificconsidertionsofyo$rsystem.
+deal
Theidel gsl&cn)e$sedtomodel thevpo$rphse.Thismodel is
ppropriteforlo&press$resndforvpo$rphse&ithlittle
intermolec$lrinterction.Themodel isthedef$ltvpo$rphse
f$gcityclc$ltionmethodforctivitycoefficientmodels.
Peng'o!inson(S'*or'*
Tomodelnon-idelitiesinthevpo$rphse(the6R(#R>(orR>
optionscn)e$sedinconI$nction&ithnctivitymodel.
PRandSRKvaporphasemodelshandlethesametypesofsitationsasthePRandSRKe$ationsofstate)
=henselectingoneofthesethreemodels(ensrethatthe!inaryinteractionparameterssedfortheactivitymodelremainapplica!lewiththechosenvapormodel)
Borapplicationswithcompressorsandtr!ines(PRorSRKwill!esperiortotheRKor+dealvapormodel)
/irial
Careshouldbeexercisedinchoosing2$,($3,$0or0irialtoensure binarycoefficientshave beenregressedwiththecorrespondingvapourphasemodel.
The8iriloptionen)lesyo$to)ettermodelvpo$rphsef$gcities
ofsystemsdisplyingstrongvpo$rphseinterctions.Typiclly this
occ$rsinsystemscontiningcr)o+yliccids(orcompo$ndsththve
thetendencytoformst)le!2)ondsinthevpo$rphse.
!"#"#continstempert$redependentcoefficientsforcr)o+yliccids."o$cnover&ritethese)ychngingtheAssocitioniIor
#olvtioniicoefficientsfromthedef$ltvl$es.
Thisoptionisrestrictedtosystems&herethedensityismoderte(
typicllylessthnone-hlfthecriticldensity.
12
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ThermodynamicsandHYSYS 13
Thenumbersappearinginthematrixareinitiallycalculatedby45(5(, butyouhavetheoptionofoverwritinganylibraryvalue.
inaryCoefficients3orthe6roperty6c'ges&hichdoincl$de)inrycoefficients(the
=inryCoefficientst)continsmtri+&hichliststheinterction
prmetersforechcomponentpir.5ependingontheproperty
methodchosen(differentestimtionmethodsmy)evil)lend
differentvie&my)esho&n."o$hvetheoptionofover&ritingny
li)rryvl$e.
E$ationofState+nteractionParameters
TheE/$tionof#ttenterction6rmetersgro$ppperssfollo&s
onthe=inryCoeffst)&hennEO#istheselectedpropertypc'ge7
3orllEO#prmeterse+cept6R#8(
3i'63'i
so&henyo$chngethevl$eofoneofthese()othcellsofthepir
$tomticlly$pdte&iththesmevl$e.nmnycses(theli)rry
interctionprmetersfor6R#8dohve3i'63'i()$t!"#"#doesnot
forcethisifyo$modifyoneprmeterin)inrypir.
1"
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14 ThermodynamicsandHYSYS
f yo$re$sing6Ror#R>oroneofthe#o$roptions(t&ordio
)$ttonsredisplyedtthe)ottomofthepgeintheTretmentof
nterctionCoefficientsnvil)lefromthe*i)rrygro$p7
*s+ima+eH,-H,#Se+"onH,-H,+o).)Dthisradio!ttonisthedefaltselection):;S;Sprovidestheestimatesfortheinteractionparametersinthematri,(settingallnon&hydrocar!onpairsto@)
Se+!//+o).)Dwhenthisisselected(:;S;Ssetsallinteractionparametervalesinthematri,to@)@)
ActivityModel+nteractionParameters
ActivityBodelsrem$chmoreempiriclinnt$re&hencompredto
thepropertypredictionsinthehydrocr)onind$stry.Theirt$ning
prmeterssho$ld)efittedginstrepresenttivesmpleof
e+perimentldtndtheirpplictionsho$ld)elimitedtomoderte
press$res.
TheActivityBodelnterction6rmetersgro$ppperssfollo&s
onthe=inryCoeffst)&hennActivityBodelistheselected
propertypc'ge7
Theinterctionprmetersforech)inrypir&ill)edisplyed."o$
cnover&ritenyvl$eor$seoneoftheestimtionmethods.
%otethtthe3i'63'ir$ledoesnotpplytoActivityBodel interction
prmeters.
1#
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ThermodynamicsandHYSYS 15
EstimationMethods
;hen$singActivityBodels(!"#"#providesthreeinterction
prmeterestimtionmethods.#electtheestimtionmethod)y
choosingoneoftherdio)$ttonsintheCoeffEstimtion&indo&.The
optionsre7
U3+BAC/6E
U3+BAC66E
+mmisci!le
"o$cntheninvo'etheestimtion)yselectingoneofthevil)le
cells.
3or%3ACmethodstheoptionsre7
0ndiidua/PairDcalclatestheparametersfortheselectedcomponentpair(Ai9 andA9i)%hee,istingvalesinthematri,areoverwritten)
nnons n/yDcalclates theactivityparameters forallthe nknown pairs) +f yo delete the contents of cells or if:;S;S does not provide defalt vales( yo can se thisoption)
!//inariesDrecalclatesallthe!inariesofthematri,)+fyohadchangedsomeoftheoriginal:;S;Svales(yocoldsethistohave:;S;Sre&estimatetheentirematri,)
.
ret$rntheoriginlli)rry vl$es.Estimtionvl$es&ill)eret$rned$singtheselected%3ACmethod.Toret$rntotheoriginlli)rry vl$es(yo$m$stselectne&propertymethodndthenre-selecttheoriginlpropertymethod
The 89:AC;89quacgroup":unctionalActivityCoefficient
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16 ThermodynamicsandHYSYS
=hichActivityCoefficientModelShold+Use
Thisisto$gh/$estiontons&er()$tsomeg$idelinesreprovided.f
yo$re/$iredditionl ssistnce(itis)esttocontct!yprotech4s
Technicl#$pportdeprtment.
asicFata
Activitycoefficientmodelsreempiricl)ynt$rendthe/$lityof
theirpredictiondependsonthe/$lityndrngeofdt$sedto
determinetheprmeters.#omeimportntthingsyo$sho$ld)e&re
ofin!"#"#.
%heparameters!iltin:;S;Swerefittedat1atmwhereverpossi!le(orwerefittedsingisothermaldatawhichwoldprodcepressresclosestto1atm)%heyaregoodforafirstdesign(!talwayslookfore,perimentaldataclosertotheregionyoareworkingintoconfirmyorreslts)
%hevalesinthe:;S;Scomponentdata!asearedefinedfor/6Eonly(hencethe66Epredictionmaynot!everygoodandadditionalfittingisnecessary)
Fatasedinthedeterminationof!iltininteractionparametersveryrarelygoes!elow@)@1molefraction(ande,trapolatingintotheppmorpp!regioncan!erisky)
Again(!ecasetheinteractionparameterswerecalclatedatmodestpressres(sally1atm(theymay!einade$ateforprocessesathighpressres)
Checktheaccracyofthemodelfora?eotropicsystems)Additionalfittingmay!ere$iredtomatchthea?eotropewithaccepta!leaccracy)Checknotonlyforthetemperatre(!tforthecompositionaswell)
+fthreephase!ehaviorissspected(additionalfittingoftheparametersmay!ere$iredtorelia!lyreprodcethe/66Ee$ili!rimconditions)
U3+BACornoU3+BAC
%3ACishndytool togiveinitilestimtesforctivitycoefficient
models.%evertheless'eepinmindthefollo&ing7
5ropcontri!tionmethodsarealwaysappro,imateandtheyarenots!stittionsfore,perimentaldata)
U3+BACwasdesignedsingrelativelylowmoleclarweightcondensa!lecomponents.thshigh!oilersmaynot!ewellrepresented0(singtemperatres!etween@&1-@oCanddataatmodestpressres)
1
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ThermodynamicsandHYSYS 1
5enerally(U3+BACdoesnotprovidegoodpredictionsforthedilteregion)
ChoosinganActivityModel
Agin(somegenerl g$idelinestoconsider.
8ar9u/esoran&aar&generallychosenifcomptationspeedisaconsideration)=iththecompterswehavetoday(thisissallynotanisse)Mayalso!echosenifsomepreliminaryworkhas!eendonesingoneofthesemodels)
:i/son&generallychosenifthesystemdoesnote,hi!itphasesplitting)
"RT&or"0;!,&generallychosenifthesysteme,hi!itsphasesplitting)
%enera/"RT&&sholdonly!esedifana!ndantamontofdataoverawidetemperatrerangewassedtodefineitsparameters)8therwiseitwillprovidethesamemodellingpoweras3'%6)
ExploringwiththeSimlation6roper$seofthermodynmicpropertypc'geprmetersis'eyto
s$ccessf$lly sim$ltingnychemiclprocess.Effectsofpress$rendtempert$recndrsticllylterthecc$rcyofsim$ltiongiven
missingprmetersorprmetersfittedfordifferentconditions.
!"#"#is$serfriendlyinllo&ing/$ic'vie&ingndchngingofthe
prtic$lrprmetersssocited&ithnyofthepropertypc'ges.
Additionlly(the$seris)leto/$ic'lychec'theres$ltsofonesetof
prmetersndcompreginstnother.
17
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1' ThermodynamicsandHYSYS
E,ercise1
Fi&iso&Propyl&EtherG:28inary
Thise+mpleeffectivelydemonstrtestheneedforhvinginterction
prmeters.othefollo&ing7
,. Opencse6E.hsc.
2. Enterthefollo&ingconditionsforstrem6EA!2O7
Conditions
8po$r3rction 0.0
6ress$re ,tm
Bolr3lo& ,'gmoleAh,l)moleAhr
Composition
di-i-6-Ether 50mole
!2O 50mole
#hatphasesarepresent>??????????
M. Closethestremvie&ndpressthe1nter7asis1nvironment)$tton.
J. #electthe=inryCoeffst)ofthe3l$id6c'ge.%oticethttheinterctionprmetersforthe)inryre)othsetto0.0.
5. 6ressthe$eset2arams)$ttontorecll thedef$lt%RT*ctivity
coefficientmodelinterctionprmeters.
. Closethe3l$id6c'gevie&.
L. Ret$rntothesim$ltionenvironment)ypressingthe$eturnto
(imulation1nvironment)$tton.
K. Openthestremvie&)ydo$)leclic'ingonthestrem6EA
!2O.
#hatphasesarenowpresent>??????????
#hatisthecompositionofeach>??????????
1
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ThermodynamicsandHYSYS 1(
Clerly(itcn)eseenho&importntitistohveinterction
prmetersforthethermodynmicmodel.The+yphsedigrmson
thene+tpgefig$res,nd2ill$strtethehomogeneo$s)ehvio$r
&hennoprmetersrevil)lendtheheterogeneo$s1eotropic
)ehvio$r&henproperlyfittedprmetersre$sed.ThemIorityof
thedef$ltinterctionprmetersforctivitycoefficientmodelsin
!"#"#hve)eenregressed)sedon8*EdtfromEC!EBA(
Chemistryt#ervices.
1>
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2) ThermodynamicsandHYSYS
3ig.,-nterction6rmeterssetto0.
3ig.2-singtheef$lt!"#"#nterction6rmeters.
2@
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ThermodynamicsandHYSYS 21
E,ercise2
PhenolG:28inary
This)inrysho&stheimportnceofens$ringthtproperlyfitted
interctionprmetersfortheconditionsofyo$rsim$ltionre$sed.
Thedef$ltprmetersforthe6henolA!2Osystemhve)een
regressedfromtheEC!EBAChemistrydtseriesndprovidevery
cc$rtevpo$r-li/$ide/$ili)ri$msincetheoriginldtso$rce,
&sinthisformt.!o&ever(the6henolA;tersystemislsosho&nto
e+hi)itli/$id-li/$id)ehvio$r2.Asetofinterctionprmeterscn
)eo)tinedfromso$rcess$chsEC!EBAndenteredinto!"#"#.
Thefollo&inge+mpleill$strtesthepoor**Epredictionthncn)e
prod$ced)ycompringtheres$lts$singdef$ltinterction
prmetersndspecillyregressed**Eprmeters.
,. Openthecse6henolh2o.hsc.
2. Enterthefollo&ingconditionsforstrem6henolA!2O7
Conditions
Tempert$re J0PC
6ress$re ,tm
Bolr3lo& ,'gmoleAh,l)moleAhr
Composition
6henol 25mole
!2O L5mole
#hatphase;s??????????
21
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22 ThermodynamicsandHYSYS
Toprovide)etterpredictionfor**EtJ0oC,05o3thefollo&ingAiI
interctionprmetersreto)eentered.Toentertheprmetersdo
thefollo&ing7
,. Closethestremvie&ndpressthe1nter7asis1nvironment)$tton.
2. Ens$rethe3l$id6c'gevie&isopenndselectthe=inry
Coeffst).
M. EntertheAiIinterctionprmetersssho&nhere7
J. #electtheAlphai'@Ci'rdio)$tton.
5. EnternAlphiIQ0.2.
. Closethe3l$id6c'gevie&.
L. Ret$rntothesim$ltionenvironment)ypressingthe$eturnto
(imulation1nvironment)$tton.
K. Openthestremvie&for6henolA!2O.
#hatphase;s??????????
#hatarethecompositions>??????????
Thefig$resonthefollo&ingpgefig$resMndJsho&thedifference
)et&eenthet&osetsofinterctionprmeters.Therefore(crem$st)e
e+ercised&hensim$lting**Eslmostllthedef$ltinterctionprmetersforthectivitycoefficientmodelsin!"#"#refor8*E.
22
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ThermodynamicsandHYSYS 23
3ig.M-singtheef$lt8*Enterction6rmeters.
3ig.J-singthe3itted**EOptimi1iednterction6rmeters.
2"
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24 ThermodynamicsandHYSYS
E,ercise"
en?eneGCyclohe,aneG:28%ernary
This e+mple gin ill$strtes the importnce of hving
interctionprmetersndlsodisc$ssesho&the$sercno)tin
prmeters from regression. To ill$strte theprinciples do the
follo&ing7
,. OpenthecseTernry.hsc.
2. Enterthefollo&ingstremconditionsfor=en1eneACCA!2O7
Conditions
Tempert$re 25PC
6ress$re ,tm
Composition
=en1ene 20mole
!2O 20mole
CC 0mole
4owmanyphasesarepresent>??????????
Toprovidemoreprecisesim$ltionthemissingCCA!2Ointerction
prmeterhsto)eo)tined.3ort$ntely(somedtisvil)let
25PCgivingtheli/$id-li/$ide/$ili)ri$m)et&eenCCnd!2O.sing
thisdt(ndtheregressioncp)ilities&ithin#T*(nAEA
TechnologyEngineering#oft&reconcept$ldesignnd
thermodynmicregressionprod$ct(yo$cno)tinne&interction
prmeters.Thetempert$redependent=iIprmetersreto)eleftt
0ndthelphiItermisto)esetto0.2fortheCC!2O.Toimplement
theseprmeters(proceed&iththestepsonthefollo&ingpge.
2#
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ThermodynamicsandHYSYS 25
,. Ret$rntothe=sisEnvironment)ypressingthe1nter7asis1nvironment)$tton.
2. Openthe3l$id6c'gevie&ndmovetothe=inryCoeffst).
M. EnterthedtintheAiImtri+ssho&nhere7
J. #electtheAlphai'@Ci'rdio)$tton.
5. EnterCCA!2OlphiIvl$eof0.2.
. Closethe3l$id6c'gevie&.
L. Ret$rntothe#im$ltionEnvironment.
K. Openthestrem=en1eneACCA
!2O.
4owmanyphasesarenowpresent>??????????
#hatarethecompositions>??????????
Thefig$resonthefollo&ingpgefig$res5ndclerlysho&the
)ehvio$roftheternrysystem.;itho$ttheregressedCCA!2O
)inry(thethermodynmicpropertypc'geincorrectlypredictsthe
systemto)emisci)lethigherCCconcentrtions.Thispredictionis
correctgivenproperlyregressedCCA!2Oprmeters.
'eferences
,.#chreinem'ers3.A.!.(?.2hys.Chem.M5(J5H,H00.
2.!illA.E.ndBlisoff;.B.(@.Am.Chem.(oc.
JK,H2H,K.
2-
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26 ThermodynamicsandHYSYS
3ig.5-;itho$tRegressedCCA!2Onterction6rmeters.
3ig.-;ithRegressedCC!2Onterction6rmeters.
2