Thermodynamics and HYSYS

Thermodynamics and HYSYS

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Thermodynamics and HYSYS

Workshop
One of the m in ssets of !"#"# is its strong thermodyn mic fo$nd tion. %ot only c n yo$ $se &ide v riety of intern l property p c' ges( yo$ c n $se t )$l r c p )ilities to override specific property c lc$l tions for more cc$r cy over n rro& r nge. Or( yo$ c n $se the f$nction lity provided thro$gh O*E to inter ct &ith e+tern lly constr$cted property p c' ges.

The )$ilt-in property p c' ges in !"#"# provide cc$r te thermodyn mic( physic l nd tr nsport property predictions for hydroc r)on( non-hydroc r)on( petrochemic l nd chemic l fl$ids. The d t ) se consists of n e+cess of ,500 components nd over ,-000 fitted )in ry coefficients. .f li)r ry component c nnot )e fo$nd &ithin the d t ) se( comprehensive selection of estim tion methods is v il )le for cre ting f$lly defined hypothetic l components.

!"#"# lso cont ins regression p c' ge &ithin the t )$l r fe t$re. E+periment l p$re component d t ( &hich !"#"# provides for over ,000 components( c n )e $sed s inp$t to the regression p c' ge. Altern tively( yo$ c n s$pplement the e+isting d t or s$pply set of yo$r o&n d t . The regression p c' ge &ill fit the inp$t d t to one of the n$mero$s m them tic l e+pressions v il )le in !"#"#. This &ill llo& yo$ to o)t in sim$l tion res$lts for specific thermophysic l properties th t closely m tch yo$r e+periment l d t .

!o&ever( there re c ses &hen the p r meters c lc$l ted )y !"#"# re not cc$r te eno$gh( or c ses &hen the models $sed )y !"#"# do not predict the correct )eh vio$r of some li/$id-li/$id mi+t$res 0 1eotropic mi+t$res2. 3or those c ses it is recommended to $se nother of !yprotech4s prod$cts( 5.#T.*. This po&erf$l sim$l tion progr m provides n environment for e+plor tion of thermodyn mic model )eh vio$r( proper determin tion nd t$ning of inter ction p r meters nd physic l properties( s &ell s ltern tive designs for distill tion systems.

Thermodynamics and HYSYS

6roper $se of thermodyn mic property p c' ge p r meters is 'ey to s$ccessf$lly sim$l ting ny chemic l process. Effects of press$re nd temper t$re c n dr stic lly lter the cc$r cy of sim$l tion given missing p r meters or p r meters fitted for different conditions. !"#"# is $ser friendly )y llo&ing /$ic' vie&ing nd ch nging of the p rtic$l r p r meters ssoci ted &ith ny of the property p c' ges. .n ddition( yo$ re )le to /$ic'ly chec' the res$lts of one set of p r meters nd comp re those res$lts &ith nother set.

.n this mod$le( yo$ &ill e+plore the thermodyn mic p c' ges of !"#"# nd the proper $se of their thermodyn mic p r meters.

Learning Objectives
Once yo$ h ve completed this mod$le( yo$ &ill )e )le to7

Select an appropriate Property Package Understand the validity of each Activity Model Enter new interaction parameters for a property package Check m ltiphase !ehavio r of a stream Understand the importance of properly regressed !inary coefficients

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Thermodynamics and HYSYS

Selecting Property Packages

The property p c' ges v il )le in !"#"# llo& yo$ to predict properties of mi+t$res r nging from &ell defined light hydroc r)on systems to comple+ oil mi+t$res nd highly non-ide l 0non-electrolytic2 chemic l systems. !"#"# provides enh nced e/$ tions of st te 06R nd 6R#8 2for rigoro$s tre tment of hydroc r)on systems9 semiempiric l nd v po$r press$re models for the he vier hydroc r)on systems9 ste m correl tions for cc$r te ste m property predictions9 nd ctivity coefficient models for chemic l systems. All of these e/$ tions h ve their o&n inherent limit tions nd yo$ re enco$r ged to )ecome more f mili r &ith the pplic tion of e ch e/$ tion. The follo&ing t )le lists some typic l systems nd recommended correl tions7 Type of #ystem
TE: 5ehydr tion #o$r ; ter Cryogenic : s 6rocessing Air #ep r tion Atm Cr$de To&ers 8 c$$m To&ers Ethylene To&ers !igh !2 #ystems Reservoir #ystems #te m #ystems !ydr te .nhi)ition Chemic l #ystems !3 Al'yl tion TE: 5ehydr tion &ith Arom tics

Recommended 6roperty 6 c' ge

6R 6R( #o$r 6R 6R( 6R#8 6R( 6R#8 6R( 6R Options( :# 6R( 6R Options( :# <,0mm !g( =r $n >,0( Esso > *ee >esler 6loc'er 6R( ?@ or :# 0see TA6 limits2 6R( 6R Options #te m 6 c' ge( C# or :# 6R Activity Bodels( 6R#8 6R#8( %RT* 0Cont ct !yprotech2 6R 0Cont ct !yprotech2

Thermodynamics and HYSYS

E$ ations of State
3or oil( g s nd petrochemic l pplic tions( the 6eng-Ro)inson EO# 06R2 is gener lly the recommended property p c' ge. !"#"# c$rrently offers the enh nced 6eng-Ro)inson 06R2 nd #o ve-Redlich->&ong 0#R>2 e/$ tions of st te. .n ddition( !"#"# offers sever l methods &hich re modific tions of these property p c' ges( incl$ding 6R#8( ?$d'evitch @offee 0?@2 nd > ) di 5 nner 0>52. *ee >esler 6loc'er 0*>62 is n d pt tion of the *ee >esler e/$ tions for mi+t$res( &hich itself & s modified from the =;R e/$ tion. Of these( the 6engRo)inson e/$ tion of st te s$pports the &idest r nge of oper ting conditions nd the gre test v riety of systems. The 6eng-Ro)inson nd #o ve-Redlich->&ong e/$ tions of st te 0EO#2 gener te ll re/$ired e/$ili)ri$m nd thermodyn mic properties directly. Altho$gh the forms of these EO# methods re common &ith other commerci l sim$l tors( they h ve )een signific ntly enh nced )y !yprotech to e+tend their r nge of pplic )ility.

%he Peng&'o!inson property package options are PR( Sour PR( and PRSV) Soave&'edlich&*wong e$ ation of state options are the SRK( Sour SRK( KD and ZJ)
3or the Chemic l ind$stry d$e to the common occ$rrence of highly non-ide l systems( the 6R#8 EO# m y )e considered. .t is t&o-fold modific tion of the 6R e/$ tion of st te th t e+tends the pplic tion of the origin l 6R method for highly non-ide l systems.

+t has shown to match vapo r press re c rves of p re components and mi,t res( especially at low vapo r press res) +t has !een s ccessf lly e,tended to handle non&ideal systems giving res lts as good as those o!tained !y activity models) A limited amo nt of non&hydrocar!on interaction parameters are availa!le)

Activity Models
Altho$gh e/$ tion of st te models h ve proven to )e very reli )le in predicting properties of most hydroc r)on ) sed fl$ids over l rge r nge of oper ting conditions( their pplic tion h s )een limited to prim rily non-pol r or slightly pol r components. 6ol r or nonide l chemic l systems h ve tr dition lly )een h ndled $sing d$ l model ppro ches. Activity Bodels re m$ch more empiric l in n t$re &hen comp red to

Thermodynamics and HYSYS

the property predictions in the hydroc r)on ind$stry. 3or e+ mple( they c nnot )e $sed s reli )ly s the e/$ tions of st te for gener li1ed pplic tion or e+tr pol ting into $ntested oper ting conditions. Their t$ning p r meters sho$ld )e fitted g inst represent tive s mple of e+periment l d t nd their pplic tion sho$ld )e limited to moder te press$res. 3or every component i in the mi+t$re( the condition of thermodyn mics e/$ili)ri$m is given )y the e/$ lity )et&een the f$g cities of the li/$id ph se nd v po$r ph se. This fe t$re gives the fle+i)ility to $se sep r te thermodyn mic models for the li/$id nd g s ph ses( so the f$g cities for e ch ph se h ve different forms. .n this ppro ch7

an e$ ation of state is sed for predicting the vapo r f gacity coefficients .normally ideal gas ass mption or the 'edlich *wong( Peng&'o!inson or S'* e$ ations of state( altho gh a /irial e$ ation of state is availa!le for specific applications0 an activity coefficient model is sed for the li$ id phase)
Altho$gh there is consider )le rese rch )eing cond$cted to e+tend e/$ tion of st te pplic tions into the chemic l ind$stry 0e.g.( 6R#8 e/$ tion2( the st te of the rt of property predictions for chemic l systems is still governed m inly )y Activity Bodels. Activity coefficients re Cf$dgeD f ctors pplied to the ide l sol$tion hypothesis 0R o$lt4s * & in its simplest form2 to llo& the development of models &hich ct$ lly represent re l d t . Altho$gh they re Cf$dgeD f ctors( ctivity coefficients h ve n e+ ct thermodyn mic me ning s the r tio of the f$g city coefficient of component in mi+t$re t 6 nd T( nd the f$g city coefficient of the p$re component t the s me 6 nd T. Consequently, more caution should be exercised when selecting these models for your simulation.

Activity Models produce the best results when they are applied in the operating region for which the interaction parameters were regressed.

Thermodynamics and HYSYS

The follo&ing t )le )riefly s$mm ri1es recommended ctivity coefficient models for different pplic tions 0refer to the )$lleted reference g$ide )elo&27 Applic tion
=in ry #ystems B$lticomponent #ystems A1eotropic #ystems *i/$id-*i/$id E/$ili)ri 5il$te #ystems #elf-Associ ting #ystems 6olymers E+tr pol tion

B rg$les
A *A A A G G %AA G

v n*
A *A A A G G %AA G

;ilson
A A A %AA A A %AA :

%RT*
A A A A A A %AA :

E%.FEAC
A A A A A A A :

! 2 Applica!le "#! 2 3ot Applica!le $ 2 4 estiona!le % 2 5ood &! 2 6imited Application

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Thermodynamics and HYSYS

8verview of Models
Marg les
One of the e rliest ctivity coefficient e+pressions & s proposed )y B rg$les t the end of the ,Hth cent$ry.

%he Marg les e$ ation was the first 5i!!s e,cess energy representation developed) %he e$ ation does not have any theoretical !asis( ! t is sef l for $ ick estimates and data interpolation) +n its simplest form( it has 9 st one ad9 sta!le parameter and can represent mi,t res which feat re symmetric activity coefficient c rves)
!"#"# h s n e+tended m$lticomponent B rg$les e/$ tion &ith $p to fo$r dI$st )le p r meters per )in ry. The fo$r dI$st )le p r meters for the B rg$les e/$ tion in !"#"# re the iI nd Ii 0temper t$re independent2 nd the )iI nd )Ii terms 0temper t$re dependent2.

The Margules equation should not be used for extrapolation beyond the range over which the energy parameters have been fitted.

%he e$ ation will se parameter val es stored in :;S;S or any ser s pplied val e for f rther fitting the e$ ation to a given set of data) +n :;S;S( the e$ ation is empirically e,tended and therefore ca tion sho ld !e e,ercised when handling m lticomponent mi,t res)

van 6aar
The v n * r e/$ tion & s the first :i))s e+cess energy represent tion &ith physic l signific nce. This e/$ tion fits m ny systems /$ite &ell( p rtic$l rly for **E component distri)$tions. .t c n )e $sed for systems th t e+hi)it positive or neg tive devi tions from R o$lt4s * &. #ome of the dv nt ges nd dis dv nt ge for this model re7

The van Laar equation performs poorly for dilute systems and CA !T represent many common systems, such as alcohol" hydrocarbon mixtures, with acceptable accuracy.

5enerally re$ ires less CPU time than other activity models) +t can represent limited misci!ility as well as three phase e$ ili!ri m) +t cannot predict ma,ima or minima in the activity coefficient and therefore( generally performs poorly for systems with halogenated hydrocar!ons and alcohols) +t also has a tendency to predict two li$ id phases when they do not e,ist)

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Thermodynamics and HYSYS

The v n * r e/$ tion implemented in !"#"# h s t&o p r meters &ith line r temper t$re dependency( th$s m 'ing it fo$r p r meter model. .n !"#"#( the e/$ tion is empiric lly e+tended nd therefore its $se sho$ld )e voided &hen h ndling m$lticomponent mi+t$res.

=ilson
The ;ilson e/$ tion( proposed )y :r nt B. ;ilson in ,H-J( & s the first ctivity coefficient e/$ tion th t $sed the loc l composition model to derive the :i))s E+cess energy e+pression. .t offers thermodyn mic lly consistent ppro ch to predicting m$lticomponent )eh vio$r from regressed )in ry e/$ili)ri$m d t .
The #ilson equation CA !T be used for problems involving liquid" liquid equilibrium.

Altho gh the =ilson e$ ation is more comple, and re$ ires more CPU time than either the van 6aar or Marg les e$ ations( it can represent almost all non&ideal li$ id sol tions satisfactorily e,cept electrolytes and sol tions e,hi!iting limited misci!ility .66E or /66E0) +t performs an e,cellent 9o! of predicting ternary e$ ili!ri m sing parameters regressed from !inary data only) +t will give similar res lts to the Marg les and van 6aar e$ ations for weak non&ideal systems( ! t consistently o tperforms them for increasingly non&ideal systems) +t cannot predict li$ id&li$ id phase splitting and therefore sho ld only !e sed on pro!lems where demi,ing is not an iss e)
O$r e+perience sho&s th t the ;ilson e/$ tion c n )e e+tr pol ted &ith re son )le confidence to other oper ting regions &ith the s me set of regressed energy p r meters.

3'%6
The %RT* 0%on-R ndom-T&o-*i/$id2 e/$ tion( proposed )y Renon nd 6r $snit1 in ,H-K( is n e+tension of the origin l ;ilson e/$ tion. .t $ses st tistic l mech nics nd the li/$id cell theory to represent the li/$id str$ct$re. These concepts( com)ined &ith ;ilson4s loc l composition model( prod$ce n e/$ tion c p )le of representing 8*E( **E( nd 8**E ph se )eh vio$r. *i'e the ;ilson e/$ tion( the %RT* model is thermodyn mic lly consistent nd c n )e pplied to tern ry nd higher order systems $sing p r meters regressed from )in ry e/$ili)ri$m d t . The %RT* model h s n cc$r cy comp r )le to the ;ilson e/$ tion for 8*E systems.

The additional parameter in the $TL equation, called the alpha term, or non" randomness parameter, represents the inverse of the coordination number of molecule %i& surrounded by molecules %'&. (ince liquids usually have a coordination number between ) and *, you might expect the alpha parameter between +.,- and +.)).

%he 3'%6 com!ines the advantages of the =ilson and van 6aar e$ ations)

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Thermodynamics and HYSYS

+t is not e,tremely CPU intensive) +t can represent 66E $ ite well) :owever( !eca se of the mathematical str ct re of the 3'%6 e$ ation( it can prod ce erroneo s m ltiple misci!ility gaps)
The %RT* e/$ tion in !"#"# cont ins five dI$st )le p r meters 0temper t$re dependent nd independent2 for fitting per )in ry p ir.

U3+4UAC
The E%.FEAC 0E%.vers l FEAsi Chemic l2 e/$ tion proposed )y A)r ms nd 6r $snit1 in ,HL5 $ses st tistic l mech nics nd the /$ sichemic l theory of :$ggenheim to represent the li/$id str$ct$re. The e/$ tion is c p )le of representing **E( 8*E nd 8**E &ith cc$r cy comp r )le to the %RT* e/$ tion( )$t &itho$t the need for nonr ndomness f ctor( it is t&o p r meter model. The E%.FEAC e/$ tion is signific ntly more det iled nd sophistic ted th n ny of the other ctivity models.

+ts main advantage is that a good representation of !oth /6E and 66E can !e o!tained for a large range of non&electrolyte mi,t res sing only two ad9 sta!le parameters per !inary) %he fitted parameters s ally e,hi!it a smaller temperat re dependence which makes them more valid for e,trapolation p rposes) %he U3+4UAC e$ ation tili?es the concept of local composition as proposed !y =ilson) Since the primary concentration varia!le is a s rface fraction as opposed to a mole fraction( it is applica!le to systems containing molec les of very different si?es and shape( s ch as polymer sol tions) %he U3+4UAC e$ ation can !e applied to a wide range of mi,t res containing :28( alcohols( nitriles( amines( esters( ketones( aldehydes( halogenated hydrocar!ons and hydrocar!ons)
.n its simplest form it is t&o p r meter model( &ith the s me rem r's s ;ilson nd %RT*. E%.FEAC needs v n der ; ls re nd vol$me p r meters( nd those c n sometimes )e diffic$lt to find( especi lly for non-condens )le g ses 0 ltho$gh 5.66R h s f ir n$m)er v il )le2.

E,tended and 5eneral 3'%6

The E+tended nd :ener l %RT* models re v ri tions of the %RT* model( simple %RT* &ith comple+ temper t$re dependency for the iI nd Ii terms. Apply either model to systems7

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Thermodynamics and HYSYS

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with a wide !oiling point range !etween components where yo re$ ire sim ltaneo s sol tion of /6E and 66E( and there e,ists a wide !oiling range or concentration range !etween components
E+treme c $tion m$st )e e+ercised &hen e+tr pol ting )eyond the temper t$re nd press$re r nges $sed in regression of p r meters. 5$e to the l rger n$m)er of p r meters $sed in fitting( in cc$r te res$lts c n )e o)t ined o$tside the origin l )o$nds.

The general $TL model is particularly susceptible to inaccuracies if the model is used outside of the intended range. Care must be ta.en to ensure that you are operating within the bounds of the model.

Chien&3 ll
Chien-%$ll is n empiric l model designed to llo& yo$ to mi+ nd m tch models &hich &ere cre ted $sing different methods nd com)ined into m$lticomponent e+pression. The Chien-%$ll model provides consistent fr me&or' for pplying e+isting ctivity models on )in ry )y )in ry ) sis. .n this m nner( Chien-%$ll llo&s yo$ to select the )est ctivity model for e ch p ir in the c se. 3or e+ mple( Chien-%$ll c n llo& the $ser to h ve )in ry defined $sing %RT*( nother $sing B rg$les nd nother $sing v n * r( nd com)ine them to perform three component c lc$l tion( mi+ing three different thermodyn mic models. The Chien %$ll model llo&s M sets of coefficients for e ch component p ir( ccessi)le vi the A( = nd C coefficient m trices.

The Thermodyn mics ppendi+ in the !"#"# Eser B n$ l provides more inform tion on 6roperty 6 c' ges( E/$ tions of #t te( nd Activity Bodels( nd the e/$ tions for e ch.

:enryAs 6aw
!enry4s * & c nnot )e selected e+plicitly s property method in !"#"#. !o&ever( !"#"# &ill $se !enry4s * & &hen n ctivity model is selected nd Nnon-condens )leN components re incl$ded &ithin the component list. !"#"# considers the follo&ing components non-condens )le7 Beth ne( Eth ne( Ethylene( Acetylene( !ydrogen( !eli$m( Argon( %itrogen( O+ygen( %O( !2#( CO2( nd CO.

o interaction between /non" condensable/ component pairs is ta.en into account in the 0L1 calculations.

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Thermodynamics and HYSYS

The e+tended !enry4s * & e/$ tion in !"#"# is $sed to model dil$te sol$teAsolvent inter ctions. N%on-condens )leN components re defined s those components th t h ve critic l temper t$res )elo& the system temper t$re.

Activity Model /apo r Phase 8ptions

There re sever l methods v il )le for c lc$l ting the 8 po$r 6h se in conI$nction &ith the selected li/$id ctivity model. The choice &ill depend on specific consider tions of yo$r system.

+deal
The ide l g s l & c n )e $sed to model the v po$r ph se. This model is ppropri te for lo& press$res nd for v po$r ph se &ith little intermolec$l r inter ction. The model is the def $lt v po$r ph se f$g city c lc$l tion method for ctivity coefficient models.

Peng 'o!inson( S'* or '*

To model non-ide lities in the v po$r ph se( the 6R( #R>( or R> options c n )e $sed in conI$nction &ith n ctivity model.

PR and SRK vapo r phase models handle the same types of sit ations as the PR and SRK e$ ations of state) =hen selecting one of these three models( ens re that the !inary interaction parameters sed for the activity model remain applica!le with the chosen vapo r model) Bor applications with compressors and t r!ines( PR or SRK will !e s perior to the RK or +deal vapo r model)

/irial
The 8iri l option en )les yo$ to )etter model v po$r ph se f$g cities of systems displ ying strong v po$r ph se inter ctions. Typic lly this occ$rs in systems cont ining c r)o+ylic cids( or compo$nds th t h ve the tendency to form st )le !2 )onds in the v po$r ph se.
Care should be exercised in choosing 2$, ($3, $0 or 0irial to ensure binary coefficients have been regressed with the corresponding vapour phase model.

!"#"# cont ins temper t$re dependent coefficients for c r)o+ylic cids. "o$ c n over&rite these )y ch nging the Associ tion 0iI2 or #olv tion 0ii2 coefficients from the def $lt v l$es. This option is restricted to systems &here the density is moder te( typic lly less th n one-h lf the critic l density.

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Thermodynamics and HYSYS

13

Cinary Coefficients
3or the 6roperty 6 c' ges &hich do incl$de )in ry coefficients( the =in ry Coefficients t ) cont ins m tri+ &hich lists the inter ction p r meters for e ch component p ir. 5epending on the property method chosen( different estim tion methods m y )e v il )le nd different vie& m y )e sho&n. "o$ h ve the option of over&riting ny li)r ry v l$e.

E$ ation of State +nteraction Parameters

The E/$ tion of #t te .nter ction 6 r meters gro$p ppe rs s follo&s on the =in ry Coeffs t ) &hen n EO# is the selected property p c' ge7

The numbers appearing in the matrix are initially calculated by 45(5(, but you have the option of overwriting any library value.

3or ll EO# p r meters 0e+cept 6R#8 2( 3i' 6 3'i so &hen yo$ ch nge the v l$e of one of these( )oth cells of the p ir $tom tic lly $pd te &ith the s me v l$e. .n m ny c ses( the li)r ry inter ction p r meters for 6R#8 do h ve 3i' 6 3'i( )$t !"#"# does not force this if yo$ modify one p r meter in )in ry p ir.

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Thermodynamics and HYSYS

.f yo$ re $sing 6R or #R> 0or one of the #o$r options2( t&o r dio )$ttons re displ yed t the )ottom of the p ge in the Tre tment of .nter ction Coefficients En v il )le from the *i)r ry gro$p7

*s+ima+e H,-H,#Se+ "on H,-H, +o ).) D this radio ! tton is the defa lt selection) :;S;S provides the estimates for the interaction parameters in the matri,( setting all non& hydrocar!on pairs to @) Se+ !// +o ).) D when this is selected( :;S;S sets all interaction parameter val es in the matri, to @)@)

Activity Model +nteraction Parameters

Activity Bodels re m$ch more empiric l in n t$re &hen comp red to the property predictions in the hydroc r)on ind$stry. Their t$ning p r meters sho$ld )e fitted g inst represent tive s mple of e+periment l d t nd their pplic tion sho$ld )e limited to moder te press$res. The Activity Bodel .nter ction 6 r meters gro$p ppe rs s follo&s on the =in ry Coeffs t ) &hen n Activity Bodel is the selected property p c' ge7

The inter ction p r meters for e ch )in ry p ir &ill )e displ yed. "o$ c n over&rite ny v l$e or $se one of the estim tion methods. %ote th t the 3i' 6 3'i r$le does not pply to Activity Bodel inter ction p r meters.

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Thermodynamics and HYSYS

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Estimation Methods
;hen $sing Activity Bodels( !"#"# provides three inter ction p r meter estim tion methods. #elect the estim tion method )y choosing one of the r dio )$ttons in the Coeff Estim tion &indo&. The options re7

U3+BAC /6E U3+BAC 66E +mmisci!le

"o$ c n then invo'e the estim tion )y selecting one of the v il )le cells. 3or E%.3AC methods the options re7

0ndi1idua/ Pair D calc lates the parameters for the selected component pair( Ai9 and A9i) %he e,isting val es in the matri, are overwritten) 2n3no4ns 5n/y D calc lates the activity parameters for all the nknown pairs) +f yo delete the contents of cells or if :;S;S does not provide defa lt val es( yo can se this option) !// 6inaries D recalc lates all the !inaries of the matri,) +f yo had changed some of the original :;S;S val es( yo co ld se this to have :;S;S re&estimate the entire matri,) . ;hen the All 7inaries )$tton is $sed( !"#"# does not ret$rn the origin l li)r ry v l$es. Estim tion v l$es &ill )e ret$rned $sing the selected E%.3AC method. To ret$rn to the origin l li)r ry v l$es( yo$ m$st select ne& property method nd then re-select the origin l property method

3or the .mmisci)le method the options re7

The 8 9:AC ;8 9quac group" :unctional Activity Coefficient< method is a group contribution technique using the 8 9=8AC model as the starting point to estimate binary coefficients. This, however, should be a last solution as it is preferable to try and find values estimated from experimental data.

Ro4 in ,/m 7air D estimates the parameters s ch that the row component .90 is immisci!le in the col mn component .i0) ,/m in Ro4 7air D estimates parameters s ch that the col mn component .90 is immisci!le in the row component .i0) !// in Ro4 D estimates parameters s ch that !oth components are m t ally immisci!le)
.n Bod$le ,( yo$ chose the %RT* Activity Bodel( then select the E%.3AC 8*E estim tion method 0def $lt2 )efore pressing the En'no&ns Only cell.

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Thermodynamics and HYSYS

=hich Activity Coefficient Model Sho ld + UseE

This is to$gh /$estion to ns&er( )$t some g$idelines re provided. .f yo$ re/$ire ddition l ssist nce( it is )est to cont ct !yprotech4s Technic l #$pport dep rtment.

Casic Fata
Activity coefficient models re empiric l )y n t$re nd the /$ lity of their prediction depends on the /$ lity nd r nge of d t $sed to determine the p r meters. #ome import nt things yo$ sho$ld )e & re of in !"#"#.

%he parameters ! ilt in :;S;S were fitted at 1 atm wherever possi!le( or were fitted sing isothermal data which wo ld prod ce press res closest to 1 atm) %hey are good for a first design( ! t always look for e,perimental data closer to the region yo are working in to confirm yo r res lts) %he val es in the :;S;S component data!ase are defined for /6E only( hence the 66E prediction may not !e very good and additional fitting is necessary) Fata sed in the determination of ! ilt in interaction parameters very rarely goes !elow @)@1 mole fraction( and e,trapolating into the ppm or pp! region can !e risky) Again( !eca se the interaction parameters were calc lated at modest press res( s ally 1 atm( they may !e inade$ ate for processes at high press res) Check the acc racy of the model for a?eotropic systems) Additional fitting may !e re$ ired to match the a?eotrope with accepta!le acc racy) Check not only for the temperat re( ! t for the composition as well) +f three phase !ehavio r is s spected( additional fitting of the parameters may !e re$ ired to relia!ly reprod ce the /66E e$ ili!ri m conditions)

U3+BAC or no U3+BACE
E%.3AC is h ndy tool to give initi l estim tes for ctivity coefficient models. %evertheless 'eep in mind the follo&ing7

5ro p contri! tion methods are always appro,imate and they are not s !stit tions for e,perimental data) U3+BAC was designed sing relatively low molec lar weight condensa!le components .th s high !oilers may not !e well represented0( sing temperat res !etween @&1-@ oC and data at modest press res)

11

Thermodynamics and HYSYS

5enerally( U3+BAC does not provide good predictions for the dil te region)

Choosing an Activity Model

Ag in( some gener l g$idelines to consider.

8ar9u/es or 1an &aar & generally chosen if comp tation speed is a consideration) =ith the comp ters we have today( this is s ally not an iss e) May also !e chosen if some preliminary work has !een done sing one of these models) :i/son & generally chosen if the system does not e,hi!it phase splitting) "RT& or 2"0;2!, & generally chosen if the system e,hi!its phase splitting) %enera/ "RT& & sho ld only !e sed if an a! ndant amo nt of data over a wide temperat re range was sed to define its parameters) 8therwise it will provide the same modelling power as 3'%6)

Exploring with the Sim lation

6roper $se of thermodyn mic property p c' ge p r meters is 'ey to s$ccessf$lly sim$l ting ny chemic l process. Effects of press$re nd temper t$re c n dr stic lly lter the cc$r cy of sim$l tion given missing p r meters or p r meters fitted for different conditions. !"#"# is $ser friendly in llo&ing /$ic' vie&ing nd ch nging of the p rtic$l r p r meters ssoci ted &ith ny of the property p c' ges. Addition lly( the $ser is )le to /$ic'ly chec' the res$lts of one set of p r meters nd comp re g inst nother.

17

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Thermodynamics and HYSYS

E,ercise 1
Fi&iso&Propyl&EtherG:28 Cinary
This e+ mple effectively demonstr tes the need for h ving inter ction p r meters. 5o the follo&ing7 ,. 2. Open c se 5..6E.hsc. Enter the follo&ing conditions for stre m 5..6EA!2O7

Conditions 8 po$r 3r ction 6ress$re Bol r 3lo& Composition di-i-6-Ether !2O 50 mole O 50 mole O 0.0 , tm , 'gmoleAh 0, l)moleAhr2

#hat phases are present> ??????????

M. J. 5. -. L. K.

Close the stre m vie& nd press the 1nter 7asis 1nvironment )$tton. #elect the =in ry Coeffs t ) of the 3l$id 6 c' ge. %otice th t the inter ction p r meters for the )in ry re )oth set to 0.0. 6ress the $eset 2arams )$tton to rec ll the def $lt %RT* ctivity coefficient model inter ction p r meters. Close the 3l$id 6 c' ge vie&. Ret$rn to the sim$l tion environment )y pressing the $eturn to (imulation 1nvironment )$tton. Open the stre m vie& )y do$)le clic'ing on the stre m 5..6EA !2O. #hat phases are now present> ?????????? #hat is the composition of each> ??????????

1<

Thermodynamics and HYSYS

1(

Cle rly( it c n )e seen ho& import nt it is to h ve inter ction p r meters for the thermodyn mic model. The +y ph se di gr ms on the ne+t p ge 0fig$res , nd 22 ill$str te the homogeneo$s )eh vio$r &hen no p r meters re v il )le nd the heterogeneo$s 1eotropic )eh vio$r &hen properly fitted p r meters re $sed. The m Iority of the def $lt inter ction p r meters for ctivity coefficient models in !"#"# h ve )een regressed ) sed on 8*E d t from 5EC!EBA( Chemistry 5 t #ervices.

1>

2)

Thermodynamics and HYSYS

3ig. , - .nter ction 6 r meters set to 0.

3ig. 2 - Esing the 5ef $lt !"#"# .nter ction 6 r meters.

2@

Thermodynamics and HYSYS

21

E,ercise 2
PhenolG:28 Cinary
This )in ry sho&s the import nce of ens$ring th t properly fitted inter ction p r meters for the conditions of yo$r sim$l tion re $sed. The def $lt p r meters for the 6henolA!2O system h ve )een regressed from the 5EC!EBA Chemistry d t series nd provide very cc$r te v po$r-li/$id e/$ili)ri$m since the origin l d t so$rce 0,2 & s in this form t. !o&ever( the 6henolA; ter system is lso sho&n to e+hi)it li/$id-li/$id )eh vio$r 022. A set of inter ction p r meters c n )e o)t ined from so$rces s$ch s 5EC!EBA nd entered into !"#"#. The follo&ing e+ mple ill$str tes the poor **E prediction th n c n )e prod$ced )y comp ring the res$lts $sing def $lt inter ction p r meters nd speci lly regressed **E p r meters. ,. 2. Open the c se 6henolh2o.hsc. Enter the follo&ing conditions for stre m 6henolA!2O7

Conditions Temper t$re 6ress$re Bol r 3lo& Composition 6henol !2O 25 mole O L5 mole O J0PC , tm , 'gmoleAh 0, l)moleAhr2

#hat phase;s< are present> ??????????

21

22

Thermodynamics and HYSYS

To provide )etter prediction for **E t J0 oC 0,05 o32 the follo&ing AiI inter ction p r meters re to )e entered. To enter the p r meters do the follo&ing7 ,. 2. M. Close the stre m vie& nd press the 1nter 7asis 1nvironment )$tton. Ens$re the 3l$id 6 c' ge vie& is open nd select the =in ry Coeffs t ). Enter the AiI inter ction p r meters s sho&n here7

J. 5. -. L. K.

#elect the Alphai'@Ci' r dio )$tton. Enter n Alph

iI Q

0.2.

Close the 3l$id 6 c' ge vie&. Ret$rn to the sim$l tion environment )y pressing the $eturn to (imulation 1nvironment )$tton. Open the stre m vie& for 6henolA!2O. #hat phase;s< are present now> ?????????? #hat are the compositions> ??????????

The fig$res on the follo&ing p ge 0fig$res M nd J2 sho& the difference )et&een the t&o sets of inter ction p r meters. Therefore( c re m$st )e e+ercised &hen sim$l ting **E s lmost ll the def $lt inter ction p r meters for the ctivity coefficient models in !"#"# re for 8*E.

22

Thermodynamics and HYSYS

23

3ig. M - Esing the 5ef $lt 08*E2 .nter ction 6 r meters.

3ig. J - Esing the 3itted 0**E Optimi1ied2 .nter ction 6 r meters.

2"

24

Thermodynamics and HYSYS

E,ercise "
Cen?eneGCyclohe,aneG:28 %ernary
This e+ mple g in ill$str tes the import nce of h ving inter ction p r meters nd lso disc$sses ho& the $ser c n o)t in p r meters from regression. To ill$str te the principles do the follo&ing7 Open the c se Tern ry.hsc. Enter the follo&ing stre m conditions for =en1eneACC-A!2O7 ,.

2.

Conditions Temper t$re 6ress$re Composition =en1ene !2O CC20 mole O 20 mole O -0 mole O 25PC , tm

4ow many phases are present> ?????????? To provide more precise sim$l tion the missing CC-A!2O inter ction p r meter h s to )e o)t ined. 3ort$n tely( some d t is v il )le t 25PC giving the li/$id-li/$id e/$ili)ri$m )et&een CC- nd !2O. Esing this d t ( nd the regression c p )ilities &ithin 5.#T.*( n AEA Technology Engineering #oft& re concept$ l design nd thermodyn mic regression prod$ct( yo$ c n o)t in ne& inter ction p r meters. The temper t$re dependent =iI p r meters re to )e left t 0 nd the lph iI term is to )e set to 0.2 for the CC-A!2O. To implement these p r meters( proceed &ith the steps on the follo&ing p ge.

2#

Thermodynamics and HYSYS

25

,. 2. M.

Ret$rn to the = sis Environment )y pressing the 1nter 7asis 1nvironment )$tton. Open the 3l$id 6 c' ge vie& nd move to the =in ry Coeffs t ). Enter the d t in the AiI m tri+ s sho&n here7

J. 5. -. L. K.

#elect the Alphai'@Ci' r dio )$tton. Enter CC-A!2O lph

iI v

l$e of 0.2.

Close the 3l$id 6 c' ge vie&. Ret$rn to the #im$l tion Environment. Open the stre m =en1eneACC-A!2O. 4ow many phases are now present> ?????????? #hat are the compositions> ??????????

The fig$res on the follo&ing p ge 0fig$res 5 nd -2 cle rly sho& the )eh vio$r of the tern ry system. ;itho$t the regressed CC-A!2O )in ry( the thermodyn mic property p c' ge incorrectly predicts the system to )e misci)le t higher CC- concentr tions. This prediction is correct given properly regressed CC-A!2O p r meters.

'eferences
,. #chreinem 'ers 3.A.!.( ?. 2hys. Chem. M5( J5H 0,H002. 2. !ill A.E. nd B lisoff ;.B.( @. Am. Chem. (oc. JK 0,H2-2 H,K.

2-

26

Thermodynamics and HYSYS

3ig. 5 - ;itho$t Regressed CC-A!2O .nter ction 6 r meters.

3ig. - - ;ith Regressed CC-A!2O .nter ction 6 r meters.

21