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BrazilianJournalofChemicalEngineering

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Braz.J.Chem.Eng.vol.17n.47SoPauloDec.2000

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SIMULATIONANDOPTIMIZATIONOF
ANINDUSTRIALPSAUNIT

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C.Barg1,J.M.P.Ferreira2,J.O.Trierweiler 1andA.R.Secchi 1*
1DepartamentodeEngenhariaQumica,UniversidadeFederaldoRio
GrandedoSul,
RuaSarmentoLeite,288/24,90050170,PortoAlegreRS,Brazil
2COPESUL,CompanhiaPetroqumicadoSul,IIIPloPetroqumico,Triunfo
RS,Brazil

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(Received:November26,1999Accepted:April6,2000)

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AbstractThePressureSwingAdsorption(PSA)unitshavebeen
usedasalowcostalternativetotheusualgasseparationprocesses.
Itslargestcommercialapplicationisforhydrogenpurificationsystems.Severalstudieshavebeen
madeaboutthesimulationofpressureswingadsorptionunits,butthereareonlyfewreportsonthe
optimizationofsuchprocesses.Theobjectiveofthisstudyistosimulateandoptimizeanindustrial
PSAunitforhydrogenpurification.Thisunitconsistsofsixbeds,eachofthemhavethreelayersof
differentkindsofadsorbents.Themainimpuritiesaremethane,carbonmonoxideandsulfidricgas.
Theproductstreamhas99.99%purityinhydrogen,andtherecoveryisaround90%.A
mathematicalmodelforacommercialPSAunitisdeveloped.Thecycletimeandthepressureswing
stepsareoptimized.Allthefeaturesconcerningwithcomplexcommercialprocessesareconsidered.
Keywords:Pressureswingadsorption,simulation,optimization,gasseparation.

INTRODUCTION
Thepressureswingadsorption(PSA)systemshavereceivedincreasingattentionfromthespecializedliterature.
Severalarticleshavebeenpublishedinthepastyears,withfocusonthenumericalsimulationofsuchunitsand
onexperimentalresults.Ingeneral,thesestudiedunitsareverysimple,andhavetoomanysimplifications
whencomparedtoindustrialunits.Thisfactreflectstherequiredcomputationalcomplexitywhenworkingwith
realindustrialsystems,mainlywhentheobjectiveistooptimizesomeprocessparameters.
Inthepastyears,someworksonoptimizationofpressureswingadsorptionunitshavebeendone.Almostall
thoseworksarerelatedtosimpleexperimentalunits.KvamsdalandHertzberg(1995a)haveworkedwiththree
systemsoftraceseparationtoinvestigatetheeffectofmasstransferduringtheblowdownstep.Theypresented
anotherwork(KvamsdalandHertzberg,1995b)onoptimizationofatraceseparationsystem,wherethe
importanceofmodelsimplificationstosavetimewasemphasized,andtheadsorptionpressure,purgerateand
columnlengthwereoptimized.Chlendietal.(1995)haveproposedamethodtocharacterizethebehaviorof
pressureswingadsorptioncyclesbasedonexperimentsdesignandpolynomialfittingstorepresentthesystem.
Theobjectiveofthisworkwastomaketheproblemeasiertobeoptimized.Therearesomestudies(Parket
al.,1998Kumar,1994)ontheoptimalheightofdifferentkindsofadsorbentstoseparatemulticomponent
mixtures.Nilchan(1997)presentedamoresystematicapproachtosolveoptimizationofperiodicadsorption
process.Itisproposedthediscretizationofthetimedomainwiththeinclusionofcyclicsteadystateconditions.
Themaindisadvantageofthismethodistheincreaseinthecomputermemoryrequirement.
Inthepresentwork,modelingandsimulationofanindustrialhydrogenpurificationunitismade.Thesystemis
fedwithastreamcontainingabout95%hydrogen,almost5%methane,andtracesofcarbonmonoxide,
humidityandbenzene.Theproducthasabout99.99%purityinhydrogen,andtheunitrecoversabout90%of
thehydrogenfed.Thebedshavethreeadsorbentlayers,atfeedentrancethereisonecomposedofalumina,
followedbyanactivatedcarbonlayer,andafterthat,thereisazeolitelayer.Thealuminaisusedasaguard
bed,inordertopreventirreversiblecontaminationoftheotheradsorbentswithwaterorbenzene.Thisoccurs
becauseofthestronginteractionoftheseheaviercompoundswiththeadsorbents.Asaluminahasweaker
adsorptionstrength,theycanbedessorbedbypressurereduction,whichwouldbeimpossiblefortheactivated
carbonorforthezeolite.
Thisworkdoesnotconsiderthepresenceofwaterorbenzeneinthefeed,andtheadsorptionofcarbon
monoxideormethaneinaluminaisnotconsideredtoo.Thusthealuminabedhavenoinfluenceinthemodel
results.Becauseoftheweakinteractionofhydrogenwithalladsorbents,itistreatedasaninert.

Firstofall,amodeltodescribeanindustrialpressureswingadsorptionunitforhydrogenpurificationwasmade.
Alltheprocesscharacteristicsareconsideredforthemodelconception,inordertodescribethesystem
behaviorcorrectly.ThemodelwasthenimplementedingPROMS,andsomerealindustrialcaseswere
simulated.Afterverifyingthatthemodelisinaccordancewithplantdata,theinfluenceofsomeprocess
parameterswerestudied,enablingtheidentificationofoptimalpoints.Themainfocusistheinfluenceofthe
pressureswingstepsontheprocessperformance,whichisrepresentedbytherelationoftwocharacteristic
times,T1andT2.Intheindustry,forthisparticularsystem,thecycletimeismanipulatedtocontroltheproduct
purity,buttherelationofthepressureswingstepsissettoconstantvalue.Theobjectivesofthisworkareto
studytheinfluenceofvariationsontherelationofthepressureswingstepsandtoidentifyitsoptimalvalue.

PROCESSDESCRIPTION
Thehydrogenpurificationplanthassixvesselsandoperatesintwelvesteps.Eachvesselisfilledwiththree
differentadsorbents,alumina,activatedcarbonandzeolite.Thesequencingofthedifferentstepsfollowsa
predefinedrule,whichisbestunderstoodinFig.1.

Thestepsperformedforeachbedinacompletecyclearethefollowing:pressureequalization1(provide),hold,
pressureequalization2(provide),pressureequalization3(provide),providepurge,blowdown,purge,pressure
equalization3(receive),pressureequalization2(receive),pressureequalization1(receive),repressurization,
andadsorption.Figure1showsthedurationofeachstep,whichisacompositionoftwocharacteristictimes,T1
andT2.Thepressureequalization1hasafixeddurationof25seconds,thustheholdsteptake(T125)
seconds,andtherepressurizationsteptake(T2+T125)seconds.Atypicalpressurevariationwithtimeis
showninFig.2.

Thepurgeisthemainregeneratingstep,whichenablesthedessorptionoftheadsorbedmaterial.Theother
stepsareusedbasicallytoreducethebedpressuretothepurgepressure,and,afterthepurgestep,toincrease
ittotheadsorptionpressure.Theequalizationstepsareusedtoimproverecovery,becausetheyusethegas
thatislivingabedatahigherpressureandhastobedepressurizedtofillabedthatisincreasingpressureto
enteradsorptionstep.Itisobviousthatinthepressureequalizationstepthereceivingpressurevesselcannot
reachtheadsorptionpressure,oncethefinalpressureofthatbedmustbelowerorequaltothefinalpressure
oftheprovidingpressurevessel.Inordertoreachtheadsorptionpressure,thebedreceivesafractionofthe
productgasintherepressurizationstep.
Figure3representsabriefdescriptionoftheunit.Thevalvesmarkedareopen.Thisdiagramshowstheway
thebedsareconnectedonetoanother.Thevalveshavetoopenandclosesynchronizedtochangethesystem
fromonesteptoanother,inaccordancewiththenecessaryconnectionsbetweenthebeds.Thedifferentbed
connectionschemescanbeknownbytheanalysisofFig.1.


Thepressurevariationinthevariablepressurestepshasalineardependencywithtime.Thereisacontrol
systemthatcontrolstheinterconnectionvalvesinordertofollowapredefinedlinearsetpoint.Inthediagram
describedinFig.3thebed1isequalizingpressurewithbed3,bed6isequalizingpressurewithbed4,bed5is
inblowdown,andbed2isinadsorptionstep.ThisconfigurationcorrespondstothefirststepintheFig.1.

MATHEMATICALMODELANDOPTIMIZATIONSTRATEGY
ThePSAisadistributedsystemthatcanbemodeledusingasetofpartialdifferentialandalgebraicequations.
Althoughithasanintrinsicallydynamicbehavior,itcanachieveacyclicsteadystateafteracertainnumberof
cycles.AmathematicalmodelforacomplexcommercialPSAunitisdeveloped.Theassumptionsadoptedare
summarizedbelow.
(1)Theflowmodeladoptedistheplugflowwithaxialdispersion.Noradialgradientsareconsidered.
(2)Thesystemisnonisothermal,withthermalaxialdispersion.Isconsideredlocalthermalequilibriumbetween
thegasandthesolidphases.
(3)Tomaintainthemodelgenerality,thesystemisconsideredabulkseparationprocess,thenthechangeof
velocityduetoadsorption(ordesorption)istakenintoaccountbytheoverallmaterialbalance.
(4)ThemulticomponentadsorptionequilibriumiscomputedadoptingtheextendedLangmuirmodel.The
isothermconstantsaretakenfromliterature,obtainedfromexperimentswithasinglecomponent(Parketal.,
1998).Noconsiderationwasmadeconcerninginteractionamongdifferentmolecules.
(5)Theadsorptionofhydrogenisconsiderednegligible.
(6)Alineardrivingforcemodelisadoptedtocomputethemasstransferdynamics,withconstantoverallmass
transfercoefficient.
(7)DarcysLawisusedtocomputethepressuredropacrossthebed.
(8)Theidealgaslawisassumed.
(9)Alineartimedependenceofthepressureinthepressureequalization,providepurge,andrepressurization
stepsisknownfromplantdata.
(10)Alltransportparameters,aswellasphysicalpropertiesofgasandsolidphasesaretakenfromthe
literatureorestimatedfromempiricalcorrelations.
(11)Heattransfertothesurroundingsisnegligible.
Thedifferentlayersobeythesamebalanceequations,butwithdifferentsetsofphysicalpropertiesand
equilibriumparameters.Thusabalanceequationmustbedoneforeachadsorbentlayer.
TheadsorptionisothermparametersaretakenfromParketal.(1998).
BalanceEquations
Withtheprecedingassumptions,thebalanceequationstomodelthesystemaregivenbelow.
a)Overallmaterialbalanceappliedtothegasphase,wherethelatesttermontherighthandsideofthe
equationtakesintoaccounttheadsorbedquantity:

(1)
where isthegasdensity,visthegasinterstitialvelocity,isthebedporosity,qiistheamountof
componentiadsorbed,zistheaxialdimension,andtisthetime.
b)Componentmaterialbalance,forthegasphase:

(2)
wherenisthenumberofcomponents,Dzistheaxialdispersioncoefficient,andCiisthemolarconcentrationof
componentiinthegasphase.
c)Energybalance:

(3)

whereCpgisthemeanheatcapacityofthegas,Cpsistheheatcapacityoftheadsorbent,Kzisthethermal
axialdispersioncoefficient,Tisthetemperature,andHads,iistheheatofadsorptionofcomponenti.
d)Adsorptionisothermforadsorbedcomponents:

(4a)

(4b)

(4c)
wherea1,i,a2,i,b0,i,b1,iaretheadsorptionisothermparametersforthecomponentiineachadsorbent
material,Piisthepartialpressureofcomponentiinthegasphase,andqi,eqistheamountofiadsorbedin
equilibriumwiththegasphasepartialpressureofiatsystemtemperatureinthatpoint.
e)Lineardrivenforceequation,tomodelthemasstransportbetweengasandsolid:

(5)
wherekiistheoverallmasstransfercoefficientforthecomponentiineachadsorbentmaterial.
f)Darcy'sequation:

(6)
wherePisthepressure,istheviscosity,anddpisthemeanparticlediameter.
g)Idealgasequation:

(7)
whereRistheuniversalgasconstant.
Initialconditions
Thesolutionofthepreviousequationsneedssomeinitialconditionstosolvetheequationswithtemporal
derivatives.Thebedisconsideredinitiallyclean,andthepressureisequaltotheinitialpressureofthefirst
stepofthebed.Thetemperatureisassumedtobeequaltothefeedtemperature.
Thefollowinginitialconditionsareusedtosolvethesetofdifferentialandalgebraicequations.

(8)

whereTFisthetemperatureofthefeedstream.
BoundaryConditions
Thebalanceequationsareappliedtoallthestepsoftheprocess.Thedifferencesfromonesteptoanotherare
accountedbytheboundaryconditions.Onpressurevariablesteps,thepressurechangesareassumedtohavea
lineardependencywithtime,hererepresentedbyP(t).Thislineardependencyisusedasaboundarycondition
onthepressure.TheboundaryconditionsusedinthemodelareshowninEqns.9to14.
Fluidenteringabed:

(9)

whereXiisthemolarfractionofcomponentiinthegasphase,Xi,inisthemolarfractionofcomponentiandTin
isthetemperatureinthestreamthatisenteringthebed.
Fluidleavingbedandclosedend:

(10)

Forpressureandvelocity,theboundaryconditionsarethefollowing:
Adsorption

(11)
wherevfistheinterstitialvelocityatfeedentrance,andPadsistheadsorptionpressure.
Pressureequalizations,repressurizationandprovidepurge:

(12)
whereP(t)isthepreviouslyknownpressurevariationwithtime.
Blowdown:

(13)
Purge:

(14)

wherePDisthepurgepressure,Poutisthepressureandvoutistheinterstitialvelocityintheexitofthebed
whichisprovidingpurgegas.
IntersectionoftheLayers
Theintersectionofthelayersismodeledwithasetofcontinuityequations.Inordertoavoidnumerical
problemswhencalculatingthederivativesneartheborderbetweenthetwoadsorbentlayers,theaxial
dimensionisdividedintwoparts,relatedtoeachadsorbent.
Thenthederivativesneartheborderlinearecalculatedwithoutusingvaluesoftheotheraxialdistribution
domain,becausethesoftwarecalculatesthisderivativeswithbackwardorforwardfinitedifferenceformula,in
exceptionofthecenteredfinitedifferenceapproximationusedonthepointsinsidetheinterval.Thisway,there
isaseparationofthetwoaxialdistributiondomains.Theymustbeconnectedbyasetofcontinuityequations
(Eqns.1516).

(15)

(16)

wherethesubscripts1and2indicatetheactivatedcarbonandthezeolitelayersrespectively.
OptimizationStrategy
Duetothemathematicalcomplexityoftheproblem,thestrategyselectedtoachievetheoptimalpointisthe
simplestpossible.Thecompletediscretizationmethod,describedintheworkofNilchan(1997)hasrequiredan
unavailableamountofcomputermemory,becauseoftheelevatednumberofvariablesgeneratedbythetime
discretization.
Theobjectiveistostudythecombinedeffectofthecycletime,hererepresentedbytheT1+T2parameter,and
oftheT1/T2ratioonthesystembehavior.Ameshwithdifferentvaluesfortheseparameterswasgenerated,as

canbeseeninTable1,resultingintwentyfivedifferentsimulationcases.

Withtheresultsofproductpurityandrecoveryforthesecasesitispossibletofindanoptimalvalueforthetwo
parametersforthisspecificcasestudy.
NumericalSolutionoftheModel
Tosolvethesetofpartialdifferentialandalgebraicequations(PDAE)thegPROMS(Pantelides,1996)software
isused.Thisprogramisageneralpurposeprocesssimulatorthatcanworkwithmodelsinvolvingdistributed
systems.
Thesetofequationshastobechangedwhenabedgoesfromonesteptoanother,duetothechangeonthe
boundaryconditions.Thisworkisalsoexecutedbythesimulator.Theusershouldjustimplementaroutinethat
defineswhenthestepchangesshouldbemade.Thisway,anymodificationtobedoneinthesimulationcanbe
madequickly.
Thespatialdiscretizationofthesetofpartialdifferentialandalgebraicequations(PDAE)resultsasetof
differentialandalgebraicequations(DAE)whichisintegratedinrelationtotimeusingtheSRADAUcode.
ThemainadvantageinusinggPROMSisthereductionofthetimespenttoimplementthemodel,oncethe
simulatordoesseveralmathematicalmanipulations,asthespatialdiscretisation,thechangingamongdifferent
stepsandthetemporalintegrationoftheresultingsetofdifferentialandalgebraicequations.

ThemodelwassolvedinaPCwithPentiumII 350MHzprocessor.Eachdomainisdiscretizedwiththecentered
finitedifferenceapproximation,usingfourthintervals.Thesimulationstookaboutonefifthoftheplanttime,
andhaverequiredabout75Mbofmainmemory.Thustosimulateonecycleofaboutthreethousandseconds,it
spentaboutsixhundredsecondsofcomputertime.

RESULTSANDDISCUSSION
Thefirstobjectiveoftheworkistoreproducetheplantbehaviorbynumericsimulation,andthentofindthe
optimalcycletimeandoptimalratioofthecharacteristictimes(T1andT2).Theoperationalparameters
optimizedinthisstudyarethesumofthecharacteristictimesT1andT2,anditsratio,T1/T2.
Theanalysisoftheplantbehaviorismadewithtwomainparameters,theproductpurityandthehydrogen
recovery.
Theproductpurityisdefinedastheratiobetweenthemolaramountofhydrogencollectedintheproductduring
thelastcycleandthetotalmolaramountoftheproduct.

(17)

whereTcycle isthecycletime,Riistheadsorbentvesselinternalradius,isthebedporosity,Vpisthegas
velocityatproductend,andXH2,pisthehydrogenmolarfractionatproductstream.
Thehydrogenrecoveryisdefinedastheratioofthemolaramountofhydrogencollectedintheproductduring
thelastcycleandthemolaramountofhydrogenfedtothebedinthelastcycle.

(18)

whereXH2,fisthehydrogenmolarfractionatfeedstream.
Thustheproductpurityandthehydrogenrecoveryarecalculatedatthebeginningofacycle,remaining
constantuntilanothercyclestarts.Table2showsthattheproductpurityandthehydrogenrecoveryinthe
simulationagreewithplantdata,forthesameoperationalconditions.

Abasiccasewasfirstsimulated.Figure4showstheproductpurityandhydrogenrecoveryofthesystemasa
functionoftime.Theplantisassumedtostartwithahundredpercentpurityandrecovery.Thissimulationis
madewiththecycletimeequalto5568seconds.Thesystemisconsideredtoachievethecyclicsteadystate

(CSS)whenthedifferenceofproductpuritybetweenonecycleandtheproceedingislessthen105.

Thecyclicsteadystateisachieved,andthenusedasinitialconditiontotheothersimulations.Allperturbations
onthevaluesofT1andT2aredoneasstepvariations,afterinitializingthesystemwiththecyclicsteadystate
withT1+T2equalto928secondsandT1/T2equalto0.48.ThenthevaluesofT1andT2are302and626
secondsrespectively,andthecycletimeis5568seconds.Thevariationsofthecycletimearebasedon
variationsof30%,andthevariationsonT1/T2arechosentocoverawideoperationalrange.
Figure5showsthevariationofhydrogenrecoveryandproductpuritywiththeparameterT1+T2,which
reflectsthevalueofthecycletime.Theresultsshowedthatproductpuritydecreaseswiththeincreaseofthe
cycletime,whilethehydrogenrecoverypresentedlowreduction.Thisrelationshipamongcycletime,recovery
andpurityisqualitativelywellknown.Theutilityofthiskindofworkistoidentifytheoptimalcycletimein
ordertoavoidproductoverspecification.Theoptimalcycletimewouldbethevaluethatbringstheproduct
insidespecificationlimitswiththegreatestpossiblerecovery.Theoptimalcycletimemayberelatedto
differentfeedconditions.

Intheindustrialunitthereisafeedforwardcontroltoautomaticallychangethecycletimewhenthefeedflow
rateischanged,actinginalinearway.Suchrelationshipassumesthat,reducingthefeedflowrateinfifty
percent,thecycletimewillbeincreasedbytwotimes.Averyinterestingstudywouldbetheinvestigationof
thevariationoftheoptimalcycletimewiththefeedflowrate,thefeedtemperature,andtheadsorption
pressure,inordertoverifyiftheoptimalvalueisreallyinverselyproportionaltotheamountfedtotheunit.
Suchstudyisgoingtobedoneasacontinuationofthisstudy,oncetheinvestigationoftheoptimalvalueforthe
ratioT1/T2seemstobeunnecessary.
Figure6showsthevariationoftheproductpurityandthehydrogenrecoverywiththeratioT1/T2fortwo
differentvaluesfortheT1+T2parameter.Thevariationsareverifiedonlyinthefourthdecimal.


Thevariationsofthepurityandrecoveryshowedaverylowdependencywiththevariationsmadeintheratio
T1/T2.Itcanbeattestedthat,inthisspecificcase,variationsontheratioT1/T2causenoeffectontheproduct
purityoronthehydrogenrecovery.Infact,theamountofgasusedtopurgethebedisthesame,becausethe
differenceoftheinitialandthefinalpressureoftheprovidepurgestepisequal,onlytherateofvariationofthe
pressurewithtimeischanged.Thedifferenceonthetimetodepressurizethebedcausesdifferentpurgegas
velocities,whichpresentednoeffectontheproductpurityorhydrogenrecoveryinthiscase.Thechoiceofthe
ratioT1/T2tobeusedisprobablymadebasedonmechanicalaspectsofthesystem.
Afactthatisalsoobservedisthesimultaneousincreaseinhydrogenrecoveryandproductpuritywhentheratio
T1/T2isreduced.Obviously,ifthecycletimeremainsunchangedandthehydrogenpurityisincreased,thenthe
additionalhydrogentransferredtotheproductstreamwillreflectinreductionoftheamountofhydrogen
purged,increasingalsotherecovery.

CONCLUSIONS
AmodeltosimulateandoptimizeanindustrialPSAunitwasdeveloped.Allthefeaturesconcerningwitha
complexindustrialplantwereconsidered.Thecharacteristicsoftheprocesswerewellrepresentedbyanon
isothermalmodelusingtheextendedLangmuirisothermtorepresenttheadsorptionequilibriumandalinear
drivingforcemodeltodescribetheadsorptiondynamics.
TheeffectsofthecycletimeandtheratioT1/T2,twocharacteristicparametersoftheprocess,werestudied.
Theinfluenceofthecycletimeonproductpurityandhydrogenrecoverywasstudied,showingthatitispossible
toforeseetheoptimalcycletimetoachieveadefinedproductspecificationwithmaximumrecovery.Theeffect
oftheratioT1/T2showedanegligibleinfluenceinproductpurityandhydrogenrecovery.

REFERENCES
ChlendiM.,TondeurD.,RollandF.(1995),"Amethodtoobtainacompactrepresentationofprocess
performancesfromanumericalsimulatorexampleofpressureswingadsorptionforpurehydrogen
production",GasSep.Purif.,vol.9,125135.[Links]
KumarR.(1994),"Pressureswingadsorptionprocess:Performanceoptimumandadsorbentselection,"Ind.
Eng.Chem.Res.,vol.33,16001605.[Links]
KvamsdalH.M.,HertzbergT.(1995),"OptimizationofpressureswingadsorptionsystemsTheeffectofmass
transfer",Chem.Eng.Sci.,vol.50,12031212.[Links]
KvamsdalH.M.,HertzbergT.(1995),"PressureswingadsorptionOptimizationofatraceseparationsystem."
Comp.Chem.Eng.,vol.19,S339S344.[Links]
Nilchan,S.(1997),"TheOptimizationofPeriodicAdsorptionProcesses",PhD.Thesis.Imperial
College.[Links]
PantelidesC.C.(1996),"AnAdvancedToolforProcessModelling,SimulationandOptimisation,"Presentedat
ChemputersEuropeIII,Frankfurt.[Links]
ParkJ.,KimJ.,ChoS.,KimJ.andR.T.Yang.(1998),"Adsorberdynamicsandoptimaldesignoflayeredbeds
formulticomponentgasadsorption,"Chem.Eng.Sci.,vol.53,39513963.[Links]

*Towhomcorrespondenceshouldbeaddressed

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