MethaneReforming DemonstrationProblem

Revision0;October14,2008
Reference:WangShuyanet.al.,Simulationofeffectofcatalyticparticleclusteringonmethane steamreforminginacirculatingfluidizedbedreformer,ChemicalEngineeringJournal139(2008)136 146.

PurposeandOverview
Steamreformingofmethane(conversionofCH4intosyngas:COandH2)isofinterestforapplications suchasfuelcells,conversionofnaturalgastoliquidfuels,etc.Similarreactorsareofinterestforcoal toliquid(CTL)andbiofuelsynthesisapplications. AsimpledemonstrationproblemhasbeendevelopedinSINDA/FLUINT,usingboththeSinaps nongeometric(sketchpad)GUIandtheThermalDesktopwithFloCADgeometric(CADbased)GUI. Sincebothsetsofmodelsareavailableforinspectionandforuseasastartingpointortemplate,only briefdescriptionsareincludedinthisdocumentasgeneralguidance.Abasicunderstandingof SINDA/FLUINTmodelingisassumed.

ReactionKinetics
Twosimultaneousreactionsoffivespeciesareconsidered: CH4+H2OCO+3H2 CO+H2OCO2+H2 (reaction1) (reaction2)

Reaction2isthewatergasshift(WGS)reaction. Thereferencedpaper(Shuyan,et.al.)containsthereactionkineticsusedinthisproblem,basedonthe presenceofHaldorTopsoeNi/MgAl2O4spinelcalatyticparticles.Becauseofthedemonstrativenature ofthisproblem,thedetailsofthecatalystareneglected:thecatalystisassumedtooperateatfull activity. Shuyanlistsformulaeforforwardreactionratesforthesereactions,1usingequilibriumconstantsasthe basisforestimatingreverserates.Assumingfullcatalyticactivity,thecurrentreactionratecanbe calculatedasafunctionoftemperature,pressure,andpartialpressures.Thetemperaturedependencies forboththereactionrateconstantsandtheequilibriumconstantsareexponentialfunctionsofan Arrheniusform.

Specifically,equations8,9,11,12,13,and1520.

NotesonFluidProperties
InSINDA/FLUINT,eachspeciesisassignedaletteridentifier: Species Methane Water Carbonmonoxide(gas) Hydrogen Carbondioxide Symbol LetterID CH4 M H2O W CO G H2 H CO2 C

Watermaybeacondensable(twophase)fluid.However,inthiscasethetemperatureswillalwaysbe highenoughsuchthattheliquidphasewillneveroccur.2Therefore,eitheraperfectgas(8000series fluid)orarealgas(NEVERLIQ6000seriesfluid)couldhavebeenused.Versionsofsuchfilesare available(http://www.crtech.com/properties.html)thatwerebuiltfromtheNISTprogramREFPROP, perhapssubsequentlysimplifiedtoaperfectgasusingtheSINDA/FLUINTPR8000utility. Unfortunately,theNISTdatabasedoesnotextendtosufficientlyhightemperaturesforCO,CH4,andH2. Forexample,theuppertemperaturelimitforCOisonly500KinthecurrentversionofREFPROP. Therefore,propertiesforallfivegasesweregeneratedusingNASAsfreeCEAchemicalequilibrium programcombinedwithaC&RutilityforconvertingoutputstoFPROPDATAformat.3Whilethis interfaceisintendedtopreparefluidsrepresentingequilibriumreactingmixtureswithvariable molecularweights,theonlymodeinCEAcanbeusedtoproducepropertiesforsingleconstituents withconstantmolecularweights.Therefore,despitetheresultinggeneralized6000seriesrealgas fluidtables,itshouldbenotedthattheactualpropertiesreflectCEAsintrinsicassumptionofperfect gases.Heatofformation(HFORM)anddiffusionvolume(DIFV)informationwerethenaddedtothese fluidfiles,notingthatCEAusestheheatofformationasthebasisoftheenthalpyat25C.Theheatof formationofwateristhereforediminishedbytheheatofvaporizationtoreflecttheallgasnatureof thisCEAderivedfluidfile.(Forafulltwophasewaterdescription,theuncorrectedheatofformation shouldinsteadbeapplied,sincealiquidstateexistsatstandardtemperatureandpressure.)

ReactorDesign
Anintentionallygenericandsimplifiedplugflowreactor(PFR)isassumed. Inclusionofthesolidcatalystparticlescouldtakeseveralformsasapackedbedofstationaryparticles heldinplacebystructuredcatalystssupports,freeflowingwiththegastransport,orother configurationsbutinclusionofthecatalystsinanyformovershadowstheillustrativeintentofthis demonstrationproblem.Thechosenscenariofocusesonhowtoincorporatethereactionkineticsinto SINDA/FLUINT.
Iftemperaturesbelowthedewpointareincluded,afulltwophasedescriptionofwatershouldbeusedinstead. Indeed,suchadescription(http://www.crtech.com/properties.html)wasusedaspartofthevalidationeffort whentemperaturesaslowas25Cwereusedasafeedtemperature. 3 http://www.crtech.com/EQfluids.html
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Temperatures,pressures,inletflows,anddimensionsmaybechangedparametricallyinthemodel,with asubsetofpossibleparametricsettingsusedforthebaselinerunsshowninthetablebelow. Parameter Reactorlength Register Name length Value 1 Units m Comment

Reactorhydraulicdiameter Reactorflowarea

diam area

Inlettemperature

temp_in

Assumed equaltothe inlet Inletflowrate moles_in InletmolefractionsofCH4,H20 mol_in_m, mol_in_w, andotherinletstream constituents,plusexcesssteam SteamX fractionbeyondstoichiometric Outletpressure pres

Walltemperature

(Arbitrarychoice.)Longerlengths mightbeconsideredasneededto bringtheoutletconditionscloser totheequilibriumcondition 0.008 m (Arbitrarychoice) 4.e4 m2 Undefinedfinsorslitshapeis assumed,asneededtoprovide adequateheattransferarea 800 C (Arbitrarychoice,but representativeoftypical applications.) 800 C Inletandwalltemperaturesare assumedtobeequal,butcanbe independentlyadjustedifneedbe 0.03e3 kmol/s (Arbitrarychoice) 0.5, Stoichiometric(equalmole 0.5, fractions)plus2timesmore 3.0 steam.UseSteamX=1.0for stoichiometricfeedrates. 101325. Pa Thisindirectlysetsthereactor pressureduetothesmall pressuredropthroughthereactor

ARefresher:ModelingReactionsinSINDA/FLUINT
TherateofcreationofmassofanyspeciesiisdesignatedXMDOTiinSINDA/FLUINT,withthecaveat thatiXMDOTi=0:thereisnonetgenerationorlossoftotalmassasaresultofachemicalreaction.A speciesthatisbeingconsumedwillhaveanegativeXMDOT,andaspeciesthatisbeingproducedwill haveapositiveXMDOT.Sincethismodelusesmetricunits,XMDOThasunitsofkg/s(lbm/hrwouldbe theunitsintheEnglishsystem). WhenXMDOTsarenonzero,thecodewillautomaticallycalculateandapplyacorrectiveheatofreaction (QCHEM)basedonthefluidproperties(heatsofformationandenthalpybasis).Ifeachfluidusesthe heatofformationastheenthalpybasisatSTP,thiscorrectiveQCHEMtermiszero. Whenthedesiredconcentrationofoneormorespeciesisknown(e.g.,wheneithertheequilibrium concentrationorthereaction/combustionefficiencyisknown),theEQRATEutilitycanbeusedto generateXMDOTvalues,perhapsobeyingoneormorechemicalreactions(suppliedasstoichiometric numbers).Forexample,preliminaryCEArunscouldhavegeneratedequilibriumstatepredictions (perhapsasfunctionsoftemperature),whichcouldhavebeenusedasinputstotheEQRATEutility.

Ifinsteadonlytherateofreactionisknown(asisthecaseinthisexample),thenEQRATEisnot applicableandtheXMDOTvaluesshouldinsteadbecalculatedexplicitlybytheuserinuserlogicblock FLOGIC0atthestartofeachsolutioninterval(i.e.,timesteporsteadystaterelaxationstep).The XMDOTvalueforeachspeciesiwillbethesumofallthereactionsinwhichitparticipates. TheresultingsetofXMDOTvaluesisassumedtobeconstant(alongwiththecorrespondingQCHEM) overthenextsolutioninterval.Inotherwords,thespeciesproductionandextinctionratesarebasedon thetemperaturesandpressuresatthestartoftheinterval,andarenotimplicitlyadjustedfor temperatureorpressurechangesthatareabouttooccur.4 Asignificantrestrictiononchemicalreactionsisthattheycanonlyapplytotanks(controlvolumes),and nottojunctions(massless/volumelessstatepoints).NotingthatthemainsolutionroutineSTEADY(aka FASTIC)treatstankstemporarilyasjunctions,thismeansthatsteadystatesolutionscanonlybe achievedusingSTDSTL(pseudotransientintegrationtowardatimeindependentstate).Thisinturn meansthat,unlikemoststeadystateanalyses,chemicalreactionsteadystatesolutionsaredependent oninitialguesses(especiallyspeciesfractions).

ReactorModel
Thesourceofgasesisrepresentedbytwoplena:one(reactor.1000)representingastoichiometric mixtureofmethaneandsteam,andanother(reactor.1100)representingexcesssteamthatcanbe addedtothereactor.Themixtureratiowithinplenumreactor.1000issetusingregisters(e.g.,mol_in_w forsteam,mol_in_mformethane)basedonmolefractions,whicharethenconvertedintogasmass fractions(XGiforeachspeciesiasrepresentedbytheregisterxin_m,xin_w,xin_h,xin_c,andxin_g. Notethatwhilexin_candxin_garebothzero(noinflowingCO2orCO),xin_hisnonzero:itissettoa verysmallvalue.Anextremelysmallamountofhydrogenisaddedsimplytoavoidtheneedtodealwith themathematicalsingularitycausedbythepresenceofthepartialpressureofhydrogeninthe denominatoroftherateequations. Therearemanywaystorepresenttheinletconditions.Forexample,themassfractionsonasingle plenumcouldbeset.Alternatively,NplenacouldbeusedforeachoftheNspeciesinvolved,settingthe massorvolumetricflowrateofeachspeciesbeinginjected. Inthiscase,asingleSetFlow(SINDA/FLUINTMFRSETconnector)isappliedfromeachplenum,withthe ratiooftheflowratesbeingcontrolledviatheSteamXregister:SteamX=1forstoichiometricflow,2for twicethesteamrequired,etc.Thesteadystatecase(namedPFR)isrunatSteamX=1:stoichiometric inletconditions,orequalmolarflowsofmethaneandsteam,withzeroexcesssteamflowaddedfrom plenumreactor.1100.

Bydefault,SINDA/FLUINTdoesimplicitlyreducereactionsforreactantsthatarepresentinlowconcentrations andthatvanishduringthesolutioninterval,asdescribedintheUsersManual.Inotherwords,XMDOTscanbean implicitfunctionofconcentration,buttheyareassumedindependentoftemperatureandpressureduringeach solutioninterval.Normally,theyareadjustedinastairstepfashionbetweensolutionintervalsaccordingto calculationsinuserlogic.

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A10segmentSinapsorFloCADPipe(SINDA/FLUINTHXmacropluswallmodel)isusedtorepresentthe reactor.Whileincludingthedetailsoftheheatexchange(structural/thermalmodel)isastrengthofthe C&Rtoolsuite,toavoiddistractingfromtheintentofthisdemonstrationproblem,aninfinitesourceof energyat800Cisassumed.ThenodesinthePipearethereforechosentobeconstanttemperature boundarynodes. Thechoiceof10segmentscanbeadjustedbychangingboththeintegerregisterresolpluseditingthe Pipemacro.5Higherresolutions(atleastresol=20)areneededtocapturethestronggradientsatthe inletandtoguaranteethatequilibriumisachievedattheexit.6However,fordemonstrationpurposes thespatialresolutionisleftintentionallylow.TheSinapsdiagramforthereactorisshowbelow.

ThecorrespondingFloCADdiagramisasfollows:

TanksmustbeusedwithinthePipetoallowspeciessource/sinkrates(XMDOTs)tobespecified: reactionsarenotpossibleinjunctions.NotethatSTUBEconnectors(inertialessductelements)areused insteadoftubessincetheflowsconsistoflowdensitygases.Eventhoughthesubsequenttransient operatesoveranextremelyshorttimescale,tubeswouldnotberequiredunlesssignificant condensationweretooccur. TheSTDSTLsolutionmustbeusedtoarriveatasteadystateanswersincechemicalreactionsarenot possibleinSTEADY,whichtreatstanksasiftheywerejunctions.NormallyaSTEADYsteadystate solutionisnotverydependentoninitialconditions,andoftenonlyrequires1050iterationstoresolve. However,anSTDSTLsolutionusesthefulltransienthydrodynamicsolutionalongwithasimultaneous

Therestartrecordnumber(integerregisterrecord)willalsohavetobeadjustedbasedontheoutputsofthefirst case(pfr)sincethesizeoftheSAVEandRSI/RSOfileswillchangeifthemodelsizechanges. 6 Assumingtemperaturesarehighenoughtoensureequilibrium.Also,thereactorlengthmayneedtobe increasedaswell(thiscanbechangedindependentlyofthenumberofsegmentsusedtoresolvethatlength).
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thermalsolution.STDSTLissimilartorunningatransientsolutionuntileverysystemresponseis constant.Itthereforeissensitivetoinitialconditions(assetviathemolefractionregistersminit_h, minit_g,etc.whichsetmassfractionsxinit_h,xinit_g,etc.).Thismeansthatsomespeedsavingscanbe realizedbysettingreasonableinitialconditions,perhapsbasedonpriorruns.Otherwise,poorlyguessed initialconditionsinvoketheevaluationofasevereyetspurioustransient,wastingcomputational resourcesandrequiringmorestepNum(aregisterusedtosetthecontrolconstantNLOOPS)to converge. Normally,steadystatesolutionsaresoinexpensivethattheyareoftenrecalculatedbeforeeach transientcaseasinitialconditions.WhilethespeedoftheSTDSTLsolutionisgoodinthiscase,amore detailed(perhaps2Dor3D)modelmightnotenjoythesameresult.Therefore,theabilitytosavethe resultsofapriorsteadystatecase(casepfr)andreusetheminafuturetransientcase(case pfrTransient)isdemonstratedinthismodel(seeRESAVE/RESTARoperationsintheSINDA/FLUINT manual).BothcasescanbeselectedintheSinapsCaseManagerortheThermalDesktopCaseSet Managerandexecutedsequentially.Ifthisusagewerefrequent,thenthetwosolutionsshouldbe combinedintoasinglecasetoavoidtheinefficienciesoftheextrapreprocessandcompilesteps. Foreachtankinthesystem,atthestartofeachsolutionstep(namely,inFLOGIC0),thefollowing calculationsshouldbemade: 1. Theratefactors(equilibriumKconstantsandpreexponentialkterms)shouldbeupdatedas afunctionofcurrenttemperature(TL),pressure(PL),andpartialpressures(e.g.,PPGHisthe partialpressurefractionforspeciesH). Thetemperaturesandpressuresshouldbeconvertedintoabsoluteunits(e.g.degreesK insteadofC),whichmeanssubtractingABSZROfromtemperaturesandPATMOSfrom pressures.Forexample:TLabs=TLrelABSZRO.Inthelogicblocks,theregisteratemp containstheabsolutetemperatureandaprescontainstheabsolutepressure. 2. Themolarrateforreaction1shouldbecalculated,andusedtosettheXMDOTforeach speciesinthatequationusingthestoichiometricnumber,notingthatXMDOThasunitsof kg/s(orlbm/hrforUID=ENG)andthereforethemolecularweightofeachspeciesmustbe usedasamultiplier.ThesemolecularweightscanbecalculatedviaroutinessuchasVMOLW orVMOLWPT,butinthisdemonstrationproblemtheyhavebeensetusingregisters(e.g., mw_h2o,mw_co2,etc.).Ifaspeciesisnotparticipatinginreaction1(e.g.,CO2inthiscase), itsXMDOTshouldbezeroed. 3. Themolarrateforreaction2shouldbecalculated,andusedtoupdatetheXMDOTforeach speciesinthatequation.SinceXMDOTshavealreadybeenupdatedforreaction1,thisstep involvessummingintothesevalues,whichexplainswhyXMDOTforCO2(XMDOTC)was zeroedinthepriorstep. Iftherewereany3rdor4threactions,thesecouldsimilarlyhavebeensummedintothe XMDOTvalues.Toavoidanyconfusionwhenthenumberofreactionsislarge,theXMDOTs shouldbezeroedatthestartofthelogicblock,thenalwayssummedinto(ratherthan replaced)soasnottooverwritetheeffectsofreactionscalculatedearlierinthesequence.

Therearetwoplaceswheresuchreactionupdatelogiccanbeplaced: 1. HEADERSUBROUTINES:userdefinedsubroutines,whichcanthenbecalledfromFLOGIC0 viaaDOloopincrementingloopID.SincetheIDofeachtankwillchangeforeachcalltothe updateroutine,dynamictranslationroutines(e.g.,INTLMP,INTSPE)willberequiredto converttheuseridentifierintotheinternalarraylocation. 2. Networklogic:7logicassociatedwitheachnetworkelement(tanks,inthiscase).Expression styleindirectreferencingcanbeusedintheseblocks.Forexample,VOL#thisreferstothe volumeofthecurrenttank,PPGH#thisreferstothepartialpressurefractionofhydrogen (speciesH)inthecurrenttank,andXMDOTH#thisreferstotheXMDOTofthesamespecies H. FortheSUBROUTINESapproach(whichisusedinthemodelnotbecauseitisrecommendedbutbecause itismorewidelyaccessibletoolderversionsandexperiencedusers),theFLOGIC0blockappearsas:
do itest = 1,resol call reform enddo

whereitest,thevalueiteratedintheDOloop,referstotheuserlumpID(from1toresol=10).Itestisa globalvaluethatisaccessiblewithintheusersubroutineREFORMaspartoftheCALLCOMMON commandinthatroutine(whichisinsertedasafile):

subroutine reform call common fstart integer methane,water,co,co2,h2,lump c c c c c c c c c reactions 1 and 2, from "Simulation of effect of catalytic particle clustering on methane steam reforming in a circulating fluidized bed reformer" Shuyan et al, Chem Eng Jnl 139 (2008) p.136-146 H=H2, W=H20, G=CO, M=CH4, C=CO2 itest is assigned lump methane co2 co h2 water in FLOGIC = intlmp('reactor',itest) = intspe('reactor','m') = intspe('reactor','c') = intspe('reactor','g') = intspe('reactor','h') = intspe('reactor','w')

c if(ppg(h2,lump) .le. 0.0) call abnorm(' reform ',itest, & ' User routine REFORM cannot handle zero H2 partial pressure ') c convert to absolute units (if not) atemp = tl(lump)-abszro apres = pl(lump)-patmos c 1/Pa, except for KH20 which is unitless KCH4 = 6.65e-9*EXP(4604.28/atemp)

AvailableinSinapsandFloCADVersions5.2andlater.

KH2 KCO KH2O

= 6.12e-14*EXP(9971.13/atemp) = 8.23e-10*EXP(8497.71/atemp) = 1.77e5*EXP(-10666.35/atemp)

DEN = 1.0 + apres*(KCH4*PPG(methane,lump) & + KH2*PPG(h2,lump) + KCO*PPG(co,lump)) & + KH2O*PPG(water,lump)/PPG(h2,lump) c reaction 1

c mol-sqrt(Pa)/kg-s klc1 = 8.336e17*EXP(-28879./atemp) c Pa^2 Kuc1 = 10266.76e6*EXP(-26830./atemp+30.11) rxn1 = klc1*(ppg(methane,lump)*ppg(water,lump)/ppg(h2,lump)**2.5 & - apres**2*ppg(co,lump)*sqrt(ppg(h2,lump))/Kuc1) & /sqrt(apres)/DEN**2 rate1 = rxn1*dl(lump)*vol(lump) rate1 = (1.0-rateLag)*rate1 + rateLag*cx(lump) xmdot(methane,lump) = -rate1*mw_ch4 xmdot(water,lump) = -rate1*mw_h2o xmdot(co,lump) = rate1*mw_co xmdot(h2,lump) = 3.0*rate1*mw_h2 xmdot(co2,lump) = 0.0 c reaction 2

c mol/kg-Pa-s klc2 = 12.19*EXP(-8074.3/atemp) c unitless Kuc2 = EXP(4400.0/atemp-4.063) rxn2 = klc2*(ppg(co,lump)*ppg(water,lump)/ppg(h2,lump) & - ppg(co2,lump)/Kuc2)*apres/DEN**2 rate2 = rxn2*dl(lump)*vol(lump) rate2 = (1.0-rateLag)*rate2 + rateLag*cy(lump) xmdot(co,lump) xmdot(water,lump) xmdot(co2,lump) xmdot(h2,lump) = xmdot(co,lump) - rate2*mw_co = xmdot(water,lump) - rate2*mw_h2o = xmdot(co2,lump) + rate2*mw_co2 = xmdot(h2,lump) + rate2*mw_h2

c store key data away in otherwise unused CX, CY, CZ cells c for ease of postprocessing, damping c cx(lump) = rate1 cy(lump) = rate2 c a little out of step (uses last QCHEM), and QCHEM is for both reactions, c but ... if(rate1 .ne. 0.0) cz(lump) = 1.e-6*qchem(lump)/rate1 c return end fstop

Theequivalenttotheabove,usingthenetworklogicapproach,istoplacethefollowingintheFLOGIC0 formforalltanks(whichcanbeeditedsimultaneously):

c c c c c c c c

reactions 1 and 2, from "Simulation of effect of catalytic particle clustering on methane steam reforming in a circulating fluidized bed reformer" Shuyan et al, Chem Eng Jnl 139 (2008) p.136-146 H=H2, W=H20, G=CO, M=CH4, C=CO2 if(ppgh#this .le. 0.0) call abnorm(' reform ',#this, & ' User logic cannot handle zero H2 partial pressure ')

c convert to absolute units (if not) atemp = tl#this-abszro apres = pl#this-patmos c 1/Pa, except KCH4 = KH2 = KCO = KH2O = for KH20 which is unitless 6.65e-9*EXP(4604.28/atemp) 6.12e-14*EXP(9971.13/atemp) 8.23e-10*EXP(8497.71/atemp) 1.77e5*EXP(-10666.35/atemp)

DEN = 1.0 + apres*(KCH4*PPGM#this + KH2*PPGH#this + KCO*PPGG#this) & + KH2O*PPGW#this/PPGH#this c reaction 1

c mol-sqrt(Pa)/kg-s klc1 = 8.336e17*EXP(-28879./atemp) c Pa^2 Kuc1 = 10266.76e6*EXP(-26830./atemp+30.11) rxn1 = klc1*(ppgm#this*ppgw#this/ppgh#this**2.5 & - apres**2*ppgg#this*sqrt(ppgh#this)/Kuc1) & /sqrt(apres)/DEN**2 rate1 = rxn1*dl#this*vol#this rate1 = (1.0-rateLag)*rate1 + rateLag*cx#this xmdotm#this xmdotw#this xmdotg#this xmdoth#this xmdotc#this c reaction 2 = -rate1*mw_ch4 -rate1*mw_h2o rate1*mw_co 3.0*rate1*mw_h2 0.0

= = = =

c mol/kg-Pa-s klc2 = 12.19*EXP(-8074.3/atemp) c unitless Kuc2 = EXP(4400.0/atemp-4.063) rxn2 = klc2*(ppgg#thisppgw#this)/ppgh#this & - ppgc#this/Kuc2)*apres/DEN**2 rate2 = rxn2*dl#this*vol#this rate2 = (1.0-rateLag)*rate2 + rateLag*cy#this xmdotg#this xmdotw#this xmdotc#this xmdoth#this = xmdotg#this - rate2*mw_co = xmdotw#this - rate2*mw_h2o = xmdotc#this + rate2*mw_co2 = xmdoth#this + rate2*mw_h2

c store key data away in otherwise unused CX, CY, CZ cells for ease of postprocessing, damping

c cx#this = rate1 cy#this = rate2 c a little out of step (uses last QCHEM), and QCHEM is for both reactions, c but ... if(rate1 .ne. 0.0) cz#this = 1.e-6*qchem#this/rate1

TheaboveisthebasisoftheSinapsmodelpfr_nl.smdlandtheFloCADmodelpfr_nl.dwg,wherethe nlinthenamesreferstotheNetworkLogicoption. Thedifferencetothetwoapproachesislargelyamatterofuserpreference.Networklogicis expanded/translatedbySinapsorFloCADandinsertedintothespecifiedlocation(FLOGIC0inthiscase). Notethatthekeydifferenceishowtoreferenceeachproperty: dl(lump)inHEADERSUBROUTINES,wherelumphasbeencalculatedusingthedynamic translationfunctionINTLMP,isequivalenttodl#thisinnetworklogic. ppg(methane,lump)inHEADERSUBROUTINES,wheremethaneisanintegercalculatedusing thedynamicfunctionINTSPE,isequivalenttoppgm#thisinnetworklogic.

DampingandTimeStepControl:DealingwithTemperatureSensitivities
Inspectionofthekineticratecalculationsaboverevealsthatsomeextrastepswerenecessarytoassure steadystateconvergence:thepriormolarreactionrates(rate1andrate2)arestoredfromtheprevious iterationinunused8lumpcoordinatesCXandCY,respectively.(Thisapproachhasaconvenientside effect:itallowsthosevaluestobepostprocessed.)Thesepriorratesarethenusedtoslowtherateof changeofXMDOTvaluestoencourageconvergenceinsteadystatesaccordingtotheregisterrateLag, whichvariesfromaninitialvalueof0.5(midrangedampingviaarunningaveragebetweenthecurrent andlastvalue)to1.0(heavydampingbytheendofthesteadystate): rateLag=0.5+0.5*(loopct/stepNum) wheresstepNumisthenumberofpseudotimestepsallows(usedtosetNLOOPS)andloopctisthe currentstepnumber.ForreactionN,thisdampingtakesthegeneralformat: rateNnew=(1.0rateLag)*rateNnew+rateLag*rateNold Intransients,rateLagissettozero(meaningnodamping)viacasedependentregisters.Inother words,nodampingisrequiredintransients.However,thedefaulttimesteperrortolerancefactor DTSIZF,whichdefaultsto0.1(10%max.changepertimestepinanykeyparametersuchaspressure, speciesfraction,etc.),mustbereducedtoatmost0.02(2%max.change)topreventoscillationsinthe timeplots.9
Ifbodyforceshadbeenimportant,thesevariableswouldnotbeavailableforthisusage.Eitherotheropen variablesmustbesought,orextraregistersmustbedeclaredtoholdthememoryforeachtanksreactionhistory. 9 TheexperiencedusermightbewonderingwhysimilarlyreducingRSSIZFisntavalidapproachforSTDSTL solutions,avoidingtheneedforrunningaveragedamping.ThereasonisthatsmallRSSIZFvalueswouldrequire excessiveiterations(highLOOPCT)unlesslargevaluesareusedinitially.Moreimportantly,theconvergence
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Whiletheapproachdiffersbetweensteadystate(STDSTL)andtransient(TRANSIENT)solutions,the causeforthisunusualstepisthesame:theextremetemperaturedependenceofthereactionrates, whichistobeexpectedbecauseofthepresenceofexponentialintheArrheniusrateequation. Specifically,theXMDOTvaluesarenotadjustedimplicitlybythecodeasafunctionoftemperature. Rather,XMDOTvaluesareassumedconstantovereachsolutionstep.Iftoolargeofastepistaken,the temperatureinthetankwillchangetoomuchandtheassumptionofconstantreactionratesisinvalid: theabsolutevalueofthepartialderivativeofXMDOTiwithrespecttoTListoohigh.Therefore,either thetimestepmustbereducedinanticipationofasignificantchangeinXMDOT(thetransient approach),ortheXMDOTvaluemustbedampedtopreventbinaryoscillations(thesteadystate approach).

SteadyStateResults
With3timesasmuchsteamasneededforstoichiometricconditions(SteamX=3),andgivenafeed temperatureof800Candwalltemperaturesof800Caswell,theresultingtemperaturegradientsat steadystateareshownbelow.

Inthediagramabove,thefluidspeciesaremixedinjunctionreactor.1001(withoutreactionsyet permitted),theninjectedattheleftofthediagram,exitingattheright.Thetemperaturesdroptoabout 550Cattheinlet,beforerisingtoabout780Cattheoutlet.Ifalongerreactorhadbeenused,theexit temperatureswouldhavebeenclosertothewalltemperatureof800C.Iffinerspatialresolutionhad beenused(forexample,20segmentsinsteadof10),theresultswouldhaverevealedthatthecoldest spotinthereactorisnotexactlyattheinlet,butisinsteadlocatedafewcentimetersdownstream whereendothermicreaction#1reachesitspeakrate. Thecorrespondingpartialpressurefraction(molefraction)forhydrogenisshownnext.

checkerwouldstillpreventconvergencefrombeingdeclaredattheendoftherunsinceitalsocheckstheabsolute sizeofthepseudotimestepasanindicationofahavingachievedatimeindependentstate.

 Recallingthepresenceofexcesssteam,themolefractionofhydrogenproducedisabout56%inthe outletstream. Steadystateanalysesareakeytoolforsizing,sensitivitystudies,etc.Recallthat,unlikemost SINDA/FLUINTmodels,thetypeofsteadystatesolutionusedforchemicalreactionsisnotinsensitiveto guessedinitialconditions.Therefore,eithertheruntimeallowed(stepNum)mayhavetobeenlarged,or moreaccurateinitialconditionsmayneedtobeguessed(registersminit_h,minit_c,etc.),orboth.For parametricsweepsorSolverruns(sizing,correlationtotest,etc.),theguessedinitialconditionsshould reflectthefirstcasetobesolved,withonlymodestincreasesinstepNumtoaccommodatevariations thatmightbeexperiencedduringwhilesolvingforvariedconditions.Moresignificantincreasein stepNummayberequiredforstatisticaldesignruns(usingtheReliabilityEngineeringModule)sincethe variationsbetweensamplingsarenotnecessarilygradual:thepriorsteadystateanswersmightnotbe goodinitialconditionsforthenextsamplingruntobemade.

TransientDemonstrationEvent
AkeyfeatureofSINDA/FLUINTreactingflowmodelingistheabilitytosimulatetransients,includingfast transienteventssuchaspressurewaves,flowinstabilities,controlsystemactions,andvalvedynamics. Asademonstrationofthesecapabilities,thesteadystatesolutiondescribedinthelastsectionwillbe usedastheinitialconditionforanarbitraryevent:thereductionofsteaminjectiontostoichiometric conditions:athreefolddecreaseinsteamfeedattimezero,withanapproximatelytwofoldreductionin overallflowrate. Normally,atransientcaseisrunsimplybyaddingacalltotheTRANSIENTsolutionroutinefollowingthe calltothesteadystatesolution(STDSTL)withinOPERATIONS.Inthesamplemodelsassociatedwiththis document,thesteadystateandtransientanalysesareperformedastwoseparatecases:pfrand pfrTransient,respectively.ThepfrTransientcasestartsbyreadingbacktheinitialconditionsleftforitby thepfrcase,whichmusthavebeenexecutedbeforehand.Ifsomedimensionorboundaryconditionis changedthataffectsbothcases,theyshouldbothbeselectedandreruntogether. Theplotbelowshowsthetransienttemperatureresponseofthereactortoastepreductioninsteam injection.Astheflowratediminishes,thetemperaturesattheexit(e.g.,TL10,thetemperatureoflump #10)risereflectingtheirtemporarystagnationnexttoahotwall.Neartheinlet(TL1)thetemperature actuallygoesdownbeforerisingsincethereislesssteamtocoolfrom800Cbuttheendothermic

reactioncontinuesataboutthesamerate.Asanewsteadyconditionisestablished,thenetchangeisa warmingofthemiddleofthereactorandthereforemorecompletereformingoftheinflowingmethane.

Analternativeviewofthissameeventisdepictedbelowintermsofthepartialpressurefraction(mole fraction)ofhydrogengas.Astheexcesssteamiswithdrawn,thefractionofhydrogenjumpsfirstatthe inlet,andthisfrontcanbeseenprogressingthroughthereactorforthefirst0.16seconds.Thereactor shiftsfromproducing55%H2tomoreoptimum72%(themaximumpossibleis75%).

ValidationwithAspenPlus
LikeNASAsCEA,AspenTechsAspenPluscanbeusedtopredictequilibriumconstituentfractionsbased ontheminimizationofGibbsfreeenergy.Inaddition,theenergyinputsneededtosustainan isothermalprocesscanbecalculated,ascantheenergyrequiredwhenthefeedtemperatureis substantiallycolderthantheproducttemperature.Finally,thetemperaturedropexperiencedbyhot steamandmethaneinjectedintoanadiabaticreactorcanalsobecalculated. ItisimportanttorememberthatalloftheAspenPluscalculationsassumedequilibriumconditionsto exist,whereastheSINDA/FLUINTpredictionsweremadebysimulatingfiniteratereactionsasaprocess. Inotherwords,tobeabletopredicttheheataddedtoastoichiometricstreaminjectedat25Cand heatedto(say)1200C,thereactorwallsweresetto1200Candsufficientreactorlengthwasaddedas neededtoprovidetheheattransferrequiredtoaccomplishthistask.Theexitstatewasthencompared withAspenPluspredictions,andtheheataddedtothestreamviaheattransferwastalliedtogeneratea totalnetpower. Comparedwiththemodelspresentedabove(andincludedwiththissample),uptothreedifferences weremadeinthevariationofthedemonstrationmodelthatwasusedtogeneratecomparisonresults: 1) Thelengthwasincreased(upto40m)

2) Theresolutionwasincreased(from10segmentsto20) 3) Atwophasedescriptionofwater(REFPROPderivedf6070_water.inc)wassubstitutedwhen 25Cinletconditionswereused,suchthatthefactthatwaterisliquidatSTPcouldbe included. Theresultsofthisvalidationexercisearesummarizedbelow. Sixdiabaticcaseswerecompared,threewithbothfeedandproductsatthesametemperature(500C, 800C,and1000C),andthreewithfeedat25Cwhileproducttemperaturesremainedthesame.The predictedspeciesmolefractionsaretabulatedbelow,alongwiththetwopowerrates(QfpforTf=Tp, andQ25forTf=25C).Thedifferencesareexpressedaspercentages,whicharecalculatedbasedontotal massforspeciesfractions.
CH4 H2O CO CO2 H2 Qfp(kJ/mol) Aspen 500C S/F diff. 0.14% 0.18% 0.04% 0.03% 0.25% 0.89% 1.22% 0.3203 0.3188 0.2493 0.2475 0.0189 0.0193 0.0710 0.0713 0.3406 0.3431 126.99 128.13 42.70 Aspen 0.0269 0.0199 0.2296 0.0069 0.7166 319.45 201.77 800C S/F 0.0262 0.0196 0.2304 0.0066 0.7173 318.64 202.14 diff. 0.07% 0.03% 0.07% 0.04% 0.06% 0.26% 0.19% Aspen 0.0009 0.0008 0.2495 0.0001 0.7488 393.94 225.40 1000C S/F 0.0009 0.0008 0.2495 0.0001 0.7487 393.49 224.58 diff. 0.00% 0.00% 0.00% 0.00% 0.00% 0.11% 0.36%

Q25(kJ/mol) 42.18

Notethattheagreementimprovesasthetemperaturerises(fasterreactionratesmakingequilibriuma morelikelyresult),butisverygoodevenforthe500Ccaseconsideringthatthetwoprogramsdonot usethesameapproach(theAspendataassumesequilibrium,andthisparticularSINDA/FLUINTrunuses reactionkinetics),nordotheyusetheexactsameequilibriumconstants(thoughapparentlytheyare veryclose),andthattheenthalpyfunctions(fluidproperties)aredifferentaswell. Threemorecaseswerecomparedbasedonisothermalprocesses,withinlettemperaturesbeing500C, 800C,and1000C.Equalmolefractionsofmethaneandsteamwereused:stoichiometricconditions. Theresultsareshownbelow.Again,thespeciesfractiondifferenceswerecalculatedonthebasisoftotal mass.Thetemperaturedifferenceswerecalculatedonthebasisoftemperaturedropfromtheinlet.

Aspen 500C S/F diff. 0.04% 0.06% 0.00% 0.02% 0.08% 0.61% 0.4342 0.4346 0.4020 0.4026 0.0006 0.0006 0.0323 0.0320 0.1309 0.1301 367.5 368.3 Aspen 0.3438 0.2775 0.0118 0.0663 0.3006 477.6 800C S/F 0.3430 0.2765 0.0120 0.0665 0.3020 476.9 diff. 0.08% 0.10% 0.02% 0.02% 0.14% 0.22% Aspen 0.2842 0.2103 0.0340 0.0739 0.3977 531.3 1000C S/F 0.2828 0.2087 0.0345 0.0741 0.3999 530.3 diff. 0.14% 0.16% 0.06% 0.02% 0.23% 0.21%

CH4 H2O CO CO2 H2

Tprod(C)

DemonstrationUseofaCEAderivedEquilibriumFluid
ItisnoteworthythattheAspenPlusequilibriumcalculationyieldedresultssimilartoafiniterate approach,evenattemperaturesaslowas370C.Thisobservationmeansthatavariablemolecular weightequilibriumfluidmaybeappropriate,atleastwhenthefeedratiosarenotalteredduringthe courseofananalysis.10 Todemonstratethismodelingapproach,avariationoftheabovemodelwasmadeandisavailablein Sinapsform. First,CEAwasrunforastoichiometricmixtureofwaterandmethane,restrictingtheresultingmixture toonlythefivespeciesusedintheoriginalanalysis(i.e.,excludingcarbon,otherminorspecies,ions, etc.).ThistableofCEAequilibriumdatawasconvertedintoasingleSINDA/FLUINTFPROPblockusing thecea2fproputility,11andtheheatofformationwassettobethesameastheenthalpyofthisnew fluidatSTP. ThisnewfluidwasthenusedinthePFRmodelasspeciesE,suchthatwhenM(methane)andW (water)arereacted,theyresultinthisvariableweightequilibriumfluidasfollows: CH4+H2OE (equivalentreaction)

ThespeciesH(hydrogen),G(carbonmonoxide),andC(carbondioxide)arethereforeeliminatedfrom themodel.NotethatmethaneandwaterconstitutesignificantportionsoffluidE,especiallybelow 600C. Byassumingequilibrium,thekineticratecalculationsareeliminated.Infact,reactionsinallbutthefirst tankareeliminatedaswell:downstreamreactionsaretakencareofbytemperatureandpressure dependentshiftswithintheequilibriumfluiditself.WhiletheutilityEQRATEcouldhavebeenusedtoset XMDOTvalues,insteadthereactionratesinthefirsttank(tank1)weresetinFLOGIC0applyinga reactionefficiencybasedoninflowingmethane,whichwaspresumedtobethelimitingreagent.A newregisterconvert,setto0.999,declaresthat99.9%ofincomingmethanewillbecombinedwithan equalmolaramountofwaterandreplacedbyanequalmassofequilibriumfluidE.Inflowingmethane massflowiscalculatedastheproductofthemassfractionupstreaminjunction1000,xgM1001and theincomingmassflowrateinpath3,fr3:
xmdotM1 = -xgM1001*fr3*convert xmdotW1 = xmdotM1*mw_h2o/mw_ch4 xmdotE1 = -(xmdotM1+xmdotM1)

Becauseexcesssteamaffectstheequilibriumpoint,theequilibriumfluidEshouldonlybeusedto replaceastoichiometricmixtureofmethaneandwater.Indeed,whensuchastoichiometric(SteamX=1)
Excessoxidizer(e.g.,air)canusuallybeaddedorsubtractedfromanequilibriumfluidrepresentingthehot productsofcombustion.Thiswouldonlybetrueforamethanereformerinthespecialcaseoftheadditionor subtractionofachemicallyinertsubstance.Seewww.crtech.comandtheSINDA/FLUINTUsersManualforfurther details. 11 http://www.crtech.com/EQfluids.html
10

mixturewastested,theresultingtemperaturesinadiabaticcasesmatchedverywellagainsttheAspen PlusanalysisandfullreactingflowmixtureSINDA/FLUINTanalysispresentedabove. Asafirstapproximation,iftheexcesssteamcouldbeassumedtobeindependentoftherestofthe mixture, CH4+3H2OE+2H2O (equivalentreaction,excesssteam:SteamX=3)

thentheSteamX=3steadystatecasepresentedinapriorsectioncouldberepeatedwiththe equilibriumfluidapproach,yieldingsimilar(butnotcompletelyequivalent)results:

Ifthemolarratioofsteamtomethaneweretoremainat3:1,amoreaccurateapproachwouldbeto createanewequilibriumfluidEforthatscenariousinganotherCEArunandFPROPconversion(whichis atriviallyeasyprocess): CH4+3H2OE (equivalentreaction,SteamX=3,newequilibriumfluid)

Usinganequilibriumfluidapproachreducesthenumberofspeciestrackedfrom5to3,andalso eliminatestheextremesensitivityofthereactionratestotemperaturebyassumingtheyreinfinitely large.Theresultisasignificantincreaseincomputationalspeed,andmorerobustconvergencethatis muchlesssensitivetocoarselyguessedinitialconditions. However,theabilitytoresolvetheinternaldetailsoftheequilibriumfluidarelostasacompromise.For example,onecannolongerplotthefractionofhydrogensincetheactualcurrentamountofhydrogenis hiddenwithinthechemicalcontrolvolumethattheequilibriumfluidrepresents.Toovercomethis limitation,aseparateCEAruncouldbemadeusingtheSINDA/FLUINTpredictedtemperaturesand pressurestocalculatethefractionalconstituentsoftheequilibriumfluidatoneormorepoints.12 Whenusedwithappropriatecautions,validatingassumptionsasneeded,theequilibriumfluidmethod canbeapowerfulcompanionapproachtoperformpreliminarysizingandsensitivityanalyses,for example.Ifkineticratesarenotknown,itmightbetheonlyapproachavailableforfirstorder estimationsandbracketinganalyses.
FutureplanscallfortheinclusionofallCEAcapabilitieswithinSINDA/FLUINT,whichwouldeliminatethis additionalpostsimulationstep.
12

SideNote:Carbon(coke)Formation
Atonebarpressure,withequalmolarinputsofmethaneandsteam(stoichiometricconditions),CEA predictsthefollowingmolefractionsversustemperature(indegreesC).

Asisevidencedbytheaboveequilibrium(Gibbsfreeenergyminimization)analysis,thefractionof carbon(coke,graphite)peaksatabout600C,atwhichpointtherearemoremolesofcarboninthe mixturethaneitherCOorCO2.Whilethepresenceofcarbonhasbeenneglectedinthisdemonstration case,itclearlymustbeincludedforamorecompletetreatment.Therefore,thissectionprovidesbrief notesonhowsuchamoredetailedmodelcouldbeconstructed. Toincludecarboninthemethanereformingmodel,anotherspeciesmustbeintroduced:onethatdoes notcontributetothegaspressure.EventhoughtherearenosolidspeciesperseinSINDA/FLUINT,a 9000seriesnonvolatileliquidisanadequatesubstitute,withfakeviscosityandsurfacetensionvaluesas neededtocomplywithinputrequirements.Bydefault,thisfluidwillbeassumedtomixhomogeneously withtheremainingspecies. Threemorechemicalreactionswouldneedtobeincluded: CH4C+2H2 2COC+CO2 CO+H2C+H2O (reaction3) (reaction4) (reaction5)

Equations2530ofthereferencedpaper(Shuyan,et.al.)providetherelevantequilibriumKconstants andpreexponentialktermsforthesereactions.

Acknowledgments
TheassistanceofJohnPersichettiofColoradoSchoolofMinesindevelopingandvalidatingthismodelis gratefullynoted.