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12.DIFFUSIONANDREACTIONINPOROUS
CATALYSTS
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R12.3CMassTransferinFluidizedBeds*
Therearetwotypesofmasstransportareimportantin
fluidizedbedoperations.Thefirstisthetransportbetweengas
andsolid.Insomesituationsthiscanaffecttheanalysisof
fluidizedbedbehaviorsignificantly,andinothersitmightnot
enterthecalculationsatall.Itwillbeseenthatthetreatment
ofthistypeoftransportisquitesimilartogassolidmass
transferinothertypesofoperations.
Thesecondtypeofmasstransferisuniquetofluidizedbed
operations.Itconcernsthetransferofmaterialbetweenthe
bubblesandtheclouds,andbetweenthecloudsandthe
emulsion(FiguresCD123.3,CD123.5,andCD123.6).In
almosteverytypeoffluidizedbedoperation,thereare
significantgasphaseconcentrationdifferencesbetweenthe
variouselementsofthefluidizedbed.Consequently,
calculationsinvolvingthistypeofmasstransferoccurin
almosteveryfluidizedbedanalysis.

GasSolidMassTransfer
Inthebubblephaseofafluidizedbed,thesolidparticlesare
sufficientlyseparatedsothatineffectthereismasstransfer
betweenagasandsingleparticles.Themostwidelyused
correlationforthispurposeistheequationofFressling20for
masstransfertosinglespheres:

(CD12
3.25)

Therelativevelocitybetweenthesolidparticleandthegas
usedincalculatingtheReynoldsnumberwillbetakenasu0.
Intheemulsionphase,theequationwouldbeonethatapplied
tofixedbedoperationwithaporosityinthebedequaltoand
avelocityof
.TheequationrecommendedbyKuniiand
Levenspiel21is

Transport
fromgasto
single

(CD12
3.26)

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FigureCD123.5
Transferbetweenbubble,cloud,andemulsion.

Masstransfercoefficientsobtainedfromtheserelationshipsmaythenbe
combinedwithmasstransferamongthevariousphasesinthefluidized
bedtoyieldtheoverallbehaviorwithregardtothetransportofmass.
Owingtothesmallparticlesizesandhighsurfaceareapervolumeof

solidsusedinfluidizedbeds,themasstransferfromthegastothesolid
surfaceisusuallyquiterapid,andconsequently,itseldomlimitsthe
reaction.

MassTransferbetweentheFluidizedBedPhases

(CD12
3.27)

Forgasinterchangebetweenthebubbleandthecloud,Kuniiand
Levenspiel22definedthemasstransfercoefficientKbc(s1)inthe
followingmanner:

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FigureCD123.6
Sketchofflowpatterninafluidizedbedfordownflowofemulsiongas,
ue/u0,<0oru0/umf>6to11.
AdaptedfromD.KuniiandO.Levenspiel,FluidizationEngineering
(Melbourne,Fla.:RobertE.KriegerPublishingCo.,1977).

WhereCAbandCAcaretheconcentrationofAinthebubbleandcloud,

respectively(mol/dm3),andWAbcrepresentsthenumberofmolesofA
transferredfromthebubbletothecloudperunittimeperunitvolumeof
bubble(mol/dm3 s).Theconceptofbasingallmasstransfer(and
later,allreaction)onthebubblevolumeprovestosimplifythe
calculationsmarkedly.Fortheproducts(e.g.,BinA B)therateof
transferintothebubblefromthecloudisgivenbyasimilarequation:

WBcb=Kcb(CBcCBb)

(CD12
3.28)

WBcb=qbCAbqcCAc=q0(CAbCAc)

(CD12
3.29)

ThemasstransfercoefficientKbccanalsobethoughtofasanexchange

volumeqbetweenthebubbleandthecloud:

whereqbisthevolumeofgasflowingfromthebubbletothecloudper
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unittimeperunitvolumeofbubble,qcthevolumeofgasflowingfrom
thecloudtothebubbleperunittimeperunitvolumeofbubble,andq0
theexchangevolumebetweenthebubbleandcloudperunittimeperunit
volumeofbubble(i.e.,Kbcq0=qc=q).

UsingDavidson'sexpressionforgastransferbetweenthebubbleandthe
cloud,andthenbasingitonthevolumeofthebubble,Kuniiand
Levenspiel23obtainedthisequationforevaluatingKbc

(CD12
3.30)

isincm/s,dbisincm,DABisthediffusivity(cm2/s),
where
andgisthegravitationalconstant(980cm/s2).Wenotethat

Kbc=Kcb

andatypicalvalueofKbcis2s1

Similarly,theseauthorsdefinedamasstransfercoefficientforgas

interchangebetweenthecloudandtheemulsion:

(CD12
3.31)

Mass
transfer
between
bubbleand
cloud

whereWAceisthemolesofAtransferredfromthecloudtotheemulsion
perunittimeperunitvolumeofbubble.Notethateventhoughthismass
transferdoesnotinvolvethebubbledirectly,itisstillbasedonthe
bubblevolume.

UsingHigbie'spenetrationtheoryandhisanalogyformasstransferfrom
abubbletoaliquid,KuniiandLevenspiel24developedanequationfor
evaluatingKce:

Mass
transfer
between
cloudand
emulsion

(CD12
3.32)

whereubisthevelocityofthebubbleriseincm/sandtheother
symbolsareasdefinedbelowEquation(CD123.30).AtypicalvalueofK
1
ce is1s .Kce canalsobethoughtofastheexchangevolumebetween
thecloudandtheemulsion.
Withknowledgeofthemasstransfercoefficients,theamountofgas
interchangebetweenthephasesofafluidizedbedcanbecalculatedand
combinedtopredicttheoverallmasstransferbehaviororreaction
behaviorofafluidizedbedprocess.

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R12.3DReactioninaFluidizedBed

InordertousetheKuniiLevenspielmodeltopredictreactionratesina
fluidizedbedreactor,thereactionratelawfortheheterogeneous
reactionpergram(orotherfixedunit)ofsolidmustbeknown.Thenthe
reactionrateinthebubblephase,thecloud,andtheemulsionphase,all
perunitofbubblevolume,canbecalculated.Assumingthatthese

reactionratesareknown,theoverallreactionratecanbeevaluated
usingthemasstransferrelationshipspresentedintheprecedingsection.
Allthisisaccomplishedinthefollowingfashion.Weconsiderannthorder
constantvolumecatalyticreaction.Inthebubblephase

andsimilarlyintheemulsion,

whereke,kc,andkbarethespecificreactionratesintheemulsion,
cloud,andbubble,respectively.Inthelattertwoequations,thereaction
rateisalsodefinedperunitvolumeofbubble.

Ratelaws

inwhichthereactionrateisdefinedperunitvolumeofbubble.Inthe
cloud,

MoleBalanceontheBubble,Cloud,andEmulsion
Phases

Materialbalanceswillbewrittenoveranincrementalheight for
substanceAineachofthethreephases(bubble,cloud,andemulsion)
(FigureCD123.7).

FigureCD123.7
Sectionofabubblingfluidizedbed.

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BalanceontheBubblePhase

Dividingby

(CD12
3.33)

Balanceon
thebubble

TheamountofAenteringat isthebubblephasebyflow,

AsimilarexpressioncanbewrittenfortheamountofAleavinginthe
bubblephaseinflowat + :

andtakingthelimitas

yields

AbalanceonAinthebubblephaseforsteadystateoperationinsection

is

BalanceontheCloudPhase

(CD12
3.34)

Balanceon
theclouds

Inthematerialbalanceonthecloudsandwakesinsection ,itis
easiesttobasealltermsonthebubblevolume.Thematerialbalancefor
thecloudsandwakesis

BalanceontheEmulsionPhase

Thefractionofthebedintheemulsionphaseis1

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balanceforAintheemulsionresultsinthefollowingexpressionforthe
emulsionphasematerialbalanceonA:

(CD12
3.35)

Thethreematerialbalancesthusresultinthreecoupledordinary
differentialequations,withoneindependentvariable( )andthree
dependentvariables(CAb,CAc,CAe).Theseequationscanbesolved
numerically.TheKuniiLevenspielmodelsimplifiesthesestillfurtherby
assumingthatthederivativetermsonthelefthandsideofthematerial
balancesonthecloudandemulsionarenegligiblecomparedwiththe
termsontherighthandside.Usingthisassumptionandletting
t= /ub(i.e.,thetimethebubblehasspentinthebed),thethree
equationstaketheform

Balanceon
the
emulsion

(CD12
3.36)

Balance
equations

(CD12
3.37)

(CD12
3.38)
onedifferentialequationandtwoalgebraicequations.
Note

Inallequations,
representsthegrammolespersecondreactedin
theparticularphasepervolumeofbubbles.

PartitioningoftheCatalyst

Tosolvetheseequations,itisnecessarytohavevaluesofkb,kc,and

ke.Threenewparametersaredefined:

First,thespecificreactionrateofsolidcatalyst,kcatmustbeknown.It

isnormallydeterminedfromlaboratoryexperiments.Thetermkcat
representsthegrammolesreactedpervolumeofsolidcatalyst.Then

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Relatingthe
specific

reaction
rates

(CD12
3.39)

Thetermk'isthespecificreactionrateperweightofcatalyst.

Thevalueof brangesbetween0.001and0.01,with0.005beingthe
moretypicalnumber.Thevolumefractionofcatalystinthecloudsand

wakesis1
.Thevolumeofcloudandwakespervolumeofbubbleis

sotheexpressionfor cis

Thevolume
of
catalystsin
theclouds
is c

(CD12
3.40)

Itturnsoutthatthevalueof isnormallyfarfrominsignificantinthis
expressionfor candrepresentsaweaknessinthemodelbecausethere
doesnotyetexistareliablemethodfordetermining .Thetypicalvalues
of crangefrom0.3to0.4.Thevalueof ccanbequiteincorrecton

occasion,inparticular,avalueof =1.

Thevolumefractionofthesolidsintheemulsionphaseisagain1

Thevolumeofemulsionpervolumeofbubbleis

sotheexpressionfor eis

Thevolume
of
catalystsin
thecloudsis
e

(CD12
3.41)

Typicalvaluesof b, c,and eare0.005,0.2,and1.5,

respectively.Usingtheexpressionsgivenabove,thethreebalance
equationsbecome

Forreactors
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otherthan
firstorzero
orderthese

equations
mustbe
solved
numerically.

R12.3ESolutiontotheBalanceEquationsfora
FirstOrderReaction

3.42)
(CD12
3.43)
(CD12
3.44)

Ifthereactionisfirstorder,CAcandCAecanbe
eliminatedusingthetwoalgebraicequations,andthe
differentialequationcanbesolvedanalyticallyforCAbas
afunctionoft.Ananalogoussituationwouldexistifthe
reactionwerezero.Exceptforthesetwosituations,
solutionstothesetwoequationsmustbeobtained
numerically.
Forfirstorderreactionswecancombinethethree
balanceequationsintoonedifferentialequationwhichwe
canthensolvetodeterminetheconversionachievedina
fluidizedbedreactor.Inaddition,theclosedform
solutionallowsustoexaminecertainlimitingsituationsto
determinewhichoperatingparametersaremost
influentialindictatingbedperformance.Herewecan
poseandaskanumberofwhatifquestions.Toarriveat
ourfluidizedbeddesignequationforafirstorder
reaction,wesimplyexpresstheconcentrationofAinboth
theemulsionCAeandinthecloudCAcintermsofthe
bubbleconcentrationCAb.Firstweusetheemulsion
balance

tosolveforCAeintermsofCAc.RearrangingEquation
(CD123.45)forafirstorderreaction(n=1),weobtain

WenowusethisequationtosubstituteforCAeinthe
cloudbalance:

SolvingforCAcintermsofCAbgives

(CD12
3.45)

(CD12
3.46)

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(CD12
3.47)

WenowsubstituteforCAcinthebubblebalance:

Rearrangingyields

Aftersomefurtherrearrangementweobtain

(CD12
3.48)

Overall
transport
coefficient
KR
fora
firstorder
reaction.

(CD12
3.49)

(CD12
3.50)

ExpressingCAbasafunctionofX,thatis,

(CD12
3.51)

wecansubstitutetoobtain

andintegratingyields

Design
Equation

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Theheightofthebednecessarytoachievethisconversionis

h=tub

(CD12
3.52)

Thecorrespondingcatalystweightis(CD1276)

(CD12
3.53)

(CD12
3.54)

Procedure

Unfortunately,onemustuseaniterativeprocedureto
calculatethecatalystweight.Thispredicamentisa
consequenceofthefactthatbothKRandubdependonthe
bubblediameter,whichdependsonthebedheight,Equation
(CD123.52).Consequently,oneshouldchecktheestimated
averagebubblediameterusingthevalueofhcalculated
fromEquation(CD123.52).Aflowchartoutliningthis
procedureisshowninFigureCD123.8.However,either

POLYMATHorMATLABcanbeusedtoeliminatesomeof
theassumptionsusedinarrivingatFigureCD123.8.
Specifically,onecouldusetheequationforbubblesizeasa
functionofheight(i.e.,EquationCD123.15)directlyinthe
equationsforthetransportcoefficients(EquationsCD12
3.30andCD123.32)andthemuseanODEsolverrather
thanevaluatingthebubblesizeatthemidpointinthe
column.Onecouldalsocoupletheunsteadystatebalances
onthecloudandemulsionphases(EquationsCD123.34and
CD123.35)tothemolebalanceonthebubbleratherthan
neglectingthetransienttermsinthesebalances.

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FigureCD123.8
Computationalalgorithmforfluidizedbedreactordesign.
ReprintedwithpermissionfromH.S.FoglerandL.F.Brown,"Reaction
ControlandTransport,"inChemicalReactors,ACSSymposiumSeries168,
H.S.Fogler,ed.(Washington,D.C.:AmericanChemicalSociety,1981).

ExampleCD124
CatalyticOxidationofAmmonia

*ThismaterialwasdevelopedfromnotesbyDr.LeeF.BrownandH.

ScottFogler.
Backtotop

NextLimitingSituations
Fogler&Gurmen
2008UniversityofMichigan

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