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adsorption

adsorption

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Published by Greg'g Osas's Ogie
prediction of break through curve
prediction of break through curve

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Published by: Greg'g Osas's Ogie on Jul 18, 2012
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Clmnk'"E"~","mw
S"<II"Vol.l!.No.2,
pp.
.11-'-)42.
1\1111
Prinlw
inGreatBnlain
roJ9--
!jQ9/8J/ll1lll15-1J8S(lJOO/f!
©
1
lSJ
Pergar-onPre"Ud.
PREDICTIONOFBREAKTHROUGHCURVESFROMFIXED-BEDADSORBERSWITHFREUNDLICH-TYPEMULTISOLUTEISOTHERM
C.SHEINDORF*andM.REBHUNDivisionof
Environmenial
EngineeringandWalerResourcesandM.SHEINTUCHDepartmentofChemicalEngineering,Technion,IsraelInstituteofTechnology,
Haifa32000,
Israel
(Received
8
Stop/ember
1981;
accepted
2S
Iune1982)
Abstract-Anovel
Freundlich-type
multisohneadsorptionisotherm,recentlyproposedbytheauthors,isin-corporatedinto
a
modeloffixed-bedadsorbertoadequatelydescribe
the
breakthroughcurvesoftwoandthreecompetingorganicmicropollutsnts.Thecurvesareapproximatedbytheconstantpatternasymptoticsolution.Batchkineticstudies,employedtodetermineapparentdiffusivities,revealedthatalthoughsurfacediffusionisnotnegligibleaporediffusionmodelissatisfactoryfordescribingtheadsorptioninmostoftheconcentrationrange.Severalsurprisingfeatures,likeanoscillatoryoutputoranundershootbelowthefeedconcentrationwereobservedinbi-andtrisolutesystemsandtheirreflectiononthemodelisdiscussed.
INTRODUCTION
Adsorptionoforganicmicropollutantsonactivatedcar-bonisnowadaysanintegralpartofmostadvancedwaterandwastewaterpurificationsystems.Areliabledesignofactivatedcarbonadsorptionplantsrequireseitherextensivepilot-plantstudiesortheconstructionofasatisfactorymodeltorpredictionofthebreakthroughcurves-thetimedependenceofconcentrationsineffluent.Suchamodelshouldincorporateinformationonequilibriumpropertiesofthesystemandonthekineticsof
diffusion
ofthesolutesintotheporouscarbonpar-ticle.Inamulticomponent(multi-solute)system,theac-curacyoftheadsorptionequilibriummode!willbeofgreatsignificanceinthesimulationofbreakthroughcur-veswhen
adsorption
competitionbetweentheadsorbatesisstrongandwhenoneoralltheadsorbatesarecharac-terizedbyafavorableisotherm.Thatisusuallythe
situation
inwastewateradsorptiononactivatedcarbon.ThemulticomponentcompetitiveLangmuirisotherm,whichiscommonlyusedtodescribeadsorptiondatainsuchsystems,can
be
appliedwhenallthecomponentsobeyindividuallytheLangmuirisotherm.Inmanysys-tems,however,theadsorptionisothermofsinglecom-ponentsisoftheFreundlichtypeandtheapplicationtomulticomponentadsorptionisnotstraightforward.SomeresearchershavefittedthemonocomponentFreundlichisothermintoaLangmuirtypebydividingtheequilibriumdataintoseveralsec-tionssothateachsectioncanbecharacterizedbyasingleadsorptioncoefficient.ThesemultisectionLang-muirisothermswerethenincorporatedintothemulti-•Authortowhomcorrespondenceshouldbeaddressed.componentadsorptionmodel.ThisprocedurerequiresthedeterminationandutilizationofalargenumberofparameterswhichintummayintroduceadegreeofinaccuracyinthemulticomponentadsorptionmodeLRecently,anovelFreundlich-typemulticomponentadsorptionisothermwasproposedbytheauthorsll]forsystemswherethesingle-componentisothermsareoftheFreundlich-type(eqn
I).
Theadsorptionofcomponenl
j
inthemixtureisgivenby
(2)
where
K;
and
n;
aretheparametersofthemonocom-ponentsystems(eqn
I),
andthecompetitioncoefficients
(a;;)
whichdescribetheinhibitionbycomponent
i
otheadsorptionof
j
can
be
determinedfromthermodynamicdata,ormorelikely,fromequilibriumdataofbicom-ponentsystems.Theassumptionsincorporatedinthederivation
111
arethat:(a)anexponentialdistributionofadsorptionenergiesofsitesexistsfortheadsorptionofeachcomponentand,(b)thefractionofsiteshavingadsorptionenergy
Q
coveredbycomponent
j
isgivenbytheLangmuirisotherm
(I)
(3)
Undertheseassumptionseqn(2)isobtainedwith
O;j
=
b();lb
o;,
thus
0;;'"
I
and
O;joji""
1.
Theproposedisothermwasshowntorepresentsuccessfullyequilibriumdataof
organic
bicomponentjl]andtricomponentadsorption[2]fromaqueoussolutionsontoactivatedcarbon.Inthelattercasecompetitioncoefficientsfrombicomponentsystemwereemployed
10
describetheadsorptioninthetricomponentsystem.Thepossibilityofincorporationofdatafroma
335
 
336
C.
SKEINDORF
ilof.
bicomponentsystemtoamorecomplexsystemisoneoftheadvantagesoftheproposedisotherm.Thenovelisothermissuperiortootherempiricallyproposediso-thermsbecauseitrequiresfewerparametersandhenceshorterexperimentation.Thus,onlyoneadditionalparametershouldbedeterminedexperimentallytodes-cribetheproposedisotherminabisolutesystem
ql'"
K,CdC,
+
0
12
C,)"I-1
q,""
K,C,(C,
+
a,JC0"'-'
(3)
andtwoadditionalparametersarerequiredforthetrisoluteisothermsince
a110'3a31'"
1.
Themaindisadvantageoftheproposedisothermistheneedforexperimentaldeterminationofthecompetitioncoefficients.FritzandSchlunder(3]madeextensiveuseoftheideal-adsorbedsolutiontheoryforthepredictionofmultisoluteadsorptionequilibriafromsinglesolutedata.Theyobserved,however,thatdeviationfromexperimentalresultsmaybesignificantwhenbothcom-petitioncoefficients
(ai"
a,d
arelarge.Thesubjectoffixed-bedadsorbentmodelingwasre-viewedbyWeberandChakravorti[4]forthecaseofsingleadsorbatesystems.Theymadethedistinction
be-
tweenahomogeneous(solid)diffusionmodel,wherediffusionisassumedtotakeplaceintheadsorbedstate,andaporediffusionmodelandshowedthatastheisothermbecomesfavorable(concave)thebreakthroughcurvebecomesincreasinglysharpandthecurvebasedontheformermodelisdelayedincomparisonwiththatbasedonthelatter.Fritz,MarkandSchliinder[5]haveconductedalargenumberofexperimentsofbatchandfixed-bedadsorp-tionofdissolvedorganicsontoactivatedcarbonandfoundthattheapparentdiffusivitydecreaseswithin-creasinginitialsoluteconcentration.Theapparentdiffusivity,whichwasestimatedbycomparisonofexperimentalandsimulateddataofbatchstudiesatonetimewhere
q
is2/3ofitsvalueinequilibrium,wasfoundtobelargerthantheeffectiveporediffusivitygivenby
16]
Theseobservationsledtheinvestigatorstoconcludethatsurfacediffusionisthedominanttransportmechanismatlowsoluteconcentrations.Comparisonofexperimentalandsimulatedcurvesofadsorptionfrombisolutesys-tems,employingsingle-solutediffusivities,suggeststhat:theheterogeneousdiffusionmodel,accountingforporeandsoliddiffusion,isslightlybetterthanthehomo-geneousmodel.inthisworkthesignificanceofintraparticlesurfacediffusionisassessedbycomparisonoftheporediffusionmodelandtheheterogeneousmodelpredictionswithadsorptionkineticstudiesofsinglesolute.Thesinglesolutediffusivitiesandtheproposednovelisothermsareincorporatedintoafixed-bedmodelinordertostudyitsabilitytopredictthebreakthroughcurvesobtainedexperimentallyinsingleandbisolutesystems.Finally,severalsurprisingdynamicobservations,likeanoscil-latorybreakthroughcurve,aredescribed,andtheirreflectionsuponthemathematicalmodelarediscussed.
TBIEXPERIMENTALPROCEDURE
Granularactivatedcarbon,CalgonFiltrasorb400,
(pp'"
O.707/f
p'"
0.664)whichwasusedastheadsorbentwassievedintoanarrowrangeofparticlesizes(0.055-0.065cmindia.),beforewashingitwithdistilledwatertoremoveimpuritiesandcarbonpowderanddryingitat10Cfor24he.Stocksolutionsoftheadsorbatewerepreparedwithanalyticalgradephenol,parabromophenolandsodiumbenzensulfonateindistilledwater.Theadsorptionkineticswasstudiedina10I.solutiontowhichtbeactivatedcarbonwaschargedat
t'"
0andwaskeptinsuspensionbymeansofastirrerrotatingat1400rpm.15mlsamplesweretakenatknownintervals,filteredthroughafilterpaperandanalyzed.Thebreakthroughcurveswereobtainedwitha25cmlongand2.5cmindiameterfixedbedof0.06cmcarbonparticle(40
gr
ofadsorbent),towhichthesolutionwasfedatarateof4.021./hr(linearvelocitY-O.227cm/s).The'bedwassupportedbyglasswoolinsidea100cmlongglasscolumn.Theoutletstreamwassampledautomaticallyatconstantintervals.ThesoluteconcentrationsweredeterminedbyaUVspectrophotometer(BaushandLomb710UV).Thead-sorbancevaluesofthemulticomponentsolutionweremeasuredatthewavelengthcorrespondingtoeachcomponent,andthecompositionwasdeterminedbysimultaneoussolutionoftheBeer-Lambertequations.
(4)
ADSORPTIONEQUlLlBRL4.ANDKINETICS
Theproposedisotherm(eqn2)wassuccessfullyemployedtodescribetheadsorptionequilibriumofphenol(P),parabromophenol(PBP)andbenzensulfonate(BS)onactivatedcarbonfromtherespectivebi-andtrisoluteaqueoussolutions[2],Thesinglesoluteiso-thermsareofthefavorabletype(small
n;,
Figs.1and2),andtheadsorptioncapacityfollowsthesameorder(PBP
>
P
>
BS)asthatoftheinhibitioneffectexertedbyonecomponentontheadsorptionoftheother.Thus,BSadsoprtionissignificantlyinhibitedinthepresenceofP(Fig.1)orPBPandtheisothermbecomeslinearatlargeconstantinhibitorconcentrations(large
a;j,IajjC
J'"
const.ineqn2).PhenoladsorptionismildlyinhibitedbyBS(Fig.2)andstronglyinhibitedbyPBP,andPBPadsorptionismildlydecreasedinthepresenceofPandalmostunaffectedbythepresenceofBS(small
ail)'
Theaimoftheinvestigationintoadsorptionkineticswas(a)todeterminetheapparentdiffusivitiesand
(b)
toassesstheimportanceofintraparticlesurfacediffusionforthedescriptionoftheadsorptionkinetics.Surfacediffusionisexpectedtobesignificantintheadsorptionofstronglyadsorbedcomponentsonadsorbentswithlargesurfacearea.Thediscriminationbetweenaporediffusionmodelandaheterogeneousdiffusionmodelmaybepossiblewithanon-linearisotherm
14],
whenamodelaccountingforporediffusiononlyisunableto
 
Predictionofbreakthroughcurvesfromfixed-bedadsorberswithFreundlich-tyPemultisoluteisotherm337
008
006
..
,.
2
8
10
6
Cp(rnglht)
Fig.2.Phenol(P)adsorptioniso
therms
a
I
constan
I
concen-tralwnsofbenzenselfonate(BS).
daryconditionsare
Fig.I.Benzensulfonate(BS)adsorptionisothermsatconstantconcentrationsof
phenol
(P).
andthebulkconcentrationisgivenby,
(7)
adequatelydescribetheexperimentalcurve.
If
thetor-
tuosity
oftheporousstructure,
Ip,
andthemoleculardiffusivitiesareknown.
the
effectiveporediffusivity
call
beapproximatedby
eqn
(4)andthesurface
diffusivity
can
be
determinedbyfittingtheexperimentaltimetraceofthesoluteconcentrationsinabatchexperiment.Adsorptionkineticsofsinglesoluteswassimulatedbysolvingthediffusionequationforasphericalisotropicparticle,accountingforporeandsurfacediffusion,cou-pledwithamassbalanceonthesoluteconcentrationinthebalch.Assuminginstantadsorptionandtheexistenceofequilibriumbetweenthesolidandporeconcentrationatanytimeandeverywhereinsidetheparticle,thediffusionequationtakestheform
(e,
+
Anc"-')~~'"
(I
+
g;
AC·-')
V1c
+
D,A(n
-1)c"-2
(ac)!
Dp
a1j
with
c'"
CIC
o;
l
=
tD
p
la
1;
A
=
(JpKC3-';
1j
=
rla.
(6)
Thesecondtermonthe
l.h.s.
ofeqn
(5)
accountsforadsorbateaccumulationintheadsorbedphase,whichexceptatlowconcentration,ismuchlargerthanthatintheliquidporevolume.Filmresistancewasfoundtobenegligibleinthebatchexperiments,andthustheboun-Equations
(5)-(8)
weresolvednumericallyusinga
20
radialincrementsfinitedifferenceschemeand
a
4thordervariablestep
Runge-Kutta
integrationprocedure,yield.ingacurveof
Cb
vs
l
foragivenvalueof
D,IDp.
Thatcurvewascomparedwiththeexperimentalcurveof
Cb
vs
I
byplotting
a
2
l(
=
Dpt)
against
the
experimentaltimewhichcorrespondstothesameconcentration,
C~.
If
aporediffusionmodelissatisfactorythensuchaplot(with
D,
=
0)
wouldyieldastraightlineofslope
Dp
aswasobtainedforphenol(Fig.
3)
andbenzensulfonate(notshown).For
parabromophenol
deviationsfromtheporediffusionmodelwereobservedatlargetimes(Fig.
4a)
andtheprocesswasrepeatedforvarious
D,ID
p
ratios,yieldingasatisfactorycorrelationwith
D,
==
10-·
o,
(Fig.4b).Theapparentdiffusiviliesaredisplayed
in
Table
I
alongwiththemolecular
diffusivities
thatWereestimatedfrom
(5)
(9)
Table
I.
Diffusivities
of
tilethreecomponents
(X
10-"cm1/sec)
DilfusivilY
PPBPBS
Apparent
pore
(D,~
0)
6.7
5.0
3.75
Apparentpore
(D,;O0)
3.2
Apparen
t
surface
0.0032Molecular
(eqn9)
8.5
7.67.16

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