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Fixe Bed Catalytic Reactor
Fixe Bed Catalytic Reactor
MethaneOxidationonSupportedPalladium
Objectives:
1.
Thegeneralgoalistounderstand:
a)
b)
theinfluenceofthepresenceofcatalystsonthemechanismandrateofchemicalreaction
thecatalyticmaterials,theiractivitiesandthechemicalandphysicalnatureoftheir
surfaces.
2.
Thespecificgoalsare:
a)
Tounderstandthekineticsofthecatalyzedoxidationofmethaneinagradientless
(perfectlymixed)reactorby:
b)
Determiningtherateconstant
Findingtheactivationenergy
Evaluatingtheorderofthereactionthroughexperiments
Thusobtainingtherateexpression
Toapplythechemicalengineeringconceptstocompareandinterprettheobserved
performanceofFixedBedReactorwithandwithoutbackmixing(PFTR&RR).
Theoreticalbackgrounds
TheoxidationofMethaneisenvisionedasasinglestepreaction
Pd
Tr n n
r(C, T) k(T )C k0 e [ ] Cr
T
n
(1)
Tristhereferencetemperature,takentobe250C
Howtomeasuretheglobalreactionrate[r(C,T)]?
Weneedtostartfromspeciesmassbalanceequationfor
particularreactor.
accumulation=flowinflowout+generationbyreaction
PFR
PFRR
(2)
EquationsForaGradientlessReactor(CSTRorPFRR)
Gradienlessreactor(Perfectlymixed)inwhichallphysicalrate
limitationsareneglected,anduniformtemperatureandconstant
pressure
(3)
qr Cor qrCr Vr
qr
r(C, T)
(Cor Cr )
V
CSTR
PFRR
qr
qr
canbe
V
m
qr
r(C, T)
CorX
m
(4)
PFRR
Wheremistheweightofthecatalyst
(5)
WhereX,thefractionalconversionofthereactant,isgivenby
X 1
Cr
Cor
(6)
Substitutionfromeq(1)forr(C,T)andfromeq(5)forCr
castseq(4)inthefollowingform,whichrelatesthereactant
(Methane)conversiontorateconstantandoperating
conditions
X
m n1 Tr n
Cor ( ) k0e
n
(1 X)
qr
T
E
RT
(7)
Co
AnIdealPlugFlowReactor
Thismodelcanbedescribedbythefollowing
differentialequationforthemethanematerial
balance
dC
m T
n
qr T
k( T)C
Co
(8)
Tr
T
whereistheaxialposition,madedimensionlessbythereactorlength.The
initialconditionforEq8.istheconcentrationat=0.
C(o ) Co r
(9)
Fortheconstanttemperaturecase,Eq.(8)isreadilyintegratedtogivetheconcentrationasa
functionofposition.ApplicationofEq.(9)andsubstitutionofthefractionalconversionx
(nowtheconversionat=1)fromEq.(6)leadstothefollowingequationforthereactor
conversion.
Cr
X 1
Cor
nm 1 Tr n
X 1 [1
(
) k(T)]
qr Cor T
(6)
1
n
(10)
Ifthereactionorder(n)is1/2thenthefractionalconversion
ofMethanewillbeinthefollowingform
1
2
m 1 Tr
2
X 1 [1
(
) k(T)]
2qr Cor T
11
Vent
Flow
Controller
Preheater
Reactor
Gas
Chromatograp
h
Integrator
He
O2
He
CH4
R.P.
T
Temperature
Controller
EXPERIMENTSETUP
TheExperimentalSetup
Keywords
1=rotameters
2=bubbleflowmeter
3=controlvalves
4=4wayvalve
5=massflowmeters
6=temperatureindicatorscontrols
7=thermocouples
8=recyclepump
9=preheatingzone
10=furnace
11=catalystsection
12=moisturetrop
13=gaschromatograph
ExperimentProcedure
Firstsession
Runthereactorwithzerorecycle(PFR)
Secondsession
Runthereactorwithrecycleflowabove7liters/min
Thirdsession
Runthereactorasinthesecondsessionwithdifferent
Methaneconcentration.
P.S.Keepsamefeedcompositioninthefirstandsecond
sessions
Feedgasesare:
Oxygen
Flowsatrateof(30ml/min),
Mixtureof2%(byvolume)MethaneinHelium
Flowsatdifferentrates(30,25,20,or16ml/min)
Heliumforbalance
Totalflowtothereactoris100ml/min
CATALYSTDEACTIVATIONDIAGRAM
PdSites
Al2O3
A
FreshCatalyst(highdispersion;highsurfacearea)
CinteredPd
Al2O3
B
OldCatalyst
Lowdispersion(lowactivity)
Porecintering
Al2O3
C
Oldcatalyst
Lowsurfacearea(lowactivity)
Activation energy
without catalyst
Activation energy
with catalyst
Product
Reactant
Howtoanalyzeourdata
2.
ApplythedataonEq.(6)tocalculateexperimentalconversion(x)forPFRandRPFR.
PlotxvsT(reactiontemperatures)forbothreactorsforsameinitialconcentrationof
CH4.
Toevaluatethereactionorder(usetheexperimentaldataofRPFR):
A) ConstructcurvesbyplottingxversusCor(initialconcentrationofCH4)forvarying
temperatures,seeiftheslopesoftheselinesshownegative,zeroorpositivevalues.
B)
UseEq.(5)[r(C,T)=qr/mCorx]tocalculater(C,T)(reactionrate)asafunctionof
reactiontemperatureforallinitialconcentrationsofmethane.
C)
PlotratedataversusC(i.e.,CrTr/T)forvaryingtemperaturesonlogarithmic
coordinates.AccordingtoEq.(1)thestraightlinesshouldhaveslopeequaltothe
RR
RR
reactionordernandtheinterceptequaltok(T).
T1 T
2
RRPFTR
x
x
1.
1<n<1
r
T
Cor
T5
n&k(T)
CrTr/T
3.
Usek(T)valuesandcorrespondingtemperaturestocreateanArrhenius
plot.ThekoandE/R(activationenergy)valuescanbefindfromthe
interceptandtheslopeofthestraightline.
4.
Totestthekineticmodel,Eq.(7)and,n=1/2,koandE/Rvaluescanbeusedto
calculatetheconversionxasafunctionofthereactortemperature.Plot
x(Cor/1x)1/2vsTofobservedandpredicted.Seeifalldatapointsfallonsame
line,ifsothenthemodeliscorrect.
5.
Totesttheconsequencesofvaryingtheinitialconcentrationsofmethaneon
thereactionrate,plotrversusTforvariousC
or.
RR
Lnk r
x(Cor/1x)1/2
RR
RR
Slope=E/R
Intercept=ko
Ifn=1/2
1/T
T
6.
UseEq.(11)tocalculateconversionxforPFTR.
1
m 1 Tr 2
X 1 [1
(
) k(T)]2
2qr Cor T
7.
PlotexperimentalandcalculatedconversionvaluesversusTforboth
reactors(P.S.forsameinitialfeedconcentration).
RR
PFTR
x
RR
PFTR
x
T
RR
T1 T
2
RR
1<n<1
Cor
r
T5
n&k(T)
CrTr/T
RR
1/T
RR
x(Cor/1x)1/2
Lnk
Slope=E/R
Intercept=ko
Ifn=1/2
RR
r
T
RR
PFTR
x