FixedBedReactorforstudyingtheKineticsof

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

CH4 +2O2 CO2 +2H2O

Theglobalrateofasolidcatalyzedreactionisnormallyexpressed
as:
Molesofreactantconsumedperunittimeperunitmassofcatalyst
(orperunitvolumeofthereactorcontainingthecatalyst)
n

E
RT

r(C, T) =k(T)C =k0 e

Tr n n
[ ] Cr
T

(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

qr
V

PFRR

qr
can be
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
mT
n

qr T

k(T)C

Co

(8)

Tr
T

whereistheaxialposition,madedimensionlessbythereactorlength.The
initialconditionforEq8.istheconcentrationat=0.

C(o) =Cor

(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

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

Activation energy
without catalyst

Activation energy
with catalyst
Product
Reactant

Progress of the reaction

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)
C
rTr/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