ChE471:LECTURE2B.

FallSeptember2004

2. IDEALREACTORS
Oneofthekeygoalsofchemicalreactionengineeringistoquantifytherelationshipbetweenproduction
rate,reactorsize,reactionkinetics andselected operatingconditions. Thisrequires amathematical
modelofthesystem,whichinturnrestsonapplicationofconservationlawstoawelldefinedcontrol
volumeofthereactionsystemandonuseofappropriateconstitutiveexpressionsforthereactionrates.
Theconceptsof ideal reactorsallowustoquantifyreactorperformanceasafunctionofitssizeand
selectedoperatingconditions.
Toillustrate this usefulconceptwedealherewithasingle,homogeneous phase,singlereactionat
constanttemperature.Weintroducethentheidealbatchreactor,andtwoidealcontinuousflowreactors.
Ineachcaseweapplytheconservationofspeciesmassprinciplewhichstates
(RateofAccumulation)=(RateofInput)(RateofOutput)+(RateofGeneration)

(21)

Equation(21)isappliedtoanappropriatelyselectedcontrolvolume,thelargestarbitrarilyselected
volumeofthesysteminwhichtherearenogradientsincomposition.

2.1 BatchReactor
Theidealbatchreactorisassumedtobeperfectlymixed.Thisimpliesthatatagivenmomentintime
the concentration is uniform throughout the vessel. The volume, V in the development below is
assumedequaltothevolumeofthereactionmixture.ThisisthenequaltothereactorvolumeV Rincase
ofgasphasereactionbutnotincaseofliquids(V<VR,then).ThebatchreactorcanbeanautoclaveofV
=const(Figure2.1a)andaconstantpressure,P=const)(Figure2.1b)vessel.Theformerisalmost
alwaysencounteredinpractice.
Ourgoalis:
a)

Tofindarelationshipbetweenspeciesconcentration(reactantconversion)andtimeonstream.

b)

Torelatereactorsizeandproductionrate.
1

Letusconsiderasingleirreversiblereaction A P withannthorderirreversiblerateofreaction

RA kC An

(22)

Att=0abatchofvolumeVisfilledwithfluidofconcentrationC Ao.Reactionisstarted(nAo=CAoVo).
Find how reactant conversion depends on reaction time? Also determine the production rate as a
functionofreactiontime.
Weapply(eq21)toreactantA:

0 0 (RA V)

dnA d(VCA )

dt
dt

(23)

a)V=const

b)P=const

FIGURE21: SchematicofBatchReactors
2

Inourcaseduetothefactthat j 0 ,V=constirrespectiveofthebatchreactortype,sothateq(2
j1

3)becomes

dC A
RA
dt
dC
n
A ( RA ) kC A ; t 0 C A CAo
dt

(24)
(25)

Separationofvariablesandintegrationyields:
t

CA

dt kdCCAn 1k
o
CAo
A

CA

dC
C

CA

A
n
A

(26)

1 C 1n
A
to
k 1 n

CAo

(27)

CA

1
1n
t0
C 1n
Ao C A
k(1 n )

C 1n
1n
Ao
t
1 (1 x A )

k(1 n)

(28a)

or

1
1n
1
n1 (1 x A )
k(n 1)CAo

(28b)

Onceorderofreaction,n,isspecified(asshownbelowforn=0,1,2,1.5),therelationbetweentandx A
isreadilyfound

n0
CAo x A
t
k
n 1.5;

n 1
1
1
t ln
k 1 x A
t

1
0.5k C Ao

n2

1 1
t
1
kC Ao 1 x A

(29)

1
(1 x ) 0.5 1
A

ProductionRateofProductPcanberelatedbystoichiometrytoheconsumptionrateofAas

mol
F x
FP
Ao A
s
1
TheproductionrateofPisgivenby:

FP

(moles of P processed per batch)

(reaction time shut down time per batch)

FP

C AoV x A

t ts

NOTABENE:

(210)

C AoV x A

1
1n
(1 x A ) t s
n1
k(n 1)C Ao

(211)

Equation(211)isvalidonlyforsystemsofconstantdensity.Thus,itisvalidforall
systems,gasorliquid,conductedinanautoclaveatV=const(seeFigure21a).Itis
alsovalidforgaseoussystemswithnochangeinthenumberofmoles j 0
conductedinP=const.systematT=const(Figure21b).
3

Thefirstequalityinequation(211)givesthegeneralresult,thesecondequalitypresentstheresultfor
annthorderirreversiblereactionwithrespecttoreactantA.
Tousethisequationtheshutdowntime,i.e.thetimeneededbetweenbatches,t s,mustbeknown.
ConsidernowthefollowingsecondorderreactionwithstoichiometryA=P.
mol
2
RA 0.1CA
L min

a)

FindthebatchreactorvolumeneededtoproduceFP=38(mol/min)ifreactorshutdowntimeis
60minutesandthedesiredconversionis0.95.InitialreactantconcentrationisCAo=1(molL).
Usingtherightformofequation(29)forn=2wegetthereactiontime.
t

1
1
1

1
190.0(min)

0.1 1 1 0.95 1 0.95

Then,solvingequation(211)forthevolumeweget

FP (t ts ) 1.38(190 60)

10,000L 10m 3
C Ao x A
1x0.95

b) Whatisthemaximumproductionrate,FP,achievableintheabovebatchreactorofvolumeV=10m3
ifts,T,CAoallarefixedatpreviousvalues.
Considereq(211)forproductionrateasafunctionofconversion
4

CAo V x A
10 x A
10 x A
FP

xA
xA
1 x A
10

60
6
ts
1
x
1
x

A
A
kC Ao 1 x A
2
x A (1 x A )
3 xA x A
FP 10
10
x A 6(1 x A )
6 5x A
3

Thisexpressionhasamaximumwhichwecanlocatebydifferentiation

dFP
2
0 (1 2x A )(6 5x A ) 5 (x A x A ) 0
dx A
4

6 5x A 12x A 10x 2A 5x A 5x 2A 0
6 12x A 5x 2A 0
x A1, 2

6 36 30 6 6

0.710
5
5

Clearly,thepositivesignisnotpermissibleasconversioncannotexceedunity. Weneedtocheck
whethertheanswerisamaximumoraminimum.
dFP
0 for x A 0.710
dx A
dFP
0 for x A 0.710
dx A
MaximumatxA=0.710.
FPmax

0.710 0.710 2
mol
10
84.0
6 5x0.710
min
3

Anincreaseinproductivityof

84 38
x100 121% canbeachievedattheexpenseofmoreunreactedA
38

toberecycled.
Onemustincludethecostofseparationintotherealeconomicoptimization.

2.2

ContinuousFlowReactors(SteadyState)

2.2.1 ContinuousFlowStirredTankReactor(CFSTRorCSTRorSTR)
TheCSTRisassumedperfectlymixed,whichimpliesthattherearenospatialgradientsofcomposition
throughoutthereactor. Sincethereactoroperatesatsteadystate,thisimpliesthatasinglevalueof
speciesconcentrationisfoundineachpointofthereactoratalltimesandthisisequaltothevalueinthe
outflow.Theoutflowstreamisatruerepresentativeofthereactionmixtureinthereactor.

FA FAo 1 x A

FAO
C AO

CA
V
5

FIGURE22: SchematicofaContinuousFlowStirredTankReactor(CSTR)
WhatdoestheaboveidealizationofthemixingpatterninaCSTRimply?Itpostulatesthattherateof
mixingisinstantaneoussothatthefeedloosesitsidentifyinstantlyandallthereactionmixtureisat
thecompositionoftheoutlet. Practicallythisimpliesthattherateofmixingfrommacroscopiclevel
downtoamolecularscaleisordersofmagnitudefasterthanthereactionrateandissofastinevery
pointofthevessel.
Thenthemassbalanceofeq(21)canbeappliedtothewholevolumeofthereactorrecognizingthatat
steadystatetheaccumulationtermisidenticallyzero.Again,takingasimpleexampleofanirreversible
reactionA Papplicationofeq(21)toreactantAyields:
FAoFA+((RA)V=0

(212)

MolarflowrateofunreactedAintheoutflowbydefinitionisgivenbyF A=FAo(1xA)=QCAo(1xA).
TheproductionrateofPisgivenby

FP (R A )V (R P )V

(213)

Reactorvolumeisgivenbyeq(212)

FAox A Q oC Aox A

(R A )
(R A )

(214)

Reactorspacetimeisdefinedby

V C Aox A

Q o (R A )

(215)

Usingstoichiometrywereadilydeveloptherelationbetweenproductionrate,FP,andreactorvolume,V.
Letusconsideragaintheexampleofour2ndorderreaction,A=P,withtheratebelow:
R A kC nA 0.1C A2

mol
L min

FindCSTRvolumeneededtoprocessFP=38mol/min.SupposewechooseagainxA=0.95forourexit
conversion.
Fromeq(213)weget
2

FP=0.1C Ao (1xA)2V
AndsolvingforvolumeV

FP
38
3
2
2 152,000L 152m
0.1C (1 x A )
0.1x1(1 0.95)
2
Ao

Ifweconsidereq(213)itisclearthatnowthemaximumproductionrateisobtainedwhenthereaction
rateisthehighest.Thatfornthorderreactionsisatzeroconversion.SothemaximumF PfromVCSTR=
12,000LisobtainableatxA=0.

FPmax =0.1x1x152,000=15,200mol/min.
The penalty or this enormous production rate is that the product is at zero purity. Hence, the
separationcostswouldbeenormous.TheaveragerateinaCSTRisequaltotherateatexitconditions.
( RA ) ( R A ) exit 0.1C 2Ao (1 x A )2exit 0.1x1(1 0.95) 2 2.5x10 4 (mol / L min)

2.2.2 PlugFlowReactor(PFR)
Themainassumptionsoftheplugflowreactorare: i)perfectinstantaneousmixingperpendicularto
flow,ii)nomixingindirectionofflow
Thisimpliespistonlikeflowwiththereactionrateandconcentrationthatvaryalongreactor
C AO
FAO

dV

C AO

FAo dx A R A dV

FA FAo 1 x A

FIGURE23: SchematicofaPlugFlowReactor(PFR)
Sincetherearenowcompositiongradientsinthedirectionofflow,thecontrolvolumeisadifferential
volume V towhicheq(21)isapplied.LetusagainusethemassbalanceonreactantA
7

FA

FA

V V

RA V 0

(216)

FA RA V 0
FA
lim (R A )
V 0 V
V 0
dF
A ( RA )
dV
lim

(217)

Since FA FAo (1 x A ) then dFA FAo dx A

sothat

FAo

dx A
( RA )
dV

(218)

Withinitialconditions:

V 0 xA 0

(219)

Uponseparationofvariablesin(eq218)andintegration:
V

dV FAo
o

xA

dx A
o (R A )

(220)

Forannthorderreaction(with A 0 )weget

F
V Aon
kC Ao

xA

1n
dx A
Q o (1 x A ) 1

n1
(1 x A ) n kC Ao
(n 1)

(221)

TheexpressionforthePFRspacetime

V
1

(1 x A )1n 1
n1
Qo kC Ao (n 1)

(222)

isnowidenticaltotheexpressionforreactiontime,t,inthebatchreactor.
Fortheexampleofthesecondorderreactionusedearlierweget

xA

A
dx A
FAo 1
V FAo 2

kC Ao (1 x A ) 2 kC 2Ao 1 x A o
o

F x A
FAo 1
1 Ao2
2
kCAo 1 x A kCAo 1 x A

FAo=QoCAo

V
1
xA

Q o kC Ao 1 x A

(Sameastheexpressionforreactiontime,t,inthebatchreactor)

LetusconsiderourexampleofthesecondorderreactionandfindthePFRvolumeneededtoproduceF P
=38mol/min
mol
2
( RA ) 0.1CA
L min

mol
when C Ao 1
anddesiredconversionxA=0.95.
L
Fromstoichiometryitfollowsthat

FAo x A FP

FAo

FP
xA

Substitutionintheexpressionforreactorvolume(eq(221))weget:
x A
FP

2
1 x A kCAo
(1 x A )

FP
2
kCAo x A

38
7,600L 7.6m 3
0.1x1(1 0.95)

Themaximumproductionratefromthatvolumecanbeobtainedatzeroconversion

FP kC 2Ao (1 x A )V
FPmax 0.1x1x7600 760mol / min

AveragerateinPFR RA

FAo x A FP
38
mol

5.0x10 3
V
V 7,600
min

( RA ) entrance 0.1C 2Ao 0.1 10 1

mol
L min

mol
( RA ) exit 0.1C 2Ao (1 0.95)2 2.5x10 4
L min)

Clearlythereisabigvariationinthereactionratebetweentheentranceandexitoftheplugflowreactor
(PFR).

2.3 STYSpaceTimeYield
VolumetricReactorProductivityRVP
Reactorvolumetricproductivity(RVP)isdefinedby:
RP

FP
V

(223)

Forour2ndorderreactionexampleofstoichiometryA=P,RVPforthetwocontinuousflowreactorsis:
2

CSTR RP (RP )exit ( R A ) exit kC Ao (1 x A )

PFR RP

(224a)

FP
2
kCAo
(1 x A )
V

(224b)

Forthesameexitconversion
2
(R P )PFR kC Ao
(1 x A )
1

2
(RP ) CSTR
kC Ao
(1 x A )

AtxA=0.95

(RP ) PFR
20
(RP ) CSTR
Indeed20x7,600L=152,000L
ThisiswhyhigherCSTRvolumeisneeded.
AtxA=0 ( RP ) PFR RP CSTR
Thereisnodifference!
Letusconsideranotherexampletoillustratesomeimportantpoints.

10

Ex:

2A+3B=P+Sstoichiometry

mol
rateofreaction
r 0.1C A C B2
L min

mol
C Ao 2
and
L

x A 0.95 arethefeedreactantconcentrationanddesiredconversion,respectively.

FP=10mol/ministhedesiredproductionrate
AssumefirstthatwewilloperateatstoichiometricratiosothatC Bo=3(mol/L).Thereactionoccursin
theliquidphasesothat A 0 .Findtheneededreactorvolume.

11

a)

Batch(ts=60min)
RA 0.2CAo (1 x A )(C Bo

b
CAo x A )2
a

2
3
3
2
RA 0.2CAo (1 x A ) (1 x A )
2
3
3 3
RA 0.2CAo (1 x A )
2

Reactiontimeis:
xA

0.2C 2Ao

3
2

1
g
t
2
0.2x2 a
t

xA

dx A

(1 x
o

)3

dx
1 1
1
3
(1 x)
1.8 2 (1 x )2

xA

1
1
1
1

1
2
3

3.6 (1 x A )
36 (1 0.95)

t=110.83min
1
C Ao x A V
0.95xV
FP 2

10 (mol/min)
t ts
110.83 60
V=

170.83 x10
3
1,798 L 1.8m
0.95

b) CSTR

FAo FP

fromstoichiometry
2
1
V
x
A basicdesignequation(214)
FAo R A

V
V

FAo x A
2FP
2FP

2
RA ( RA ) 0.2CA C B
FP
FP
2
2
CBo 3
3 3
3
3

0.1C
(1 x A )
0.1CAo (1 x A )
xA
Ao

2
CAo 2
10
10
1
3
3
3 4,444 (L ) 44.4m
0.1 2 9(1 0.95)
1.8 0.05

( RA ) ( R A ) exit 0.2xC 3Ao

3
(1 x A ) 3exit

12

=0.2x2x9(10.95)3=4.5x104(mol/Lmin)
c) PFR

FAo

2FP
xA

fromstoichiometry

Basicdesignequation(221)
xA

xA
dx A
V FAo
FAo
o R A
o

2FP
V
2
3 3
0.2C Ao
x
2 A
V
=

xA

dx

0.2C 3Ao (1 x)

3
(1 x )2

dx
100 xA dx

(1 x )3 18x 0.95 o (1 x )3

100 1
1
1
2

18x0.95 2 (1 x A )

50
1

3
2 1 1,167(L ) 1.17 m

10 0.95 (1 0.95)

Nowtherate,atstoichiometricfeedratio,alongthePFRasafunctionofconversionis
2

3
R A 0.2C
(1 x A ) 3 3.6(1 x A ) 3
2
3
Ao

PFRreactorvolumeasfunctionofconversionatstoichiometricfeedratiois

2FP
V
3.6x A

xA

dx
F
(1 x) 3 1.8xP A
o

xA

dx

(1 x)

Hence,theproductionratefromagivenPFRvolumeasafunctionofconversion(atstoichiometricfeed
rate)is

FPstoich

1.8x A V
3.6x A V

1
(1dxx) 3 (1 x ) 2 1
A
o

xA

HowmuchcanweincreasetheproductionratebydoublingC BotoCBo=6(mol/L),i.e.byusingBin
excess?

13

Nowtherateasafunctionofconversion(note(CBo/CAo=6/2=3=2x3/2),is:
2

2
C 3
3
R A 0.2C 1 x A Bo x A 0.2x2 3 x (1 x )(2 x A )2
2
C Ao 2
3
Ao

R A 3.6(1 x A )(2 x A )

a)

Batch
xA

dx A
2
t C Ao

( RA ) 3.6
o

xA

dx

(1 x)(2 x)

Tointegrateusepartialfractions:

A
B Cx A(2 x) 2 (B Cx)(1 x)

1 x (2 x)2
(1 x)(2 x)2
4 A 4 Ax Ax 2 B Bx Cx Cx 2 1

4A+B=1

4A3A=1

A=1

4AB+C=0

3AB0

B=3A

AC=0

C=A=1

dx

(1 x)(2 x)

B=3

dx
x3

2 dx
1 x (2 x)

xA

dx
2x
1

2 dx
2 dx
1 x (2 x)
(2 x)
o
x

1 A

l n(1 x) l n(2 x)

2 x o

l n(1 x A ) 0 l n(2 x A ) l n2

ln
t

1
1

2 x A 2

2 x A
2 xA
1
2
xA
1

l
n

2(1 x A 2(2 x A )
2(1 x A ) 2 2 x A

1 2 x A
xA
ln

1.8 2(1 x A 2(2 x A ) x

A 0.95

1
1.05
0.95
1
0.95
ln

l n10.5

1.8 2x0.05 2x1.05 1.8

2.1

t=1.055min

Batchreactorinilladvisedattheseconditionssincets>>t!

14

FPnew

1
C Ao x A V 0.95x1,798
mol
2

27.97
t ts
1.06 60
min

FP
27.97 10
100
100 179.7%
FPold
10
ByoperatingatdoublethestoichiometricrequirementofBweincrease,atsamex A,theproductionrate
ofthebatchreactorby180%.
b) CSTR

RA 3.6(1xA )(2 xA) 3.6(10.95)(2 0.95)

mol
RA 3.6x0.05x1.052 0.19845
L min

FPnew R P V

R A
0.19845
mol
V
44,494 4,410
2
2
min

FP
4,410 10
100
x100 44,000%
FPold
10
InaCSTRweincreasetheproductionrateby44,000%!
c) PFR
xA

V FAo
o

FPnew

dx
3.6(1 x)(2 x)2

Vx A

2
dx
3.6 o (1 x)( x)3

FPn ew

FPn ew

xA

1.8x AV
dx
(1 x)(2 x)3
o

xA

1.8x A V
2 x A
x A

ln
2(1 x A ) 2(2 x A )
1.8x0.95x1,167
1.8x0.95x1,167

2 0.95
0.95
1.05 0.95
ln

ln

2(1 0.95) 2(2 0.95)

0.1 2.10
15

FPn ew 1,051 mol / min

FP
1,051 10
x100
x100 10,419%
FPold
10
InaPFRover10,000%increaseinFPisobtained.
We present below these ratios of production rate obtainable at nonstoichiometric ratio of

C Bo C Ao 2 C Bo C Aostoich andatstoichiometricratioofCBo/CAo=3/2forourexamplereaction.
Thisratiois:
ForaPFR:

FP(n o nsto ich )

FP( sto ich )

1.8x A V
1
2 x A
xA

2 1
l n

(1
x
)
A
2(1 x A 2(2 x A V

2 x
x A
3.6x A
A
2 l n

2(1 x A 2(2 x A )
1
1
(1 x A )2

Specificallyfor x A 0.95 weget

FP(nonstoich)
FP(stoich)

1
1
2
199.5
0.05

105.0
1.05
0.95 l n10.5 0.4524

2 l n

2x 0.05 2x1.05

ForaCSTR

FP(non stoich )
FP(stoich)
FP(non stoich )
FP(stoich)

3.6(1 x A )(2 x A )2 (2 x A )2 (2 0.95) 2

3.6(1 x A ) 3
(1 x A )2
1 0.95)2
2

1.05

212 441
0.05

LetusnowexaminethesituationwhenthereactionjustconsideredoccursatP=const,T=constinthe
gaseousphase.Thenduetostoichiometrywehave
2B+3B=P+S
16

1 1 2 3 3

ConsiderstoichiometricfeedofreactantsatCBo/CAo=3/2.

y Ao

2
0.4 ( A ) 2
5

A y Ao

C A C Ao

( A )

1 x A
1 0.6x A

0.4
2

0.6

CBo 3
xA
CAo 2
CB CAo
1 0.6x A

2
(1 x A )3
3 (1 x A )3
RA 0.2xC
3.6
2 (1 0.6x A )3
(1 0.6x A )3
3
Ao

CSTR

FP

( RA )
V
2

2FP 2x10x (1 0.6x 0.95)3

V

3
R A
3.6(1 0.95)
10 (1 0.57)3
3
V
44,444x0.43 3,534(L)
3
1.8 0.05

Tremendousreductioninrequiredvolumecomparedtothe A =0caseoccurs!
PFR
xA

2Fp
dx
V FAo A
RA
xA
o
FP
V
1.8x A

x A 0.95

xA

(1 0.6x)3 dx
o 3.6(1 x)3

(1 0.6x)3
10
dx
3
(1 x)
1.8x0.95

0.95

1 06x)
dx
1 x

V 125.6(L)
AgainasignificantreductioninPFRreactorvolumerequirementisobserved.Why?

2.4

GraphicComparisonofPFRandCSTR
17

 V
xA

FAo CSTR ( RA ) exit

V

FAo

PFR

x Ao

dx A
RA

Thegraphicrepresentationoftheabovetwodesignequationsisrepresentedbelowforannthorder
reaction.Clearly,forfixedfeedconditionsandfeedrateandforchosendesiredconversionthevolume
oftheCSTRwillalwaysbelargerthanorequaltothePFRvolume.

1
R A

areaofbox
FA o CSTR

areaunderthecurve
FA o PFR

xA

FIGURE24: GraphicalComparisonofCSTRandPFR

18