Review for Isothermal Reactor Design

Objectives
Define (refresh) common terminologies
eg. Conversion, concentration, etc.
Quick review for design of isothermal and ideal reactors
Batch reactor, continuous-stirred tank reactor (CSTR), plug flow
reactor (PFR), and packed bed reactor (PBR)
Outline
Reaction equilibrium and equilibrium conversion
Conversion, concentration, and stoichiometry
Mole balance and reactor design equations
Algorithm for reactor design
Examples
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 Interdisciplinary Lecture

ForReactionEngineering,weneedtocombine
1. ReactionKinetic
2. MassTransfer
3. HeatTransfer
4. FluidMechanics(velocityprofile,residencetime,pressure)
5. Thermodynamics(Finalrxnrate)
6. Numerical

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 Reaction Equilibrium
Definition
Atcertainrxn.conditions,thefinaldestination(orstate)a
reactioncanreach.
BeforeEquilibrium,thereactionresults(inkineticregion)changeswiththecontact
(residence)time.
Closedsystem
Residencetime=Reactiontime

Flowsystem
V=reactorvolume
v0 =volumetricflowrateatinlet
Residencetime, =V/v0
Spacevelocity=v0/V
ForPlugFlowReactor(PFR):
dFA d(FA/v0)
rA = rA =
dV d 3
(looksliketobesteady) (becomesdynamic)
 Equilibrium Conversion
ForReaction,

aA+bBcC+dDatequilibrium,

Changeoftotalfreeenergy,dG=0
G G G G
dG=(dN
NC C +dN
ND D)+(dN
NA A +dN
NB B)=GCdNC +GDdND +GAdNA +GBdNB

whereGA,GB,GC,GD:partialmolarfreeenergy
DefineextentofReaction,:
N -N
A0 A N -N
B0 B N -N
C C0 ND-ND0
====
a b c d
NA =NA0 a,NB =NB0 b,NC =NC0 +c,ND =ND0 +d
dNA = ad,dNB = bd,dNC =cd,dND =dd
However,
Gj Gj0 =RTlnaj
(whereGj0 =freeenergyatstandardstate,aj =activityofcompoundj)

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Therefore,
dG=[(GC0 +RTlnaC)c+(GD0 +RTlnaD)d (GA0 +RTlnaA)a (GB0 +RTlnaB)b]d =0

AndifwedefineGR0 =cGC0 +dGD0 aGA0 bGB0

GR0 +RT(clnaC +dlnaD alnaA blnaB)=0
GR 0 aC aD
c d
=ln=lnK
RT aAa aBb
whereKisequilibriumconstant

Standardstate:
Gasphase:idealgasatP=1bar(1.023atm)
Liquidphase:eitherthepurematerialoritinasolutionatconcentrationofunity

Foridealliquidsolution,aj =Cj
Foridealgas,aj =Pj (samevaluewhenmeasuringpressureintheunitofatm)

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 How to Obtain K(T)
SinceGR0 =HR0 TSR0,
GR0 HR0 SR0
lnK==+
RT RT R
dlnK HR0
=(vantHoffEq.)
dT RT2
HR0
lnK=(1/R)dT+I
T2

However,HR0 = Cp0 dT+J (whereCp = +T+ T2)

HR0 =T+(/2)T2 + (/3) T3 +J.(1)

lnK=(/R)lnT+(/2R)T+ (/6R)T2 (J/RT)+I

GR0=RTlnK=J (T)lnT (/2)T2 (/6)T3 RTI.(2)

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where,, ,HR0 and GR0 at25oCcanbeobtainedfromthermodynamicdata,
from(1)&(2)tosolveIandJat25oC,
HR0 and GR0 canbecalculatedatanygivenTemp.
K=exp(GR0/RT)canbecalculatedatanygivenTemp.

Forgasphaserxn.(ideal):aA+bBcC+dD

K=exp(GR0/RT)
=(PCcPDd/PAaPBb)
=(RT)(c+dab)(CCcCDd/CAaCBb)
KC (CCcCDd/CAaCBb)=K(RT)(a+bcd)

Equilibrium conversion
Equilibriumconstant=fn(conc.)
Concentration=fn(conversion)

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 Conversion and Concentration

ForReaction,
aA+bBcC+dD
ConversionofA:
forclosedsystembasedonmoleofA,NA0,atthebeginningofreaction(t=0),
NA0 NA
att=t,xA =,NA =NA0(1xA)
NA0
ForflowsystembasedonmoleflowrateofA,FA0,atreactorinlet,
FA0 FA
xA =,FA =FA0(1xA)
FA0

Concentration:
inclosedsystem,CA =NA/V(moleofAinaunitvolume)
inflowsystem,CA =FA/v(v=totalvolumetricflowrate)

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 Concentration vs. Conversion
For a single rxn., how to correlate concentration with conversion?
(i) For a closed system, eg. batch reactor, V = const.
N A N A0 (1 x A )
CA C A0 (1 x A )
V V
b b
N B 0 N A 0 x A N A 0 ( B x A ) N B0
N a a b
CB B C A 0 ( B x A ) B
V V V a N A0
i i
N I 0 N A 0 x A N A 0 ( I x A ) NI0
NI a a i
CI C A 0 ( I x A ) I
V V V a N A0
c d
CCe C De
With given initial condition, xAe can be solved from the equli. eq., i.e. K C a b
C AeC Be

(ii) For a flow system, if it is isotherm, isobar and a equimolar rxn.(for gas phase
rxn.), total flow volumetric flow rate remains constant throughout the system,
i.e. v = v0 at the inlet. i
F F (1 x A ) FA0 ( I xA )
a i
C A A A0 C A0 (1 x A ) CI C A 0 ( I xA )
v v v a
xAe can be estimated with given inlet condition 9
(iii) For an Ideal gas system, v v P0 FT T .
0
P FT 0 T0
From stiochoimetric table,
FT c d b a , where y = F /F
1 y A0 x A ( ) A0 A0 T0
FT 0 a
For equilibrium conversion x = xAe,
c d
FC 0 FA0 x Ae FD 0 FA0 x Ae
c d ( a )c ( a )d
CCe C De v v
KC a b
C AeC Be b
FB 0 FA0 x Ae
F FA0 x Ae a a
( A0 ) ( )b
v v
Numerical method is required for most cases.

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Expressing Concentration as
a Function of Conversion

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Concentration in a Gas Flow System

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 Thermodynamics vs. Kinetic

GR
Reactants
GR0
Products

If GR0 <0,K=exp( GR0 /RT)maybealargenumber,rxn.isfavoredforproducingthe

productsfromThermodynamicpointofview.
However,thereisaactivationenergyfromKineticpointofview,

GR H R S R S R H R
i.e.rateconstant, k exp( ) exp( ) exp( ) exp( )
RT RT R R RT
E
A exp( )
RT
whereA:Arrheniusenergy,E:activationenergy

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 Reaction Rate
Definition
Change of mole of reactants or products due to reaction
per unit time per unit size of the reaction system
Unit Size
1. Unit reaction volume: for homogeneous reaction
2. If reaction occurs only on the surface of the catalyst (solid)
(1) unit catalyst surface
(2) unit catalyst weight (if surface area per weight is constant)
(3) unit catalyst volume (if surface area per volume is constant)
3. Unit interface area: two phase reaction occurs only at interface

Rxn.Rate=fn(Temp.,Conc.)
eg.rA =kCAaCBb
Whereconc.=moleofreactantsorproducts(availablefortherxn.)per
unitreactorvolume
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* Self review for rate law (chap.3) and analysis of rate data (chap.5)
Mole Balance

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 Design Equations 1
DesignEquationsforfourcommomreactorsderivedfrommole
balance:

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 Design Equations 2
Intermsoftheconversion,thereactordesignequationsbecome

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18
Solution Algorithm 1. Conversion

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~ Differential form of Ergun Eg. for packed bed
(p.180 on Fogler 4th ed.)

* Analytical soln. of Ergun eq.

- for = 0 or x << 1,
and isothermal (T = T0)
dy

dW 2y
P
I.C. : at W 0, y 1
P0
P
y (1 W )0.5
P0 20
Solution Algorithm 2. Not conversion

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 IsothermalIdealReactor 1.IdealBatch

aA+bBcC+dD

1 dN A

From mole balance, Ar
V dt
i NI0

From stiochoimetric table, N I N A0 ( I x A ) , where I
a N A0
P N T
For ideal gas, V V0 0 T
P N T 0 T0
c d a b
NT 0 N A0 x A
NT a
If T = T0, P = P0, V V0 V0
NT 0 NT 0

then Ci = (Ni / V) can be expressed in terms of NA or xA

* therefore, in ideal batch reactor, we can have only one variable, NA (or xA).
c d a b N A0
Define A , y A0
a NT 0
N N A0 (1 x A ) (1 x A )
CA A C A0 C A0 fn( x A )
V V0 (1 A y A0 x A ) (1 A y A0 x A )
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If rA kC n1 n2
A CB ,

1 dN A
then rA
V dt
dx A
kC An1 C Bn2 C A0 f1 ( x A )
dt
dx A
k[C A0 f 2 ( x A )] [C B 0 f 3 ( x A )] C A0 f1 ( x A )
n1 n2

dt
n1 1 n2 [ f 2 ( x A )] [ f 3 ( x A )]
n1 n2
dx A
kC A0 C B 0
f1 ( x A ) dt
dx A
kC An101C Bn20 f ( x A )
dt
I.C.:att=0,xA =xA0,Ci =Ci0

Scaleup:thesameconversionwillbereachedatthesametimeaslongastheinitial
conditionsandreactionconditionarethesameevenforreactorswithdifferentsize

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 IsothermalIdealReactor 2.IdealCSTRatS.S.

{FA,FB,FC,FD, v} From mole balance,

FA0 FA
rA kC An1 C Bn2
V
FA0 x A C A0 v0 x A
kC An1 C Bn2
V V
{FA0,FB0,FC0,FD0, vo}
C A0 x A
or {CA0,CB0,CC0,CD0} k[C A0 f1 ( x A )]n1 [C B 0 f 2 ( x A )]n2

xA
kC An101C Bn20 f ( x A )

Scaleup:thesameconversionwillbereachedatthesameresidencetimeas
longastheinletconditionsandreactionconditionarethesameevenfor
reactorswithdifferentsize

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 IsothermalIdealReactor 3.PFR
dFA
From mole balance, rA , B.C.: at V = 0, FA = FA0
dV
Since FA = FA0(1-xA), FA = CAv, FA0 = CA0V0
dx A
thus rA FA0 kC An1 C Bn2 kC An10C Bn20 f1 ( x A )
dV
dx A
kC An101C Bn20 f1 ( x A )
d
Scaleup:thesameconversionwillbereachedattheresidencetimeaslongasthe
inletconditionsandreactionconditionarethesameevenforreactorswithdifferent
size
In order to satisfy 1 = 2, we should choose V2 to satisfy (V1/v01) = (V2/v02)

* Considering the backmixing, CSTR and PFR represents two extreme situation
Partial backmixing: PFR with recycle or CSTR in series
PFR can be considered as infinite CSTRs in series
dC
In reality, FA C Av DA AC ( A )
convection dz
Diffusion (=0, in PFR, since v predominates FA)
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Example 1

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27
d) In series:
(i) CSTR + PFR
V (rA1 ) 200 0.07 12 (1 x1CSTR ) 2 x2 PFR dx 800
x1CSTR
FA0

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x1CSTR (1 x) 2 0.007 0 dV
x12CSTR 2.71x1CSTR 1 0 x2 PFR 0.865
x1CSTR 0.441
(ii) PFR + CSTR at 300K
x1PFR = 0.85
V (rA 2 ) 200 0.07 12 (1 x2CSTR ) 2
( x2CSTR x1PFR )
FA0 10
x22CSTR 2.71x2CSTR 1.61 0
x2CSTR 0.880

In parallel:
xCSTR = 0.554, xPFR = 0.918

10 (1 xFinal ) 5 (1 xCSTR ) 5 (1 xPFR )

xCSTR xPFR
xFinal 0.736
2
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 Example 2

CH3CH2OH + CH3COOH CH3COOCH2CH3 + H2O

A + B C + D

-rA = kCA = kCA0 (1-xA)(P/P0)

k = 1.2 (dm3/g-cat/min)
FT0 = 10 (mol/min)
FA0 = FB0 = 5 (mol/min)
P0 = 10 (atm)
T = 118 oC
= 0.01 (g-1) 29
 dx kC
A0 (1 0.01W ) 0.5 dw
(1 x) FA0
kC A0 100
[ln(1 x)] xif [ (1 0.01W )1.5 ] Wif
x W

FA0 1.5
0.5 10
1.2
(1 0.9) 0.082 391 100 [(1 0.01W )1.5 1]
ln 0.9
(1 0) 5 1.5
W0.9 81.87 g
W0.05 1.38 g , W0.85 61.41g

1.38 g
81.87 g

20.46 g 30
Example 3

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Combine (E4-9.1) and (E4-9.3)

(E4-9.1)

(E4-9.3)

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Reaction Equilibrium
Substituting Kc = 1.2, CT0 = 0.1, FBe = 2(FA0-FAe)

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