L13-1

Review: Nonisothermal Reactor Design

Steadystate total energy balance (TEB):
dE sys
dt

i1

i1

& W
& F H H H T F X
0Q
s
A0
i0
i
i
RX
A0 A

Simplified TEB:
n T
For a SS nonisotherm 0 Q
& W
& F C dT H T F X
s
A0
i p,i
RX
A0 A
flow reactor:
i1T
i0

n
Constant (average)
&
&
0 Q Ws FA0 iCp,i T Ti0 HRX (T)FA0 X A
heat capacities :
i1

Can rearrange this equation to solve for T

n

& W
& F C T T Ho (T ) C
T T F X
0Q
s
A0
i p,i
i0
RX
R
P
R
A0 A

i1
T = reaction temp

Ti0 = initial (feed) temperature

TR= reference temp

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13-2

Review: Solve TEB for Conversion

n

& W
& F C T T Ho (T ) C
T T F X
0Q
s
A0
i p,i
i0
RX
R
P
R
A0 A

i1
n

Solve for XA:

&
& Q
FA0 iCp,i T Ti0 W
s

i1
HoRX (TR ) CP

T TR

FA0

XA

Plug in Q for the specific type of reactor

For an adiabatic reaction (Q=0) and shaft work can be neglected (S=0)
n

iCp,i T Ti0

T = reaction temp

i1
HoRX (TR ) CP

T TR

XA

Ti0 = initial (feed) temperature

TR= reference temp

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13-3

Review: Application to CSTR

Case 1: Given FA0, CA0, A, E, Cpi, HI, and XA, calculate T & V
a) Solve TEB for T at the exit (Texit = Tinside reactor)
b) Calculate k = Ae-E/RT where T was calculated in step a
c) Plug the k calculated in step b into the design equation to calculate V CSTR
Case 2: Given FA0, CA0, A, E, Cpi, HI, and V, calculate T & XA
a) Solve TEB for T as a function of XA (make a table of T vs XA using EB)
b) Solve CSTR design equation for XA as a function of T (plug in k = Ae-E/RT )
(use design eq to make a table of XA vs T)
c) Plot XA,EB vs T & XA,MB vs T on the same graph. The intersection of these 2
lines is the conditions (T and XA) that satisfies the energy & mass balance
XA,EB = conversion determined from the TEB equation
XA,MB = conversion determined using the design equation
XA,exit

XA,MB Intersection is T and XA that

XA

satisfies both equations

XA,EB

Texit

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13-4

Review: Application to a SS PFR

PFR
PFR

FA0

FA
XA

distance
Negligible shaft work (S=0) and adiabatic (Q=0)
a)
b)
c)
d)

Use TEB to construct a table of T as a function of XA

Use k = Ae-E/RT to obtain k as a function of XA
Use stoichiometry to obtain rA as a function of XA
XA
dX A
May use numerical
Calculate:
V FA0
rA X A ,T methods
X
A0

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13: Equilibrium Conversion in

Nonisothermal Reactor Design

L13-5

The highest conversion that can be achieved in reversible

reactions is the equilibrium conversion
For reversible reactions, the equilibrium conversion is
usually calculated first
The equilibrium conversion increases with increasing
temperature for endothermic reactions
The equilibrium conversion decreases with increasing
temperature for exothermic reactions

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13-6

Review of Equilibrium Kinetics

k

A
c C d D
Gas-phase reaction: aA b B
k
c

CC CD
KC: equilibrium
K
constant (capital K): C C a C b
A
B

Cproducts raised to stoichiometric coefficients

Creactants raised to stoichiometric coefficients

HoRX TR 1 1
If KC is given at a single
K C T K C T2 exp

temperature T2, & CP can

R
T2 T

be neglected then:
KP: equilibrium constant in
terms of partial pressures Pi:

KP

PCcPDd
a

PA PBb

Pi CiRT

For ideal gases, KP = KC(RT)n where n c d b a

o

H
T

H
dlnK

Temp dependence of KP is
Rx
Rx TR CP T TR
P

dT
given by vant Hoffs equation:
RT 2
RT 2
o
If CP can be K T K T exp H RX TR 1 1

P
P 2

R
neglected then:
T2 T

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13-7

Equilibrium Conversion XAe

1

endothermic

A heat

XA,e

exothermic

A
0
Example) AB
KC

B heat

T
CA0=1 CB0=0

CBe CA0 0 X Ae
X Ae

KC
CAe CA0 1 X Ae
1 X Ae

K C 1 X Ae X Ae K C X Ae K C X Ae

Rearrange to solve
in terms of XAe

K C X Ae 1 K C

KC
X Ae This equation enables us to
1 KC
express Xae as a function of T

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13-8

XAe and Temperature

X Ae

KC

1 KC

Substitute X
Ae
for KC:

HoRX TR 1 1
K C T K C T2 exp

R
T2 T

HoRX TR 1 1
K C T2 exp

R
T2 T

HoRX TR 1 1
1 K C T2 exp

R
T2 T

X Ae

HoRX TR 1 1
1
exp
1

K C T2
R
T T2

Divide numerator &

denominator by KC
1

e
eX
Changed sign

H
1
o
RX TR 1
Exothermic: H RX 0, when T exp
and X Ae

R
T T2

H
1
o
RX TR 1
Endothermic: H RX 0, when T exp
and X Ae

R
T T2

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13-9

XAe and Temperature

X Ae

Exothermic & CP =0:

HoRX TR 1 1
1
exp
1

K C T2
R
T T2

HoRX

TR

HoRX TR 1 1
0 , when T exp
T T & X Ae
R

Makes sense from Le Chateliers principle A

B heat

Exothermic rxn produces heat

increasing temp adds heat (product) & pushes rxn to left (lower conversion)
Endothermic & Cp 0:

HoRX

TR

HoRX TR 1 1
0, when T exp
& X Ae

R
T T2

Makes sense from Le Chateliers principle A heat

Heat is a reactant in an endothermic rxn

increasing temp adds reactant (heat) & pushes rxn to right (higher conversion)
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13-10

Adiabatic Equilibrium T Example

For the elementary solid-catalyzed liquid-phase reaction

CB
rA k CA
A B
K C

1. Make a plot of equilibrium conversion as a function of temperature.

2. Determine the adiabatic equilibrium temperature and conversion when
pure A is fed to the reactor at a temperature of 298 K.
HoA (298K) 40000 cal / mol
HBo (298K) 60000 cal / mol
CP 50 cal / mol K
A

CPB 50 cal / mol K

K e 100,000 at 298K

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

A B

HoA (298K) 40000 cal / mol

CP 50 cal / mol K

CP

CB
Rate law: rA k C A
K e

K e (T)

HBo (298K) 60000 cal / mol

50 cal / mol K

equilibrium
-rA = 0

C A0 Xe
CA0 1 Xe

C Ae

L13-11

K e 100000 at 298K
CBe
Ke
Xe

Ke T
1 Ke T

d lnK e
H

The Vant Hoff equation:

dT
RT 2
o
HRX T HRX
TR TTR CpdT
Cp Cp - Cp 0
B

o
HR
1 1
X
K e K e (T1)exp
-

R T1 T

Xe = f (T)

o
HRXo HB
- Ho A -20000

T1=298K

Xe only depends on thermodynamics!

Nothing to do with the energy balance!

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13-12

Reaction A B is carried out adiabatically with an inlet temp of 298 K, CPA =

50 cal/molK, & the heat of reaction = 20,000 cal/mol. The energy balance is:
n
o
&
&
Q Ws FA 0 iC%pi( T Ti0 ) FA 0 X HRX
( TR ) Cp( T TR ) 0 Rearrange

i1
0 0
n
&
& Q
FA0 iCp,i T Ti0 W
s
T
o

H
T

H
(T
)

RX
RX R
TR CPdT
XA
T T F
HoRX (TR ) C
P
R
A0

n
n
CP T T0
% TT
iC
A
pi
0
iCpi 1 Cp A
X

EB
i1
XEB i1
HRX T
HRX T
50 T 298
XEB
X From thermodynamics
KC
20000
X Ae
1 KC
From energy balance
CPA T T0
XEB
HRX T
How to increase the conversion?
T

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13-13

X A,EB

XA

Does increasing the entering temperature increase X A?

1
X Ae
Cp,A T TA0
HoRX TR 1 1

1
exp
1
HoRX (TR )

K C T2
R
T T2

Eq
for uilibr
ex ium
oth
erm curv
ic e
rxn

XA,e at Ti0,1
XA,e at Ti0,2
X A,EB

for

tic
a
b
a
adi

op

on
i
t
a
er

su
t
n
(s l a

xo
e
r
fo

xn)
r
c
mi
r
e
th

tic
a
b
a
Adi

X A,E
,
p
o

0,2
at T i

XAe

T (K)
Higher T moves XA,EB curve to the right

XA,e (Tadiabatic) decreases for an exothermic reaction

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13-14

Optimum Feed Temperature

For a reversible and exothermic reaction, the feed temperature

should be optimized to maximize the conversion
High T0: reaction reaches equilibrium fast, but XA is low

XEB

From thermodynamics
XA

0.75

T0 = 500
T0 = 600
T0 = 350

0.33
0.15
350

500

600

Low T0 would give high XA,e but the specific reaction rate k is so small that most
of the reactant passes through the reactor without reacting (never reach X A,e)
There is an optimum inlet temperature!
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

How does one increase XA for adiabatic operation

of an exothermic reaction?
L13-15

with interstage cooling!

XA,EB4

XEB

XA,EB3

final conversion

Each reactor
operates
adiabatically

XA,EB2

XA,EB1
cooling process

Cooling, C1
T0

Reactor 1

Reactor 2

C2

T
Reactor 3

C3
Reactor 4

Endothermic reactions are similar, but with heating instead of cooling

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13-16

Endothermic Reactions
The equilibrium conversion increases with increasing temperature, so
use interstage heating to increase the conversion

XEB

final conversion

heating process

Red lines are from

the energy balance,
slant backwards
because HRX >0 for
endothermic reaction
T

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13-17

Suppose pure A enters a reactor at 298K . What is the maximum XA

achievable in an adiabatic reactor? Assume S=0, and CP = 0, CP.A=60
J/molK, HRX(TR)= 20,000 J/mol, KC=10 exp[2405T-7.2]
Solve TEB for XA:
n
&
&
0 Q Ws FA0 iCp,i T Ti0 HoRX (TR ) CP T TR FA0 X A

i1
0
0
n
FA0 iCp,i T Ti0 HoRX (TR ) CP T TR FA0 X A

i1
A 1 and A is only species, solve for X A :

Cp,A T TA0
HoRX (TR ) CP T TR

X A C 0 so Cp,A T TA0 X
P
A
HoRX (TR )

Plot XEB vs T and XA,e vs T to compute the maximum XA graphically

X Ae

1
HoRX TR 1 1
1
exp
1

K C T2
R
T T2

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13-18

Suppose pure A enters a reactor at 298K . What is the maximum XA

achievable in an adiabatic reactor? Assume S=0, and CP = 0, CP.A=60
J/molK, HRX(TR)= 20,000 J/mol, KC=10 exp[2405T-7.2]
1
X Ae
Cp,A T TA0
HoRX TR 1 1
X A,EB
1
exp
1
HoRX (TR )

K C T2
R
T T2

T
200
250
298
325
350
375
400
425
450
500
550
600

XA,EB
0.294
0.144
0
-0.081
-0.156
-0.231
-0.306
-0.381
-0.456
-0.606
-0.756
-0.906

T
200
250
298
325
350
375
400
425
450
500
550
600

XAe
0.000149
0.001634
0.007612
0.014746
0.024722
0.038481
0.056318
0.078262
0.10407
0.165203
0.234315
0.305584

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

Suppose pure A enters a reactor at 298K . What is the maximum XL13-19

A
achievable in an adiabatic reactor? Assume S=0, and CP = 0, CP.A=60
J/molK, HRX(TR)= 20,000 J/mol (endothermic), KC=10 exp[2504T-7.2]
X A,EB

Cp,A T TA0

X Ae

HoRX (TR )

HoRX TR 1 1
1
exp
1

K C T2
R
T T2

XAe
Nearly 0
conversion,
not good!

E
(sla B for a
d
nts
dow iabatic
n fo
r en operati
o
doth
erm n,
ic rx
Energy balance conversion
n)
Equilibrium conversion

Tadiabatic
Tadiabatic: Outlet T if reactor had an infinite volume
XA,e at Tadiabatic is max achievable XA in adiabatic reactor
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13-20

Does increasing the inlet temperature to 600K improve the conversion of this
reaction? S=0, and CP = 0, CP.A=60 J/molK, HRX(TR)= 20,000 J/mol
(endothermic), & KC=10 exp[2504T-7.2]
1
X Ae
Cp,A T TA0
HoRX TR 1 1
X A,EB
1
exp
1
HoRX (TR )

K C T2
R
T T2

XAe
Nearly 0
conversion

EB
f
Tadiabatic or adiab
atic
ope
ratio
n (e
Energy balance
ndo
ther
mic
conversion
)T
0 =29
8K

Tadiabatic: Outlet T if reactor had an infinite volume

XA,e at Tadiabatic is max achievable XA in adiabatic reactor
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.

L13-21

Does increasing the inlet temperature to 600K improve the conversion of this
reaction? S=0, and CP = 0, CP.A=60 J/molK, HRX(TR)= 20,000 J/mol
(endothermic), & KC=10 exp[2504T-7.2]
1
X Ae
Cp,A T TA0
HoRX TR 1 1
X A,EB
1
exp
1
HoRX (TR )

K C T2
R
T T2

EB fo
r

adiab
a

tic op
erati
on T

XAe 0.2 when T0 = 600K

XAe 0
EB f o
r adia
at T0 = 298K T
batic
adiabatic

=600

Tadiabatic
oper

(T0=600K)
ation
(

endo
therm
ic) T

=298
K

Yes, higher conversion is achieved

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.