L13-1

Review: Nonisothermal Reactor Design

Steadystate total energy balance (TEB):
dE sys n n
& F H H H T F X
& W
0Q s A0 i0 i i RX A0 A
dt i1 i1
Simplified TEB:

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

Constant (average) n
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
& F C T T Ho (T ) C
& W
0Q T T F X
s A0
i1
i p,i i0 RX R P R A0 A

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
& F C T T Ho (T ) C
& W
0Q T T F X
s A0
i1
i p,i i0 RX R P R A0 A

n
Solve for XA: FA0 iCp,i T Ti0 W &
& Q
s
i1 XA


HoRX (TR ) CP T TR FA0

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
i1 XA


HoRX (TR ) CP T TR

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.
 L13-3

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

T 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

FA0 PFR
PFR FA

XA
T

distance
Negligible shaft work (S=0) and adiabatic (Q=0)

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

b) Use k = Ae-E/RT to obtain k as a function of XA
c) Use stoichiometry to obtain rA as a function of XA
XA
d) Calculate: dX A May use numerical
V FA0
X rA X A ,T methods
A0
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L13-5

L13: Equilibrium Conversion in

Nonisothermal Reactor Design
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
Gas-phase reaction: aA b B c C d D
k A
c d Cproducts raised to stoichiometric coefficients
KC: equilibrium CC CD
K
constant (capital K): C C a C b Creactants raised to stoichiometric coefficients
A B
If KC is given at a single HoRX TR 1 1
K C T K C T2 exp
temperature T2, & CP can R T2 T
be neglected then:
KP: equilibrium constant in PCcPDd
KP Pi CiRT
terms of partial pressures Pi: PA PBb
a

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

Temp dependence of KP is dlnK P HRx T

Ho
Rx TR CP T TR
given by vant Hoffs equation: dT RT 2 RT 2
If CP can be K T K T exp H RX TR 1 1
o
P P 2
neglected then: R 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
XA,e A heat B

exothermic
A B heat
0
T
Example) AB CA0=1 CB0=0
CBe CA0 0 X Ae X Ae Rearrange to solve
KC KC
CAe CA0 1 X Ae 1 X Ae in terms of XAe

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

KC HoRX TR 1 1
X Ae K C T K C T2 exp
1 KC R T2 T
HoRX TR 1 1
K C T2 exp
R T2 T
Substitute X Divide numerator &
Ae
for KC: HoRX TR 1 1 denominator by KC
1 K C T2 exp
R T2 T 1 X
e
1 eX
X Ae
1 HoRX TR 1 1 Changed sign
exp 1
K C T2 R T T2

RX TR 1
o
Ho
1
Exothermic: H RX 0, when T exp and X Ae
R T T2
RX TR 1
o
H o
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

1
X Ae
1 HoRX TR 1 1
exp 1
K C T2 R T T2
HoRX TR 1 1
Exothermic & CP =0: HoRX TR 0 , when T exp T T & X Ae
R 2

Makes sense from Le Chateliers principle A B heat

Exothermic rxn produces heat

increasing temp adds heat (product) & pushes rxn to left (lower conversion)
HoRX TR 1 1
Endothermic & Cp 0: HoRX TR 0, when T exp & X Ae
R T T2

Makes sense from Le Chateliers principle A heat B

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
A B rA k CA
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.
 HoA (298K) 40000 cal / mol HBo (298K) 60000 cal / mol
L13-11

A B
CP 50 cal / mol K CP 50 cal / mol K K e 100000 at 298K
A B

CB equilibrium CBe
Rate law: rA k C A C Ae
K e
-rA = 0 Ke

C A0 Xe Ke T
K e (T) Xe
CA0 1 Xe 1 Ke T

d lnK e H
The Vant Hoff equation:
dT RT 2
HRX T HRX
o
TR TTR CpdT
Cp Cp - Cp 0
B A

HRo
1 1 HRXo HB
o
- Ho A -20000
K e K e (T1)exp X -

R T1 T T1=298K

Xe = f (T) 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
Q Ws FA 0 iC%pi( T Ti0 ) FA 0 X HRX
& & o
( TR ) Cp( T TR ) 0 Rearrange
i1
n 0 0
FA0 iCp,i T Ti0 W & Q
s
&
XA i 1 H RX T Ho
RX R (T )
T
TR CPdT
HoRX (TR ) C T T F
P R A0
n
iC % TT n CP T T0
pi 0 iCpi 1 Cp A X EB A
XEB i1 i1 HRX T
HRX T
50 T 298
X From thermodynamics XEB
X Ae
KC 20000
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
Does increasing the entering temperature increase X A?
1
Cp,A T TA0 X Ae
X A,EB 1 HoRX TR 1 1
HoRX (TR ) exp 1
K C T2 R T T2

Eq
for uilibr
ex ium xn)
oth c r
erm curv er mi
ic e xo th
rxn r e at T i
0,2
p fo
XA XA,e at Ti0,1 su
B
nt p, X A,E
(s l a atic
o
a b
a t i on Adi
XA,e at Ti0,2 op er
batic XAe
a
adi
for
X A,EB
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
From thermodynamics
XEB
XA

0.75

0.33 T0 = 500
T0 = 600
0.15
T0 = 350
350 500 600 T W
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 L13-15

of an exothermic reaction?
with interstage cooling!
XA,EB4
XEB

final conversion
XA,EB3 Each reactor
operates
XA,EB2 adiabatically

XA,EB1
cooling process

T
Cooling, C1 C2 C3
T0 Reactor 1 Reactor 2 Reactor 3 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
Red lines are from
the energy balance,
slant backwards
heating process 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
X A C 0 so Cp,A T TA0 X
HoRX (TR ) CP T TR P
HoRX (TR )
A

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

1
X Ae
1 HoRX TR 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
Cp,A T TA0 X Ae
X A,EB 1 HoRX TR 1 1
HoRX (TR ) exp 1
K C T2 R T T2

T XA,EB T XAe
200 0.294 200 0.000149
250 0.144 250 0.001634
298 0 298 0.007612
325 -0.081 325 0.014746
350 -0.156 350 0.024722
375 -0.231 375 0.038481
400 -0.306 400 0.056318
425 -0.381 425 0.078262
450 -0.456 450 0.10407
500 -0.606 500 0.165203
550 -0.756 550 0.234315
600 -0.906 600 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]
1
Cp,A T TA0 X Ae
X A,EB 1 HoRX TR 1 1
HoRX (TR ) exp 1
K C T2 R T T2

XAe
E
Nearly 0 (sla B for a
nts d
dow iabatic
conversion, n fo
r en operati
not good! doth o
erm n,
Energy balance conversion ic rx
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
Cp,A T TA0 X Ae
X A,EB 1 HoRX TR 1 1
HoRX (TR ) exp 1
K C T2 R T T2

XAe

Nearly 0 EB
f
conversion Tadiabatic or adiab
atic
ope
ratio
n (e
Energy balance ndo
ther
conversion mic
)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
Cp,A T TA0 X Ae
X A,EB 1 HoRX TR 1 1
HoRX (TR ) exp 1
K C T2 R T T2

EB fo
r adiab
a tic op
erati
on T
0 =600
K
XAe 0.2 when T0 = 600K

XAe 0
EB f o Tadiabatic
at T0 = 298K T r adia (T0=600K)
adiabatic batic
oper
ation
( endo
therm
ic) T
0 =298
K
Yes, higher conversion is achieved
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.