L13-1

Review: Nonisothermal Reactor Design

Steady–state total energy balance (TEB):
dEˆ sys n n
 0  Q  Ws  FA0  Hi0  Hi  i   HRX  T FA0 X A
dt i1 i1
“Simplified” TEB:

For a SS nonisotherm n T
0  Q  Ws  FA0   iCp,idT  HRX  T  FA0 X A
flow reactor: i1T i0

Constant (average) n
0  Q  Ws  FA0  iCp,i  T  Ti0   HRX (T)FA0 X A
heat capacities : i1
Can rearrange this equation to solve for T

n
0  Q  Ws  FA0  iCp,i  T  Ti0    H RX (TR )  C
ˆ  T  T  F X
i1
 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
0  Q  Ws  FA0  iCp,i T  Ti0    H RX (TR )  C
ˆ  T  T  F X
i1
 P R  A0 A

n
Solve for XA: FA0  iCp,i  T  Ti0   Ws  Q
 i1  XA
  H RX (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 (ẆS=0)
n
 iCp,i  T  Ti0 
i1  XA
  H RX (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, H°I, 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 VCSTR
Case 2: Given FA0, CA0, A, E, Cpi, H°I, 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 FA

XA
T

distance
Negligible shaft work (ẆS=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
d) Calculate: XA
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

kA
Gas-phase reaction: aA  b B cC  dD
k A
KC: equilibrium CCc CDd Cproducts raised to stoichiometric coefficients
K 
constant (capital K): C
CA a CBb Creactants raised to stoichiometric coefficients

If KC is given at a single  H RX  TR   1 1  
temperature T2, & CP can C  
K T  K C  T2  exp    
 R  T2 T  
be neglected then:

KP: equilibrium constant in PCc PDd

KP  Pi  CRT
i
terms of partial pressures Pi: a
PA PBb
For ideal gases, KP = KC(RT)Δn where n  c  d  b  a

Temp dependence of KP is dlnKP HRx  T  H Rx  TR   CP  T  TR 

 
given by van’t Hoff’s equation: dT RT 2
RT2
If CP can be K T  K T exp  H RX  TR   1  1  
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) A⇌B 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  KC  XAe  KC XAe  K C  X Ae 1  K C 

KC
  X Ae This equation enables us to
1  K C  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  H RX  TR   1 1  
XAe  K C  T   K C  T2  exp    
1  KC   R  T2 T  
 H RX  TR   1 1  
K C  T2  exp    
Substitute X  R  T2 T   Divide numerator &
Ae 
for KC:  H RX  TR   1 1   denominator by KC
1  K C  T2  exp    
 R  T2 T   1 X
1  e
 XAe  eX
1  H RX  TR   1 1   Changed sign
exp      1
K C  T2   R  T T2  

 H RX  TR   1 1  
Exothermic: H RX  0, when T  exp       and X Ae 
 R  T T2  
 H RX  TR   1 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
XAe 
1  H RX  TR   1 1  
exp      1
K C  T2   R  T T2  
 H RX  TR   1 1  
Exothermic & CP =0: H RX  TR   0, when T  exp   T  T    & X Ae 
 R  2  

Makes sense from Le Chatelier’s principle A B  heat

Exothermic rxn produces heat→

increasing temp adds heat (product) & pushes rxn to left (lower conversion)
 H RX  TR   1 1  
Endothermic & Cp  0: H RX  TR   0, when T  exp       & X Ae 
 R  T T2  

Makes sense from Le Chatelier’s 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.

HA (298K)  40000 cal / mol

HB (298K)  60000 cal / mol
CPA  50 cal / mol  K
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.
 L13-11
HA (298K)  40000 cal / mol HB (298K)  60000 cal / mol
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   CAe 
K Ke
 e -rA = 0

K e (T) 
CA0 Xe Ke T 
CA0 1  Xe  Xe 
1 Ke T 

d lnK e  H
The Van’t Hoff equation: 
dT RT 2
HRX  T   HRX
o
 TR   TTR CpdT
Cp  Cp - Cp  0
B A

 HR
o
 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/mol∙K, & the heat of reaction = 20,000 cal/mol. The energy balance is:
n
Q  Ws  FA 0  iC pi( T  Ti0 )  FA 0 X  HR X( TR )  Cˆ p( T  TR )  0 R earrange
i1  
n 0 0
FA0  iCp,i  T  Ti0   Ws  Q
 XA  i 1 H RX  T    H (T
RX R )  
T
TR CPdT
  H RX (TR )  C ˆ  T  T  F
 P R  A0

CP  T  T0 
n
 iCpi  T  T0 
n
 iCpi  1 Cp A X  A
 XEB  i1 i1
EB
HRX  T 
HRX  T 
From thermodynamics 50  T  298 
X  XEB 
XAe 
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 XA?
1
Cp,A  T  TA0  XAe 
XA,EB  1  H RX  TR   1 1  
H RX (TR ) exp      1
K C  T2   R  T T2  

XA XA,e at Ti0,1

XA,e at Ti0,2

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 XA,e)

There is an optimum inlet temperature!

Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.
 L13-15
How does one increase XA for adiabatic operation
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 H°RX >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 ẆS=0, and CP = 0, CP.A=60
J/molK, H°RX(TR)= 20,000 J/mol, KC=10 exp[2405T-7.2]

Solve TEB for XA:

n
0  Q  Ws  FA0  iCp,i T  Ti0    H RX (TR )  CP  T  TR   FA0 X A
i 1
 
0 0
n
 FA0  iCp,i  T  Ti0     H RX (TR )  CP  T  TR   FA0 X A
i1
 
A  1 and A is only species, solve for XA :

Cp,A  T  TA0 
  X A C  0 so  Cp,A  T  TA0   X
  H RX (TR )  CP  T  TR   P
H RX (TR )
A
 

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

1
XAe 
1  H RX  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 ẆS=0, and CP = 0, CP.A=60
J/molK, H°RX(TR)= 20,000 J/mol, KC=10 exp[2405T-7.2]
1
Cp,A  T  TA0  XAe 
XA,EB  1  H RX  TR   1 1  
H RX (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 XA L13-19
achievable in an adiabatic reactor? Assume ẆS=0, and CP = 0, CP.A=60
J/molK, H°RX(TR)= 20,000 J/mol (endothermic), KC=10 exp[2504T-7.2]
1
Cp,A  T  TA0  XAe 
XA,EB  1  H RX  TR   1 1  
H RX (TR ) exp      1
K C  T2   R  T T2  
0.4
0.2
0
200XAe 300 400 500 600
-0.2
XA

-0.4 Nearly 0
conversion,
-0.6
not good!
-0.8 Energy balance conversion
Equilibrium conversion
-1
Tadiabatic T (K)
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? ẆS=0, and CP = 0, CP.A=60 J/molK, H°RX(TR)= 20,000 J/mol
(endothermic), & KC=10 exp[2504T-7.2]
1
Cp,A  T  TA0  XAe 
XA,EB  1  H RX  TR   1 1  
H RX (TR ) exp      1
K C  T2   R  T T2  
0.4
0.2
XAe
0
200 300 400 500 600
-0.2
XA

Nearly 0
-0.4 conversion Tadiabatic
-0.6
Energy balance conversion
-0.8
Equilibrium conversion
-1
T (K)
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? ẆS=0, and CP = 0, CP.A=60 J/molK, H°RX(TR)= 20,000 J/mol
(endothermic), & KC=10 exp[2504T-7.2]
1
Cp,A  T  TA0  XAe 
XA,EB  1  H RX  TR   1 1  
H RX (TR ) exp      1
K C  T2   R  T T2  
1
0.75
0.5
0.25 XAe ≈ 0.2 when T0 = 600K
XA

0
200 300 400 500 600
-0.25 XAe ≈ 0 Tadiabatic
at T0 = 298K T (T0=600K)
-0.5 adiabatic

-0.75 Equilibrium conversion

-1
T (K)
Yes, higher conversion is achieved
Slides courtesy of Prof M L Kraft, Chemical & Biomolecular Engr Dept, University of Illinois, Urbana-Champaign.