Chemical Reaction Engineering

Topic 4

Non-Isothermal, Non-Adiabatic
Reactor Design and Multiple
Steady States
(Chapter 12- Foglers Essentials)
1

Items to be covered in this Topic:

Nonisothermal Reactor Design
Develop Energy Balance equations for flow
reactors.

Enthalpy, Heat Capacity, and Heat of Reaction

and relationship between them
Heat transfer rates for CSTR and PFR/PBR
Algorithms for Non-isothermal CSTR and PFR
2

Heat added to the Reactor

Heat transfer (Q) to CSTR and PFR/PBR
(sections 8.2.8 Fogler 4th Ed)
Steady State Non-isothermal Continuous
Flow Reactors (section 8.3 Fogler 4th Ed)
Class Problem demonstrating the
application to a CSTR (sections 8.3.1
Fogler 4th Ed)
3

Heat Transfer to a CSTR

Heat transferred between coolant and reactor
(from energy balance on the coolant)

cCpc (Ta1 Ta 2 )
Q m

UA(Ta1 Ta 2 )
ln[ (T Ta1 ) /(T Ta 2 )]

8.46

Assuming CSTR temperature,T, is spatially uniform

UA

c Cpc (Ta1 T ) 1 exp
Qm
c Cpc )]

(m

8.49

For high coolant flow rates , Ta1 Ta2=Ta and the 2nd order terms
are neglected in the Taylor expansion of exp function. Therefore,

Q UA(Ta T )

8.50

Heat Transfer to a PFR/PBR

Remember, in PFR/PBR the concentration and reaction rates
vary along the reactor length. Q will likely vary too.

Total heat transferred to the reactor

A

Q U (Ta T ) dA

U a (Ta T ) dV

a = heat exchange area/volume

Heat transfer rate at a given location in a PFR

(differentiate the above)
dQ
Ua (Ta T )
dV

dQ

Ta
T

Heat transfer rate at a given location in a PBR

dQ
a
U
(Ta T )
dW
cat
5

Non-isothermal Flow Reactor

n
Q W s FA0
i 1

dE
T i Cpi dT ] FA0 X H Rxn (T ) dt
0

Now, that we have seen how Q can be described, let us reexamine the general energy balance equation
At Steady State, the energy balance equation for
a single rxn system is
8.48

Q W s H Rxn (Tref ) C p(T Tref ) FA0 X FA0 i Cpi (T T0 )

i 1

Cp

C p

dT

Tref

T Tref

Mean over Tref and T

8.28

~
Cpi

Cp

dT

T0

8.29

T T0

Mean over T0 and T

Non-isothermal Flow Reactor

Q Ws H Rxn (Tref ) Cp(T Tref ) FA0 X FA0 i Cpi (T T0 ) 8.48

i 1

Now that we have the Steady State EB equation, what next?

Lets see some application
Application-1: special case; adiabatic reactor with no shaft work
n ~

C
p
(
T

T
)
0
i i
i 1

X
H Rxn (Tref ) C p(T Tref )

8.49

XEB

Q 0
W 0

Non-isothermal Flow Reactor

Q Ws H Rxn (Tref ) Cp(T Tref ) FA0 X FA0 i Cpi (T T0 )

i 1

Application-2: CSTR with Heat Exchange; no shaft work

n
UA(Ta T )
~
H Rxn (Tref ) C p(T Tref ) X i Cpi (T T0 )
FA0
i 1

Let us see if we can apply these concepts

to solve a CSTR problem.
8

Non-isothermal Flow Reactor

Q W s

F
i 1

i0

Hi0

FH
i 1

Application-3: PFR with Heat Exchange

FA0

T0

dQ
Ua (T T )
a
dV

Ta

FAe
T

Te

V V+V

Differentiating the the Energy Balance equation with respect to V

n
n
dFi
dH i
dQ dW s

0
H i Fi
0
dV dV
dV
i 1 dV
i 1

10
Let us evaluate each term to obtain an equation in terms of dT/dV

Non-isothermal Flow Reactor

Application-3: PFR with Heat Exchange (cont.)
dQ
Ua(Ta T )
dV

dFi
(ri )
dV

i (rA )

H i (T ) H io (Tref )

dH i
dT
Cpi
dV
dV

C pidT

T Tref
T

Substituting, the differential terms into the Energy Balance Eqn

n

i 1

i 1

Ua(Ta T ) 0 0 i (rA ) H i Fi Cpi

dT
0
dV

Rearranging,
n

dT

dV

U a (Ta T ) i (rA ) H i (T )
i 1

F Cp (T )
i 1

11

Non-isothermal Flow Reactor

Application-3: PFR with Heat Exchange (cont.)
How do we solve non-isothermal PFR problems?
n

dT

dV

U a (Ta T ) i (rA ) H i (T )
i 1

F Cp (T )
i 1

dFi
i (rA )
dV

or

g( X ,T )

dX
FA0
(rA )
dV

f ( X ,T )

We MUST solve the two differential equations, g(X,T) and f(X,T),

simultaneously.

We will need Ordinary Differential Equation (ODE) solver -- MATLAB

12

Alternate forms of EB equation for PFRs

n

dT

dV

U a (Ta T ) i (rA ) H i (T )
i 1

F Cp (T )
i 1

dT U a (Ta T ) (rA ) [H Rxn (T )]

n
dV
Fi Cpi (T )
i 1

dT U a (Ta T ) (rA ) [H Rxn (T )]

n
dV
FA0 [ i Cpi (T ) X Cp]
i 1

You may note

that for
exothermic
reaction, this
term will
result in an
increase in T
13

CSTR with a cooling coil:

Bimolecular reaction example
Similar to the previous system.
However, a cooling coil is now used.
It has 40 ft2 of cooling surface and the
cooling water flow rate inside the coil is
sufficiently large that a constant coolant
temperature of 85 F can be maintained.
A typical overall heat transfer coefficient
for such a coil is 100 Btu/h ft2 F.
14

CSTR with a cooling coil (Example

12-4)
page
554
E / RT
Ae

1 Ae E / RT

Q Ws FA0 i C pi (T Ti 0 ) FA0 X H RX
(TR ) C p (T TR ) 0
i 1

n
UA(Ta T )
~

X H RX (TR ) C p (T TR ) i C pi (T Ti 0 )
FA0
i 1

~
iC pi (T Ti 0 ) UA(T Ta ) / FA0
i 1

H RX
(TR ) C p (T TR )

15

Ae E / RT
X
1 Ae E / RT

H RX
(TR ) H C (68 F ) H B (68 F ) H A (68 F )

36400 Btu / lb mol propylene oxide ( A)

C C C C
p

pC

pB

pA

7 Btu / lb mol propylene oxide ( A) F

~
~
~
~

C
i pi A pA B pB M pM
i 1

FB 0 ~
FM 0 ~
~
C pA
C pB
C pM
FA0
FA0
403.3Btu / lb mol propylene oxide ( A) F

C
i pi (T Ti 0 ) UA(T Ta ) / FA0
i 1

H RX
(TR ) C p (T TR )

V
V

0.1299h
v0 v A0 vB 0 vC 0

Ti 0 75 F
TR 68 F

Ta 85 F

UA 100 40

92.9 Btu / lb mol propylene oxide ( A) F

FA0
43.04

Solve the two equations simultaneously using Polymath and we obtain X = f (T

The conversion would be about 0.36, at a temperature of 564R.

16

Non-isothermal Flow Reactor

Q W s

F
i 1

i0

Hi0

FH
i 1

Application-3: PFR with Heat Exchange

FA0

T0

dQ
Ua (T T )
a
dV

Ta

FAe
T

Te

V V+V

Differentiating the the Energy Balance equation with respect to V

n
n
dFi
dH i
dQ dW s

0
H i Fi
0
dV dV
dV
i 1 dV
i 1

17
Let us evaluate each term to obtain an equation in terms of dT/dV

Non-isothermal Flow Reactor

Application-3: PFR with Heat Exchange (cont.)
dQ
Ua(Ta T )
dV

dFi
(ri )
dV

i (rA )

H i (T ) H io (Tref )

dH i
dT
Cpi
dV
dV

C pidT

T Tref
T

Substituting, the differential terms into the Energy Balance Eqn

n

i 1

i 1

Ua(Ta T ) 0 0 i (rA ) H i Fi Cpi

dT
0
dV

Rearranging,
n

dT

dV

U a (Ta T ) i (rA ) H i (T )
i 1

F Cp (T )
i 1

18

Non-isothermal Flow Reactor

Application-3: PFR with Heat Exchange (cont.)
How do we solve non-isothermal PFR problems?
n

dT

dV

U a (Ta T ) i (rA ) H i (T )
i 1

F Cp (T )
i 1

dFi
i (rA )
dV

or

g( X ,T )

dX
FA0
(rA )
dV

f ( X ,T )

We MUST solve the two differential equations, g(X,T) and f(X,T),

simultaneously.

We will need Ordinary Differential Equation (ODE) solver -- MATLAB

19

Alternate forms of EB equation for PFRs

n

dT

dV

U a (Ta T ) i (rA ) H i (T )
i 1

F Cp (T )
i 1

dT U a (Ta T ) (rA ) [H Rxn (T )]

n
dV
Fi Cpi (T )
i 1

dT U a (Ta T ) (rA ) [H Rxn (T )]

n
dV
FA0 [ i Cpi (T ) X Cp]
i 1

You may note

that for
exothermic
reaction, this
term will
result in an
increase in T
20

Adiabatic Operation & Equilibrium Conversion

For a reactor operating adiabatically, the maximum conversion that may
be achieved is equilibrium conversion. How can we calculate this ?
Step-1: Calculate Xe as a function of T
c/a
Ce
1
Ae

d /a
De
b/a
Be

C C
KC [
C C

Equilibrium

]
X

Step-2: Calculate XEB as a function of T

from SS Energy Balance Equation
X EB

~
i C pi (T T0 )

H Rxn (T )

The above equation is obtained by putting Q =0 and Ws=0 in the general EB

T
equation below
n
Q W s FA0 i Cpi dT ] FA0 X H Rxn (T ) 0
i 1

T0

21

Exothermic Reaction: A Closer Look at

Adiabatic Conversion

Equilibrium
Increasing the inlet
temperature results in
shifting of the EB
equation to the
RIGHT

Xe

Adiabatic Temperature

T01

T02

22

23

Exothermic Reversible Reactions

Energy balance equation

Xe

The inlet temperature

increases, the
adiabatic equilibrium
conversion decreases

Xe for inlet T01

Xe for inlet T02

T01

T02

To determine the maximum conversion that can be achieved in

an exothermic reaction carried out adiabatically:

Find the intersection of the equilibrium conversion as a

function of temperature with temperature-conversion
relationships from energy balance :
n

i 1

Ti 0

Q W s FA0 i C pidT H RX (T ) FA0 X 0

X EB

C
i pi (T T0 )
i 1

H RX (T )

24

Adiabatic equilibrium temperature example

For the elementary solid-catalyzed liquid-phase reaction

AB
Make a plot of equilibrium conversion as a function of time.
Determine the adiabatic equilibrium temperature and conversion
when pure A is fed to the reactor at a temperature of 300 K.

H A (298K ) 40000 cal / mol

H B (298K ) 60000 cal / mol
C PA 50 cal / mol K
C PB 50 cal / mol K
K e 100000 at 298K

25

AB

Rate law : rA k C A B

K e (T )

equilibrium
-rA = 0

C A0 X e
C A0 (1 X e )

C Ae

CBe
Ke

K e (T )
Xe
1 K e (T )

d (ln K e ) H

The Vant Hoff equation:

dT
RT 2
T

H RX (T ) H RX
(TR ) C p dT
TR

C p C pB C p A 0

H 1 1 H RX H B H A 20000

K e K e (T1 ) exp
R T1 T T1 298K
Only thermodynamics!
Xe = f (T) nothing to do with the energy
balance

RX

26

Now, the reaction is carried out adiabatically (energy balance)

n

X EB

~
iC pi (T T0 )
i 1

C
i 1

1 C p A

pi

H RX (T )

X EB

X EB

XEB

From thermodynamics

CPA (T T0 )
H RX (T )

50(T 300)

20000

From energy balance

How to increase the conversion?

Optimum feed temperature

27

At a very low feed

temperature,
the specific reaction rate
For a reversible and exothermic reaction:
will be so small that
virtually all of
From thermodynamics
XEB
X
the reactant will pass
through the reactor without
reacting.
0.75
There is an optimum inlet
temperature!
T = 500
0.33

T0 = 600
T0 = 350

0.15
350

500

600

Exothermic Reactions: Achieving Higher

Conversion by Inter-stage Cooling

28

29

XEB
final conversion

cooling process
(with interstage cooling)

Inter-stage cooling example

30

Following the previous example, what conversion could be achieved if two

interstage coolers were available that had the capacity to cool the exit stream
to 350 K?
Also determine the heat duty of each exchanger for a molar feed rate of A of
40 mol/s. Assume that 95% of equilibrium conversion is achieved in each
reactor. The feed temperature to the first reactor is 300 K. The coolant
temperature is 270K and it should not exceed 400K.
From previous work, we found that the adiabatic equilibrium conversion:

X e 0.41T0 300K
Temperature leaving
the first reactor
X

T1 460K

(T 300)

EB
400

cooling to 350 K

Cooling duty ?

95 % of equilibrium conversion

X 0.4

31
n

Q W s Fi 0 H i 0 Fi H i 0
i 1

i 1

Q Fi H i Fi 0 H i 0
i 1

(Energy balance in the heat exchanger)

i 1

No reaction take place

in the exchanger
Q

Fi Fi 0

F
i 1

i0

(Hi Hi0 )

Q Fi 0C pi (T2 T1 )
i 1

Q
220000
m C

94 mol / s

C pC (Tout Tin ) 18(400 270)

Q m C C pC (Tout Tin )

Q ( FAC p A FBC pB )(T2 T1 )

FA0 FA FB C p C p
A
B

being absorbed by
Q FA0C p A (T2 T1 )
the coolant stream

40 50 (350 460)
220 kcal / s

32

Th2= 460 K

Th1= 350 K

Reaction mixture

Heat Exchanger
Tc2= 400 K

Tc1= 270 K

From heat exchanger eqns :

[(T T ) (Th1 Tc1 )]
Q UA h 2 c 2
(T T )
ln h 2 c 2
(Th1 Tc1 )

Coolant

A = 31.6 m2

T : 350K and X 0.4

The condition entering the second reactor
T 430K

X EB

(T 300)
400

energy balance

X 0.6

95 % of equilibrium
conversion

following similar procedure again (page 519)

X EB 0.63

33

Endothermic reactions

The equilibrium conversion increases with increaing temperature

XEB

final conversion

heating process
(with interstage heating)

Endothermic Reaction: A Closer Look at

Adiabatic Conversion
Equilibrium
Increasing the inlet
temperature results in
shifting of the EB
equation to the
RIGHT

Xe

Adiabatic Temperature

T01

T02

34

Endothermic Reactions: Achieving Higher

Conversion by Inter-stage Heating

Xe
X3

X EB

X2
X1

~
i C pi (T T0 )
H Rxn (T )

35

Non-adiabatic reactor
operation :

36

oxidation of sulfur dioxide example

S O2 SO2

1
2O5
SO2 O2 V
SO3
2

2 k
rSO

PSO2
PSO3

PO
2

PSO3

K p PSO
2

for X > 0.05

The feed to an SO2 converter is 7900 lb mol/h and consists of 11% SO2, 10%
O2, and 79% inerts. The converter consists of 4631 tubes packed with
catalyst,
each 20 ft long.
The tubes are 3 in. o.d. and 2.782 in i.d. The tubes will be cooled by a boiling
liquid at 805 F, so the coolant temperature is constant over this value. The
entering pressure is 2 atm.

For inlet temperatures of 740 and 940 F, plot the conversion, temperature,
equilbrium conversion, and reaction rate profile down the reactor.

37

From thermochemical tables, the equilibrium constant at any temperature T is :

42311

K p exp
11.24
RT

T in R, Kp in atm-1/2

From the data of Eklund (1956), the rate constants :

176008

k exp
(110.1ln T ) 912.8
T

T in R

H RX (800 F ) 42471 Btu / lb mol SO2

C pSO 7.208 5.633 10 3 T 1.343 10 6 T 2 Btu / lb mol R

2

C pO2 5.731 2.323 10 3 T 4.886 10 6 T 2 Btu / lb mol R

C pSO3 8.511 9.517 10 3 T 2.325 10 6 T 2 Btu / lb mol R
C pN 6.248 8.778 10 4 T 2.13 10 8 T 2 Btu / lb mol R
2

1
A B C
2

1
2O5
SO2 O2 V
SO3
2

Mole balance
(PFR) :
dX
FA0
rA
dW

dX
k

dW FA0

Rate law :
PSO2
PO
2 k
rSO
PSO3 2

38

Stoichiometry :

(i i X )( RT ) P
Pi Ci RT C A0

(1 X )(T / T0 ) P0
2

PSO3

K p PSO
2

PA0

( i i X ) P
(1 X ) P0

X
O2
1 X P
2 SO3 X 1
P

A0
1 X K 2
SO3 X P0
1 X

per tube

dX
1 X P 0.2 0.11X
X
dX f ( X , T , P)
5.32k

dW
X P0 1 0.055 X (1 X ) K p dW

39

Operation of a tubular reactor with heat changer :

T

Ua(Ta T ) (rA ) H RX (TR ) C p dT

TR
dT

n
dW
FA0 ( i C pi XC p )
i 1

Highly temperature sensitive heat capacities

Ua(Ta T ) (rA ) H RX
(TR ) T T 2 dT

TR
dT

n
dW
FA0 ( i C pi XC p )
i 1

dT 5.11(Ta T ) (rA ) H RX (T )

n
dW
0.188( i C pi XC p )

dT
f ( X , T , P)
dW

i 1

4 parameters (X,W,P, and T), we need more relations!

40

Ergun equation:
dP
T P0 FT

dW
2 T0 P / P0 FT 0
2 0

AC C (1 ) P0
G
0
0 gc Dp

1 150(1 )
3
1.75G
Dp

GTP0 (1 X )
dP

dW
b Ac 0T0 PD p g c

1 150(1 )
3
1.75G
Dp

Viscosity is also a function of
temperature,
but we ignore here.

dP
1.12 108 (1 0.55 X )T
5500 2288

dW
P
dP
f ( X , T , P)
dW

41

Mole balance

dX
1 X P 0.2 0.11X
X

5.32k

dW
X P0 1 0.055 X (1 X ) K p

Energy balance

dT 5.11(Ta T ) (rA ) H RX (T )

n
dW
0.188( i C pi XC p )

i 1

dP
1.12 108 (1 0.55 X )T
5500 2288

Momentum balance
dW
P

Three O.D.E.s are solved simultaneously.

Multiple steady states

When more than one intersection occurs of the energy and
mole balance curves, there will be multiple steady states at
which the reactor may operate.
Energy balance :
n

T
T

Q Ws FA0 i C pidT H RX (TR ) C p dT FA0 X 0

T
TR
i 1 i 0

Assume no shaft work

Set Cp = 0

UA(T Ta )
~

FA0 i C pi (T T0 )
FA0 XH RX
(T )
FA0
i 1
n

= Cp0

CSTR

FA0 X rAV

FA0C p 0 (T T0 ) UA(T Ta ) (rAV )(H RX

)

42

Multiple Steady State (MSS)

Unsteady State Simplified Energy Balance Equation
n

i 1

T0

W
F
Q
s
A0

i Cpi dT ] FA0 X H Rxn (T ) Ni Cpi

i 1

dT
dt

Multiple Steady State for

CSTR Operation
dT
~
U A (Ta T ) FA0 i C pi (T T0 ) FA0 X H Rxn (T ) N i Cpi
dt
i 1

Knowing [(-rA) = FA0 X], the above equation can be rearranged as

dT
~
U A (T Ta ) FA0 i C pi (T T0 ) (rA V ) H Rxn (T ) N i Cpi
dt
i 1

Heat Removed term, R(T)

43

Heat Generated term, G(T)

Multiple Steady States - CSTR

Defining new variables
~
i C pi C p0

and UA

FA0C p 0

and Tc T0 FA0 C p 0 U A Ta
U A FA0 C p 0

We will now rearrange the following equation

dT
~
U A (T Ta ) FA0 i C pi (T T0 ) (rA V ) H Rxn (T ) N i Cpi
dt
i 1

as
C p 0 (1 ) (T Tc ) (rA V ) H Rxn (T ) Ni Cpi
i 1

dT
dt

At steady state, dT/dt =0

C p 0 (1 ) (T Tc ) (rA V ) H Rxn (T ) 0

i.e.

R(T) = G(T); Heat generated = Heat Removed

44

Multiple Steady States - CSTR

T0

R(T)

R(T ) C p 0 (1 ) (T Tc )

Tc

T0 FA0 C p 0 U A Ta
U A FA0 C p 0

R(T)
Ta

T0
T

UA
FA0C p 0
45

Multiple Steady States - CSTR

G(T ) (rA V ) H Rxn (T )

G(T)

Low Ea

High Ea

46

Multiple Steady States - CSTR

How do we find the Steady State Reactor Temperature ??

G(T)
&
R(T)

T
47

48

FA0C p 0 (T T0 ) UA(T Ta ) (rAV )(H RX

)

UA
C p 0 FA0

Tc

T0 FA0C p 0 UATa
UA C p 0 FA0

R(T)

Ta T0

Increase T0

T
C p 0 (1 )(T Tc )

rAV

(H RX
)
FA0

R(T)

=0

Increase

For Ta < T0
Ta

T0

Heat-generated term G(T)

For CSTR :

Heat-removed term R(T)

G(T ) (H RX
)X

function of T ...
i.e. mole balance, energy balance .

49

Temperature ignition-extinction curve

Ts, steady-state temperature

The points of intersection of R(T) and G(T) give the temperature

at which the reactor can operate at steady state and they are
termed Ts.

Upper steady state

Lower steady state

ignition temperature
extinction temperature

T0, entering temperature

Ignition temperature is very important, since once the

entering temperature exceeds this value, transition to the
upper steady state will occur :
undesirable
dangerous
Runaway reactions
Bifurcation analysis is usually applied to analyze whether or not
multiple steady states are possible.

50