Chemical Engineering

Department
CDB 2043 KINETICS AND REACTOR DESIGN
CHAPTER 8. STEADY STATE NON
ISOTHERMAL REACTOR

LEARNING OUTCOME OF CHAPTER 8

At the end of this chapter, student should be able to:
1. Explain the importance of energy balance in designing
reactors
2. Apply the concept of energy balance to reactor design
for both adiabatic reaction and reaction involving heat

exchange
3. Evaluate the optimum conversion in reactors where

chemical equilibrium is the limitations.

2

LECTURE 1
WHY WE NEED THE ENERGY BALANCE EQUATION?
HOW TO DEVELOP THE ENERGY BALANCE EQUATION

Why we need energy balance equation?

What do we have so far?
Mole balance
(design) equation

Rate law &

Arrhenius
equation

Example :
For PFR
dX rA

dV FA0

Stoichiometry
v v0

rA kC A

FA C Av0

E 1 1
k k1 exp
R T1 T2

FA C A0 v0
C A C A0 (1 X )

Why energy balance?

Mole balance
(design) equation
Example :
For PFR
dX rA

dV FA0

Rate law &

Arrhenius
equation
rA kC A
E 1 1
k k1 exp
R T1 T

Stoichiometry
v v0
FA C Av0
FA C A0 v0
C A C A0 (1 X )

Why energy balance?

1st order, exothermic, adiabatic reaction

Why energy balance?

Combining these three equations gives:
dX rA

dV FA0

E 1 1
rA k1 exp C A
R T1 T

E 1 1
k1 exp
T T
R

dX
1

C A0 1 X
dV
FA0

C A C A0 (1 X )

For non-isothermal operation:

k depends on T (affects final
conversion, X)
T varies with V (reactor length)

Need either
X=f(T) or
T=f(V)

General approach in solving non-isothermal

reactor problem

Use energy
balance to
relate X
and T

Set value
for X

Calculate
T

Calculate
k

Calculate
rA

Use Levenspiel
Calculate plot technique
to solve
(FA0/-rA)
problem

The energy balance

General energy balance for open system

d Esys
dt

Fin Ein

Fout Eout

Zero for closed system

The energy balance

For n species, the equation becomes:

^

d E sys
dt

F E
i

i 1

i in

F E
i

i 1

i out

Qs is how can we
make this equation
USEABLE @ USERFRIENDLY?

Steps to a more user-friendly equation

Evaluate the work term to get the equation in terms of enthalpies

Dissect the steady state molar flow rate terms to get the equation in terms of heats of
reaction
Dissect the enthalpies terms to get the equation in terms of heat capacity.

d E sys
dt

F E
i

i 1

i in

F E
i

i 1

d Esys
^

d Esys
dt
11

f C pi

dt

f H i

d Esys
dt

f H Rx

i out

The energy balance

Resulting equation based on energy balance* for steady state
flow system:
where:
.

Q W s FA0

C
i

pi (T

Tio ) FA0 X A H RX T 0

i 1

0
TR C p T TR
H RX T H RX

*Full derivation: pg 474 - 486, Fogler

How do we apply the equation in designing

reactors?

Q W s FA0

C
i

pi (T

Tio ) FA0 X A H RX T 0

i 1

dX rA

dV FA0

FA0 X
V
rA

N A0 dX
V
rA dt
Numerical technique

Solve using

ODE solver

Graphical method

e.g: Levenspiel plot

method
13

8.3 Adiabatic energy balance

General Energy Balance Equation
.

Q W s FA0

C
i

pi (T

Tio ) FA0 X A H RX T 0

i 1

Consider an adiabatic system with no work done.

.

Q 0, W s 0

C T T
i

pi

io

o
H Rx (TR ) C p T TR

(1)

Adiabatic tubular reactor

Rearrangement of equation 1 gives:
T

X H RX TR

C
i

Pi

Pi T0

XC PTR

XC P

(2)

Couple with mole balance equation:

FA0

dX
rA ( X , T )
dV

we can develop the temperature, conversion and

concentration profiles along the reactor.

Adiabatic energy balance

Since the second term in the denominator is usually zero, a
plot of XEB vs T gives:
i C pi T Tio
X EB

XEB

o
H Rx
(TR )

XMB
Use together with mole balance
equation in solving reaction
engineering problem

CHECKPOINT!
For non-isothermal system, we need 2
equations to describe the conversion, X
XMB, which is based on Material
Balance
XEB, which is based on Energy
Balance

The final conversion is the value that satisfy

both these equations

Example 8-2: Heat of reaction

Calculate the heat of reaction for the synthesis of ammonia from hydrogen
and nitrogen at 150oC in kcal/mol of N2 reacted and also in H2 reacted. The
reaction is given below:
N2 + 3H2 2NH3

Info:
Heat of formation of NH3 at 25oC = -11,020 cal/mol.N2 reacted
Heat of formation of elements at 25oC = 0

Heat capacities at 25oC

CP,NH3 = 8.92 cal/mol.K
CP,N2 = 6.984 cal/mol.K
CP,H2 = 6.992 cal/mol.K

Solution to Example 8.2

Heat of formation at reference temperature (25oC):
0
H Rx
(TR )

d 0
c 0
b 0
H D (TR ) H c (TR ) H B (TR ) H A0 (TR )
a
a
a

Heat of reaction at any temperature:

0
H Rx (T ) H Rx
(TR ) C P T TR

19

Solution to Example 8.2

Using these equations, we will get:
0
298K 22.04
H Rx

C p 10.12

cal
mol N 2 reacted K

H Rx 23.3

20

kcal
mol N 2 reacted

kcal
mol N 2

Example 8-3: Liquid phase isomerisation of normal

butane

Additional Information:
HRx = -6900 J/mol butane
Activation Energy = 65.7 kJ/mol
Kc = 3.03 at 60oC
CA0 = 9.3 kmol/dm3

Handout

CPn-B = 141 J/mol.K

CPi-B = 141 J/mol.K
CPi-P = 161 J/mol.K

END OF LECTURE

22

LECTURE 2
STEADY STATE TUBULAR REACTOR WITH HEAT EXCHANGE
CASE 1: CONSTANT TEMPERATURE HEAT EXCHANGE
CASE 2: VARIABLE TEMPERATURE HEAT EXCHANGE

23

Steady state tubular reactor with heat

exchange (Case 1)

Steady state tubular reactor with heat

exchange (Case 1)
From:

Q WS Fi H i v Fi H i v v 0

Deriving the energy balance equation

General energy balance equation, with no work done:
.

Q Fi H i v Fi H i v v 0
where :
.

Q UaV Ta T

Steady state tubular reactor with heat

exchange (Case 1)
Deriving the energy balance equation
After further substitution of the terms, the energy balance
equation for tubular reactor with heat exchange is:
Heat generated Heat removed

rA H Rx Ua T Ta
dT

dV
Fi C Pi

VALID FOR CONSTANT

TEMPERATURE HEAT EXCHANGE
MEDIUM ONLY!!
Full derivation: Fogler, pg 496

Example 8.4: Butane Isomerisation

From Example 8.3, the vapour pressure at the exit to the
adiabatic reactor at 360K is 1.5MPa for isobutene, which is
greater than the rupture pressure of the glass vessel used. Given
the information below, will the reactor temperature rise above
325K?
Reactor volume (10 banks): 6 m3 (volume of each reactor)
Ua: 5000 kJ/h.m3.K
Ta = 37oC
All other information : refer to Example 8.3

27

WHAT IF THE
TEMPERATURE OF THE
COOLING / HEATING
MEDIUM IS NOT A
CONSTANT?
28

Steady state tubular reactor with heat

exchange (Case 2)
Energy balance on coolant fluid

Steady state tubular reactor with heat

exchange (Case 2)
Energy balance on coolant fluid
For co-current case:
dTa Ua T Ta
.
dV
m c C Pc

For counter-current case:

dTa Ua Ta T
.
dV
m c C Pc

Example 8-5: Production of acetic anhydride

One of the steps in the production of acetic anhydride is the vapour
phase cracking of acetone to ketene and methane. The reaction is first
order with respect to acetone and the reaction rate is given below (T in
K).
CH 3COCH 3 CH 2CO CH 4
ln k 34.34

34,222
T

The feed to the reactor consist og 7850 kg/hr acetone. The reactor
consist of a bank of 1000 tubes of 1 inch diameter. The inlet
temperature and pressure are the same of both cases at 1035 K and 162
kPa. Plot the conversion and temperature profile along the length of the
reactor for the following cases:

Example 8-5: Production of acetic anhydride

1.
2.

3.

The reactor is operated adiabatically

The reactor is surrounded by a heat exchanger where the heat
transfer coefficient is 110 J/m2.s.K and the temperature of the
heating medium is constant at 1150 K.
Same as part (2) but reactor is subjected to heating medium with
changing temperature

END OF LECTURE 2

33

LECTURE 3
EQUILIBRIUM CONVERSION

34

Equilibrium conversion

Will consider the following:

A. How adiabatic temperature is related to equilibrium
conversion for the following cases:
1.
2.

Exothermic reaction
Endothermic reaction

B. How to find optimum feed temperature

A. Adiabatic temperature vs Xe
Exothermic reaction

Equilibrium

TO1>TO

X EB

Xe

TO

TO1 Adiabatic
temperature

i C pi T To
H RX

A. Adiabatic temperature vs Xe
How do we increase Xe for exothermic reaction?

A. Adiabatic temperature vs Xe
Endothermic reaction

X EB
Xe

Adiabatic
temperature

TO

i C pi T To
H RX

A. Adiabatic temperature vs Xe
How do we increase Xe for endothermic reaction?

B. Optimum feed temperature

Consider reversible & exothermic reaction under adiabatic
operation

Analysis on Xe vs. T
(from energy
balance) gives the
following profile:

B. Optimum feed temperature

Analysis on conversion vs. reactor length gives the following profile:

B. Optimum feed temperature

Therefore, if we analyse the achievable conversion in a reactor for a
given entering temperature, we will find:

END OF LECTURE

43

STEP 1: Evaluate the work term to get the equation in terms

of enthalpies

44

STEP 2: Dissect the steady state molar flow rate terms to

get the equation in terms of heats of reaction

45

STEP 2: Dissect the steady state molar flow rate terms to

get the equation in terms of heats of reaction

46

STEP 3: Dissect the enthalpies terms to get the equation in

terms of heat capacity.

47

STEP 3: Dissect the enthalpies terms to get the equation in

terms of heat capacity.

48

STEP 3: Dissect the enthalpies terms to get the equation in

terms of heat capacity.

49