Lecture 6

REACTION ENGINEERING
CHAPTER 6
NON-ISOTHERMAL
REACTOR DESIGN
NOOR ROSYIDAH SAJUNI
rosyidah@ucsi.edu.my
Note: Please make appointment first
before consultations and come fully
prepared
CHAPTER 6
NON-ISOTHERMAL REACTOR
DESIGN
6.1 The energy balance
6.2 Algorithms for non-isothermal
reaction design
6.3 Equilibrium conversion
6.4 Multiple steady-state
6.1 THE ENERGY BALANCE

WHY WE NEED TO LEARN ENERGY BALANCE IN REACTION
ENGINEERING?
1. At times we need to calculate the volume necessary to
achieve a conversion, X in a reactor (for example PFR)
given a first order, exothermic liquid reaction carried out
adiabatically (no heat loss or gained in the system).
2. For an exothermic reaction, the temperature profile vs.
volume is
Reaction Temperature
influenced
the Reactor Volume

WHY WE NEED TO LEARN ENERGY BALANCE IN REACTION
ENGINEERING?
3. For the reaction previously, we know from the combined
mole balance, rate law, and stoichiometry yield:
X
Design equation for PFR:
dX
V FA 0
rA
0
Rate Law (First order reaction)

There is change of temperature
during the reaction therefore
It has to taken into consideration
Ea
rA k 1 exp
R
Stoichiometry for liquid phase reaction gives
1 1
C A
T1 T
C A C A 0 (1 X )
3

WHY WE NEED TO LEARN ENERGY BALANCE IN REACTION ENGINEERING?
3. We combine equation 1, 2 and 3 to obtain
V FA0
0
4.
5.
dX
Ea
k 1exp
R
FA0
1 1

T1 T
C A0 (1 X)
dX
0 (1 X)
Ea 1 1
C
(V,T
In this equation, wekhave
3 unknowns
and
1exp
A0 X) which need to be
R T1 relationship
T
solved. Therefore we need another
relating X and T or T and
V.
This additional relationship can be found through energy balance
calculations

FIRST LAW OF THERMODYNAMICS
Inlet Molar
Flow Rate
Heat to the
system
Outlet Molar
Flow Rate
Inlet
Enthalpy
Inlet Enthalpy
Work done by
system
8.2

8.2
General Energy Balance of An Open System
Heat to the
system
i 1
i 1
Q W EioFio EiFi
Work done by
the system
Total sum or
energy in
d E sys
dt
Total sum or
energy out

ENERGY BALANCE IN TERMS OF ENTHALPY
1. In terms of enthalpy, the energy balance becomes
Q W HioFio HiFi
i 1
i 1
d E sys
dt
2. And for steady state operation, the energy balance now becomes
Q W HioFio HiFi 0
i 1
i 1
3. With manipulation of the molar flow rates, we obtain the energy

balance as
Q W s FAO i (Hio Hi ) HRx (T )FAO X 0

i 1

4. From equation 3 previously
n
Q WS FAO i (Hio Hi ) HRx (T )FAO X 0
i 1
5. We know the enthalpy term is defined as following
Tio
Hio Hi Hi (T ) H (TR )
o
i
C dT
P
TR
Ti
H (TR ) CPdT
TR

o
i
Ti
CPidT CPi (Ti Tio )

Tio
6. Therefore the energy balance now becomes
Q WS FAO iCPi (Ti Tio ) HRx (T )FAO X 0

i 1

7. From equation 5 previously
n
Q WS FAO iCPi (Ti Tio ) HRx (T )FAO X 0
i 1
8. We know the heat of reaction, Hrx term is defined as following
HRx (T ) HoRx (TR ) CP (T TR )

9. Therefore the energy balance now becomes
Q WS FAO iCPi (T Tio ) FAO X HoRx (TR ) CP (T TR ) 0

i 1

10.From equation 6 previously

i 1
A. HEAT CAPACITY, Cpi

1. Typical unit for heat capacity, Cpi of a reactant i is represented as
J/mol.K
2. The
terms of could be calculated for any species of
REACTANT ONLY based on the following method


i 1
A. HEAT CAPACITY, Cpi

2. For example given a reaction of
basis of calculations, therefore:
~
C
i
Pi
A+B
C PA B C PB
POSITIVE SIGN
FOR REACTANT
with
C + D with A as the
FB 0
FA0
REMEMBER:
ONLY TAKE THE REACTANT
INTO CONSIDERATION


i 1
B. TEMPERATURE SYMBOLS DEFINITION AND DIFFERENCE

1. T
= Reaction Temperature in which the reaction is conducted
2. Ti0
= Entrance/Inlet Temperature of the reactant
3. TR
= Reference Temperature (usually 25oC) unless stated other

values


i 1
C. Heat of reaction at reference temperature Ho Rx (TR)

1.Heat of reaction at reference temperature (usually 25 oC unless stated
other values) can be calculated based on the following method
2. The enthalpies of formation of many compounds, Ho i (TR) are usually
tabulated at 25oC and can readily be found in any handbook.
REMEMBER
Ho Rx (TR) is to indicate that in the formula, the heat of reaction Ho Rx is
calculated at the reference temperature.
DONT NEED TO TIMES (X) THE REFERENCE TEMPERATURE (TR) VALUE TO
THE HEAT OF REACTION VALUE.


i 1
C. Heat of reaction at reference temperature Ho Rx (TR)

A + b/a B
c/a C + d/a D
with A as the basis of calculations, therefore:
POSITIVE SIGN
FOR PRODUCT
NEGATIVE SIGN
FOR REACTANT
REMEMBER: REACTANT AND PRODUCT SHOULD BE TAKEN INTO

CONSIDERATION

EXAMPLE ON HOW TO CALCULATE Ho Rx (TR)
Calculate Ho Rx (TR) when given the reaction as following:
SOLUTION:
For the above reaction, the heat of reaction at reference temperature is as
following:
From reference, it is found that the heat of formation of the elements

hydrogen Ho H2 (TR) and nitrogen Ho N2 (TR) are zero at 25oC, while Ho NH3 (TR) =
-11,020 cal/mol therefore


i 1
D. OVERALL CHANGE IN THE HEAT CAPACITY, Cp

1. The overall change in the heat capacity is based on per mole of A
reacted during the reaction
2. The heat capacity for each species, Cpi can be found from any
handbook.


i 1
D. OVERALL CHANGE IN THE HEAT CAPACITY, Cp

1. It can be calculated based on the following method
A + b/a B
with A as the basis of calculations, therefore:
c/a C + d/a D
POSITIVE SIGN NEGATIVE SIGN

FOR PRODUCT FOR REACTANT
REMEMBER: REACTANT AND PRODUCT SHOULD BE TAKEN INTO
CONSIDERATION

EXAMPLE ON HOW TO CALCULATE OVERALL CHANGE IN THE HEAT
CAPACITY, Cp
Calculate Cp when given the reaction as following:
SOLUTION:

E. HEAT ADDED TO CSTR WITH HEAT EXCHANGER,Q
TO, FAO
Ta1, mc
Heat
exchanger
Heat transfer fluid enters
the exchanger at a mass
flow rate mc (kg/s) at a
temperature Ta1 and
leaves at a temperature
Ta2.
T, FA
Ta2
CSTR
reactor
For exothermic
reactions (T>Ta2>Ta1)
For endothermic
reactions (Ta1>Ta2>T)


i 1
E. HEAT ADDED TO THE REACTOR

1. Q is HEAT added to the reactor when heating up a reaction is required
2. For CSTR, the Q value can be calculated from a specified equation
UA
Q m c C pc {(Ta1 T)[1 exp(
)]}
m c C pc
.
U = Overall heat transfer coefficient A = Heat exchange area

Cpc = Heat capacity of the heat transfer fluid

6

i 1
In CSTR, the work done by the stirrer can usually be

neglected (WS=0).
Therefore the FINAL ENERGY BALANCE for CSTR with heat
exchanger can be written as
Q FAO i C Pi (T Tio ) FAO X H oRx (TR ) C P (T TR ) 0

i 1
6.2 ALGORITMS FOR NON-ISOTHERMAL REACTOR DESIGN

CSTR ALGORITHM FOR NON-ADIABATIC SYSTEM
X is given,
calculate V and T
Vk
v 0 Vk
V is given,
Calculate X and T

X is given, calculate T first using energy balance equation

i 1
CALCULATE k
E 1 1
k(T ) k 1 exp

R TO T
CALCULATE V
FA 0 X
V
kC AO (1 X )
Using the T above

to calculate the k

V is given, Calculate X and T
CALCULATE X MB AND T FROM MASS BALANCE EQUATION

1. X MB
Vk
v 0 Vk
CALCULATE X EB AND T FROM ENERGY BALANCE EQUATIONS

i 1
We need to plot graphs for conversion,

X versus temperature, T and compare
the plot to find the intersection point.

APPLICATION FOR CSTR (NON-ADIABATIC SYSTEM)
EXAMPLE 1
FROM QUESTION 8.4B PAGE 513 FOGLER 3RD EDITION
Given the following reaction in a non adiabatic CSTR.
(V)
(A)
Cp steam= 0.47 Btu/lb.oF

mc = 1000 lb/hr
(Ta1)

EXAMPLE 1
Given the following reaction in an non adiabatic CSTR.
(FA0)
(T0)
(CPA)
(CPB)
(CPC)

EXAMPLE 1
1. Reaction in a non-adiabatic CSTR (endothermic) for irreversible liquid
phase elementary reaction.
2. In the question, CSTR volume, V = 125 gal and conversion, X = 1.0
(proceeds to completion) so find the reaction temperature, T.
3. From the energy balance equation
n

i 1
4. From question,
U
Ta1
FAO

EXAMPLE 1
n

i 1
6. From question,
o
HRx
(TR )
CP
c
b
CP CPC CPB CPA 2(47.5) 44.0 51.0 0
a
a

EXAMPLE 1

i 1
8. From question,
i CPi CPA BCPB , B
10
1
10
Therefore i C Pi C PA C PB 51.0 44.0 95.0 Btu / lb mol.o F

EXAMPLE 1

i 1
10.Calculate the heat added into the reactor by the heat exchanger
UA
Q m c C pc {(Ta1 T )[1 exp(
)]}
m c C pc
.
- (150)(10)
(1000lb / hr )(0.47 Btu/lb. F){(365.9 - T) F[1 - exp(
)]}
(1000)(0.47)
450.68(365.9 T)
o

EXAMPLE 1
11.From the energy balance equation

i 1
12.Substitute in all the values into the equation to obtain T as
450.68Btu / hr.o F(365.9 T ) o F (10 lb mol / hr )(95 Btu / lb mol.o F)(T 80o F)
(10 lb mol / hr )(1) 20,000Btu / lb mol 0
T?

APPLICATION FOR CSTR (ADIABATIC SYSTEM)
For adiabatic system,
The energy balance for CSTR with no heat exchange, Q= UA (Ta-T) = 0
(ADIABATIC SYSTEM)
n
FAO iCPi (T Tio ) FAO X HoRx (TR ) CP (T TR ) 0

i 1

EXAMPLE 2
FROM QUESTION IN FOGLER 3RD EDITION
Given the following reaction in an adiabatic CSTR.
FAO
FBO

EXAMPLE 2
Given the following reaction in an adiabatic CSTR.
You are feeding 2500 lb mol/h of A and equal molar flowrate of B to the
reactor. The feed stream consist of 46.62 ft3/hr of A and 233.1 ft3/hr of
B. The temperature of both feed stream is 58oF prior to mixing but
there is an immediate 17oF temperature rise upon mixing of the 2 feed
streams caused by the heat of mixing. The entering temperature of all
feed streams is thus taken to be 75oF.
For the conditions similar to those, it is found that that the reaction is
first order with respect to A and zero order with respect to B with the
specific reaction rate given as
k = Ae-Ea/RT = 16.96x1012(e-32,400Btu/lb mol/RT)/hr
Calculate the exit temperature at which the reaction is conducted and
subsequently the CSTR volume when given the conversion as 10%

EXAMPLE 2
Following data are given as following:

EXAMPLE 2
SOLUTION
1. In this question, the exit conversion is given, X therefore we need to
find the temperature, T at which the reaction is conducted and
subsequently the volume of the CSTR, V
2. Based on the algorithm for adiabatic system,
CALCULATE T
n

i 1
Using the T
above to
calculate the k
CALCULATE k
E 1 1
k(T ) k 1 exp

R TO T
CALCULATE V
FA 0 X
V
kC AO (1 X )

EXAMPLE 2
CALCULATE T
FAO iCPi (T Tio ) FAO X H oRx (TR ) CP (T TR ) 0

i 1
2. Given FAO = 2500 lb mol/hr (43.04 lb/h) of A to the reactor. The feed
stream consist of 46.62 ft3/hr of A and 233.1 ft/hr of B
Tio = 75oF
TR = 68oF
i CPi CPA BCPB , B
2500
1
2500
Therefore i C Pi C PA C PB 35.0 18.0 53.0 Btu / lb mol.o F

EXAMPLE 2
CALCULATE T

i1
o
We know HRx
(TR )
c o
b
HC (TR ) HBo (TR ) HoA (TR )
a
a
Therefore
o
HRx
(TR ) HoC (TR ) HBo (TR ) HoA (TR )
-226,000 - (-123,000) - (-66,600)

-36,400 Btu/lb mol

EXAMPLE 2
CALCULATE T
n

i1
c
b
We know C p C pC C p B C pA
a
a
Therefore Cp CpC CpB Cp A

46 - 18 - 35 - 7 Btu/lb mol. o F

EXAMPLE 2
CALCULATE T

i1
2. Substitute in all the values we calculate previously to determine the

reaction temperature, T when given the conversion, X = 0.1
CALCULATE T
n
FAO i C Pi (T Tio ) FAO X H oRx (TR ) C P (T TR ) 0

i 1
2500 lb mol/hr (53.0 Btu / lb mol.o F)(T 75o F)

(2500 lb mol/h)(0.10)[-36,400 Btu/lb mol (7 Btu / lb mol.o F)(T - 68o F)] 0
Therefore T 7.13o F

EXAMPLE 2
SOLUTION
From the logarithm, we have solved T value. Therefore next is to find k
(T) value
CALCULATE T
n

i 1
Using the T
above to
calculate the k
CALCULATE k
E 1 1
k(T ) k 1 exp

R TO T
CALCULATE V
FA 0 X
V
kC AO (1 X )

EXAMPLE 2
SOLUTION
From the logarithm, we have solved T value. Therefore next is to find k
(T) value
Given from the question that k = Ae-Ea/RT = 16.96x1012(e-32,400Btu/lb mol/RT)/hr
We calculated that T = 7.13 oF. Therefore
k 16.96 x1012 e
32 , 400 Btu/lb mol

RT
32 , 400 Btu/lb mol
16.96 x10 e
0.0115 / hr
12
(1.987 Btu / lb mol.o R )( 7.13 459.69 o R )
/ hr

EXAMPLE 2
SOLUTION
Next we obtain the volume of the reactor, V
To find the initial concentration of A, we know FA0 = 2500 lb mol/hr and
The initial volumetric flowrate, as given in question as 46.62 ft3/hr of A
and 233.1 ft/hr of B.
Therefore v0,TOTAL = 46.62 + 233.1 ft/hr = 279.72 ft3/hr
CALCULATE V
FA0 X
V
kC AO (1 X )
2500 lb mol/hr(0.10)
2702.6 ft 3
2500 lb mol/hr
[0.0115 / hr (
)(1 0.1)]
3
279.72 ft / hr
6.3 EQUILIBRIUM CONVERSIONS

(EXOTHERMIC REACTIONS)
1. The highest conversion can be achieved in reversible
reactions is the equilibrium conversion.
2. For exothermic reactions, the equilibrium decreases with
increasing temperature
6.3 EQUILIBRIUM CONVERSIONS

(EXOTHERMIC REACTIONS)
1. To determine the maximum conversion that can be achieved in an
exothermic reaction carried out adiabatically, we find the intersection
of the equilibrium conversion as a function of temperature with
temperature-conversion relationships from the energy balance.
Equilibrium
conversion
If the entering temperature in

increased from T0 to T01, the energy
balance line will be shifted to the
right and parallel to the original
line, as shown by the dashed line.
Note: As the inlet temperature
increases, the adiabatic equilibrium
conversion decreases
Inlet
Temperature
6.4 MULTIPLE STEADY-STATE

1. From the figure below, one would observe that if a parameter were
changed slightly, there might be more than one intersection of the
energy and mole balance curves
2. When more than one intersection occurs, there is more than one set
of conditions that satisfy both the energy balance and mole balance
3. This is called as multiple steady states at which the reaction may
operate
Inthermodynamics, the termexothermic("outside heating")

describes a process or reaction that releasesenergyfrom the
system, usually in the form ofheat, but also in the form oflight
(e.g. a spark, flame, or explosion),electricity(e.g. a battery), or
sound(e.g. burning hydrogen).
Inthermodynamics, the wordendothermic("within-heating")
describes a process or reaction in which the system absorbs
energyfrom the surroundings in the form ofheat.
Inthermodynamics, anadiabatic processis a conversion that
occurs without input or release ofheatwithin a system. Many
rapid chemical and physical processes are described in this way.
Such processes are usually followed or preceded by events that
do involvel heat.

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REACTION ENGINEERING

6.1 THE ENERGY BALANCE

6.1 THE ENERGY BALANCE

Design equation for PFR:

Rate Law (First order reaction)

Stoichiometry for liquid phase reaction gives

6.1 THE ENERGY BALANCE

6.1 THE ENERGY BALANCE

6.1 THE ENERGY BALANCE

General Energy Balance of An Open System

6.1 THE ENERGY BALANCE

3. With manipulation of the molar flow rates, we obtain the energy

Q W s FAO i (Hio Hi ) HRx (T )FAO X 0

6.1 THE ENERGY BALANCE

Q WS FAO i (Hio Hi ) HRx (T )FAO X 0

5. We know the enthalpy term is defined as following

CPidT CPi (Ti Tio )

6. Therefore the energy balance now becomes

Q WS FAO iCPi (Ti Tio ) HRx (T )FAO X 0

6.1 THE ENERGY BALANCE

Q WS FAO iCPi (Ti Tio ) HRx (T )FAO X 0

8. We know the heat of reaction, Hrx term is defined as following

HRx (T ) HoRx (TR ) CP (T TR )

Q WS FAO iCPi (T Tio ) FAO X HoRx (TR ) CP (T TR ) 0

6.1 THE ENERGY BALANCE

Q WS FAO iCPi (T Tio ) FAO X HoRx (TR ) CP (T TR ) 0

A. HEAT CAPACITY, Cpi

6.1 THE ENERGY BALANCE

Q WS FAO iCPi (T Tio ) FAO X HoRx (TR ) CP (T TR ) 0

A. HEAT CAPACITY, Cpi

6.1 THE ENERGY BALANCE

Q WS FAO iCPi (T Tio ) FAO X HoRx (TR ) CP (T TR ) 0

B. TEMPERATURE SYMBOLS DEFINITION AND DIFFERENCE

= Reaction Temperature in which the reaction is conducted

= Entrance/Inlet Temperature of the reactant

= Reference Temperature (usually 25oC) unless stated other

6.1 THE ENERGY BALANCE

Q WS FAO iCPi (T Tio ) FAO X HoRx (TR ) CP (T TR ) 0

C. Heat of reaction at reference temperature Ho Rx (TR)

6.1 THE ENERGY BALANCE

Q WS FAO iCPi (T Tio ) FAO X HoRx (TR ) CP (T TR ) 0

C. Heat of reaction at reference temperature Ho Rx (TR)

REMEMBER: REACTANT AND PRODUCT SHOULD BE TAKEN INTO

6.1 THE ENERGY BALANCE

From reference, it is found that the heat of formation of the elements

6.1 THE ENERGY BALANCE

Q WS FAO iCPi (T Tio ) FAO X HoRx (TR ) CP (T TR ) 0

D. OVERALL CHANGE IN THE HEAT CAPACITY, Cp

6.1 THE ENERGY BALANCE

Q WS FAO iCPi (T Tio ) FAO X HoRx (TR ) CP (T TR ) 0

D. OVERALL CHANGE IN THE HEAT CAPACITY, Cp

POSITIVE SIGN NEGATIVE SIGN

6.1 THE ENERGY BALANCE

6.1 THE ENERGY BALANCE

6.1 THE ENERGY BALANCE

Q WS FAO iCPi (T Tio ) FAO X HoRx (TR ) CP (T TR ) 0

E. HEAT ADDED TO THE REACTOR

U = Overall heat transfer coefficient A = Heat exchange area

6.1 THE ENERGY BALANCE

15.From equation 6 previously

Q WS FAO iCPi (T Tio ) FAO X HoRx (TR ) CP (T TR ) 0

In CSTR, the work done by the stirrer can usually be

Q FAO i C Pi (T Tio ) FAO X H oRx (TR ) C P (T TR ) 0