H83RED

Reactor Design

I took a
thoroughly
calculated
risk!

CSTR Reactors
But man, I
Victor Sans Sangorrin
am bad at
maths!! Department of Chemical Engineering

Autumn Semester 2017

 Summary

In this lecture …
So far we have developed the design equation for CSTR and linked the rate law and the
stoichiometry.

Here we apply the basic concepts learned so far to design Continuous Stirred Tank
Reactors. Following is the structure of the lecture.

• Design Equations
• Isothermal Operation with single reaction
• Isothermal operation with multiple reactions
• Non-Isothermal operations

2
 Learning outcomes

By following the lecture and reading the relevant sections of the recommended
textbooks (Fogler and also Levenspiel) you would

a. Develop an understanding of core chemical engineering principles

applied to design CSTR reactor
b. able to apply design equations, rate law and stoichiometry together to
develop a model for CSTR
c. develop skills to generate operating curves in terms of conversion
against Damkhöler number (dimensionless space time) to make
economic decisions on reactor size
d. Develop sense of safe design practices

3
 Introduction

CSTRs are large mixing vessels in which reactions take

place. The reactor is continuously stirred using
motorised agitator to achieve uniform mixing.

Perfect mixing is assumes so that the temperature

and the concentration within the reactor is
considered uniform.

This assumption lead to the mathematical model we

have derived in lecture 2, Mole Balances. Note that
achieving ideal mixing is not an easy task and the
calculated conversions may not result in reality.
However the model provides a reasonable design
basis.

CSTR is a continuous reactor that runs at steady

state.

4
 Design Equations for CSTR

Following are the key equations used in designing Batch Reactors

𝐹"% 𝑋"
Design Equation 𝑉= [1] Lecture 3, Basic Concepts of Reactor Sizing Eq [15]
−𝑟" |EF+G

𝐹"% − 𝐹"
Conversion 𝑋" = [2] Lecture 3, Basic Concepts of Reactor Sizing Eq [6]
𝐹"%

Number of moles 𝐹+ = 𝐹"% 𝛩+ − 𝑠< 𝑋 [3] Lecture 3, Basic Concepts of Reactor Sizing Eq [7]
of i at any time t

Rate Law −𝑟" = 𝑘𝑓 𝐶+ [4] Lecture 4, Stoichiometry and Rate Law Eq [2]

For elementary 𝑓 𝐶+ = 𝐶" - 𝐶. / [5] Lecture 4, Stoichiometry and Rate Law Eq [2]
reactions

4 6 6
Rate constant 𝑘 𝑇 = 𝑘(𝑇%
9
)𝑒 78 7
5 [6] Lecture 4, Stoichiometry and Rate Law Eq [20]

𝑃% 𝑇 𝑍
Volume 𝑉 = 𝑉% 1 + 𝜀𝑋 × × [7] Lecture 4, Stoichiometry and Rate Law Eq [40]
𝑃 𝑇% 𝑍% 5
 Design Equations: Heat Balance for CSTR

Modifying the general heat balance for batch reactor one can write
-

𝑄 − 𝐹"% I 𝐶J+ Θ+ 𝑇 − 𝑇% −∆𝐻5O 𝑇 𝐹"% X = 0 Lecture 6, Energy Balance Eq [16]

+L6

Compared to the heat load the shaft power could easily be neglected.
Taking the derivative with respect to time
𝑑𝑄
- = −UA 𝑇 − 𝑇V
𝑑𝑄 𝑑𝑇 𝑑 𝑑𝑡
− 𝐹"% I 𝐶J+ Θ+ −∆𝐻5O 𝑇 𝐹"% X = 0
𝑑𝑡 𝑑𝑡 𝑑𝑡
+L6

-
𝑑𝑇
−UA 𝑇 − 𝑇V − ∆𝐻5O 𝑇 𝑟" 𝑉 = 𝐹"% I 𝐶J+ Θ+
𝑑𝑡
+L6

Rearranging terms gives the useful form of the heat equation

𝑑𝑇 𝑈𝐴 𝑇V − 𝑇 − ∆𝐻5O 𝑇 𝑟" 𝑉
= [8]
𝑑𝑡 𝐹"% ∑-+L6 𝐶J+ Θ+
6
 CSTR: Isothermal operation with single reaction

Z7
Isothermal condition demands that = 0 (eq [9]) that gives the following condition.
ZG

∆𝐻5O 𝑇 𝑟" 𝑉 = 𝑈𝐴 𝑇V − 𝑇 [9]

This means that the heat generated by the reaction is

equal to the amount of heat removed.

General design principle

𝑋"
The design equation is 𝐹"% =V [1]
−𝑟"

𝐹"%
where = 𝐶"% [10]
𝑞%
𝑉
𝐹"%
−𝑟"

Evaluate the area of the rectangular area on

the Levenspiel Plot.

𝑋" 7
 CSTR: Isothermal operation with single reaction

Plug Flow Reactor with constant density system

Consider a first order liquid phase reaction

A → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

1. Molar Balance
For CSTR, the mole balance result in an algebraic equation
bc8 Oc
=𝑉 [11]
9dc

2. Rate Law
The reaction is second-order elementary. Therefore

−𝑟" = 𝑘𝐶" [12]

3. Stoichiometry
Liquid phase –constant volume system. q = q0

𝐹" 𝐹"
𝐶" = = = 𝐶"% 1 − 𝑋" [13]
𝑞 𝑞% 8
 CSTR: Isothermal operation with single reaction

4. Combine
Combining design equation, rate law and the stoichiometry gives

𝐹"% 𝑋"
𝑉= [14]
𝑘𝐶"% 1 − 𝑋"
5. Evaluate
Molar flow rate can be written as

𝐹"% = 𝑞% 𝐶"% [15]

Substituting [15] in [14]

𝑞% 𝐶"% 𝑋"
𝑉=
𝑘𝐶"% 1 − 𝑋"

𝑉 𝑋"
=
𝑞% 𝑘 1 − 𝑋"

𝑋" 𝜏𝑘
𝜏𝑘 = or 𝑋" = [16] 9
1 − 𝑋" 1 + 𝜏𝑘
 CSTR: Isothermal operation with single reaction

Concentration at any time is given by Equation [13]

𝐶" = 𝐶"% 1 − 𝑋" [13]

Substituting Equation [16] in [13] gives

𝜏𝑘
𝐶" = 𝐶"% 1 −
1 + 𝜏𝑘 1

0.9

0.8
𝑋
𝐶"% 0.7
𝐶" = [17]
1 + 𝜏𝑘 0.6

0.5

0.4

𝜏𝑘 is a dimensionless space time 0.3

𝐶"
0.2
f𝐶
"%
0.1

0
0 1 2 3 4 5 6 7
Dimensionless space time

10
 CSTR: Isothermal operation with single reaction

CSTR with second order reaction

Consider a second order liquid phase reaction

2A → 𝑝𝑟𝑜𝑑𝑢𝑐𝑡𝑠

1. Molar Balance

Design Equation bc8 Oc

=𝑉 [11]
9dc

2. Rate Law
The reaction is second-order elementary. Therefore h
−𝑟" = 𝑘 𝐶" [12]

3. Stoichiometry
Liquid phase –constant volume system. q = q0

𝐹" 𝐹"
𝐶" = = = 𝐶"% 1 − 𝑋" [13]
𝑞 𝑞%

11
 CSTR: Isothermal operation with single reaction

4. Combine 𝐹"% 𝑋"

𝑉= [14]
𝑘 𝐶"% h 1 − 𝑋" h

5. Evaluate
𝑞% 𝐶"% 𝑋" 𝑋"
Using 𝐹"% = 𝑞% 𝐶"% 𝑉= 𝜏𝑘𝐶"% =
𝑘 𝐶"% h 1 − 𝑋" h 1 − 𝑋" h

𝑋"
Since 𝜏𝑘𝐶"% = 𝐷𝑎kk 𝐷𝑎kk = h
[15]
1 − 𝑋"

𝐷𝑎kk − 2𝐷𝑎kk 𝑋" + 𝐷𝑎kk 𝑋" h − 𝑋" =0

𝐷𝑎kk 𝑋" h − 1 + 2𝐷𝑎kk 𝑋" + 𝐷𝑎kk = 0

1 + 2𝐷𝑎kk ± 1 + 4𝐷𝑎kk
𝑋" = [11]
2𝐷𝑎kk

12
Only the solution that gives 𝑿𝑨 <1 is valid
 CSTR: Isothermal operation with single reaction

Conversion as a function of the Damköhler number 1 + 2𝐷𝑎kk − 1 + 4𝐷𝑎kk

for a second-order reaction in a CSTR 𝑋" =
2𝐷𝑎kk

1.0
0.88

0.8

0.67
Conversion, X

0.6

0.4

0.2

6
0.0
0.2 1 2 5 7 10 20 30 40 50 60 70
tkCA0

When X is high: 10 times increase in Da number by increase of the reactor volume (t)
or temperature (increase in k) achieves only a relatively small increase
in the conversion.
CSTR operates under the condition of the lowest value of reactant
13
concentration (the exit concentration)
 CSTR: Isothermal operation with single reaction

CSTRs in Series
A first-order reaction with no change in the volumetric flow rate (v=v0) is to be carried
out in two CSTRs placed in series.

CA0

CA1 CA2

X1 X2
-rA1 V1 -rA2 V2

The effluent concentration of Mole balance for the second reactor:

reactant A from the first CSTR:

𝜏𝑘6 𝐹"6 − 𝐹"h

𝑋" = 𝑉h =
1 + 𝜏𝑘6 −𝑟"h

𝐶"% 𝑞q 𝐶"6 − 𝐶"h

𝐶" = 𝑉h = 14
1 + 𝜏𝑘6 𝑘h 𝐶"h
 CSTR: Isothermal operation with single reaction

Solving the mole balance for exit concentration out the second reactor:
𝑞q 𝐶"6 − 𝐶"h 𝑉h 𝐶"6
𝑉h = 𝑘h = 𝜏h 𝑘h = −1
𝑘h 𝐶"h 𝑞q 𝐶"h

𝐶"6 𝐶"%
𝐶"h = =
1 + 𝜏h 𝑘h 1 + 𝜏𝑘6 1 + 𝜏h 𝑘h

If both reactors are of equal size (t1=t2=t) and operate at the same temperature (k1=k2=k):

𝐶"%
𝐶"h = h
1 + 𝑘𝜏

For n equal-sized CSTRs connected in series (t1 = t2 =…= tn= ti= Vi/q0) operating at the same
temperature (k1 = k2 =… = kn = k) the concentration leaving the last reactor:

C A0 C A0 C A0
C An = = Substituting for CAn in terms C A0 (1 - X ) =
(1 + tk )n (1 + Da )n of conversion: (1 + Da )n
1
𝑋 =1− -
1 + 𝐷𝑎 15
 CSTR: Isothermal operation with single reaction

Conversion as a function of the number of

tanks in series
1.0
Da=tk=1 If Da is high (for instance, Da>1),
approximately 90% conversion is
0.8 Da=tk=0.5
achieved in two or three reactors.
Thus the cost of adding subsequent
Conversion, X

0.6
reactors might not be justified.
Da=tk=0.1
0.4 When Da is small (say 0.1) then the
conversion continues to increase
0.2 significantly with each reactor added.

0.0
0 2 4 6 8 10 12

Number of CSTRs, n

CSTRs in Parallel
Conversion achieved in any one of the reactors (Vi) in parallel is identical to each other
and equal to what would be achieved if the reactant were fed in one stream to one
large reactor of volume equal to volume of all reactors in parallel (V =å(Vi)) 16
 CSTR: Isothermal operation with single reaction: Example

Example
It is desired to produce 90,700 ton of ethylene glycol (EG) per year. The reactor is to
operated isothermally at 55 °C. 16 g mol/dm3 of ethylene oxide (EO) in water is fed to the
reactor together with an equal volumetric flowrate of water containing 0.9 wt% of the
catalyst H2SO4.

If 80% conversion is to be achieved, determine the necessary CSTR volume.

If two 3.0 m3 reactors were arranged in parallel, what is the corresponding conversion?
If two 3.0 m3 reactors were arranged in series, what is the corresponding conversion?

In an attempt to establish the rate information, the

reaction was carried out in a bench top batch reactor.
500 ml of 2M solution of ethylene oxide in water was
mixed with 500 ml of water containing 0.9 wt% sulphuric
acid as a catalyst. The temperature was maintained at
55C. The concentration of ethylene glycol was recorded
as a function of time. Table on the r.h.s gives the
collected data.

17
 CSTR: Isothermal operation with single reaction: Example

Example
It is desired to produce 90,700 ton of ethylene glycol (EG) per year. The reactor is to be
operated isothermally at 55 °C. 16 g mol/dm3 of ethylene oxide (EO) in water is fed to the
reactor together with an equal volumetric flowrate of water containing 0.9 wt% of the
catalyst H2SO4.

If 80% conversion is to be achieved, determine the necessary CSTR volume.

If two 3.0 m3 reactors were arranged in parallel, what is the corresponding conversion?
If two 3.0 m3 reactors were arranged in series, what is the corresponding conversion?

Solution O H2SO4 CH2 OH

CH2 CH2 + H2O
CH2 OH

𝐻 𝑆𝑂
A + B ¾¾®
h t
C
The specified EG production rate is:
kg 1 yr 1 day 1h kg kmol
FC = 90.7 ´ 10 6 ´ ´ ´ = 172.56 = 2.78
yr 365 days 24 h 60 min min min
18
From the reaction stoichiometry: FC = FA0 X
 CSTR: Isothermal operation with single reaction -Example

It is desired to produce 90,700 ton of ethylene glycol (EG) per year. The reactor is to be operated
isothermally at 55 °C. 16 g mol/dm3 of ethylene oxide (EO) in water is fed to the reactor together with
an equal volumetric flowrate of water containing 0.9 wt% of the catalyst H2SO4.

If 80% conversion is to be achieved, determine the necessary CSTR volume.

Solution
Then the required molar flow rate of the ethylene oxide (reactant A):
FC 2.78 kmol
FA0 = = = 3.479 = 58 mol/s
X 0.8 min

Water vB0 v0 vA0, CA01

Ethylene
CA0 oxide

19
 CSTR: Isothermal operation with single reaction -Example
It is desired to produce 90,700 ton of ethylene glycol (EG) per year. The reactor is to operated
isothermally at 55 °C. 16 g mol/dm3 of ethylene oxide (EO) in water is fed to the reactor together with
an equal volumetric flowrate of water containing 0.9 wt% of the catalyst H2SO4.

If 80% conversion is to be achieved, determine the necessary CSTR volume.

Solution
FA0 - FA FA0 - FA0 (1 - X ) FA0 X
1. Design Equation V= = =
- rA - rA - rA

2. Rate Law It is known that this reaction is a first-order reaction with respect to
ethylene oxide

- rA = kCA
We need to know reaction rate constant. To get it the following
experiment was set up

500 ml of 2M solution of ethylene oxide in water was mixed with 500 ml

of water containing 0.9 wt% sulphuric acid as a catalyst. The
temperature was maintained at 55C. The concentration of ethylene
glycol was recorded as a function of time
20
 CSTR: Isothermal operation with single reaction -Example
It is desired to produce 90,700 ton of ethylene glycol (EG) per year. The reactor is to operated
isothermally at 55 °C. 16 g mol/dm3 of ethylene oxide (EO) in water is fed to the reactor together with
an equal volumetric flowrate of water containing 0.9 wt% of the catalyst H2SO4.

If 80% conversion is to be achieved, determine the necessary CSTR volume.

Solution
dN A
Concentration-time Data Mole balance = rAV
dt
Rate Law
Water is present in excess, the concentration of water at
any time is virtually the same as initial concentration and
rate law is independent of water concentration

- rA = kCA
Stoichiometry
Concentrations in any time in terms of conversion:

C A = C A0 (1 - X ) CC = C A0 X

Combine dC A
- = kC A 21
dt
 CSTR: Isothermal operation with single reaction -Example

Solution

Evaluate CA
dC A t
- ò = ò kdt
C A0
CA 0

The initial condition: t=0, CA=CA0

C A0
ln = kt
CA

Defining design equation in the measurable parameter

𝐶"% − 𝐶"
𝐶u = 𝐶"% 𝑋 𝐶u = 𝐶"% 𝐶u = 𝐶"% − 𝐶"
𝐶"%

C A = C A0 - CC 𝐶"% − 𝐶"
𝑋=
𝑋
C A0 - C C
ln = -kt
C A0
22
 CSTR: Isothermal operation with single reaction -Example

Solution
Evaluate
C A0 - CC C - CC
ln A0
C A0 C A0

−1.884 − −0.629
𝑆𝑙𝑜𝑝𝑒 = −𝑘 =
6−2

𝑆𝑙𝑜𝑝𝑒 = −𝑘 = −0.31 𝑚𝑖𝑛96

𝑘 = 0.31 𝑚𝑖𝑛96

The rate law: - rA = 0.311 min -1C A 23

 CSTR: Isothermal operation with single reaction -Example
Solution Now we can proceed with the main problem according to the algorithm for
isothermal reactor design

3. Stoichiometry In flow system we deal with molar flow fluxes. Since 𝑞 = 𝑞%

𝐹" 𝐹"% 1 − 𝑋
𝐶" = = = 𝐶"% 1 − 𝑋
𝑞% 𝑞%
𝐹"% 𝑋 𝐶"% 𝑞% 𝑋 𝑞% 𝑋
4. Combining 𝑉= = =
𝑘𝐶" 𝑘𝐶"% 1 − 𝑋 𝑘 1−𝑋

5. Evaluate The entering volumetric flow rate of EO solution of concentration 16

g mol/dm3 before mixing is:

𝐹"% 58 𝑚𝑜𝑙/𝑠
𝑞"% = = •
= 3.625𝑑𝑚• /𝑠 = 217.5 𝑑𝑚• /𝑚𝑖𝑛
𝐶"% 16 𝑚𝑜𝑙/𝑑𝑚

From the problem statement vB0=vA0

Sept 2009
𝑑𝑚• 𝑔 1 𝑚𝑜𝑙
𝐹.% = 𝑞.% 𝐶.% = 217.5 × 1000 × = 12.08 kmol/min
𝑚𝑖𝑛 𝑑𝑚• 18 𝑔 24
 CSTR: Isothermal operation with single reaction -Example

Solution
The total entering volumetric flow rate of liquid is:

𝑞% = 𝑞"% + 𝑞.% = 217.5 + 217.5 = 435 𝑑𝑚• /𝑚𝑖𝑛

Now we can estimate reactor volume taking into consideration the reaction rate
constant
𝑞% 𝑋 435 𝑑𝑚• 𝑚𝑖𝑛96 0.8 • •
𝑉= = = 5594.9 𝑑𝑚 = 5.6 𝑚
𝑘 1−𝑋 0.31 𝑚𝑖𝑛96 1 − 0.8

A tank of 5.6 m3 is necessary to produce 90,700 ton of ethylene glycol (EG) per year if
conversion of reactant is 80%
If two 3.0-m3 reactors were arranged in parallel, what is the corresponding conversion?

Solution (Continuation)
For two CSTR reactors arranged in parallel each reactor will be fed by 217.5 dm3/min (v0/2)
𝑉𝑘 𝑋 𝜏𝑘
= 𝜏𝑘 = Then 𝑋 =
𝑞% 1−𝑋 1 + 𝜏𝑘
𝑉 3000 𝑑𝑚•
where 𝜏=𝑞 = = 13.94 𝑚𝑖𝑛
%f 217.5 𝑑𝑚• 𝑚𝑖𝑛96 25
2
 CSTR: Isothermal operation with single reaction -Example

Solution (Continuation)

The Damköhler number

Da = tk = 13.94 min ´ 0.311 min -1 = 4.34
tk Da 4.34
X = = = = 0.81
1 + tk 1 + Da 1 + 4.34
The conversion exiting each 3 m3 CSTR in parallel is 81%.

Note: The overall volume of 2 CSTR is slightly larger than estimated volume needed to
reach 80% conversion.
If two 3.0 m3 reactors were arranged in series, what is the corresponding conversion?

Solution
If the 3-m3 CSTR are arranged in series, the conversion in the first reactor:

tk Da 𝑉 3000 𝑑𝑚•
X = = where 𝜏= = = 6.97 𝑚𝑖𝑛
1 + tk 1 + Da 𝑞% 435 𝑑𝑚• 𝑚𝑖𝑛96
26
 CSTR: Isothermal operation with single reaction -Example

Solution

Solving for the conversion exiting second reactor:

𝑉𝑘 𝑋h − 𝑋6 X 1 + Da X 1 + tk
𝜏𝑘 = 𝐷𝑎 = Da - DaX 2 = X 2 - X 1 X2 = =
𝑞% 1 − 𝑋h 1 + Da 1 + tk

The conversion obtained with 2 CSTRs in series

0.684 + 2.167
X2 = = 0.90
1 + 2.167

Earlier it has been shown that conversion for CSTRs in series:

1 1
X = 1- = 1- = 0.90
(1 + Da )
n
(1 + 2.167)
2

This reactor arrangement will provide a higher rate of production than 90,700
ton of ethylene glycol (EG) per year

27
 CSTR: Non-isothermal operation

Consider a steady-state operation of a CSTR with

first order exothermic reaction
Heat is removed from the reactor by a cooling jacket
or a cooling coil. FA0 T0

Heat removal rate (large coolant flow rates)

Ta Ta
! = UA(T - T )
Q a

T
Steady-State No phase change, constant CP ,
no shaft work Energy Balance

é
[ ]
ù !
n
- A0 å Q - - D + D - ú +Q = 0
"
ê F i C Pi (T Ti0 ) H Rx C P (T TR ) FA0 X
ë i =1 û

é
[ ] ù
n
ê - FA0
êë
å
i =1
!
Q i C Pi ( T - Ti 0 ) - DH Rx + DC P ( T - TR ) FA0 X ú + UA( Ta - T ) = 0
úû
28
 CSTR: Non-isothermal operation

é
[ ]ù
n

ê A0 å i Pi
- Q - - D + D - ú + UA(Ta - T ) = 0
!
F C (T Ti0 ) H Rx C P (T TR ) FA0 X
ë i =1 û

Neglecting DCP
é
[ ] ù
n

ê A0 å i Pi
- Q - - D ú + UA(Ta - T ) = 0
!
F C (T Ti0 ) H Rx FA0 X
ë i =1 û
Solving for X

UA(Ta - T ) n
+ å Qi C Pi (T - Ti 0 )
Energy balance FA0 Fi 0
X EB = i =1 Qi =
[-DH Rx !
] FA0

FA0 X MB 𝜏𝑘
CSTR mole balance V= 𝑋Š. =
- rA ( X MB , T ) 1 + 𝜏𝑘

Size the CSTR by setting X MB = X EB 29

 CSTR: Non-isothermal operation

é
[ ] ù
n

ê A0 å i Pi
- Q - - D ú + UA(Ta - T ) = 0
!
Energy balance F C (T Ti0 ) H Rx FA0 X
ë i =1 û
Let ∑-+L% Θ+ 𝐶‹+ and all species/compounds at the inlet are at the same temperature
T0.
After rearrangement it follows:
UA
- XDH !
= CP0 (1 + k )(T - Tc ) with k=
Rx FA0CP0

kTa + T0
Tc =
CP0 ( 1 + k )( T - Tc ) 1+ k
X EB =
- DH Rx
!

(-DH Rx
!
) X EB
T = Tc +
CP0 (1 + k )
Sizing of a CSTR
a) X specified calculate V and T
b) V specified calculate X and T 30
 CSTR: Non-isothermal operation

CP0 (1 + k )(T - T ) c
Consider a first-order reaction X EB =
- DH Rx
!
1. CSTR mole balance
FA0 X
V=
- rA
X
2. Rate Law
1
- rA = kCA X CSTR
3. Stoichiometry 0.75

C A = C A0 (1 - X ) 𝑋Š.
0.50
4. Combining X EB
FA0 X q0 X
V= = 0.25
kC A0 (1 - X ) k (1 - X )
350 450 TCSTR 600
tk t [ A exp( - E / RT )] T
X MB = =
1 + tk 1 + t [ A exp( - E / RT )]

5. Solving mole balance and energy balance

31
 CSTR: Non-isothermal operation

Multiple Steady States

X In this example we have three solutions

1 X EB of the mole and energy balances,
X CSTR
therefore, three possible operating
0.75 X MB steady-states are possible for this
reactor
0.50 Energy balance for a CSTR

0.25 - XDH Rx
!
= CP0 (1 + k )(T - Tc )
350 450 with k =
UA kTa + T0
TCSTR 600 Tc =
T FA0CP0 1+ k
n
C P0 = å Qi C Pi
Mole balance for a CSTR i =1
FA0 X - rAV
V= X= Heat generated Heat removed
- rA FA0
Replacing in the energy balance (-rAV / FA0 )(-DH Rx
!
) = CP0 (1 + k )(T - Tc )
G (T ) = R(T ) 32
 CSTR: Non-isothermal operation

Heat Removed Term R(T) Heat generated Heat removed

(-rAV / FA0 )(-DH Rx

!
) = CP0 (1 + k )(T - Tc )
G (T ) = R(T )
UA kTa + T0
R(T ) = CP0 (1 + k )(T - Tc ) with k= Tc =
FA0CP0 1+ k
slope
Vary the entering temperature T0 Vary parameter k

R(T) Tc=Ta Tc=T0

R(T)
k =¥ k =0

Increasing T0
Increasing k

Tc1 Tc2 T Ta T0 T
33
 CSTR: Non-isothermal operation

Heat Generated Term G(T) Heat generated Heat removed

G (T ) = (-DH ) X! (-rAV / FA0 )(-DH Rx

!
) = CP0 (1 + k )(T - Tc )
Rx
G (T ) = R(T )
To plot G(T) as a function of T we must replace X = f(T)

1. Mole balance (CSTR) 2. Rate Law 3. Stoichiometry

FA0 X C A = C A0 (1 - X )
V= - rA = kCA
- rA
4. Combine
FA 0 X q0 X tk
V= = X=
kC A0 ( 1 - X ) k ( 1 - X ) 1 + tk
5. Replace into G(T)
(-DH Rx
!
)tk
G (T ) =
1 + tk
6. Replacing Arrhenius equation For others reaction order and reversible
(-DH )tA exp(- E / RT )
!
reaction similar equations can be
G(T ) = Rx
derived by solving the CSTR mole
1 + tA exp(- E / RT ) balance for X
34
 CSTR: Non-isothermal operation

(-DH Rx
!
)tA exp(- E / RT )
G(T ) =
1 + tA exp(- E / RT )
At very low temperatures the second term in the denominator can be neglected

Low temperatures G (T ) = (-DH Rx

!
)tA exp(- E / RT )

High temperatures G (T ) = (-DH Rx

!
)

G(T) G(T)
Low E
Increasing t
High E

T T
35
 CSTR: Non-isothermal operation

The point of intersection of R(T) and G(T) R(T ) = CP0 (1 + k )(T - Tc )

represents a steady-state condition for the
(-DH Rx
!
)tA exp(- E / RT )
CSTR G(T ) =
1 + tA exp(- E / RT )
kTa + T0
Tc =
1+ k
R(T) G(T) UA
k=
Upper steady states FA0CP0
G(T) 6 8 9 Ts 8
9
3 6
R(T) 3 Unstable
5 5

7 7
4
2 Ts2 4 Lower steady states
2
1 Ts1
1 Ignition temperature

. Ts3 . T07
TC1 Ts1 TC2 Ts2 Ts7 T01 T02 T0
T
Ts1 Extinction temperature
36
 CSTR: Non-isothermal operation

Stability on Multiple Steady State R(T ) = CP0 (1 + k )(T - Tc )

(-DH Rx
!
)tA exp(- E / RT )
The Steady State point 5 is unstable. Why? G(T ) =
1 + tA exp(- E / RT )

R(T)
G(T)

G(T) G(T)>R(T) 6 R(T)>G(T)

R(T)
R(T)>G(T) 5

4
G(T)>R(T)

.
Ts4 Ts5 Ts6
37
 CSTR: Non-isothermal operation

Runaway Reactions in a CSTR R(T ) = CP0 (1 + k )(T - Tc )

When ignition occurs the steady state temperature (-DH Rx
!
)tA exp(- E / RT )
will jump from the lower steady state to the upper G(T ) =
1 + tA exp(- E / RT )
steady state

R(T)
G(T)
Upper steady states 9 G(T)
Ts 8 8
6
3 Unstable R(T)
5
7
7
Ts2 4 Lower steady states
2
Ts1
1 Ignition temperature

.
T01 T02 T07 T0 .
Ts4 Ts7 Ts8 T

38
 CSTR: Non-isothermal Multiple reactions

We will consider the case of non-isothermal multiple reactions in a CSTR only

1. Single reaction: Steady-state energy balance, no phase change, constant CP , no shaft work

é
[ ] ù !
m

ê
ë
- FA 0 å
i =1
Q i C Pi
(T - T0 ) - DH Rx FA 0 X ú+Q = 0
û

2. CSTR mole balance

- rAV = FA0 X

3. Combining
é m
ù !
ê A0 å i Pi
- F Q C (T - T0 ) + [ DH Rx ][rAV ]ú +Q = 0
ë i =1 û
4. For q independent multiple reaction: Steady-state energy balance
i = Reaction number
é m q
ù !
ê A0 å i Pi
- F Q C (T - T0 ) + V å ri, j DH Rxij (T ) ú +Q = 0 j = Species
ë i =1 i =1 û
39
 CSTR: Non-isothermal Multiple reactions
é m q
ù !
ê A0 å i Pi
- F Q C (T - T0 ) + V å ri, j DH Rxij (T ) ú +Q = 0
ë i =1 i =1 û

é Moles of j reacted in reaction i ù é Joules " released" in reaction i ù

r
The term i , j DH Rxij = ê ú ´ê ú
ë Volume × Time û ë Moles of j reacted in reaction i û

é Joules " released" in reaction i ù

ri , j DH Rxij = ê ú
ë Volume × Time û

5. Heat removal rate (large coolant flow rates)

Q! = UA(Ta - T ) FA0 T0

6. CSTR energy balance, n multiple reactions

Ta Ta
é m n ù
ê - FA 0
êë
å
i =1
Q i C Pi ( T - T0 ) + V å
i =1
ri , j DH Rxij ( T )ú + UA( Ta - T ) = 0
úû
T

40
 CSTR: Non-isothermal Multiple reactions

CSTR energy balance, n multiple reactions

é m n ù
ê - FA 0 å Q i C Pi ( T - T0 ) + Vå ri , j DH Rxij ( T )ú + UA( Ta - T ) = 0
ëê i =1 i =1 ûú

For example for two parallel reactions

kD
A D (desired)
kU
A U (undesired)

é m
ù
ê- FA0 å Qi CPi (T - T0 ) + Vr1 A DH Rx1 A (T ) + Vr2 A DH Rx 2 A (T )ú + UA(Ta - T ) = 0
ë i =1 û

41
 CSTR: Non-isothermal Multiple reactions

Determination of the operating time required to attain an expected conversion for a batch
reactor with multiple reactions follows a specific algorithm.

1. Number each and every reaction separately

2. Mole balance on each and every species

3. Rate law for every reaction

Rates
4. Relative rate law for every reaction

5. Net rates of reaction for each species

Stoichiometry 6. Calculate the concentrations

7. Combine the concentration, rate law and mole balance

8. Evaluate the parameters required such as flow rates rate constants etc.

9. Solve the system of equations analytically or numerically (most likely)

calculating the temperature, rate constant and concentration while increasing
the conversion in small steps Xi+1 =Xi + DX
42
 CSTR: Non-isothermal Multiple reactions

Example : Multiple reactions in a CSTR

The elementary liquid-phase reactions take place in a 10 dm3 CSTR.
k1 k2
A B C
C PA = C PB = C PC = 200 J / (mol × K) k1 = 3.03 min -1 at 300 K, with E1 = 9900 cal/mol
DH Rx1 A = -55,000 J/molA k2 = 4.58 min -1 at 500 K, with E2 = 27,000 cal/mol
DH Rx 2 B = -71,000 J/molB UA = 40,000 J/(min × K) with Ta = 57 ! C
- What are the effluent concentrations for a volumetric feed rate of 10 dm3/min at a
concentration of A of 0.3 mol/dm3?

Solution
1. Combined mole balance and rate law for A
q ( C - CA ) C A0
V = 0 A0 CA =
k1C A 1 + tk1
2. Combined mole balance and rate law for B
q0 ( 0 - C B ) C B q0 C B q0 tk C tk1C A0
V= = = CB = 1 A =
Sept 2009 - rB ( r1B + r2 B ) G. Lik1Puma
C A -(Univ.
k 2 C Bof Nottingham) 1 + tk 2 (1 + tk1 )(1 + tk 243)
 CSTR: Non-isothermal Multiple reactions

k1C A0
- r1 A = k1C A =
1 + tk1
k 2tk1C A0
- r2 B = k 2C B =
(1 + tk1 )(1 + tk 2 )
4. Non-isothermal energy balance
é m q
ù
ê A0 å i Pi
- F Q C (T - T0 ) + V å ri, j DH Rxij (T ) ú + UA(Ta - T ) = 0
ë i =1 i =1 û
G (T ) R (T )

é tk1DH Rx1 A tk1tk2 DH Rx 2 B ù

ê- - ú = C p (1 + k )(T - Tc )
ë 1 + tk1 (1 + tk1 )(1 + tk2 ) û
UA 40,000 J/(min × K)
with k= = = 0.667
FA0C p A (0.3 mol/dm )(1000 dm /min)(200 J/(mol × K)
3 3

Numerical
Sept 2009 G. Li Puma (Univ. of Nottingham)
T0 + kTa 283 + (0.667)(330) Solution
Tc = = = 301.8 K
1+ k 1 + 0.667
44