CE 561

11-21

CSTR Design Equations

Assumptions

Perfect Mixing
One fluid volume in which reaction takes place
Every rate is normalized per fluid volume
One fluid stream leaving the reactor
Reactor is stationary
No phase changes during reaction
No net difference in fluid kinetic and potential energy between inlet and outlet

Design Equations

n!i dV fluid V fluid dn!i n!iV fluid dV!

0
!
+

=
n
n!i + V fluid
i
2
!
!
!
V dt
V dt
dt
V
Q! W! =

i=all
species

0T

dT + V
!
n
C
fluid
i pi
T0

j=all
reactions

rj H j

Steady State Design Equations

0 = n!i0 n!i + V fluid

i, j rj

j=all
reactions

Q! W! =

i=all
species

0T

dT + V
!
n
C
fluid
i pi
T0

j=all
reactions

(r H )
j

j T

i, j rj

j=all
reactions

V fluid
V!

i=all
species

dV fluid
dT
dP
n!i C pi

V
+
P
fluid
dt
dt
dt

Steady-State Example
Irreversible reaction (1) is going to take place in an adiabatic
CSTR with a volume of 500 cm3. A solution 1.0 cm3 s-1
containing equal amounts of A and B (0.015 mol cm-3) at 50 C
will be used. The heat capacity of the fluid is essentially equal
to that of the solvent, 0.35 cal g-1 K-1 and can be considered to
be constant. The (constant) density of the fluid is 0.93 gm
cm-3. The rate expression for reaction (1) is given in equation
(2), and the heat of reaction (1) may be assumed to be
constant and equal to -20 kJ mol-1. At these conditions three
different steady states are possible; determine the conversion
and outlet temperature for each of them.
A + B Y + Z!

(1)

cm 3
25 kcal mol1
r!1 = 3.24 10
exp
C AC B

RT
mol s

(2)

12

Solution

Steady state mole and energy balances

0 = n! 0A n! A V fluid r1

0 = n! B0 n! B V fluid r1

0 = n!Y0 n!Y + V fluid r1

0 = V! fluid C" p, fluid T T 0 + V fluid r1H1 T

0 = n!Z0 n!Z + V fluid r1

Substitute rate expression, heat capacities and heat of reaction

cm 3
25 kcal mol1
r1 = 3.24 10
exp
C AC B
RT
mol s

12

Reduce the number of variables until equal to the number of design

equations
n! A
CA =
V!

n! B
V!
After substitution of rate expression, expressions for concentrations and
known constants, 5 equations and 5 unknowns
Solve for the five unknowns
n! 0A n! A
Use the results to calculate the conversion: f A =
n! 0A
fA = 97.6 %
T = 538 K

CB =

The Importance of
Start-up and Shut-down

While processes may be designed to operate at steady state,

occasionally they still need to be started up or shut down.
Maintenance of equipment
Interruption of feed, heating or cooling

Some CSTR processes, particularly if they involve exothermic

reactions, can go out of control leading to an explosion or other

catastrophe if they are not started up and shut down in an
appropriate manner
We will see that some CSTR processes can have more than one
steady state operating condition for the same set of operating
parameters
The procedure used to start the reactor up will determine whether it reaches the
desired steady state or an undesired one

A Few Start-up Possibilities

Operate as a batch reactor until conversion nears the

desired steady state, then slowly add in the feed and heat
transfer.
Start the feed flow while heating and then adjust heat
transfer over time to bring the system to steady state.
Fill the reactor with a mixture with the desired final steady
state composition, then start heating, eventually start flow
and adjust heat transfer to bring the system to steady state.
Heat system to desired operating temperature with one
reagent flowing, then gradually add second reagent to the
feed while adjusting heat transfer to bring the system to
steady state.

Start-up Example (Transient CSTR)

A 500 cm3 CSTR needs to be started up. It will operate adiabatically
with a feed of 1.0 cm3 s-1 containing equal amounts of A and B
(0.015 mol cm-3) at 50 C. The heat capacity of the fluid is
essentially equal to that of the solvent, 0.35 cal g-1 K-1 and can be
considered to be constant. The (constant) density of the fluid is 0.93
gm cm-3. The reaction of interest is given in equation (1). The
standard heat of this reaction is constant and equal to -20 kJ mol-1.
The rate expression is given in equation (2). For start-up purposes,
the reactor will first be filled with pure solvent at 190 C, and then a
valve will be opened, admitting the feed. How long will it take for the
reactor to reach 260 C, and what will the conversion of A equal?
A + B Y + Z!
3
1

cm
25
kcal
mol
!r = 3.24 1012
C AC B
1
mol s exp
RT

(1)

(2)

Solution

Mole and energy balances

dn!
V!
=
( n! n! V r )
dt V
0
A

fluid 1

fluid

dn!Z
V!
=
n!Z0 n!Z + V fluid r1
dt V fluid

dn! B
V!
=
n! B0 n! B V fluid r1
dt V fluid

dn!Y
V!
=
n!Y0 n!Y + V fluid r1
dt V fluid

0
dT V! fluid C" p, fluid T T V fluid r1H1 T
=
dt
V fluid fluid C" p, fluid

Identify variables that must be re-written in terms of molar flow rates and
temperature and do so

cm 3
25 kcal mol1
r1 = 3.24 10
exp
C AC B
RT
mol s

12

CA =

n! A
V!

CB =

n! B
V!

Determine the initial values of the outlet molar flow rates and the outlet
temperature

The reactor is initially filled with only solvent, so the initial outlet molar flow rates of A, B, Y and
Z are zero
The solvent is initially at 190 C, so that will be the initial outlet temperature

Identify the stopping criterion and integrate the design equations until it is
reached

Here the stopping criterion is reaching a specified temperature

Results

Integrated numerically, stopping when the temperature reaches 260 C

This happens after 1450 s

Conversion at that time is 97.3 %

Outlet concentration of A and T versus time can be plotted

Some interesting transient behavior

System appears to be approaching steady state

CA

Steady State CSTR Design Equations

are Non-Linear

Non-linear equations can have multiple solutions

Often only one solution is physically meaningful

With steady state CSTRs, there can be multiple solutions where each
solution is physically meaningful
A simple example
AR

V fluid
E
n! n! A =
k0 exp
n! A
!
V
RT
0
A

V fluid
E
n! R =
k0 exp
n! A
!
V
RT
n!

0
solvent

V fluid
E
0

C p,solvent (T T ) =
k0 exp
n! A H
!
V
RT

The Terms in the Energy Balance

n!

0
solvent

E
0

C p, solvent T T = k0 exp
n! A H
RT

Heat being absorbed

by the fluid in order
to raise its temperature
from the feed
temperature to the
outlet temperature

Heat being generated

as a consequence of
the reaction taking
place within the
CSTR

A Graphical Solution
1.Guess the outlet T
2.Solve the A mole balance for nA
3.Solve the R mole balance for nR
4.Calculate the heat absorbed term and the heat generated
term of the energy balance
5.Plot them both on a graph of heat (as y) versus T (as x)
6.Repeat steps 1 through 5 many times to generate curves
for the heat absorbed and heat generated versus T
7.Recall, the only place where the energy balance is satisfied
is when the two heats are equal
7.1.That is, the only points on the graph that represent solutions to the
steady state CSTR design equations are points where the two curves
intersect

Results of the Graphical Approach

generated

HeatGeneratedorRemoved

absorbed

Results shown are for one particular

Temperature(K)

set of operating parameters

Inlet T, inlet molar flow rates,
reactor volume
Curves would shift if any of these
parameters was changed
In this case there are three solutions
to the steady state CSTR design
equations
In all three cases the outlet
temperature and outlet molar flow
rates make sense physically
We could have found these
solutions using algebra, too

Stability of CSTR Steady States

absorbed

generated

Suppose the system was

HeatGeneratedorRemoved

perturbed slightly away from

a given steady state
Would it tend naturally to
return to that steady state
-

if so, its a stable steady state

if not, its an unstable steady
state.

The middle steady state

Temperature(K)

here is unstable; the other

two are stable

Steady-State Example
Irreversible reaction (1) is going to take place in an adiabatic
CSTR with a volume of 500 cm3. A solution 1.0 cm3 s-1
containing equal amounts of A and B (0.015 mol cm-3) at 50 C
will be used. The heat capacity of the fluid is essentially equal
to that of the solvent, 0.35 cal g-1 K-1 and can be considered to
be constant. The (constant) density of the fluid is 0.93 gm
cm-3. The rate expression for reaction (1) is given in equation
(2), and the heat of reaction (1) may be assumed to be
constant and equal to -20 kJ mol-1. At these conditions three
different steady states are possible; determine the conversion
and outlet temperature for each of them.
A + B Y + Z!

(1)

cm 3
25 kcal mol1
r!1 = 3.24 10
exp
C AC B

RT
mol s

(2)

12

Solution

Steady state mole and energy balances

0 = n! 0A n! A V fluid r1

0 = n! B0 n! B V fluid r1

0 = n!Y0 n!Y + V fluid r1

0 = V! fluid C" p, fluid T T 0 + V fluid r1H1 T

0 = n!Z0 n!Z + V fluid r1

Substitute rate expression, heat capacities and heat of reaction

cm 3
25 kcal mol1
r1 = 3.24 10
exp
C AC B
RT
mol s

12

Reduce the number of variables until equal to the number of design

equations
n! A
CA =
V!

n! B
V!
After substitution of rate expression, expressions for concentrations and
known constants, 5 equations and 5 unknowns
Solve for the five unknowns
n! 0A n! A
Use the results to calculate the conversion: f A =
n! 0A
CB =

fA = 97.6 %!

38.8%!

0.03%

T = 538 K!

409 K!

323 K

Getting to Steady State

The start-up or transient procedure used prior to

the steady state will determine which steady state

is reached
Reactor design must include a safe and efficient start-up
procedure that will bring the system to the desired
steady state

System is typically designed to operate at one of

the steady states, not either

In the example here, one steady state corresponds to a

reactor with a high conversion of reactants
The other corresponds to nearly no conversion at steady
state, the reactants just flow in and then flow out with
almost no reaction taking place

Example of Effect of Startup

A 500 cm3 CSTR needs to be started up. It will operate adiabatically
with a feed of 1.0 cm3 s-1 containing equal amounts of A and B
(0.015 mol cm-3) at 50 C. The heat capacity of the fluid is
essentially equal to that of the solvent, 0.35 cal g-1 K-1 and can be
considered to be constant. The (constant) density of the fluid is 0.93
gm cm-3. The reaction of interest is given in equation (1). The
standard heat of this reaction is constant and equal to -20 kJ mol-1.
The rate expression is given in equation (2). For start-up purposes,
the reactor will first be filled with pure solvent at 180 C, and then a
valve will be opened, admitting the feed. How long will it take for the
reactor to reach 260 C, and what will the conversion of A equal?
A + B Y + Z!
3
1

cm
25
kcal
mol
!r = 3.24 1012
C AC B
1
mol s exp
RT

(1)

(2)

Results

Initial Solvent T = 190 C

Initial Solvent T = 180 C

When are Multiple Steady States Possible

The point where the solution to a set of equations splits into multiple

branches is known as a bifurcation point

Analyzing equations to find these points is called bifurcation analysis
Illustrate for the example of a liquid phase, exothermic, first order reaction
A B, with constant fluid volume in the reactor and constant volumetric
flow rate
Start with the transient material and energy balances
dC
! A0 VC
! A V fluid k0 exp E C A
V fluid A = VC
dt
RT
dT
E
V fluid fluid C! p, fluid
= fluid C! p, fluid (T 0 T ) V fluid H 0 k0 exp
C A UA (T Tex )
dt
RT

Define dimensionless variables

C A0 C A
x1 =
C A0

T T0 E
x2 =

T 0 RT 0

!
Vt
t =
V fluid

Then

C A = C (1 x1 )
0
A

RT 0
T = T 1+
x2
E

V fluid
t=
t
V!

 and

! A0 dx1
dC A
VC
0 dx1
= C A
=
dt
dt
V fluid dt

dT
T 0 dx2
T 0V!
dx2
=
=
E dt
dt E dt
V

fluid
RT 0
RT 0

Substitution into the material and energy balances

x
dx1
= x1 + Da (1 x1 ) exp 2 = f1 ( x1 , x2 )
x
dt
1+ 2

x
dx2
= x2 + B Da (1 x1 ) exp 2 ( x2 x2ex ) = f2 ( x1 , x2 )
x
dt
1+ 2

where

V k exp { }
Da = fluid 0
V!
x2ex

Tex T 0 E
=

T 0 RT 0

( H C )
0
A

E
B=
fluid C! p, fluidT 0 RT 0
0

E
RT 0

UA
V fluid fluid C! p, fluid

 At steady state, f

and f2 are each equal to zero, and so are equal to each

other (adding subscript s to denote steady state):

2s
2s
0 = x1s + Da (1 x1s ) exp
0 = x2 s + B Da (1 x1s ) exp
( x2 s x2ex )
x2 s
x2 s
1+

1+

x
x1s + Da (1 x1s ) exp 2 s
x
1+ 2 s

x
2s
= x2 s + B Da (1 x1s ) exp x

1+ 2 s

from which

x2 s =

Bx1s + x2ex
1+

Substitution into f

gives

Bx1s + x2ex
0 = x1s + Da (1 x1s ) exp

1
(1+ ) + ( Bx1s + x2ex )

( x2 s x2ex )

Bifurcation Points

Plots of x

vs. Da can have 2

shapes shown at right
1s

As can x2s vs. Da since

Bx1s + x2ex
1+
Multiple steady states are found in
the regions where
x2 s =

dDa
<0
dx1s

For this particular case bifurcation points are found when

d
x1s

<0

dx1s

Bx1s + x2ex

1 x exp
(
)

1s

1
(1+ ) + ( Bx1s + x2ex )

 But they are real only when

x2ex
4 1+ +

1+

x2ex
4
1+

or if x2c = 0, when

4 (1+ )
4

or if additionally, is very large (high activation energy)

B 4 (1+ )

Most generally

Any time a plot of a parameter as a function of a variable has a maximum or minimum, multiple
steady states will exist and the maximum or minimum is a bifurcation point

Stability of Steady States

It is convenient to define perturbation variables

dy dx
y1 = x1 x1s x1 = y1 + x1s 1 = 1
dt
dt
dy2 dx2
=
and similarly
dt
dt
Substitution into the transient material and energy balances gives:

x
dy1
= x1 + Da (1 x1 ) exp 2 = f1 ( x1 , x2 )
x
dt
1+ 2

x
dy2
= x2 + B Da (1 x1 ) exp 2 ( x2 x2ex ) = f2 ( x1 , x2 )
x
dt
1+ 2

Then linearize the equations by expanding f

and f2 in a Taylor series

about x1s and x2s and deleting second- and higher-order terms
1

f1 ( x1 , x2 ) f1 ( x1s , x2 s ) +
f1 ( x1 , x2 )

f1
x1

f1
x1

x1s ,x2 s

( x1 x1s ) + x1

x1s ,x2 s

( y1 ) + x1

2 x1s ,x2 s

2 x1s ,x2 s

( y2 )

( x2 x2 s )

 Linearized material and energy balances can be written in matrix form

dy
dt

= Ay

with

A=

f1
x1
f2
x1

ss

f1
x2

ss

ss

f2
x2

ss

x1 x1s
y=
x2 x2 s

With the equations in this form, the steady state used in the expansion is
stable if y 0 as t

The answer depends upon the real part of the eigenvalues of the matrix A
If Re() < 0, the yi go to zero as t goes to infinity because

yi et

If Re() < 0, the steady state is locally stable

The real part of the eigenvalues are less than zero if they meet
slope criterion:

( )

det A > 0
dynamic criterion:

( )

tr A < 0

 The criterion involving the determinant of the matrix A is called the slope criterion

If it is not satisfied, they equations will fly off to a different steady state
In the present case this criterion reduces to
2
B 2

2
x2ex
2 + B (1+ ) x1s + 1+ +

>0
2

(1 x1s ) 1+ x2 s (1+ ) + 2B 1+ + x2ex B (1+ ) x1s

The criterion involving the trace of the matrix A is called the dynamic criterion

If it is not satisfied, they system undergoes oscillations that do not die out over time
In the present case this criterion reduces to

2
2

2
2
+

B
B
2B
2Bx

(
)
3
2ex

x1s B + 2
2
x1s
2
2
(1+ )

(1+ )
(1+ )

2

2 ( 2 + ) B 2 x2ex B ( 2 + ) 2 x2ex ( x2ex )
1

+
+ 2
x1s < 0
2 + B + (1+ )
2
2

1+

1+

(
)
(
)
(1+ )

(1 x1s ) 1+ x2 s

x2ex
2 ( 2 + ) Bx2ex

2
+

+
+
2
+

(
)
(
)

(1+ )

1+

(
)