Multiple Steady States in a CSTR

Stability and Multiplicity

Stability tendency of a system to remain in a certain state Multiplicity a system to have more than one state available to it, e.g. temperature

Multiple Steady State in a CSTR

For first-order reaction From mole balance: = . = .

From the energy balance (CSTR with heat exchange):

( ) X +

=
=1

( 0)

Neglecting shaft work in CSTR and setting = 0

. . = =

Substituting mole balance into energy balance:

. ( ) = =1

( 0) +

( )

Multiple Steady State in a CSTR

Define the ratio of the amount of heat transferred relative to the amount of heat used to heat up the reaction mixture as:

=1 .

The simplified form:

. ( ) = =1

0 + ( )

. ( )=

)
=1

1 + 0

Multiple Steady State in a CSTR

We recognize on the left hand side of the equation, we have heat generated by the chemical reaction, G(T): = . ( )

Whereas the right hand, we have heat removed from the reactor (by heat transfer and mass flow), R(T):

() =
=1

1 + 0

Heat Generation term

Investigating the function: . = = .

To plot heat generated G(T) as a function of reaction temperature, solve for X as a f(T) using mole balance, rate law and stoichiometry. 1st order reaction:

=
= = (1 )

. = (1 ) (1 )

Heat Generation term

Solving for X gives: . = 1 +

Which then yields: . . = = . = 1 +

Heat generation is a function of residence time in the CSTR With: = . = 1 +
.

1+

Heat Generation term

= . = 1 +
.

1+

At low temperatures k is small and so k<<1. In this region, the above equation can be simplified with: =
.

At high temperatures k is large and so k>>1, which gives an approximation:

=

Heat Generation term

G(T) shown as a function of T for two different activation energies, E. If flowrate or reactor volume increased so as to increase , G(T) changes

Heat Generation term

G(T) can be derived for other reaction orders and for reversible reactions. For example, for second-order liquid phase reaction: = 2 + 1 4 + 1 2

[ 2 + 1 4 () = 2

+ 1]

Heat Removal term

Analysing the heat removal function:

() =
=1

1 + 0

R(T) increases linearly with temperature, with gradient varying with K. As entering temperature TiO is increased, the line retains the same slope but shifts to the right:

Heat Removal term

Varying the non-adiabatic parameter, K. If K increases either by decreasing the molar flow rate or increasing heat-exchange area, the slope of R(T) increases and intercept moves to the left

=
=1

1 + 0

=1 .

Ignition-Extinction Curve
By equating the heat generation term G(T) with the heat removal term (G(T), the steady-state operation in a CSTR can be found. The points of intersection of R(T) and G(T) give the temperature the reactor can operate at steady state. Increasing the inlet temperature, TiO:

Ignition-Extinction Curve

Entering temperature (T0) T01 (a) T02 (b) T03 (c) TS4

Steady State Reactor Temperatures (TS) TS1 TS2 TS5 TS3 TS6

T04 (d)
T05 (e) T06 (f)

TS7
TS10

TS8
TS11 TS12

TS9

Ignition Temperature
Start from T01, increase entering temperature. Follow bottom line until T05 is reached.

Any fraction of temperature increase beyond T05 the steady state T will jump to TS11.
The temperature at which jump occurs is called the ignition temperature.

Extinction Temperature
Start from T12, decrease entering temperature. Follow top line until T02 is reached.

Any fraction of temperature decrease below T02 the steady state T will drop to TS2.
The temperature at which jump occurs is called the extinction temperature.

Perturbation to steady states

If operating at TS9 or TS7. Small perturbation up in T results in R(T) > G(T), hence T move back to TS9 eventually. Vice versa for perturbation down in T. Locally stable steady states. For middle point 8 represent unstable steady state temperatures.

If steady state at TS8 and sudden increase in T, G(T) > R(T), T continue to increase until TS9.
Vice versa for sudden decrease.

Runaway Reactions
In many reacting systems, the temperature of the upper steady state may be sufficiently high that it is undesirable or dangerous to operate on. Runaway is said to occur when at the ignition temperature is exceeded. At this point, the slope of G(T) and R(T) are equal. dG(T)/dT = dR(T)/dT. From the heat generation term: ( ) =

Assuming heat of reaction ( ) is temperature independent:

( ) () = For irreversible reaction: = . =

. ()

Runaway Reactions
() . = = () 2 2

Substituting back into tangent of heat generation curve: ( ) () = = () 2 2

From the heat removal term:

() =
=1

1 + 0

() =
=1

) 0 + 1 +

1 + ( )

Runaway Reactions
The tangent of the heat removal is given by: () = () =
=1 )

1 + ( ) 1 +

)
=1

() () = At the point where the tangents are equal, we have: () () = 2 () () =

Also at this point, G(T)=R(T): 2 =

Runaway Reactions
If the difference between reaction temperature and Tc is exceeded 2 > Transition to the upper steady state will occur! Runaway! For many industrial reactions E/RT is typically between 14 and 24. Reaction temperatures, T may be 300 to 500 K.

Consequently this critical temperature difference T-Tc will be somewhere around 15 to 30 K.