Example Fi o  Vcio

N
Steady states and dynamic F
i 1
i
o
H io  F o c pm (T o  Tref )  V  c p (T o  Tref )
behavior of non isothermal CSTR
V  const
c p  const.
irreversible highly exothermal 1st order reaction
A1(l )  products
rV  k (T )c1 mol / m3 / s
 E  1 1 
k (T )  k (To ) exp      
 R  T To  

Material and energy balances

dc1
VR  V (c1o  c1 )  k (T )c1VR
dt

 Vc p (To  T )  ( r H )k (T )c1VR  S H Tm  T 

dT
VR c p Fi  Vci
dt
N

F i H i  Fc pm (T  Tref )  V  c p (T  Tref )
c1o  c1 i 1
X 
c1o
dX X
V    k (T ) 1  X 
  R dt 
V

Tad 
  r H c1o dT (To  T )
c p   Tad k (T )(1  X )   Tm  T 
dt 
S H t  0, X  X ini ( 0), T  Tini
 
V R c p
Steady states Parameters:  , k (To ), E / R, Tad ,

dX k
 0 X* 
dt 1  k
dT Tad
 0  T *  To  X*
dt 1  
Mapping of steady states
Tad k
T *  To 
1   1  k
1   1  k  T *  To   Tad k  0
T *
 To  k (T * ) 2    k (T * ) T *  To   Tad k (T * )    T *  To   0

Algorithm of steady states’ mapping:

1. we choose the T * , saying 299 K
2. we solve quadratic equation for unknown  1,2
k
3. we calculate two values of conversions X 1,2
*
given  1,2 and T * from X * 
1  k
Using Excel (or other computational tool)
T*-To k(T) 1 X1 2 X2
1 0.004733 1.07E+03 8.35E-01 2.33E+00 1.09E-02
2 0.005595 4.52E+02 7.17E-01 4.65E+00 2.54E-02
3 0.006606 2.61E+02 6.33E-01 6.81E+00 4.31E-02
Steady states’ stability. Heuristic approach

From energy balance :

k
 1    T *  To   Tad 0
1  k
Qc   1    T *  To  heat removal term
k
Qr  Tad heat generation term
1  k

120 120

Ignition Extinction E
100 H 100

Qr
80 80
Qc
Qc, Qr Qc
Qr, Qc

60 60 Qr
40 40

20 20

I L
0 0
290 310 330 350 370 390 290 320 350 380 410 440
T, K T, K
Steady states’ stability. Rigorous approach
dX
dt
   k (T )1  X   f1 ( X , T )
X


X*

 
 k (T * ) 1  X *  f1 ( X * , T * )  0

dT (To  T ) (To  T * )
dt


 Tad k (T )(1  X )   Tm  T   f 2 ( X , T )

 
 Tad k (T * )(1  X * )   Tm  T *  f 2 ( X * , T * )  0

Taylor expansion of f1 and f2 around steady state

 f   f   f   f 
     
f1 ( X , T )  f1 ( X * , T * )   1  X  X *   1  T  T *   1  X  X *   1  T  T *  
 X  *  T   X  *  T 
 f   f   f   f 
     
f 2 ( X ,T )  f 2 ( X * ,T * )   2  X  X *   2  T  T *   2  X  X *   2  T  T *  
 X  *  T   X  *  T 

dX d ( X  X * ) d X  f1   f1   f1   f1 

    X  X   T  T     X    T  J11X  J12 T
* * * *

dt dt dt  X *  T *  X *  T *

dT d (T  T * ) d T  f 2   f 2   f 2   f 2 
    X  X   T  T     X    T  J 21X  J 22 T
* * * *

dt dt dt  X *  T *  X *  T *

Jacobi matrix

 f1 f1    1 *   *  dk  

    k (T )   (1  X )    
 X T   J11
*
J12*        dT *  
J*     * * 

 f 2 f 2   J 21 J 22    1  dk  

  Tad k (T* ) X      Tad  dT  (1  X )    
  *
 *
 X T *
  * 
 Matrix notation
d  X   X 
   J *  
dt  T   T 

Characteristic equation

det  J *  I    0
 1 0 .. 0   1 0 .. 0 
   
 0 1 0  0 2 0 
I , 
 .. .. ..   .. .. .. 
   
 0 0 .. 1   0 0 .. N 

J  J 12 
det  11   J 11   J 22     J 21 J 12  2  ( J 11  J 22 )  J 11 J 22  J 21 J 12 
 J 21 J 22   

Characteristic equation has two roots, 1 , 2 , real or complex conjugate

X (t )  B11e 1t  B12e 2t
Solution
T (t )  B21e 1t  B22e 2t

In fact, the solution of the linearized CSTR balance equations is asymptotically

stable if and only if the eigenvalues of J* (Jacobi matrix evaluated in given
steady state) have strictly negative real parts.
Branch Re(1 ) Im(1 ) Re(2 ) Im(2 ) Steady state
A-I <0 ≥0 <0 ≤0 Stable
I-E >0 ≤0 <0 ≥0 Unstable
E-O <0 =0 <0 =0 Stable
O-P >0 ≥0 >0 ≤0 Unstable
oscillations
The numerical integration is done by semiimplicit Runge-Kutta method (see macro in SIRK42E.xls).
The blue lines are used to depict the conversions, red ones mean the temperatures.

  10 min   10 min
t  0, X  0, T  298K t  0, X  0, T  310 K
  11.3min   20 min
t  0, X  0, T  298K t  0, X  0, T  298K
  30 min
t  0, X  0, T  298K
Conclusions
1. The coupling of the material and energy balances for the CSTR can give rise
to some surprisingly complex and interesting behavior.
2. Even the steady state solution of the material and energy balances holds
some surprises – steady state multiplicity.
3. Parametric sensitivity near critical points (Ignition x Extinction)
4. Sustained oscillations – the steady state is not attained
5. The chemical engineer should be aware of the complex behavior that is
possible with nonlinear kinetics in chemical reactors both due to the
thermal and kinetics effects.
6. Further reading
• G.P.Bocarro et al, AICHE J. 16 (1970) 249-254.
• S.F. Bush, Proc. Roy. Soc. A, 309 (1969) 1-26.
• M. Chang, R.A. Schmitz, Chem. Eng. Sci. 30 (1975) 21-34.
• Vleeschhouwer P.H.M et al, AICHE J. 34 (1988) 1736-1739.