Advanced Chemical Reaction Engineering: Chapter 12

Compartment models

 Is a method based on various combinations of compartments (ideal mixed or plug flow vessels) and
through flow, to develop a reasonable model for a real vessel.

The following procedure should be followed:

 Experimental data of tracer concentration (pulse or step experiment) in the vessel exit should be
exist.
 Based on your knowledge about the vessel, corresponding to experimental data, suggest a proper
compartment model
 Find the equation of E(t) or C(t) at the exit of suggested compartment model by implementing
the mass balance for injected tracer: the injection type (pulse or step must be specified)
In the most cases, step injection is preferred due to ease of mathematics

 By matching the model age function or concentration curves with experimental ones, find the
model parameters
 The compartment model can be used for prediction of the vessel performance when acts as a
chemical reactor

# CASE 1

Short-circuiting is modeled
Real vessel as by-pass Suggested compartment model

Note: Vp=Va+Vd
C0, =b+p
Va b/+p/=1
C0 p C

C0

Geometric Volume, VG
Model compartments: Plug-flow vessel
F(t) Model through flow: By-pass line

Model parameters:
Compartments: Va (which means the volume of active part), Vd

Through flow: p, b

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Advanced Chemical Reaction Engineering: Chapter 12

# finding the equation of age-function: follow the following steps

1- Consider a step injection of tracer

2- Apply the definition of F(t) with respect to tracer concentration or molar flow at exit of the suggested
compartment model:
n (t ) C 0 b  b
F (t )    if 0  t  t p
n 0 C0 

n ( t ) C 0  b C 0  p  b  p  b   p 
F (t )       1 if t  t p
n 0 C 0    

F(t)

1
E
due to plug
drainage
due to by-pass:
without no time lag

3- Evaluate E(t) from F(t): in case of the plug flow is a Dirac function
at t  0 :  ( t  0)
at t  t p :  (t  t p )

4- Find the model parameters by comparing the F(t) or E(t) functions with the experimental data.

F(t)

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Advanced Chemical Reaction Engineering: Chapter 12

 Model parameters are Va , Vd ,  p ,  b

 Consider the volume of real vessel (VG) and tracer flow rate () as 2 lit and 1 lit/min

By comparing the shape of compartment model with experimental curve of F(t), we can say:
b
 0.3  b  0.3  0.31  0.3 lit/min

p
 1  0.3  0.7  p  0.7  0.7 1  0.7 lit/min

Va
tp   Va  t p  p  1 0.7  0.7lit
p
Va  VG  Vd  VG  Va  2  0.7  1.3lit

# CASE 2

Real vessel Suggested compartment model

C0 Assume no dead zone

C0

C0

Assume that t p1  t p 2
The first plug with lower residence time models the channeling
(channeling is not fast enough as short-circuiting)

F(t)
is defined as
1

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 Advanced Chemical Reaction Engineering: Chapter 12

F (t )  0 if t  t p1
n (t ) C 0 1  1
F (t )    if t p 2  t  t p1
n 0 C0 
n (t ) C 0 1 C 0 2  1  2
F (t )    1 if t  t p 2
n 0 C0 

E(t) can be derived as:

is defined for compartments

with more than one vessel

t p1 t p1
v1
A1   E ( t )dt   dF F ( t p1 )  F (0) 
0 0 v
t p2 t p2
v1 v2
A2   E ( t )dt   dF F ( t p2 )  F ( t p1 )  1  
t p1 t p1
v v

Note: In this chapter, in some cases we cannot easily find a real vessel corresponding to the represented
compartment. In these cases, only try to find the age function of compartment. That is enough!

# CASE 3

=b+m
b/+m/=1

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Advanced Chemical Reaction Engineering: Chapter 12

n ( t ) C 0 b C 1 m  b C 1 m
F (t )     if t  0
n0 C0  C0
We know the step concentration-time at the exit of a mixed flow reactor as:
t
C1 (t )  C0 (1  exp( ))
tm
So:
n (t ) C 0 b C 1 m  b C 1 m  b  m t
F (t )       (1  exp( )) where t m  Va / vm
n0 C0  C0   tm

b t=0 physically means a small time after tracer injection

Note: if t=0, F (t  0) 

or
b m t   b  m t
1  F (t )  1   (1  exp( ))   (1  exp( )) 
  tm   tm
m m t  t
 (1  exp( ))  m exp( )
  tm  tm

Finding the E(t):

dF (t ) 1  m t 2 t
E(t )   exp( )  m exp( )
dt tm  t m Va tm

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Advanced Chemical Reaction Engineering: Chapter 12

# CASE 4 C0 Assume no dead zone

C1(t)
C0 C(t)


C2(t)
C0

n (t ) C C 1 1 C 2 2  1 C 1  2 C 2
F (t )     
n 0 C0 C0  C0  C0
We know the step concentration-time at the exit of a mixed flow reactor as:
t t V1 V2
C1 (t )  C0 (1  exp( )) and C2 (t )  C0 (1  exp( )) where t m1  and tm 2 
t m1 tm2 1 2
So:
1 t  t
F (t )  (1  exp( ))  2 (1  exp( )) t0
 t m1  tm2
Finding the E(t)
dF (t ) 1  1 t 1 2 t
E(t )   exp( )  exp( ) t0
dt t m1  t m1 t m 2  tm2

1  1 1  2  12  22
if t  0 : E (0)    
t m1  t m 2  V1 V2

is defined as

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Advanced Chemical Reaction Engineering: Chapter 12

# CASE 5
C0 C0 C(t


V=Vm + Vp

Due to the time delay caused by the plug-flow vessel, initial condition for the mixed-flow vessel will
change. So, for evaluating the concentration-time profile, the relevant ODEs should be solved again.

Mass balance for tracer over the tank:

in - out +/- gen/con = acc
0 : tracer is passive (non-reactive)

d (VmC ) dC   dC C C dC dC C C0
C0  C   Vm  C0  C   0    
dt dt Vm Vm dt t m t m dt dt t m t m
Initial condition:
t  tp : C  0

By solving the above differential equation using the integral factor technique:

 t t 
C (t )  C0 1  exp( p ) 
 tm 

C (t )  t t  t t
F (t )   1  exp( p )   1  F (t )  exp( p )
C0  tm  tm
dF (t ) 1 t t
E (t )   exp( p )
dt tm tm

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Advanced Chemical Reaction Engineering: Chapter 12

Note:
The age function of

is completely similar to

Please proof this as a take home!

Note:
The sequence of plug flow with mixed flow vessels causes a time delay for tracer exit. The mathematical
equation follows the RTD of mixed flow (i.e., an exponential trend)

# CASE 6

C
C0 (1+R) C
C

C
R


How we can evaluate the area of each peak?

Note:
When the main fluid is pass through the recycle stream, inject the tracer

t  0: F (t  0)  0
C0
C (t p1 ) C (t p1 ) (1  R) 1
t  t p1 : F (t p1 )    
C0 C0 C0 1 R
t p1 t p1
1 1
A1   E (t )dt   dF (t ) F ( t p1 )  F (0)  0 
0 0 1 R 1 R

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Advanced Chemical Reaction Engineering: Chapter 12

C 0
C 0  R
C 0  R C (t p1 ) (1  R)
C (t p1  t ) C ( t p1  t ) (1  R) (1  R)
t  t p1  t : F (t p1  t )     
C 0 C0 C0 C0
1  2R
 C0
(1  R) 2 1  2R

C0 (1  R) 2
t p1 t t p1  t
1  2R 1 R 1 R R
A2   E(t )dt   dF (t ) F (t p1  t )  F (t p1 )  2
  2
  A1
t p1 t p1 (1  R) 1  R (1  R) 1  R 1  R 1 R

C0  R C (t p1  t )
C (t p1  2t ) C (t p1  2t ) (1  R)
t  t p1  2t : F (t p1  2t )     .............
C0 C0 C0

# CASE 7 C1(t)
C0 a
C0
C(t)
C0
=a+b

Overall

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Advanced Chemical Reaction Engineering: Chapter 12

n ( t ) C0 b  b Vp
F (t )    0  t  tp tp 
n0 C0  a
n ( t ) C C  C     t t  Vm
F (t )    0 b 1 a  b  a 1  exp( p )  t  t p where tm  or
n0 C0 C0    tm  a
   t  t    b  a  t t     t t 
1  F (t )  1  b  a 1  exp( p )    1  exp( p )   a  a 1  exp( p )  
   tm     tm     tm 
a t t
exp( p )
 tm
dF ( t )  a 1 t t 2 t t
E(t )   exp( p )  a exp( p )
dt  tm tm Vm tm

Vm1 Vm2
# CASE 8
C0 C1 (t) C2 (t)
 

Mass balance for tracer over the tank 1:

in - out +/- gen/con = acc
0 : tracer is passive (non-reactive)

d (Vm1C1 ) dC dC C C
C0 C1   Vm1 1  1  1  0
dt dt dt t m1 t m1
With initial condition of t=0: C1=0
 t 
C1 (t )  C0 1  exp( ) 
 t m1 

Mass balance for tracer over the tank 1:

in - out +/- gen/con = acc
d (Vm 2C2 ) dC dC C C dC C C  t 
 C1  C2   Vm 2 2  2  2  1  2  2  0 1  exp( ) 
dt dt dt t m 2 t m 2 dt t m 2 t m 2  t m1 
With initial condition of t=0: C2=0
C2 ( t ) t m1 t tm 2 t
F (t )  1 exp( )  exp( )
C0 t m1  t m 2 t m1 t m1  t m 2 tm 2

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Advanced Chemical Reaction Engineering: Chapter 12

dF (t ) 1  t t 
E(t )   exp( )  exp( )
dt t m1  t m 2  t m1 tm 2 

Note: If Vm1  Vm 2  Vm  t m1  t m 2  t m the procedure should be repeated from the beginning:

Mass balance for tracer over the tank 1:

d (VmC1 ) dC dC C C
 C0  C1   Vm 1  1  1  0
dt dt dt t m t m
With initial condition of t=0: C1=0
 t 
C1 (t )  C0 1  exp( ) 
 tm 

Mass balance for tracer over the tank 2:

d (VmC2 ) dC dC2 C 2 C1 dC2 C2 C0  t 
 C1  C2   Vm 2       1  exp( ) 
dt dt dt tm tm dt tm tm  tm 
With initial condition of t=0: C2=0
C2 (t ) t t dF (t ) t t
F (t )   1  (1  ) exp( )  E (t )   2 exp( )
C0 tm tm dt tm tm

Note:
1
For a single mixed-flow (tank) reactor at t=0, E (t )  0  whereas in tank-in-series at t=0, E(t)=0
tm
due to time delay

# CASE 9
C0
Vp
p
C0 C (t)


C0 C1 (t)
m Vm

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Advanced Chemical Reaction Engineering: Chapter 12

n (t ) C C1 m  m C1  m  t  V
F (t )      1  exp( )  where t m  m 0  t  tp
n 0 C 0 C 0  C0   tm  m
n (t ) C C 0 pC1 m  p  m C1  p  m  t  Vp
F (t )        1  exp( )  t  tp where t p 
n 0 C 0 C 0   C0    tm  p
2
dF (t )  m 1 t  t m
E (t )   exp( )  exp( ) t 0
dt  tm t m Vm tm

Impulse peak due to

Plug drainage

tp

Note:
Plug vessels in parallel with the mixed ones lead to noisy TRD curves

In continuation of discussion, use the experimental values of x=0.2, y=0.6, t p  1min , VG=2 lit and tracer

flow rate =1 lit/min to find the model parameters.

p
 y  x  0 .6  0 .2  0 .4   p  0.4   0 . 4  1  0 . 4 lit/min

Vp
tp   V p  tp  p  1  0.4  0.4 lit
 p

  p  m  m   p  1 - 0.4  0.6 lit/min

to find V m substitute the pair of ( t p , x) or ( t p , y) in the equations of F(t) :

m  t 
use pair of ( t p , x) in F ( t )   1  exp(  )  t  tp
  tm 

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Advanced Chemical Reaction Engineering: Chapter 12

  t   1 
x  m
 1  exp(  p )   0.2  0.6  1  exp(  )   t m  2 . 47 min or
  tm   tm 
 p   t 
use pair of ( t p , y) in F ( t )   m  1  exp(  ) 
   tm 
 p   t   1 
y   m  1  exp(  p )   0 . 6  0 . 4  0 . 6  1  exp( )   t m  2 . 47 min
   tm   tm 
Vm   m  t m  0 . 6  2 . 47  1 . 482 lit

V total  V p  V m  0 . 4  1 . 482  1 . 882 lit

V total  V G  V d  V G  V total  2  1 . 882  0 . 118 lit

Note:
Each compartment model has a unique age function or RTD (E(t)) but for a given RTD,
more than one compartment model may be suggested.

May represents both

Laminar flow in pipes (see chapter 15)

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Advanced Chemical Reaction Engineering: Chapter 12

# Diagnosing Reactor Ills

The compartment models are useful for diagnostic purposes, to pinpoint faulty flow and suggest causes.
VG
 If you expect plug flow and you know t  you could find.


Dead zone is closer

to this event!

 If you expect mixed flow, you may find:

---------
Dead zone is closer
to this event!

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