Advanced Chemical Engineering: Chapter 11-discussion 4 and Chapter 16

# The Convolution Integral

The aim is finding a direct relationship between Cin (t), Cout (t) and E(t)

or

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Advanced Chemical Engineering: Chapter 11-discussion 4 and Chapter 16

Applications:

 determining the output from a multi-region flow unit

If the input signal Cin, is measured and the exit age distribution functions Ea, Eb, and Ec are
known, then C1 is the convolution of E, with Cin and so on, thus

and on combining
?
---- ---- ---- ----
-

Example:

Cin=2et Cout (t) =?

Find Cout (t) if E ( t )  1  4t 0.5  t  0

t t t
Cout (t )  C in (t ) * E (t )   Cin ( t  t )  E ( t ) dt    2e t t  (1  4t ) dt    8t e t  t   10e t  t   
0 0 0

8t  10e t  10

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Advanced Chemical Engineering: Chapter 11-discussion 4 and Chapter 16

# Conversion in Non-Ideal Flow Reactors

To evaluate reactor behavior in general we have to know four factors:
 the kinetics of the reaction
 the RTD of fluid in the reactor
 whether the fluid is a micro or macro fluid (degree of segregation/aggregation)
 the earliness or lateness of fluid mixing in the reactor

# Macro and Micro fluids (degree of segregation/aggregation)

 Micro fluid
Any fluid in which the local motion of contained particles affects the behavior of the fluid as a
whole.
individual molecules are free to move about and intermix (self mixing can be occured)
all gases and a few of light liquids

 Macro fluid
Any fluid in which the molecules are kept grouped together in aggregates, pockets, clumps, clusters,
or macros
Non-coalescing droplets, solid particles, viscous liquids

Clump or macro

Molecules

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Advanced Chemical Engineering: Chapter 11-discussion 4 and Chapter 16

# Micro and macro behaviors

Sometimes, in a two-phase system of liquid and gas, either phase can be a macro- or micro fluid
depending on the contacting scheme being used

Note:
A stream of solids always behaves a macro fluid

Note:
For systems in which very fast reactions are taking place, usually a micro fluid behaves as
macro
Such as gasl combustion

 When two miscible fluids A (CH4) and B (O2) are mixed, we normally assume that they first
form a homogeneous mixture which then reacts.

 When the time required for A and B to become homogeneous is not short with respect to the
time for reaction to take place, reaction occurs during the mixing process, and the problem of
mixing becomes important

(reaction time scale, t reaction )  ( t mixing , mixing time scale)

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Advanced Chemical Engineering: Chapter 11-discussion 4 and Chapter 16

Micro fluid Micro fluid

Macro performance

# Chemical conversion of a micro fluid in the batch, mixed-flow and plug flow reactors

All the performance equations mentioned before for homogeneous reactions should be applied to
evaluate the chemical conversion:

Batch reactor

Plug-flow reactor

Mixed-flow reactor

# Chemical conversion of a macro fluid in the batch, mixed-flow, plug flow and an arbitrary vessel

aAP aA+bBP

, XA,1 , XA,3
, XA,1
, XA,2 , XA,2
, XA,3

Clumps at the reactor exit

 Each clump includes a micro fluid reacts away as a little batch

 Clumps essentially do not stay in the vessel for the same amount of time
(May have different residence time, RTD should be considered)
E(t) can be evaluated for clumps or macros
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Advanced Chemical Engineering: Chapter 11-discussion 4 and Chapter 16

 Clumps may have different composition (conversion)

 The mean composition (conversion) in the exit stream should be taken into account

finalt
 CA   CA 
   1  X A     E ( t ) dt
 C A0  t initial  C A0  Batch
-------- ------
A=0 Kinetics aspect Hydrodynamic
f(t) aspect
t final
XA   ( X A ) Batch E ( t ) dt
t initial

To find the averaged XA, (CA/CA0)Batch, E(t), tinitial and tfinal should be known:

 Finding (CA/CA0)Batch for power low kinetics of –rA=kCAn

To this end, apply the performance equation of a batch reactor

 Zero-order reaction:
dC A CA k
 rA    k  C A0  C A  kt  1 t
dt C A0 C A0

 First order reaction:

dC A CA
 rA    kC A  C A  C A0 e  kt   e  kt
dt C A0
 Second order reaction:
dC A 1 1 CA 1
 rA    kC A2    kt  
dt C A C A0 C A0 1  ktC A0

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Advanced Chemical Engineering: Chapter 11-discussion 4 and Chapter 16

 nth order reaction (n≠1)

dC A CA
 1  ( n  1)ktC An 01 
1 / 1 n
 rA    kC An  C1A- n  C 1A0n  (1  n)kt 
dt C A0

 Finding tinitial and tfinal for power low kinetics of –rA=kCAn

tinitial, kinetics=0
tinitia
tinitial, RTD: should be chosen according to E(t)-curve
 For a mixed-flow reactor
tinitial, RTD=0
 For a plug-flow reactor
tinitial, RTD= t p

 For an arbitrary E(t)-curve

tinitial, RTD=16 sec

tinitial =
0

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Advanced Chemical Engineering: Chapter 11-discussion 4 and Chapter 16

tfinal, kinetics : is dependent to order of reaction

C 1A0n
n≥1 : tfinal, kinetics=∞ n<1 : tfinal, kinetics=
k (1  n)
C
n=0: tfinal, kinetics= A0
k
tfinal
tfinal, RTD: should be chosen according to E(t)-curve

 For a mixed-flow reactor

tfinal, RTD=∞
 For a plug-flow reactor
tfinal, RTD= t p

 For an arbitrary E(t)-curve

tfinal, RTD=25 sec

tfinal = min( t final , kinetics , t final , RTD )

Examples:
A liquid macro fluid reacts according to A  R as it flows through a vessel. Find the conversion of A for the
following pattern:

1)

t initial  max(t initial , kinetics , t initial , RTD )  t initial , RTD  0.5 min

C 1A0n C A0.05 1
t final , RTD  1.5 and t final , kinetics     1 min
k (1  n) 0.5k 0.5  2
t final  min( t final , kinetics , t final , RTD )  min(1 , 1.5)  1 min

E (t )  y 1.5  t  0.5 : area  (1.5  0.5) y  1  y  1 min 1

CA 
 1  ( n  1)ktC An 01   1  0.5ktC A 00.5   1  t 
1 / 1 n 2 2

C A 0  batch
1
 CA 
   1  X A   (1 - t) 2  1 dt  X A  0.958
 C A0  0.5
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Advanced Chemical Engineering: Chapter 11-discussion 4 and Chapter 16

2)

t initial  max(t initial , kinetics , t initial , RTD )  t initial , RTD  0.5 min

C 1A0n C A0.05 2
t final , RTD  1.5 and t final , kinetics     2 min
k (1  n) 0.5k 0.5  2
t final  min( t final , kinetics , t final , RTD )  min( 2 , 1.5)  1.5 min

CA 
 1  ( n  1)ktC An 01   1  0.5ktC A 00.5   1  0.5t 
1 / 1 n 2 2

C A 0  batch
1.5
 CA 
   1  X A   (1 - 0.5t) 2  1 dt  X A  0.729
 C A0  0.5

3)

t initial  max(t initial , kinetics , t initial , RTD )  t initial , RTD  0.5 min

C 1A0n C A0.05 0.25

t final , RTD  1.5 and t final , kinetics     0.25 min
k (1  n) 0.5k 0.5  2
t final  min( t final , kinetics , t final , RTD )  min( 0.25 , 1.5)  0.25 min

CA 
 1  ( n  1)ktC An 01   1  0.5ktC A 00.5   1  4t 
1 / 1 n 2 2

C A 0  batch
0.25
 CA 
   1  X A   (1 - 4t) 2  1  dt  X A  1.08 !!!
 C A0  0.5

tinitial > tfinal !!! : Integral return a wrong answer! Logically complete conversion
should be occurred XA=1

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 Advanced Chemical Engineering: Chapter 11-discussion 4 and Chapter 16

Note:
There is only a difference between the performance (conversion and selectivity) of micro and macro
fluids when there is RTD in vessel
 Plug flow reactors has no RTD:
Performance of micro fluid ~ Performance of macro fluid
t
final
 CA   CA 
      E ( t ) dt
 C A0 macro tinitial  C A0  Batch ,micro
E (t )   (t  t p )
t initial  t final  t p
tp
 CA   CA  C 
      ( t  t p ) dt   A  at t  t p
 C A0 macro t p  C A0  Batch ,micro  C A0  Batch ,micro
------------ ------------
Macro ~ Micro

Note:
In a mixed-flow reactor, there is no difference between the performance of micro and macro fluids for
a first order reaction (n=1)
For case of macro fluid:
t
final
 CA   CA 
      E ( t ) dt
 C A0  macro t initial C
 A0  Batch , micro
 CA  1 t
   e  kt , E ( t )  exp( ) , t initial  0 , t final  
 C A0  Batch t t
 CA  1 t 1 1
    e  kt exp( )dt  or (1  X A ) macro 
 C A0  macro t 0 t 1  kt 1  kt

For case of micro fluid:

Compare! are the same
C A0 X A C A0 X A 1
t   (1  X A ) micro 
 rA kC A 0 (1  X A ) 1  kt

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Advanced Chemical Engineering: Chapter 11-discussion 4 and Chapter 16

 Except of a first order reaction, there is a difference between the performance of micro and macro
fluids in a mixed-flow reactor:

 a zero order reaction in a mixed-flow reactor contained a macro fluid

 CA  kt 1 t C A0
  1 , E (t )  exp( ) , tinitial  0 , t final 
 C A0  Batch C A0 t t k
 CA  1 CA / k
0
kt t kt  C 
    (1  ) exp(  )dt  1  1 - exp(- A0 ) 
 C A0 macro t 0 C A0 t C A0  kt 

 a second order reaction in a mixed-flow reactor contained a macro fluid

 CA  1 1 t
   , E ( t )  exp( ) , t initial  0 , t final  
 C A0  Batch 1  ktC A0 t t
 CA  1 1 t 1
    exp( )dt   e  ei( ) where 
 C A0  macro t 0 1  ktC A0 t kt C A0

exponential integral

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Advanced Chemical Engineering: Chapter 11-discussion 4 and Chapter 16

 Comparison between the volume of a mixed-flow reactor treating micro and macro fluids in a
given conversion

Micro fluid is favor for n<1

Macros is favor:
Keeps concentration at high level
-rA=kCAn

# The Life of an Element of Fluid (clumps or macros)

It is of interest that estimate how long a fluid element (macros) retains its identity
 All large elements are broken into smaller elements by stretching or folding (laminar
behavior) or by turbulence generated by baffles, stirrers, etc., and mixing theory
estimates the time needed for this breakup

 Small elements lose their identity by the action of molecular diffusion, and the
Einstein random walk analysis estimates this time as

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Advanced Chemical Engineering: Chapter 11-discussion 4 and Chapter 16

For example
1) an element of water 1 micron in size would lose its identity in a very short time:

2) an element of viscous polymer 1.0 mm in size and 100 times as viscous as water (some type
of motor oil at room temperature) would retain its identity for a long time:

# Early and late mixing of a micro fluid

 Examples of early and late mixing

Relevant compartment model Relevant compartment model

 Early and late mixing can affect the reactor behavior

Concentration is dropped immediately Concentration is kept high

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Advanced Chemical Engineering: Chapter 11-discussion 4 and Chapter 16

 Late mixing favors reactions where n>1

 rA  kC A2

The rate of reaction strongly is a function of concentration

CA  :  rA  : Vreaction 

2 2
 rA 2  C A 2   4C A1 
     16
 rA 1  C A1   C A1 

 Early mixing favors reactions where n<1

  rA  kC A0.1
2 0.1
 rA 2  C A 2   4C A1 
     1.15
 rA 1  C A1   C A1 
The rate of reaction is not seriously a function of concentration

Late mixing favors reactions where n>1 Early mixing favors reactions where n<1

XA XA
XA XA
XA XA
V V
V V

Vp Vp Vp Vp Vp Vp

Plug-flow Late mixing Early mixing Plug-flow Early mixing Late mixing

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Advanced Chemical Engineering: Chapter 11-discussion 4 and Chapter 16

Summary of Findings for a Single Fluid

 Factors affecting the performance of a reactor. In general we may write:

 Effect of kinetics, or reaction order:

Segregation and earliness of mixing affect the conversion of reactant as follows

for n = 1 conversion is unaffected by late and early mixing, and degree of segregation

 Effect of mixing factors for non first-order reactions:

Segregation plays no role in plug flow; however, it increasingly affects the reactor
performance as the RTD shifts from plug to mixed flow

 Effect of conversion level:

 At low conversion levels, XA is insensitive to RTD, earliness of mixing, and segregation

 At intermediate conversion levels, the RTD begins to influence XA; however, earliness and

segregation still have little effect

 At high conversion levels all these factors may play important roles.

 Effect on product distribution in case of multiple reactions:

 All the above factors can affect the product distribution (selectivity and yield) even at low

conversion levels.

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