CHAPTER 1

Mixed Flow Reactor

The Transfer Function
dC '
Mixed flow τ = C E' − C '
dt
CE
M.B. without reaction, in transient state: By applying Laplace transforms:

dC
= QC E − QC
[ ]
C V
dt τ sC ' − C ' (0 ) = C E' − C '
At steady state t =0 (-) 0 = QC ES − QC S
But: C ' (0 ) = C (0 ) − C S = C S − C S = 0
= Q(C E − C ES ) − Q(C − C S )
dC
V
dt
So: τsC ' = C E' − C '
Deviation variables:

dC ' dC
C =C −C
' S
= CSTR TRANSFER FUNCTION
dt dt
C E' = C E − C ES
C' 1
=
C E' 1 + τs
V
dC '
dt
(
= QC E' − QC ' = Q C E' − C ' )
32
CHAPTER 1

Mixed Flow Reactor

The Pulse Experiment 0
C' = C − C S C = C' + C S = C'

δ (t ) M M
a= = τ = C oτ
Q V
0
a
C E = aδ (t ) C = e −t τ
τ
C =0S
E
C C
C = C E = aδ (t )
'
E
E (t ) = =
MQ a
C E' = a
C' 1
CSTR transfer function =
C E' 1 + τs

1 ⁄
Then: C = ' a L−1 a
→ C ' = e −t τ =
1 + τs τ
33
CHAPTER 1

Mixed Flow Reactor

The E(t) curve
1
E (t ) = e −t τ
τ
_
1/t

E(t)

área = 1
0
t 34
CHAPTER 1

Mixed Flow Reactor

The Step Experiment
0
C =C −C
' S
C = C + C = C'
' S

C E = bH (t )
H (t ) C ES = 0 b = C MAX
C E' = C E
C = b(1 − e −t τ )
0 C E' = b s

C C
F (t ) = =
C MAX b
C' 1
MFR transfer function =
C E' 1 + τs

b
( )
F (t ) = 1 − e
L−1
C =
'
→ C ' = b 1 − e −t τ −t τ
s(1 + τs )
35
CHAPTER 1

Mixed Flow Reactor

The F(t) curve
F (t ) = 1 − e −t τ

1
F(t)

_
área = t

0 _
t t
[ ]
t t
1
F =  Edt =  e −t τ dt = − e −t τ = − e −t τ + e 0 = 1 − e −t τ
t

τ
0
0 0
36
CHAPTER 1

Plug Flow Reactor

The Transfer Function
+ Q(C z +dz − C z ) = 0
Plug flow reactor dC
Adz
dt
dz
dC C − Cz
A + Q z +dz =0
A dt dz

∂C ∂C
z z+dz dz → 0 => A +Q =0
∂t ∂z

M.B. without reaction, in transient state:

Q m3 m
dC u= =
Vdz = QC z − QC z +dz A sm 2
s
dt
∂C ∂C
But Vdz = Adz +u = 0
∂t ∂z
37
CHAPTER 1

Plug Flow Reactor

The Transfer Function C ' ( z ,s )
dC ' (z , s )
z
s
∂C
+u
∂C
=0  C '
= −
u0 
dz
∂t ∂z C ' ( 0 ,s )

CE' ( s )

=
∂C s
t =0 (-) u =0
At steady state ∂z
[ ] s
'
' C C'
∂C ' ∂C ' ln C C E' =− z⇔ s
ln ' = − z
C = C −C = C
' S
+u =0 u CE u
∂t ∂z
z L
At the exit: z =L = =τ
u u
∂C'
∂C '
+u =0 C (z , t )
∂t ∂z C'
s
− z
Therefore: = e u
C E'
By applying Laplace transforms:
PFR transfer function
dC '
sC + u
'
=0 C ' (z , s )
dz ̅
=
38
CHAPTER 1

Plug Flow Reactor

The E(t) and F(t) curves
Pulse Experiment Step Experiment

δ (t ) C E = aδ (t ) C E = bH (t )
H (t )
C E' = a C E' = b s
0
0
PFR transfer function C'
'
= e −τs t t
CE
F (t ) = E (t )dt = δ (t − τ )dt =H (t − τ )
 
C = ae
' −τs
→ C = aδ (t − τ )
L−1 '
0 0

E(t ) = δ (t −τ )
C'
E (t ) =
a
1
E(t)
area
área = 1 F(t) _
área = t
area

0 39
τ t τ t
APPENDIX A

The Transfer Function

Definition
Consider a system, with an imput x(t), presenting as output y(t):

x(t) y(t)

Y (s ) L[y (t )]
The transfer function G(s) G (s ) = = Y (s ) = G (s ) X (s )
X (s ) L[x (t )]
Ideal mixed flow
Ideal plug flow

G(s ) = e −τs
1
G(s ) =
1 + τs
40
APPENDIX A

G(s), E(t), and F(t)

Relationship

G(s) and E(t)

G (s ) = L [E (t )] E (t ) = L −1
[G(s )]

G(s) and F(t)

t
t  L [E (t )] G (s )
F (t ) = E (t )dt
 L [F (t )] = L  E (t )dt  =
 =
0  0  s s

41
APPENDIX A

The van der Laan Theorem

Introduction
Using this theorem, it is possible to calculate the moments of the RTD function, E(t), using the
transfer function G(s), and without konwing the analytical expression of E(t).

∂ nG(s )
∞
µ n = t E (t )dt = (− 1)

n n

0
∂s n
s =0

∂G (s ) ∂ 2G (s )
µ 0 = G (0 ) µ1 = − µ2 =
∂s s =0 ∂s 2 s =0

42
APPENDIX A

The van der Laan Theorem

Introduction

∂ n G (s )
∞
µ n = t E (t )dt = (− 1)

n n

0
∂ s n
s =0

∞ ∞

 tE (t )dt ∞  (t − t )2
E (t )dt
= tE (t )dt = µ1 σ2 = 0
=
t= 0
∞  ∞

 E (t )dt 0
 E (t )dt
0
0

t = µ1 σ 2 = µ2 − µ12

43
CHAPTER 1

Conversion in real reactors

Important factors

Reaction kinetics

State of aggregation:
Earliness of mixing:
- microfluid Characterization - early mixing
- macrofluid of a real reactor - late mixing

RTD
(residence time
distribution)

44
CHAPTER 1

The state of aggregation

Definition
Flowing material is in some particular state of aggregation, depending on its nature. Two
extremes states are exemplified below:

Gases and ordinary, not very viscous , Noncoalescing droplets

liquids Solid particles
Very viscous liquids

. .
. . . .. ... ... . .. . .
. .
...
MICROFLUID MACROFLUID
Individual molecules are free to
move about and intermix Molecules are kept grouped together in
aggregates or packets

45
CHAPTER 1

The state of aggregation

Examples
L

G G

L
….....
...........
..
.…. ... ..
L ….....
....... ....
.…. ... ..
G G ….....
. . . .. L

Gas bubbles in a liquid (gas is a macrofluid; Liquid drops in a gas (gas is a microfluid;
liquid is a microfluid) liquid is a macrofluid)

46
CHAPTER 1

Macrofluids
Material balance
For macrofluids (in general), imagine little clumps of fluid staying for different lengths of time in a
batch (plug flow) reactor. Each clump reacts away as a little

batch (plug flow) reactor, thus fluid elements will have different compositions. So the mean
composition in the exit stream will have to account for these two factors, the kinetics and the RTD.

CE(t) ... ... CS(t)

Qi .. .. Ci(t)
Q Q

47
CHAPTER 1

Macrofluids
Material balance

At the exit point:

∞
Q < C s (t ) >= Q C < C s (t ) >=
Qi
C i → C (t )
dQ
i
i i
i Q  Q
0

dQ
But:
= E (t )dt fraction of population with residence time between t and t+dt
Q
∞
< Cs (t ) >= C (t ) E (t )dt

0
Flow pattern
Reaction kinetics

48
CHAPTER 1

Macrofluids
Equations
BATCH
∞ kt CA kt
Xb = =1−
< C >=  C b (t )E (t )dt =  C i E i ∆t i
n = 0:
C A0 C A0 C A0
0 i
CA
∞ n = 1: X b = 1 − e
− kt = e −kt
C A0
< X >=  X b (t )E (t )dt =  X i E i ∆t i kC A0 t CA 1
0 i n = 2: Xb = =
1 + kC A0 t C A0 1 + kC A0 t

n: [
X b = 1 − 1 + (n − 1)C An0−1kt ]
1 1− n

CA
CA 0
[
= 1 + (n − 1)C An0−1kt ]
1 1−n

49
CHAPTER 1

Earliness of mixing
Examples
For microfluids

early mixing early mixing

The fluid drops immediately to a low concentration

Favourable if n < 1
Uniform mixing

late mixing

late mixing High concentration of reactant is maintained

Favourable if n > 1
50