=
0
0
) ( dt t vC N
For pulse input
0
) (
N
N
t t E
A
= A
}
=
0
) (
) (
) (
dt t C
t C
t E
17
C curve
1 ) (
0
=
}
dt t E
18
1
0
1
) ( t time residence a having Fraction dt t E
t
s =
}
1
1
) ( t time residence a having Fraction dt t E
t
> =
}
19
The age of an element is defined as the time elapsed
since it entered the system.
20
( )
1 2 1 0
0
....... ( 2
2
) (
+ + + + + =
}
n n
C C C C C
h
dt t C
21
Disadvantages of pulse input
injection must be done in a very short time
when the c-curve has a long tail, the analysis
can give rise to inaccuracies
amount of tracer used should be known
however, require very small amount of tracer
compared to step input
22
Step input of tracer
In step input the conc. of tracer is kept at this
level till the outlet conc. equals the inlet conc.
}
=
t
out
dt t E C C
0
0
) (
23
step
C
t C
dt
d
t E
|
|
.
|
\
|
=
0
) (
) (
For step input:
Disadvantages of Step input:
difficult to maintain a constant tracer conc.
RTD fn requires differentiation can lead
to errors
large amount of tracer is required
need not know the amount of tracer used
24
Characteristics of the RTD:
E(t) is called the exit age distribution function
or RTD function
describes the amount of time molecules have
spent in the reactor
25
Cumulative age distribution function F(t):
}
=
t
dt t E t F
0
) ( ) (
}
=
t
dt t E t F ) ( ) ( 1
26
Relationship between the E and F curves
27
28
Cumulative age distribution function F(t):
Washout function W(t) = 1 - F(t):
28
29
E and F Curves with bypassing
30
E and F Curves with Dead space
31
E and F Curves with Channeling
32
33
34
}
=
0
3
2 / 3
3
) ( ) (
1
dt t E t t S
m
o
What is the significance of these moments ??
Moments of RTD:
35
If the distribution curve is only known at a number of
discrete time values, t
i
, then the mean residence time is
given by:
This is what you use in the laboratory
36
Variance:
represents the square of the distribution
spread and has the units of (time)
2
the greater the value of this moment, the
greater the spread of the RTD
useful for matching experimental curves to
one family of theoretical curves
Skewness:
the magnitude of this moment measures the
extent that the distribution is skewed in
one direction or other in reference to the
mean
37
Space time vs. Mean residence time:
}
=
0
) ( dt t tE t
m
0
v
V
= t
The Space time and Mean residence time would be
equal if the following two conditions are satisfied:
No density change
No backmixing
In practical reactors the above two may not be valid
and hence there will be a difference between them.
38
Normalized RTD function E(u) :
) ( ) ( t E E t u =
t u / t =
}
=
0
) ( 1 dt t E
}
=
0
) ( 1 u u d E
What is the significance of E(u) ??
How does E(u) vs. u looks like for two ideal CSTRs
of different sizes ??
How does E(t) vs. t looks like for two ideal
CSTRs of different sizes ??
39
Using the normalized RTD function, it is possible to
compare the flow performance inside different
reactors.
If E(u) is used, all perfectly mixed CSTRs have
numerically the same RTD.
If E(t) is used, its numerical values can change for
different CSTRs based on their sizes.
40
RTD in ideal reactors:
41
RTD for ideal PFR:
) ( ) ( t o = t t E
0 0 ) ( = = t when t o
0 ) ( = = t when t o
}
=1 ) ( dt t o
}
= ) ( ) ( ) ( t t o g dt t t g
} }
= = =
0
) ( ) ( t t o dt t t dt t tE t
m
} }
= = =
0
2 2 2
0 ) ( ) ( ) ( ) ( dt t t t dt t E t t
m m
t o o
42
RTD for ideal CSTR:
} }
= = =
0
/
/ ) ( t t
t
dt te dt t tE t
t
m
} }
= =
0
/
2
2 2
) (
) ( ) ( t
t
t
o
t
dt e
t
dt t E t t
t
m
Material balance on tracer st to pulse input:
in out = accumulation
0 vC = VdC/dt C(t) = C
0
e
-t/t
t
t
t
t /
0
/
0
/
0
0
) (
) (
) (
t
t
t
e
dt e C
e C
dt t C
t C
t E
= = =
} }
u
u
= e E ) (
43
44
45
RTD for PFR-CSTR series:
For a pulse tracer input into CSTR the output
would be : C(t) = C
0
e
-t/ts
Then the outlet would be delayed by a time t
p
at the
outlet of the PFR. RTD for the system would be:
p
t t E t < = 0 ) (
p
s
t
t
e
t E
s P
t
t
t t
> =
/ ) (
) (
t
p
1/t
s
46
If the pulse of tracer is introduced into the PFR,
then the same pulse will appear at the entrance of
the CSTR t
p
seconds later. So the RTD for PFR-CSTR
also would be similar to CSTR-PFR.
Though RTD is same for both, performance is
different
47
Remarks:
RTD is unique for a particular reactor
The reactor system need not be unique for a
given RTD
RTD alone may not be sufficient to analyze the
performance of non-ideal reactors
Along with RTD, a model for the flow behaviour
is required
48
Reactor modeling with RTD:
I. Zero parameter models:
(a)Segregation model
(b)Maximum mixedness model
II. One parameter models:
(a)Tanks-in-series model
(b)Dispersion model
III. Two parameter models:
Micro-mixing
models
Macro-mixing
models
49
50
Segregation model (Dankwerts & Zwietering, 1958)
Characteristics:
Flow is visualized in the form of globules
Each globule consists of molecules belonging
to the same residence time
Different globules have different Res. Times
No interaction/mixing between different
globules
51
52
53
Mean conversion of globules spending between t and t+dt in the reactor =
(Conversion achieved after spending a time t in the reactor) X
(Fraction of globules that spend between t and t+dt in the reactor)
dt t E t x x d ) ( ) (
_
=
}
=
0
_
) ( ) ( dt t E t x x
54
Mean conversion in a PFR using Segregation model:
Example: A R, I order, Constant density
Order I for e t x
kt
=1 ) (
} }
= =
0 0
_
) ( 1 ) ( ) 1 ( dt t E e dt t E e x
kt kt
t
t o
k kt
e dt t e x
= =
}
1 ) ( 1
0
_
Mean conversion predicted by Segregation model
matches with ideal PFR
55
Mean conversion in a CSTR using Segregation model:
Example: A R, I order, Constant density
} }
= =
0
/
0
_
/ ) ( 1 t
t
dt e e dt t E e x
t kt kt
t
t
k
k
x
+
=
1
_
Mean conversion predicted by Segregation model
matches with ideal CSTR
56
Mean conversion in a practical reactor using
Segregation model:
Example: A R, I order, Constant density
} }
= =
0 0
_
) ( 1 ) ( ) ( dt t E e dt t E t x x
kt
conduct tracer experiment on the practical reactor
measure C(t) and evaluate E(t)
plot and evaluate mean conversion
57
Tanks in series (TIS) Model:
Material balance on the I reactor for tracer:
V
1
dC
1
/dt = -v C
1
C
1
= C
0
exp(-t/t
1
)
Material balance on the II reactor for tracer:
V
2
dC
2
/dt = v C
1
v C
2
dC
2
/dt + C
2
/t
2
= C
0
exp(-t/t
2)
t
2
58
2
/
2
0
2
t
t
t
e
t C
C
=
i
t
i
e
t C
C Similarly
t
t
/
2
2
0
3
2
=
i
t
i
e
t
dt t C
t C
t E
t
t
/
3
2
0
3
3
3
2
) (
) (
) (
= =
}
For n equal sized CSTRs:
i
t
n
i
n
e
n
t
t E
t
t
/
1
) 1 (
) (
Z
=
59
Total t = nt
i
u = t/t nu = t/t
i
u t
u
t
t t u
n
n
t
n
i
n
i
e
n
n n
e
n
t
n T E E
i
Z
=
Z
= =
) 1 (
) (
) 1 (
) ( ) (
1
/
1
As the number becomes large,
the behavior of the system
approaches that of PFR
60
61
}
= =
0
2
2
2
2
) ( ) 1 ( u u u
t
o
o
u
d E
We can calculate the dimensionless variance o
u
2
} } }
+ =
0 0 0
2
) ( ) ( 2 ) ( u u u u u u u u d E d E d E
1
) 1 (
1 2
) 1 (
) (
0
1
0
1
2
Z
= +
Z
=
} }
+
u u u
u
u
u u
d e
n
n
d e
n
n n
n n
n
n
n
n
n n
n n
n
n
n
n
n
1
1 ) 1 (
1
1
) 1 (
) 1 (
2 2
= + =
|
.
|
\
|
+ Z
Z
=
+
The number of tanks n = 1/o
u
2
= t
2
/o
2
If the reaction is I order:
n
i
k
x
) 1 (
1
1
t +
=
62
The Dispersion Model:
The Dispersion Model is used to describe non-ideal PFR
Axial dispersion is taken into consideration
Analogous to Ficks law of diffusion superimposed on the
flow
D
a
= Diffusivity coefficient; U = superficial velocity;
L = Characteristic length
63
Ideal Plug flow
Backmixing or dispersion, is used to represent the combined action of all
phenomena, namely molecular diffusion, turbulent mixing, and non-
uniform velocities, which give rise to a distribution of residence times in
the reactor.
If the reactor is an ideal plug flow, the tracer pulse traverses through
the reactor without distortion and emerges to give the characteristic
ideal plug flow response. If diffusion occurs, the tracer spreads away
from the center of the original pulse in both the upstream and
downstream directions.
64
Closed vessel Dispersion Model:
D
a
= Damkohler number = k C
0
n-1
t
) 1 (
2 2
2 2
2
r
Pe
r r m
e
Pe Pe t
=
o
2 / 2 2 / 2
2 /
) 1 ( ) 1 (
4
1
qPe qPe
Pe
e q e q
qe
x
+
=
Pe D q
a
/ 4 1+ =
65
66
67
68
The x-axis, labeled macromixing measures the breadth of the residence
time distribution. It is zero for piston flow, fairly broad for the exponential
distribution of a stirred tank, and broader yet for situations involving
bypassing or stagnancy.
The y-axis is micromixing, which varies from none to complete. Micromixing
effects are unimportant for piston flow and have maximum importance for
stirred tank reactors.
Well-designed reactors will usually fall in the normal region bounded by the
three apexes, which correspond to piston flow, a perfectly mixed CSTR, and
a completely segregated CSTR.
69
Without even measuring the RTD, limits on the performance of most real
reactors can be determined by calculating the performance at the three
apexes of the normal region.
The calculations require knowledge only of the rate constants and the
mean residence time.
When the residence time distribution is known, the uncertainty about
reactor performance is greatly reduced.
A real system must lie somewhere along a vertical line in Normal Region.
The upper point on this line corresponds to maximum mixedness and
usually provides one bound limit on reactor performance.
Whether it is an upper or lower bound depends on the reaction
mechanism.
The lower point on the line corresponds to complete segregation and
provides the opposite bound on reactor performance.
70
ANY CLARIFICATIONS ?
Kuhn, Thomas
. . . no theory ever solves all the puzzles with which it is confronted at a
given time; nor are the solutions already achieved often perfect.
71