Ch E 441 - Chemical Kinetics and Reaction Engineering

Residence Time Distributions

in Chemical Reactors
Residence Time Distributions
The assumption of a perfectly mixed reactor
often falls short of reality.
Residence time distributions are used to model
the imperfect mixing behavior of real reactors.
Cumulative age, F(t)
External age, E(t)
Internal age, I(t)
Residence Time Distributions
Gas-liquid CSTR (A
(g)
+ B
(l)
C
(l)
)
Reaction occurs at gas-liquid interface
Liquid phase is perfectly mixed
Rate is proportional to bubble surface area
Residence time of gas bubble in reactor is
proportional to bubble volume
Larger bubble escape rapidly
Smaller bubbles may remain in reactor until consumed
Understanding of RTDs is necessary for analysis
Residence Time Distributions
PBR
Sections of the catalyst bed may offer less resistance
to flow, resulting in a preferred pathway through the
bed.
Molecules flowing through the channel do not
spend as much time in the PBR as those taking
another path.
Consequently, there is a distribution of residence
time for the PBR.
Residence Time Distributions
CSTR
Short-circuiting may occur (the direct movement of
material from inlet to outlet.
Dead zones may exist (regions with a minimum of
mixing and thus virtually no reaction takes place).
Residence Time Distributions
Concepts that must be addressed in approaching
a solution to such problems:
distribution of residence times occurs
quality of mixing varies with position in reactor
a model must used to describe the phenomenon
Accounting for nonideality requires
knowledge of macromixing (RTD)
application of the RTD to a reactor (micromixing) to
predict reactor performance.
RTD Functions
In any reactor, the RTD can affect performance
Ideal Plug Flow and Batch Reactors
Every atom leaving reactor is assumed to have resided in
the reactor for exactly the same duration. No axial mixing.
Ideal CSTR
Some atoms leave almost immediately, others remain
almost forever. Many leave after spending a period of time
near the mean residence time. Perfect mixing.
RTD is characteristic of mixing in a reactor.
RTDs are not unique to reactor type.
Different reactor types can have the same RTD.
Measurement of RTD
RTD is measured experimentally by use of an
inert tracer injected into the reactor at t = 0.
Tracer concentration is measured at effluent as a
function of time.
Tracer must be non-reactive and non-absorbing
on reactor walls/internals.
Tracer is typically colored or radioactive to allow
detection and quantification.
Common methods of injection are pulse and step
inputs.
Pulse Input RTD Measurement
An amount of tracer N
o
is suddenly (all at once)
injected into the feed of a reactor vessel with
flow at a steady state.
Outlet concentration is measured as a function of
time.
reactor
injection detection
feed
effluent
Pulse Input RTD Measurement
reactor
injection detection
feed
effluent
pulse injection
C
t
0 +t -t
pulse response
C
t
0 +t -t
Pulse Input RTD Measurement
Injection pulse in system of single-input and
single-output, where only flow (no dispersion)
carries tracer material across system boundaries.
The amount of tracer material AN leaving the
reactor between t and t+At for a volumetric
flowrate of v is

where At is sufficiently small that the
concentration of tracer C(t) is essentially constant
over the time interval.
( ) t t C N A v = A
Pulse Input RTD Measurement
Dividing by total amount of tracer injected, N
o

yields the fraction of material that has a
residence time between t and t+At:

where E(t) represents the residence-time
distribution function.
( )
( ) t t E t
N
t C
N
N
o o
A = A
v
=
A
( )
( )
( )
}
=

0
dt t C
t C
t E
Step Input RTD Measurement
step injection
C
t
step response
C
t
reactor
injection detection
feed
effluent
Step Input RTD Measurement
In general, the output concentration from a
vessel is related to the input function by the
convolution integral (Levenspiel):



where the inlet concentration takes the form of
either a perfect pulse input (Dirac delta function),
imperfect pulse injection, or a step input.
( ) ( ) ( )dt ' t E ' t t C t C
t
0
in out
}
=
Step Input RTD Measurement
( ) ( ) ( ) ( )
}
=
}
=
t
0
o
t
0
in out
dt ' t E C dt ' t E ' t t C t C
Considering a step input in tracer
concentration for a system of constant v:
( )

>
<
=
0 t C
0 t 0
t C
o
o
constant can be brought
outside the integral
Divide by C
o


F(t) fraction of molecules that have spent a time
t or less in reactor (Cumulative age)

Differentiate to obtain RTD function E(t)
Step Input RTD Measurement
( ) ( ) t F ' dt ' t E
C
C
t
0
step
o
out
=
}
=
(

( )
step
o
out
C
C
dt
d
t E
(

=
Step Input RTD Measurement
Advantages
Easier to carry out experimentally than pulse test
Total amount tracer in feed need not be known
Disadvantages
Often difficult to maintain a constant tracer
concentration in feed.
differentiation of data, often leads to large error.
Requires large amount of tracer, which in some cases
can be expensive.
RTD Characteristics
E(t) is sometimes called the exit-age distribution
function.
If the age of an atom is regarded as the amount
of time it spends in the reactor, E(t) is the age
distribution of the effluent.
E(t) is the most often used distribution function
for reactor analysis.
Fraction of exit stream that has resided in the reactor
for a period of time shorter than a given value of t:

Fraction of exit stream that has resided in the reactor
for a period of time longer than a given value of t:

Integral Relationships
( ) ( ) t F dt t E
t
0
=
}
( ) ( ) t F 1 dt t E
t
=
}

Integral Relationships
Mean Residence Time
( )
( )
( )
}
=
}
}
=

0
0
0
m
dt t E t
dt t E
dt t E t
t
The nominal holding time, t, is equal to the
mean residence time, t
m
.
The mean value of the time is the first
moment of the RTD function, E(t).




can be used to determine reactor volume
1
st
moment mean residence time

2
nd
moment variance (extent of spread of
the RTD)

3
rd
moment skewness (extent RTD is skewed
relative to the mean)
Other Moments of the RTD
( ) ( )
}
= o

0
2
m
2
dt t E t - t
( ) ( )
}
=

o
0
3
m
1
3
dt t E t - t s
2 3
Normalized RTD Function, E(O)
t
= O
t
A normalized RTD is often used to allow
comparison of flow profiles inside reactors of
different sizes, where
( ) ( ) t E E t = O
( )
( ) ( )
O
t
= t = O
t
=
e t E E
e
1
t E
t
for an ideal CSTR
Internal-Age Distribution, I(o)
Fraction of material inside the reactor that has
been inside for a period of time between o and
o+Ao
( ) ( )
(

}
o o
t
= o
o
0
d E 1
1
I
RTD in a Batch or PFR
Simplest case
Spike at t = t (or O = 1) of infinite height and zero
width with an area of one
( ) ( ) t o = t t E ( )

=
=
= o
0 x
0 x 0
x
( ) 1 dx x =
}
o
+

( ) ( ) ( ) t =
}
t o
+

g dx x x g
Effluent concentration is identical to that of
reactor contents.
A material balance for t > 0 on inert tracer
injected as a pulse at t = 0
RTD in a CSTR
dt
dC
V C 0
acc out - in
= v
=
( )
t
=
t
0
e C t C
RTD in a CSTR
Recall definition of E(t), and substitute:
dt
dC
V C 0
acc out - in
= v
=
( )
t
=
t
0
e C t C
( )
( )
( )
t
=
}
=
}
=
t

t
t

t
0
t
0
t
0
0
e
dt e C
e C
dt t C
t C
t E
Ideal Reactor Response to Pulse
E
t
Batch/PFR
t

E
O
CSTR
1
1
Laminar Flow RTD
(
(

|
.
|

\
|

t
v
=
(
(

|
.
|

\
|
=
2
2
o
2
max
R
r
1
R
2
R
r
1 U U
Velocity profile in a pipe (cylindrical
coordinates) is parabolic according to:



Time for passage of an element of fluid is
( )
( )
( ) ( )
(

t
=
(

v
t
= =
2 2
o
2
R r 1
1
2
R r 1
1
2
L R
r U
L
r t
The fraction of total fluid passing between r
and r+dr is dv/v
0
:
Laminar Flow RTD
( )
0 0
rdr 2 r U d
v
t
=
v
v
( )
rdr
R
t 4
rdr
R r 1
2
R
4
dt
2
2
2
2 2
t
=
(

t
t
=
( )
( )
(

t
=
2
R r 1
1
2
r t
Laminar Flow RTD
Combining
dt
t 2
dt
t 4
R 2
t
L rdr 2
t
L d
3
2
2
2
0 0 0
|
|
.
|

\
|
t
=
|
|
.
|

\
|
t
|
|
.
|

\
|
v
t
=
v
t
=
v
v
( )
0 0
rdr 2 r U d
v
t
=
v
v
( )
rdr
R
t 4
rdr
R r 1
2
R
4
dt
2
2
2
2 2
t
=
(

t
t
=
Laminar Flow RTD
The minimum time the fluid will spend in the
reactor is


Therefore, the complete RTD function is
2 2
V
R
R
U 2
L
U
L
t
0
2
2
avg max
t
=
|
|
.
|

\
|
v
=
|
|
.
|

\
|
t
t
= =
( )

>
t
<
=
t
t
2 3
2
2
t
t 2
t 0
t E
( )

> O
O
< O
= O
5 . 0
2
1
5 . 0 0
E
3
Laminar Flow RTD
The RTD appears graphically as
( )

> O
O
< O
= O
5 . 0
2
1
5 . 0 0
E
3
E
O
1
0.5
RTD of PFR and CSTR in series
CSTR (t
s
) followed by PFR (t
p
)
CSTR output will be delayed by a time of t
p
( )
( )

t >
t
t <
=
t t
p
s
t
p
t
e
t 0
t E
s p
RTD of PFR and CSTR in series
PFR (t
p
) followed by CSTR (t
s
)
PFR output will delayed the introduction of the pulse
to the CSTR by a time of t
p
Regardless of the order, the RTD is the same. However, the
RTD is not a complete description of structure for a particular
reactor or system of reactors (see Example 13-4).
( )
( )

t >
t
t <
=
t t
p
s
t
p
t
e
t 0
t E
s p