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Residence Time Distributions in Chemical Reactors: CH E 441 - Chemical Kinetics and Reaction Engineering

The document discusses residence time distributions (RTDs) in chemical reactors. It describes how RTDs can be used to model imperfect mixing in real reactors. It discusses different types of reactors like CSTRs and PBRs and how non-ideal flow can occur. It also describes how RTDs are measured experimentally using tracer tests and the different functions used to characterize RTDs like the E(t) distribution and F(t) cumulative distribution. The mean residence time and other moments of the RTD are also defined.

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51 views43 pages

Residence Time Distributions in Chemical Reactors: CH E 441 - Chemical Kinetics and Reaction Engineering

The document discusses residence time distributions (RTDs) in chemical reactors. It describes how RTDs can be used to model imperfect mixing in real reactors. It discusses different types of reactors like CSTRs and PBRs and how non-ideal flow can occur. It also describes how RTDs are measured experimentally using tracer tests and the different functions used to characterize RTDs like the E(t) distribution and F(t) cumulative distribution. The mean residence time and other moments of the RTD are also defined.

Uploaded by

Abdul Qayyum
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as DOCX, PDF, TXT or read online on Scribd
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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)
• 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
• 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.
• 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).
• 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.
RTD Functions
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 No 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.
feed effluent
reactor

injection detection
pulse injection
pulse response

C C

- 0 + - 0 +
t t

feed effluent
reactor
injection detection
• 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 N leaving the
reactor between t and t+ t for a volumetric
flowrate of is N C t t
where t is sufficiently small that the
concentration of tracer C(t) is essentially constant
over the time interval.
• Dividing by total amount of tracer injected, No
yields the fraction of material that has a
residence time between t and t+ t:

• where E(t) represents the residence-time


distribution function.
C t
N t Et t Et Ct
0 C t dt
No No
Step Input RTD Measurement
step injection
step response

C C

t t

feed effluent
reactor
Step Input RTD Measurement
injection detection
Step Input RTD Measurement
• In general, the output concentration from a
vessel is related to the input function by the
convolution integral (Levenspiel):
t
Cout t Cin t' E t' dt
t
0

where the inlet concentration takes the form of


either a perfect pulse input (Dirac delta
function), imperfect pulse injection, or a step
input.
Step Input RTD Measurement
Step Input RTD Measurement
• Considering a step input in tracer
concentration for a system of constant :
0 t 0
Co t
Co t 0 constant can be brought
outside the integral

Cout t t E
Cin 0 t' t' dt
Step Input RTD Measurement
t
Co E t' dt
0
t
• Divide by Co Cout
E t' dt' Ft
Co step 0

– F(t) fraction of molecules that have spent a time


t or less in reactor (Cumulative age)

• Differentiate to obtain RTD function E(t)


d
Et C out Co
d
t
step
• 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.
Integral Relationships
• Fraction of exit stream that has resided in the reactor
for a period of time shorter than a given value of t:
t
E t dt F t
0
• Fraction of exit stream that has resided in the reactor
for a period of time longer than a given value of t:

E t dt 1 F t
t
Integral Relationships
Mean Residence Time
• The nominal holding time, , is equal to the
mean residence time, tm.
• The mean value of the time is the first
moment of the RTD function, E(t).
tE t dt
tm 0 tE t dt
E t dt 0
0
• can be used to determine reactor volume
Other Moments of the RTD
st
• 1 moment – mean residence time

• 2nd moment – variance (extent of spread of


the RTD) 2
t- E t dt
2
tm
0

• 3rd moment – skewness (extent RTD is skewed


relative to thesmean)
3 2t - t 3 E t dt
m
1
3 0
Normalized RTD Function, E( )
• A normalized RTD is often used to allow
comparison of flow profiles inside reactors of
different sizes, where
t
E Et

for an ideal CSTR


1 t
Et e

E Et e
Internal-Age Distribution, I( )
• Fraction of material inside the reactor that has
been inside for a period of time between and
+
1 1
I E d
0
RTD in a Batch or PFR
• Simplest case
• Spike at t = (or = 1) of infinite height and zero
width with an area of one
x 0 x 0
Et t
x 0
gx
x dx 1 x dx g
RTD in a CSTR
• 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

in - out acc
0 C V dC t
dt Ct C0 e
• Recall definition of E(t), and substitute:
t t
Ct C 0e e
Et
C t dt C 0e t
dt
0 0

0 C V dC t
dt Ct C0 e
Ideal Reactor Response to Pulse
Batch/PFR CSTR

E E

1
t
Laminar Flow RTD
• Velocity profile in a pipe (cylindrical
coordinates) is parabolic according to:
2 2
r 2 o r
U Umax 1 1
2 R
R R

• Time for passage of an element of fluid is


L R2L 1 1
tr
Ur 2 1 rR2 2 1 rR2
o
• The fraction of total fluid passing between r
and r+dr is d / 0: d U r 2 rdr
0
0

2
4 2 4t2
dt rdr R 2 rdr
R2 1 r R2

1
tr
2 1 rR2
• Combining
d U r 2 rdr
0
0

4 2
dt 2 4t 2
2 rdr rdr
R 1 rR 2 2
R

d L 2 rdr t
0 0
2
L2 R2
dt 4t 2dt
2t
3 t 0
• The minimum time the fluid will spend in the
reactor is L L R2 V
t
Umax 2Uavg R2 2 2
0

• Therefore, the complete RTD function is


0 t 2 0 0.5
2
Et E 1
t 2 3 0.5
2t3 2
• The RTD appears graphically as

1 0 0.5
E 1
E 3 0.5
2

0.5
RTD of PFR and CSTR in series
• CSTR ( s) followed by PFR ( p)
– CSTR output will be delayed by a time of p

0 t p
p
t
Et e s

t p
s
RTD of PFR and CSTR in series
• PFR ( p) followed by CSTR ( s)
– PFR output will delayed the introduction of the pulse
to the CSTR by a time of p

0 t p
p
t
Et e s

t p
s
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).

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