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Non-ideality in Reactors
OUTLET
INLET
The two major uses of the RTD to characterize non-ideal reactors are:
1. To diagnose problems of reactors in operation
2. To predict conversion or effluent concentrations in existing reactors when a
new reaction is used in the reactor.
10
RTD Measurement
RTD is determined experimentally by injecting an inert
chemical, molecule, or atom called a tracer, into the
reactor at some time t = 0 and then measuring the
tracer concentration, C in the effluent stream as a
function of time.
Tracer non-reactive species that easily detectable
(similar physical properties to reacting mixture and be
completely soluble in the mixture) and should not
adsorb on the walls at other surface in the reactor.
e.g. colored & radioactive materials along with inert
gases are the most common type of tracer.
C
Pulse response
Pulse injection
C
Step injection
Step response
cont..
Steps:
Choose an increment of time t sufficiently small that the
conc. of tracer, C(t) exiting between time t and t+t is
essentially the same.
The amount of tracer material, N leaving the reactor
between time, t and t+t is then
N C (t )vt
Where, v is the effluent volumetric flow rate.
N is the amount of material exiting the reactor that has
spent an amount of time between time t and t+t in the
reactor.
N C (t )vt
N vC (t )
t
No
No
N C (t )vt
dN vC(t )dt
N o vC (t )dt
vC (t )
E (t )
No
C (t )
E (t )
0 C (t )dt
The fraction of all the material that has spent time in the
reactor between t = 0 and is 1.0. So,
o E (t )dt 1
In essence
For pulse injection we define
E( t )
N
E( t )t
N0
C( t ) v
N0
The quantity E(t)dt is the fraction of fluid element exiting the reactor that has
spent between time t and (t+dt) inside the reactor.
dN C( t ) vdt
N 0 C( t )vdt
E( t )
between t1and t 2
C( t )
0 C(t )dt
t2 E (t )dt
t1
0 E(t)dt 1
20
10
12
14
C
(g/m3)
10
2.2
1.5
0.6
Solution:
C(t) as function of time - By plotting C as a function of time, the
curve is as shown in figure below:
C(t)
Time (min)
To obtain the E(t) curve from the C(t) curve, we just divide
14
10
14
10
47.4 g . min/ m
2
C (t )dt 1.5 4(0.6) 0
3
2.6 g. min/ m 3
14
10
Now,
C (t )
C (t )
E (t )
3
50
g
.
min/
m
o C (t )dt
10
12
14
C
(g/m3)
10
2.2
1.5
0.6
E(t)
(min-1)
0.02
0.1
0.16
0.2
0.16
0.12
0.08
0.06
0.044 0.03
0.012 0
E(t)
Time (min)
(b) Determine the fraction of material leaving the reactor that has spent
time between 3 and 6 min in the reactor.
Shaded area represents the fraction of
material leaving the reactor that has resided
in the reactor between 3 and 6 min.
36 E (t ) dt shaded area
3
(1)[ 0.16 3(0.2) 3(0.16 ) 0.12 ]
8
0.51
51% of the material leaving the
reactor spends between 3 and 6
min in the reactor
E(t)
Time (min)
(c) Determine the fraction of material leaving the reactor that has spent
between 7.75 and 8.25 min in the reactor.
Because of the time between 7.75 and 8.25 min is very small
relative to a time scale of 14 min, we shall use alternative technique
to determine this fraction to reinforce the interpretation of the
quantity E(t). The average value of E(t) between these times is
0.06/min.
E( t )
C( t )
0 C(t )dt
29
Inlet is switched to
red tracer since
the time 0.
Cout
Step injection
Step response
0
t<0
(Co) constant t>0
Co step
The step- and pulse-responses
of a reactor are related by the
following:
t
F (t ) E (t )dt
0
dF (t )
E (t )
dt
Integral Relationships
Fraction of effluent
t
that has been in reactor F (t )
E
(
t
)
dt
Fraction of effluent
E (t )dt that has been in reactor 1 F (t )
for longer than time t
t
which has been in reactor F (t )
E
(
t
)
dt
F(t)
0.8
t
Cumulative distribution curve
40
[1-F(t)].
Because only the white fluid have been in the reactor, at time t or >t the volume of
white fluid(dV) leaving the reactor in time dt is:
dV ( vdt )[1 F( t )]
V v [1 F( t )]dt
Volumetric flow
is constant
dF E( t )dt
tE ( t )dt t m
0
tm
tE (t )dt
tE (t )dt
E (t )dt
V v[1 F( t )]dt
0
1
1
V
t m /(1 X)
If there are no dead, or stagnant zones within the reactor, then tm will be equal to .
43
In physics
weight
M0
M1
M2
M3
M4
(mean)
Center of mass
(variance)
Moment of inertia
i X
(skewness)
2 3/ 2
i X
(kurtosis)
2 2
44
2 ( t t m ) 2 E( t )dt
0
s3
3 / 2 0
( t t m )3 E( t )dt
tm
tE (t )dt
tE (t )dt
E (t )dt
Variance
Skewness
( t t m ) 2 E( t )dt
2
s
3
1
3 / 2
( t t m )3 E( t )dt
46
10
12
14
C
(g/m3)
10
2.2
1.5
0.6
Solution;
The mean residence time,
t m tE (t )dt
0
The area under the curve of plot of tE(t) as a function of t will yield tm.
t(min)
10
12
14
10
2.2
1.5
0.6
E(t)
0.02
0.1
0.16
0.2
0.16
0.12
0.08
0.06
0.044
0.03
0.012
tE(t)
t-tm
(t-tm)2E(t)
10
14
10
t m 5.15 min
t(min)
10
12
14
10
2.2
1.5
0.6
E(t)
0.02
0.1
0.16
0.2
0.16
0.12
0.08
0.06
0.044
0.03
0.012
tE(t)
t-tm
(t-tm)2E(t)
(t t m ) 2 E (t )dt
2
Once you finished calculating this data for time 0 to 14min, we have to
use integration formula to get variance value.
10
14
10
6.1 min
2.4 min
2
t V /
in
out
E(t)
E(t ) (t )
(t ) 1
(t ) f (t )dt f ( )
0
(t 4)t ^6 dt 4^6
F (t ) (t )dt
t
in
out
1.0
E(t)
F(t)
RTD in CSTR
In an ideal CSTR, the conc. of any substance in the effluent stream is
identical to the conc. throughout the reactor.
Consider a steady flow of fluid into and out of the reactor of volume V.
At t = 0, inject the pulse of tracer into the reactor which will be evenly
get distributed and has concentration C0
A material balance of tracer at any time t after the tracer is injected is:
In Out Accumulation
dC
0 vC V
dt
dC v
1
dt
dt
C
V
(V / v)
At t = 0, C = C0; t = t, C = C;
V / v
C C0 e t /
To find E(t) for ideal mixed flow reactor, for pulse input:
C0e t /
et /
E( t )
t /
C
(
t
)
dt
C
e
dt
0
C( t )
t m tE ( t )dt
t t /
e dt
55
56
57
RTD tells us how long the various fluid elements have been in
the reactor but it does not tell anything about exchange of
matter (mixing) between the fluid elements.
For 1st order reactions, conversion is independent of
concentration. So, mixing with the surrounding molecules is
not important.
For reactions other than 1st order, knowledge of RTD is not
sufficient to predict conversion.
58
Exit Concentration
Exit Conversion
RTD tells us how long the various fluid elements have been in the reactor, but it
does not tell us anything about the exchange of matter (i.e. mixing) between the
fluid elements.
dX
k (1 X)
dt
The conversion is independent of
concentration
For a given state of macromixing (i.e., a given RTD), these two extremes of
micromixing will give the upper and lower limits on conversion in a
Non-ideal reactor.
For n>1, the segregation model will predict the highest conversion.
For n between 0 and 1, the maximum mixedness model will predict the highest
conversion.
62
A fluid in which the globules of a given age do not mix with other globules is called a
macrofluid. A macrofluid could be visualized as noncoalescent globules where all
the molecules in a given globule have the same age.
63
Zero-Parameter Models
Segregation Model
If fluid elements of different ages do not mix together at all, the elements remain
segregated from each other, and the fluid is termed completely segregated.
These globules retain their identity; i.e. they do not interchange material with
other globules in the fluid during their period of residence in the reaction
environment, i.e., they remain segregated.
In addition, each globule spends a different amount of time in the reactor.
64
Mean conversion
Fraction
Conversion
of those globules
of globules that
achieved in globules
spend between t
spending between
time
t
and
t
dt
and
t
dt
in
the
in the reactor
in the reactor
reactor
X X( t ) E( t )dt
0
If we have the RTD, the reaction rate expression, then for a segregated flow
model, we have sufficient information to calculate the conversion.
65
product
dC A
rA
dt
C A0
dX
k (1 X)
dt
X X( t ) E( t )dt
0
dX
rA kCA kCA0 (1 X )
dt
X( t ) 1 e kt
1.0
X (1 e
kt
kt
) E( t )dt E( t )dt e
kt
X 1 e
0
E( t )dt
E( t )dt
66
Example
Derive the equation of a first-order reaction using the segregation model when the
RTD is equivalent to (a) an ideal PFR, (b) an ideal CSTR, and (c) a laminar flow
reactor. Compare these conversions with those obtained from the design equation.
Solution
(a) PFR
kt
X 1 e
0
E( t )dt
dX
k (1 X )
dt
(b) CSTR
E( t ) ( t )
V
X
FA0 rA
X 1 e kt (t )dt 1 e k
0
X 1 e kt
1
E( t ) e t /
kt
X 1 e E( t )dt
0
X 1
e (1/ k ) t
1 1 (1/ k ) t
dt 1
e
k 1/
k
1 k
k
1 k
67
68
Example
Calculate the mean conversion in the reactor for a first-order, liquid-phase, irreversible reaction in
a completely segregated fluid: A products
The specific reaction rate is 0.1 min-1 at 320 K.
t(min)
E(t)
0
-1)
Solution
(min
1
0.02
2
0.1
0.16
0.2
0.16
10
12
14
0.044
0.03
0.012
X( t ) 1 e kt 1 e 0.1t
X X( t ) E( t )dt
0
69
10
14
10
[0.01896 4(0.0084) 0]
0.385
Because the reaction is first order, the calculated conversion would be valid for a
reactor with complete mixing, complete segregation, or any degree of mixing
between the two.
Although early mixing or late mixing does not affect a first-order reaction,
micromixing or complete segregation can modify the results of a second-order
system significantly.
70
71
72
Assignment-I
1.
Calculate the mean residence time and variance for the vessel from the
following data:
t(min)
E(t),
min-1
0.02
0.1
0.16
0.2
0.16 0.12
2.
10
12
14
0
The concentration vs. time data given below represent a continuous response
to a pulse input into a vessel. This vessel is to be used as a reactor for
decomposition of a liquid A.
A products with rate rA = kCA, k = 0.307 min-1
Estimate the fraction of the reactant converted in the real reactor and
compare this with the fraction converted in a PFR of same size.
t (min)
10
15
20
25
30
35
C(t), g/L
73
A first order reaction is carried out in a CSTR operating at steady state. The
flow characteristics of the CSTR are studied by introducing a tracer in the
feed stream. The tracer concentration in the exit stream is monitored as a
function of time. The reaction rate constant is 5.6 10-3 sec-1. Calculate
the fractional conversion that can be achieved in the reactor.
t
(sec)
100
200
300
460
500
670
735
840
960
1100
C(t),
g/m3
2.9
8.7
12.4
10
6.5
3.0
1.5
0.5
74
The globules at the far left correspond to the molecules that spend a long time in
the reactor while those at the far right correspond to the molecules that channel
through the reactor.
In the reactor with side entrances, mixing occurs at the earliest possible moment
consistent with the RTD.
The effect of mixing occurs as early as possible throughout the reactor, and this
situation is termed the condition of maximum mixedness.
75
In a reactor with side entrances, let be the time it takes for the fluid to move from
a particular point to the end of the reactor. In other words, is the life expectancy of
the fluid in the reactor at that point.
Moving down the reactor from left to right,
decreases and becomes zero at the exit. At
the left end of the reactor, approaches
infinity or the maximum residence time if
it is other than infinite.
v v v0 E()
dv
v 0 E ( )
d
v 0 at
v v at
v v0 E()d v0 [1 F()]
rA V rA v0 [1 F()]
Consider a mole balance on substance A between and +
In
In
Out Generation
at through side at by reaction 0
dividing by v0
0
C A 0 E ( )
77
E ( )
dF()
d
C A 0 E() [1 F()]
dC A
C A E() rA [1 F()] 0
d
dCA
E ( )
rA (CA CA 0 )
d
1 F()
CA CA0 (1 X)
CA0
dX
E ( )
rA CA 0 X
d
1 F()
dX
r
E ( )
A
X
d C A 0 1 F()
C A C A0 at
X 0 at
To obtain a solution, the equation is integrated backwards numerically,
starting a very large value of and ending with the final conversion at =0.
For a given RTD and reaction orders greater than one, the maximum
mixedness model gives the lower bound on conversion.
78
Example
The liquid-phase, second order dimerization
2A B
rA kCA2
For which k = 0.01 dm3/molmin is carried out at a reaction temperature of 320 K. The feed is
pure A with CA0 = 8 mol/dm3. The reactor is non-ideal and perhaps could be modeled as two
CSTRs with interchange. The reactor volume is 1000 dm3, and the feed rate for our
dimerization is going to be 25 dm3/min. We have run a tracer test on this reactor, and the
results are given in the Table. We wish to know the bounds on the conversion for different
possible degrees of micromixing for the RTD of this reactor. What are these bounds? Tracer
test on tank reactor: N0 = 100 g, v = 25 dm3/min
79
Solution
kC A 0 t
1 kC A 0 t
X X( t ) E( t )dt
0
80
dX
r
E ( )
A
X
d C A 0 1 F()
rA kC2A0 (1 X)
X i X i 1 kC 2A 0 (1 X i ) 2
E ( i )
Xi
CA0
1 F( i )
E ( i )
Xi1 Xi
Xi kCA 0 (1 Xi ) 2
1 F( i )
E (200)
fractio nof
volumeof
betweenti mes
willleave between
time
and d
time and d
dX
r
E ( )
A
X
d C A 0 1 F()
E ( )
d ln[ I()]
E ( )
I()
d
1 F()
d[I()]
E ( )
d
dX() rA ()
( ) X ( )
d
CA0
( )
Degree of segregation, J
J=1complete segregation
J=0maximum mixedness
82
rA kC nA
(rA )
nkC nA1
C A
(rA )
n 2
n
(
n
1
)
kC
A
C 2A
2
2 (rA )
If
0thenX
C 2A
seg
X mm
2 (rA )
If
0 thenX
2
C A
mm
X seg
2 (rA )
If
0thenX
2
C A
seg
X mm
2 (rA )
Ifn 1, then
0andX
2
C A
seg
X mm
2 (rA )
Ifn 0, then
0andX
2
C A
seg
X mm
2 (rA )
If0 n 1, then
0andX
C 2A
mm
X seg
2 (rA )
Ifn 0or1, then
0andX
2
C A
mm
X seg
83
CA C A ( t ) E( t )dt
0
CB C B ( t ) E( t )dt
0
d CA
C A ( t ) E( t )
dt
d CB
C B ( t ) E( t )
dt
q
dC A
rA riA
dt
i 1
RTD
CA ?
CB ?
att
q
dC B
rB riB
dt
i 1
RTD
CA ?
CB ?
at 0
84
I( )
1 F()
E( t )
dF( t )
dt
E ( )
d[I()]
d
For a CSTR,
1
I( ) e /
85
Simple Diagnostics and Troubleshooting Using the RTD for Ideal Reactors
CSTR
Perfect Operation (P)
C(t ) C0e
t /
et /
E( t )
F( t ) 1 e
t /
V
v0
If is large, there will be a slow decay of the output transient, C(t), and
E(t) for a pulse input.
If is small, there will be rapid decay of the transient, C(t), and E(t) for a
pulse input.
86
Bypassing (BP)
v0 vSB v b
vSB v 0
SB
SB
87
V VD VSD
VSD V
SD
The transients C(t) and E(t) will decay more rapidly than that for
perfect operation because there is a smaller system volume.
88
PFR
Perfect Operation (P)
V
v0
Bypassing (BP)
vSB v 0
SB
VSD V
SD
89
The output will be delayed by a time p at the outlet of the plug-flow section
t p
0
E ( t ) e ( t ) /
t p
PFR+CSTR
t p
0
E ( t ) e ( t ) /
t p
s
P
90
(Dispersion Model)
91
Dispersion Model
RTD
Model
Kinetic Data
Exit Concentration
Exit Conversion
Choice of models
- Models are useful for representing flow in real vessels, for scale-up, and for diagnosing
poor flow.
- Different types of model depending on the type of flow(e.g. PF, MF or in between)
2.The model must realistically describe the characteristics of the non-ideal reactor.
The phenomena occurring in the non-ideal reactor must be reasonably described physically,
chemically, and mathematically.
3.The model must not have more than two adjustable parameters.
This constraint is used because an expression with more than two adjustable parameters
can be fitted to a great variety of experimental data, and the modeling process in this
circumstance is more than an exercise in curve fitting.
A one-parameter model is superior to a two-parameter model if the one-parameter model
is sufficiently realistic.
To be fair, in complex systems (e.g., internal diffusion and conduction, mass transfer
limitations) where other parameters may be measured independently, then more than two
parameters are quite acceptable.
93
94
Dispersion Model
In addition to transport by bulk flow (UAcC), every component in the mixture is
transported through any c/s of the reactor at a rate equal to [-DeAc(dC/dz)] resulting
from molecular and convective diffusion.
This figure presents how dispersion causes the pulse to broaden as it moves down the
reactor and becomes less concentrated.
Pe
97
98
99
V = Volume of real
reactors (dispersed PF)
Vp = Volume of the
PFR
10
0
CA
2 De
1 (k )
C Ap
uL
for same V or
10
1
10
2
r 2
u (r ) 2U 1
R
0t / 2
E( t ) 2
3 t / 2
2t
r 0u 2Ut
r 3R / 4u 7U / 8t
/ 2
8 / 7
The convective-diffusion equation for solute (e.g., tracer) transport in both the axial
and radial direction can be obtained.
1 C 2C
C
C
u (r )
D AB
r
2
t
z
r
z* z Ut
1 C 2C
C
C
D AB
[u (r ) U]
r
z
*
r
z
*
z*
C(z, t )
1
R 2
0 C(r, z, t)2rdr
C
C
2C
U
D*
t
z *
z *2
D* is the Aris-Taylor dispersion coefficient
U 2R 2
D* D AB
48D AB
For laminar flow in a pipe
Da D *
10
4
Correlations for Da
Dispersion for Laminar and Turbulent Flow in Pipes
Experimental Determination of Da
For the different types of boundary conditions
at the reactor entrance and exit, to solve for the
exit concentration as a function of dimensionless
time (=t/), and then relate Da, 2, and .
CT ( UC T ) CT
z
t
z 2
2
Da
CT
z
tU
, ,
CT 0
L
L
1 2
Pe r 2
Initial condition
t 0, z 0, C
T (0
,0) 0, (0 ) 0
M UA C CT (0 , t )dt
10
6
CT 0
D C
a T
C T (0 )
U z z0
1
(0 ) 1
Pe r 0
At =1
C A
0
z
2 1
2
2
tm
tm
( t ) 2 E( t )dt
2
2
2
Pe
(
1
e
)
2
2
t m Pe r Pe r
r
RTD data
tm
2
Per
Da
10
7
CT
C T (0 , t )
z z0
C T (0 , t ) C T (0 , t )
Da CT
D C
CT (L , t ) a T
CT (L , t )
U z zL
U z z L
CT (L , t ) CT (L , t )
Da
U
Da
CT
C
(
0
,
t
)
T
U
z z0
At =1
Consider the case when there is no variation in the dispersion coefficient for all z
and an impulse of tracer is injected at z=0 at t=0.
(1 ) 2
CT (L, t )
1
(1, )
exp
CT 0
4
/
Pe
2 / Pe r
r
10
8
t m 1
Pe r
2
8
2 Pe r Pe 2r
RTD data
tm
2
2
2
8
2 Pe r Pe 2r
Per
check
t m 1
Pe r
tm
t m 1
Pe r
2
2
8
2 Pe r Pe 2r
2
2Pe r
8
t 2m Pe 2r 4Pe r 4 Pe 2r 4Pe r 4
RTD data
tm
2
VD
Per
t m 1
Pe r
10
9
in2 is the variance of the tracer measured at some point upstream (near the entrance)
out2 is the variance of the tracer measured at some point downstream (after the exit)
2
2
Pe r
t 2m
11
0
Example 14-2
The first-order reaction
AB
is carried out in a 10-cm-diameter tubular reactor 6.36 m in length. The specific reaction rate is
0.25 min-1. The results of a tracer test carried out this reactor are shown in Table E14-2.1.
Calculate conversion using (a) the closed vessel dispersion model, (b) PFR, (c) the tanks-in-series
model, and (d) a single CSTR.
11
1
Solution
(a)
t m tE ( t )dt 5.15min
0
(
1
e
)
2
2
t m Pe r Pe r
r
6.1
2
2
0
.
23
(1 e Pe )
2
2
Pe r Pe r
(5.15)
r
Pe r 7.5
4Da
4(1.29)
1
1.30
Pe r
7.5
Pe r q (7.5)(1.3)
4.87
2
2
X 1
(b)
2 (5.15) 2
n 2
4.35
6
.
1
X 1
(d)
1
1 k
n
1
0.677
4.35
(1 1.29 / 4.35)
k
1.29
0.563
1 k 1 1.29
PFR: X=72.5%
Dispersion: X=68.0%
Tanks in series: X=67.7%
Single CSTR: X=56.3%
11
3
C
(g/m3)
2.9
8.7
12.4
10
6.5
3.0
1.5
0.5
0.0
0.0
Calculate (i) the average residence time of the fluid, (ii) the variance of
the response to the pulse input, (ii) Dispersion number.
2.
A waste stabilization pond has a 2.25 days theoretical detention time. A tracer
test results as function of tracer concentration against time are mentioned in
table. Estimate (i) the average residence time of waste in stabilization pond, (ii)
the variance of the response to the pulse input, (iii) the dispersion number.
t
(min)
0.
5
C(t),
mg/L
22 23 23.
.9
4
24.
4
25.
8
5.5
28 30.3
10
30.
3
27.
5
25.9
25.
2
24.7
11
4
(Tanks-in-Series Model)
11
5
Tanks-in-Series Model
RTD
Model
Kinetic Data
Exit Concentration
Exit Conversion
11
7
One-Parameter Models
~Tanks-in-series model
modeling tubular reactors as a series of identically sized CSTRs
-Parameter is the number of tanks (n)
~Dispersion model
- Modification of the ideal reactor by imposing axial dispersion on plug
flow
- Parameter is the dispersion coefficient (De)
11
8
dC
V1 1 vC1
dt
C1 C0e
vt / V1
v v0
C0 e
V1 V2 Vi
t / 1
1 2 i
C0 N 0 / V1
dC
Vi 2 vC1 vC 2
dt
i / n
v 0 C3 ( t )dt
0
V1
dC 2 C 2 C0 t /
e
dt
i
i
C0 t 2 /( 2i2 )e t /
t 2 t /
E( t )
3e
2 t /
C t e
0 C3 (t )dt 0 0 2 dt 2i
2i
C3 ( t )
C t
C2 0 et /
i
C0 t 2 t /
C3
e
2i2
t n 1
t /
E( t )
e
(n 1)! in
11
9
X 1
1
(1 i k ) n
V
v0n
n may be a
noninteger.
12
0
Bo 2(n 1)
Bo
1
2
12
1
When a tube or pipe is long enough and the fluid is not highly viscous,
then the dispersion model or tanks-in-series model can be used to
represent the flow in these vessels.
For a viscous fluid, the velocity profile is parabolic.
Because of the high viscosity, there is slight radial diffusion between
faster and slower fluid elements. In the extreme case, we have the pure
convection model.
Convection model assumes that each element of fluid slides past its
neighbor with no interaction by molecular diffusion, i.e. the spread in
residence times is caused only by velocity variations.
12
3
r 2
r 2 2v0
U U max 1 2U avg 1 2
R
R R
r 2
1
R
t (r )
U(r )
v 0 2[1 (r / R ) 2 ] 2[1 (r / R ) 2 ]
12
4
The volumetric flow rate of fluid out between r and (r+dr) is:
dv U(r )2rdr
t (r )
dv L 2rdr
v0 t v0
dv U(r )2rdr
v0
v0
t (r )
2[1 (r / R ) 2 ]
R 2
rdr 2 dt
4t
2rdr
4
dt 2
R 2[1 (r / R ) 2 ]2 R 2
/2
4t 2
rdr 2 rdr
2
R
[1 (r / R ) ]
dv L 2rdr L 2 R 2
2
dt 3 dt E( t )dt
v0 t v0 t v0 4t 2
2t
The minimum time the fluid may spend in the reactor is:
t min
L
L R 2 V
U max 2U avg R 2v 0 2
L
U(r )
E (t ) 2
3
2t
t / 2
t / 2
12
7
12
8
Exponential Integrals
12
9
13
0
Simple Diagnostics and Troubleshooting Using the RTD for Ideal Reactors
CSTR
Perfect Operation (P)
C(t ) C0e
t /
et /
E( t )
F( t ) 1 e
t /
V
v0
If is large, there will be a slow decay of the output transient, C(t), and
E(t) for a pulse input.
If is small, there will be rapid decay of the transient, C(t), and E(t) for a
pulse input.
13
1
Bypassing (BP)
v0 vSB v b
vSB v 0
SB
SB
13
2
V VD VSD
VSD V
SD
The transients C(t) and E(t) will decay more rapidly than that for
perfect operation because there is a smaller system volume.
13
3
PFR
Perfect Operation (P)
V
v0
Bypassing (BP)
vSB v 0
SB
VSD V
SD
13
4
The output will be delayed by a time p at the outlet of the plug-flow section
t p
0
E ( t ) e ( t ) /
t p
PFR+CSTR
t p
0
E ( t ) e ( t ) /
t p
s
P
13
5
A reactor with baffles is to be used to carry out the reaction. The pulse
test results are as shown below:
A R, -rA = 0.05 CA
1.
t(min)
C (mol/L)
10
20
30
40
50
60
70
Calculate the conversion assuming (i) plug flow, (ii) the tanks-in-series
model (iii) mixed flow.
2.
t (sec)
C
(mg/L)
10
8
3
10
11
2.2
1.5
0.6
12
Calculate conversion using (a) the closed vessel dispersion number, (b)
PFR, (c) the tanks-in-series model, and (d) a single CSTR
13
6
13
7
13
8
RTD tells us how long the various fluid elements have been in the reactor, but it
does not tell us anything about the exchange of matter (i.e. mixing) between the
fluid elements.
dX
k (1 X)
dt
For a given state of macromixing (i.e., a given RTD), these two extremes of
micromixing will give the upper and lower limits on conversion in a
Non-ideal reactor.
For n>1, the segregation model will predict the highest conversion.
For n between 0 and 1, the maximum mixedness model predicts the highest
conversion.
14
0
A fluid in which the globules of a given age do not mix with other globules is called a
macrofluid. A macrofluid could be visualized as noncoalescent globules where all
the molecules in a given globule have the same age.
14
1
Segregation Model
If fluid elements of different ages do not mix together at all, the elements remain
segregated from each other, and the fluid is termed completely segregated.
These globules retain their identity; i.e. they do not interchange material with
other globules in the fluid during their period of residence in the reaction
environment, i.e., they remain segregated.
In addition, each globule spends a different amount of time in the reactor.
14
2
Because the fluid flows down the reactor in plug flow, each exit stream
corresponds to a specific residence time in the reactor.
Batches of molecules are removed from the reactor at different locations along
the reactor in such a manner so as to duplicate the RTD function, E(t).
14
3
14
4
14
5
Degree
of segregation
14
8
14
9
15
0
15
2
The globules at the far left correspond to the molecules that spend a long time in
the reactor while those at the far right correspond to the molecules that channel
through the reactor.
In the reactor with side entrances, mixing occurs at the earliest possible moment
consistent with the RTD.
The effect of mixing occurs as early as possible throughout the reactor, and this
situation is termed the condition of maximum mixedness.
15
3
In a reactor with side entrances, let be the time it takes for the fluid to move from
a particular point to the end of the reactor. In other words, is the life expectancy of
the fluid in the reactor at that point.
Moving down the reactor from left to right,
decreases and becomes zero at the exit. At
the left end of the reactor, approaches
infinity or the maximum residence time if
it is other than infinite.
v v v0 E()
dv
v 0 E ( )
d
v 0 at
v v at
v v0 E()d v0 [1 F()]
rA V rA v0 [1 F()]
Consider a mole balance on substance A between and +
In
In
Out Generation
at through side at by reaction 0
dividing by v0
0
C A 0 E ( )
E ( )
dF()
d
C A 0 E() [1 F()]
dC A
C A E() rA [1 F()] 0
d
dCA
E ( )
rA (CA CA 0 )
d
1 F()
CA CA0 (1 X)
CA0
dX
E ( )
rA CA 0 X
d
1 F()
dX
r
E ( )
A
X
d C A 0 1 F()
C A C A0 at
X 0 at
To obtain a solution, the equation is integrated backwards numerically,
starting a very large value of and ending with the final conversion at =0.
For a given RTD and reaction orders greater than one, the maximum
mixedness model gives the lower bound on conversion.
15
6
Solution
kC A 0 t
1 kC A 0 t
X X( t ) E( t )dt
0
15
7
CA C A ( t ) E( t )dt
0
CB C B ( t ) E( t )dt
0
d CA
C A ( t ) E( t )
dt
d CB
C B ( t ) E( t )
dt
q
dC A
rA riA
dt
i 1
RTD
CA ?
CB ?
att
q
dC B
rB riB
dt
i 1
RTD
CA ?
CB ?
at 0
15
8