Unit -I

BASICS OF NON-IDEAL FLOW

 Ideal Plug flow reactor No axial mixing

Ideal Mixed flow reactor Complete mixing
In reality, the flow pattern is somewhere in between
these two extremes. (Why?)

Non-ideality in Reactors

The deviation from ideal flow patterns is caused:

By creation of nearly stagnant regions (dead zones) in
the reactor

By bypassing or short-circuiting of the fluid

By channelling of fluid
By recirculation of fluid around agitator
Due to vortices and turbulence at inlet and outlet of
reactor
In all types of process equipment e.g. heat exchangers, packed
columns and reactors, this type of flow should be avoided as it lowers
the performance of the unit.

Residence-Time Distribution (RTD) function

The time the molecules have spent in the reactor is called
the RESIDENCE TIME of the atoms in the reactor.
In an ideal PFR, all the molecules of material leaving the
reactor have been inside it for exactly the same amount time.
Similarly, in an ideal batch reactor, all the atoms of materials
within the reactor have been inside it for an identical length
of time.

Residence Time Distribution

Residence time = time spent by a particle inside a continuous system
(time between entering and leaving the system).

OUTLET

INLET

Fast particle (short

residence time)

Residence time distribution E(t) = histogram of residence times of all

particles passing through outlet.
E(t)dt is relative amount of particles having residence times within the interval
(t, t+dt).

The ideal plug-flow and batch reactors are the

only two classes of reactors in which all the
atoms in the reactors have the same residence
time.
In all other reactor types, the molecules in the
feed spend different times inside the reactor
(as they take different routes through the
reactor), i.e. there exists a DISTRIBUTION OF
RESIDENCE TIMES of the material within the
reactor.

Mixed flow reactor Some molecules entering the

reactor leave almost immediately, while some other
molecules might remain for ever as all the material is
never withdrawn at one time from the reactor.
Many molecules leave the reactor after spending a
period of time close to the mean residence time.

The distribution of these times for the stream of fluid

leaving the vessel is called the exit age distribution (E)
or residence time distribution (RTD) of fluid.
The RTD of the reactor is a characteristic of the mixing
that occurs in the chemical reactor.

 In any reactor, the distribution of residence times can

significantly affect its performance.
Not all RTDs are unique to a particular reactor type; different
reactors can display identical RTDs.
The RTD exhibited by a given reactor type yields distinctive
clues to the type of mixing occurring within it and is one of the
most informative characterizations of the reactor.

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.

Three concepts were used to

describe non-ideal reactors:
Not all molecules are spending the
same time in the reactor.

the distribution of residence times

in the system,
the quality of mixing and

the model used to describe the

system.

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.

Two most used methods of injection :

A) pulse input
B) step input

C
Pulse response

Pulse injection
C

Step injection

Step response

(a) Pulse input

A known amount of tracer, No is suddenly
injected in one shot into the feed stream
entering the reactor in the shortest time
practicable.

The tracer conc. in the exit stream is then

measured from the moment of addition until it
ceases to be detected.

 Typical conc.-time curve at the inlet & outlet (pulse injection

and response) of an arbitrary reactor are shown below:

In RTD analysis, the effluent conc.-time curve is called as

the C - curve.

(a) Pulse input..

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.

Divide the total amount of material that was injected

into the reactor, No

N C (t )vt

N vC (t )

t
No
No

which represents the fraction of material that has a

residence time in the reactor between time t and t+t.
For pulse injection, we define,
vC (t )
E (t )
No
N
Therefore,
E (t )t
No

 The quantity E(t) is called the RTD function that describes

how much time different fluid elements have spent in the
reactor.
The quantity E(t)dt is the fraction of fluid exiting the reactor
that has spent between time t and (t + dt) inside the reactor.
If No is not known directly, it can be obtained from the outlet
concentration measurements by summing up all the
amounts of materials, N between time equal to 0 and .

 Writing in differential form yields,

And then integrating, we obtain

N C (t )vt

dN vC(t )dt

The volumetric flow rate, v is usually constant. So, we can

define E(t) as,

N o vC (t )dt

vC (t )
E (t )
No

C (t )
E (t )
0 C (t )dt

The integral in the denominator is the area under the

C curve.

 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

Describes about how much time

different fluid elements
spend in the reactor

Residence-time distribution function

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 )

Fraction of material leaving the reactor th at

has resided in the reactor for times

between t1and t 2

C( t )

0 C(t )dt

t2 E (t )dt
t1

0 E(t)dt 1

20

Constructing the C(t) and E(t)Curves (Pulse Input)

A sample of the tracer hytane at 320K was injected as a pulse to a
reactor and the effluent concentration was measured as a function of
time resulting in the following data:
t(min)

10

12

14

C
(g/m3)

10

2.2

1.5

0.6

The measurements represent the exact concentrations at the time

listed and not average values between the various sampling tests.
a) Construct figures showing C(t) and E(t) as functions of time.
b) Determine the fraction of material leaving the reactor that has spent time
between 3 and 6 min in the reactor.
c) Determine the fraction of material leaving the reactor that has spent time
between 7.75 and 8.25 min in the reactor.

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

C(t) by the integral o C (t )dt which is the area under the C

curve.
We break the data into 2 regions (0-10 min & 10-14 min).
The area under the C curve can be found using the
numerical integration formulas.

o C (t )dt C (t )dt C (t )dt

10
0

14
10

o C (t )dt C (t )dt C (t )dt

10
0

14
10

1 1(0) 4(1) 2(5) 4(8) 2(10) 4(8)

C (t )dt
3 2(6) 4(4) 2(3.0) 4(2.2) 1(1.5)
10
0

47.4 g . min/ m

2
C (t )dt 1.5 4(0.6) 0
3
2.6 g. min/ m 3
14
10

o C (t )dt (47.4 2.6) g. min/ m 3

50.0 g. min/ m 3

Now,

C (t )
C (t )
E (t )

3
50
g
.
min/
m
o C (t )dt

With the following results

t(min)

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 )dt 0.06 min 1 (0.5 min) 0.03

Consequently, 3% of the fluid leaving the reactor has been in the
reactor between 7.75 and 8.25min

 The major drawback of this approach is that it is impossible to produce

physically a unit impulse of infinite magnitude i.e. the principal difficulties
with the pulse technique lie in the problems connected with obtaining a
reasonable pulse at a reactors entrance.
The injection must take place over a period which is very short compared
with residence times in various segments of the reactor or reactor system,
and there must be a negligible amount of dispersion between the point of
injection and the entrance to the reactor system.
There are problems when the C vs. t curve has a long tail because the
analysis can be subjected to large inaccuracies. This problem principally
affects the denominator of the right-hand side of the following equation:

E( t )

C( t )

0 C(t )dt
29

Step Input / Step Tracer Expt.

At t = 0, switch from
ordinary fluid to fluid with
tracer of concentration Cmax

Inlet is switched to
red tracer since
the time 0.

The tracer is added at a steady rate to the reactor feed to give a

steady input concentration. The conc. of tracer in the effluent is
then monitored from the instant of tracer addition until it attains a
concentration approximating that of Cin.
Cin

Cout

Step injection

Step response

Step Input / Step Tracer Experiment

Tracer is added at a constant rate to the feed initiated at
time t = 0. Before this time, no tracer was added to the feed.
Symbolically,
Co (t )

0
t<0
(Co) constant t>0

Step Input / Step Tracer Experiment

C (t )
F (t )

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

Characteristics of the RTD

E(t) - exit-age distribution function - is the most used distribution function
connected with reactor analysis because it characterizes the length of time
various fluid elements spend at reaction conditions.

Integral Relationships
Fraction of effluent
t
that has been in reactor F (t )
E
(
t
)
dt

for less than time t

Fraction of effluent
E (t )dt that has been in reactor 1 F (t )
for longer than time t

Cumulative distribution function,

F(t).

We can calculate F(t) at various

times from the area under the
curve of an E(t) vs. t plot.

Characteristics of the RTD

fraction of effluent

t
which has been in reactor F (t )
E
(
t
)
dt

for less than time t

Cumulative distribution function, called F(t).

Can calculate F(t) at various time t from the area under the
curve of an E(t) vs t plot.

Characteristics of the RTD

The shape of the F(t) curve is shown for a tracer response to a step input
as shown in the figure below:
1.0

F(t)

0.8

80% [F(t)] of the molecules spend 40

min or less in the reactor and 20%
[1-F(t)] of the molecules spend longer
than 40 min in the reactor
40

t
Cumulative distribution curve

Step Input / Step Tracer Experiment

Disadvantages for step input method;
Sometimes difficult to maintain a constant tracer conc.
in the feed.
Required large amount of tracer (expensive)

Characteristics of the RTD

Commonly observed RTDs

RTD for Plug Flow Reactor

RTD for Near Perfectly Mixed CSTR

Characteristics of the RTD

RTD for Packed-Bed Reactor with Dead Zones & Channeling

Dead zones serve to reduce the effective reactor volume,
indicating that the active reactor volume is smaller than
expected.

Characteristics of the RTD

CSTR with dead zones and bypass

Mean residence time

Mean residence time (tm) -The amount of
time an average molecule of an element
spends in a reactor.
Space Time - For no dispersion/diffusion and v
= v0, the space time () is equal to the mean
residence time (tm).

40

Mean Residence Time

We have a reactor completely filled with white fluid.
At time t = 0, we start red fluid to replace the white fluid that currently fill the
reactor.
Initially, the reactor volume V is equal to the volume occupied by the white fluid.
Now, in a time dt, the volume of molecules that will leave the reactor is (vdt).
The fraction of these molecules that have been in the reactor at time t or >t is

[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[1 F( t )] 0 tdF 0 tdF

0
0
v

For liquid reactions, no change in

volumetric flow rate.
For gas reactions, no pressure drop,
isothermal operation, and no change in
the total number of moles ( = 0).

t m /(1 X)

If there are no dead, or stagnant zones within the reactor, then tm will be equal to .

GENERAL PRINCIPLES OF STATISTICAL MOMENTS

MOMENT: A mathematical description of a

discrete distribution.
STATISTICAL MOMENTS - Utilized in chemical
engineering to describe the flow data.

43

Examples of Statistical Moment Usage

In statistics

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

Statistical analysis of the RTD

Variance is defined as:

2 ( t t m ) 2 E( t )dt
0

It is a measure of the spreading of the tracer

quantity at the reactor outlet, which in turn gives
the variation of residence time about the mean
value tm.

The greater the value of variance (2), the greater

a distributions spread will be.
The square root of variance is known as standard
deviation () of the age distribution of the fluid
elements about the mean residence time tm.
Skewness is defined as:

s3

3 / 2 0

( t t m )3 E( t )dt

It is also a measure of deviation from ideal flow

pattern.
Skewness shows the difference between the
residence time of species constituting maximum
population in the effluent stream and the average
residence time tm.
The magnitude of this moment measures the extent
that a distribution is skewed in one direction or
45
another in reference of the mean.

Means and moments of distribution

Mean residence time

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

Residence time distributions

Exit age distribution, E(t)dt
Fraction of material in exit stream which has
age between t and t+dt
Cumulative residence time distribution, F(t)dt
Fraction of material in exit stream which has
age less than t
Internal age distribution, I(t)dt
Fraction of material within the reactor which
has age between t and t+dt
47

Mean Residence Time & Variance Calculations

Calculate the mean residence time (tm) and the variance for the reactor
characterized by the RTD obtained from a pulse input at 320 K.
t(min)

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)

To calculate tm we have to use integration formula using tE(t) data to get

area under the curve of tE(t) vs. t

10

14

10

t m tE (t )dt tE (t )dt tE (t )dt

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)

To calculate variance, we use equation,

(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

(t tm ) E (t )dt (t tm ) E (t )dt (t tm ) E (t )dt

2

10

6.1 min
2.4 min
2

RTD in Batch & Plug-Flow Reactors

In Batch & PFR, all the atoms leaving such reactors spent same amount
of time within the reactors.
The distribution function in such reactor is a spike of infinite height &
zero width with area equal to 1.
The spike occurs at

t V /

in

out

E(t)

Mathematically, this spike is represented by the Dirac delta function:

E(t ) (t )

Area under the curve is,

(t ) 1

Any integration with delta function,

(t ) f (t )dt f ( )
0

(t 4)t ^6 dt 4^6

F(t) = t6 => f( )=46

The cumulative distribution function F(t) is,

F (t ) (t )dt
t

in

out

1.0

E(t)

F(t)

PFR response to a pulse tracer input

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

Because the reactor is perfectly mixed, C in this equation

is the concentration of the tracer either in the effluent or
within the reactor.

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

Conversion in Non-ideal flow reactors

To evaluate reactor behavior in general, we should know the
following four factors:

1. the kinetics of the reaction (complete rate equation)

2. the RTD of fluid in the reactor
3. the earliness or lateness of fluid mixing in the reactor
4. State of aggregation of fluid (micro or macro fluid)

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

Early or late mixing of fluid in the reactor

- The fluid elements of a single flowing stream can mix each
other either early or late in their flow through the vessel.

Late mixing favors reactions where n>1

Early mixing favors reactions where n<1
59

State of aggregation of flowing stream

Microfluid fluid in which molecules are free to move everywhere, collide,
and intermix (e.g. gases, thin liquids)
Macrofluid fluid in which globules (each containing large number of
molecules) of a given age do not mix with other globules (e.g. highly viscous
liquids)

A macrofluid exhibits complete segregation and a microfluid exhibits no

60
segregation.

Reactor Modeling Using the RTD

RTD
Model
Kinetic Data

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 reactions other than first order, the

degree of mixing of molecules must be
known in addition to how long each molecule
spends in the reactor.
61

~Macromixing produces a distribution of residence times WITHOUT specifying

how molecules of different ages encounter one another in the reactor.
~Micromixing describes how molecules of different ages encounter one another
in the reactor.
~Complete segregation: all molecules of the same age group remain together as they
travel through the reactor and are not mixed with any other age until they exit the reactor.
~Complete micromixing: molecules of different age groups are completely mixed at the
molecular level as soon as they enter the reactor.

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.

Late mixing ~ complete segregation

Early mixing ~ maximum mixedness

A fluid in which molecules are not constrained to remain in the globule

and are free to move everywhere is called a microfluid.

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.

In the segregated flow model we visualize the

flow though the reactor to consist of a continuous
series of globules.

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

Because there is no molecular interchange between globules, each acts

essentially as its own batch reactor. The reaction time in any one of these tiny
batch reactors is equal to the time that the particular globules spends in the
reaction environment.

Mean conversion
Fraction

Conversion

of those globules
of globules that

achieved in globules

spend between t
spending between

after spending a time t

time
t
and
t

dt
and
t

dt
in
the

in the reactor

in the reactor

reactor

dX X(t ) E(t )dt

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

Consider a first-order reaction

k
A

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

v0CA0 X kCA0 (1 X)V

k
1 k
67

~For a first-order reaction whether it is complete micromixing or complete

segregation, the same conversion results.
~This phenomenon occurs because the rate of change of conversion for
a first-order does not depend on the concentration of the reacting
molecules; it does not matter what kind of molecule is next to it or
colliding with it.
~So, only RTD is necessary to calculate the conversion for a first-order
reaction in any type of reactor.
~Knowledge of neither the degree of micromixing nor the reactor flow
pattern is necessary.

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

0.12 0.08 0.06

10

12

14

0.044

0.03

0.012

Because each globule acts as a

batch reactor of constant volume, we
use the batch reactor design equation
to arrive at the equation giving
conversion as a function of time:

X( t ) 1 e kt 1 e 0.1t

X X( t ) E( t )dt
0

69

10

14

10

X X (t ) E (t )dt X (t ) E (t )dt X (t ) E (t )dt

13 [0 4(0.0019 0.0414 0.0629 0.0402 0.0261)
2(0.018 0.066 0.0541 0.0331) 0.01896]
2
3

[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

Diagnosing Reactor Ills

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

0.08 0.06 0.044 0.03 0.012

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

Maximum Mixedness Model

We return again to the plug-flow reactor with side
entrances, only this time the fluid enters the reactor
along its length.
As soon as the fluid enters the reactor, it is
completely mixed radially (but not longitudinally)
with the other fluid already in the reactor.
The entering fluid is fed into the reactor through the
side entrances in such a manner that the RTD of
the plug-flow reactor with side entrances is identical
to the RTD of the real reactor.

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.

E() is the fraction of the total that has life

expectancy between and +.
v0E() is the volumetric rate of fluid entering through
the sides of volume V.

v v v0 E()

dv
v 0 E ( )
d

V is the volumetric flow rate at

V+ is the volumetric flow rate at +
76

v 0 at
v v at

v v0 E()d v0 [1 F()]

The volume of fluid with a life

expectancy between and +
is V v [1 F()]
0
The rate of generation of
substance A in this volume is

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

v0 [1 F()]CA v0CA0 E() v0 [1 F()]CA rA v0 [1 F()] 0

dividing by v0

0
C A 0 E ( )

d{[1 F()]C A ()}

rA [1 F()] 0
d

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()

The boundary condition is

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

Conversion if fluid is completely segregated.

The batch reactor equation for a second-order reaction of this type is

kC A 0 t
1 kC A 0 t

The conversion for a completely segregated fluid in a reactor

is

X X( t ) E( t )dt
0

The calculation for this integration are

c a r r i e d o u t i n Ta b l e E 1 3 - 7 . 2 . T h e
numerical integration uses the simple
trapezoid rule. The conversion for this
s y s t e m
i f
t h e
f l u i d
were complete segregated is 0.61 or 61%.

80

Conversion for maximum mixedness.

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)

X (175) X (200) (25)

X (200) kCA0 (1 X (200)) 2
1 F (200)

0 (25)[( 0.075)(0) (0.01)(8)(1 0) 2 ] 2

The conversion for a condition of maximum
mixedness in this reactor is 0.56 or 56%.
There is little difference in the conversion for the two
conditions of complete segregation (61%) and maximum
mixedness (56%). With bounds this narrow, there may not be
much point in modeling the reactor to improve the
predictability of conversion.
CSTR58%
PFR76%
81

The intensity function, (t) can be thought of as the probability of a particle

escaping the system between a time t and (t+dt) provided the particle is still in the
system.
()d is the fraction of fluid in the vessel with age that will leave
between and +d.

fractio nof

volumeof

fluidleav ing volumeof fluid theflui dwith

remaining at age that

betweenti mes

willleave between

time
and d
time and d

v0 E()d [VI()][ ()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

var ianceofa gesbetwee nfluid " po int s"

J
var ianceofa gesofall molecules insystme m

J=1complete segregation
J=0maximum mixedness
82

Comparing Segregation and Maximum Mixedness Predictions

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

RTD and Multiple Reactions

Segregation Model

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

Maximum Mixedness Model

dC A
E ( )
riA (C A C A 0 )
d
1 F()
dC B
E ( )
riB (C B C B0 )
d
1 F()

RTD

CA ?
CB ?

at 0

84

Internal-Age Distribution, I()

~I() is the fraction of material inside the reactor that has been inside the
reactor for a period of time between and +.
~E() is the fraction of material leaving the reactor that has spent for a
time between and + in the reactor.

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

v0 is the total volumetric flow rate

vSB is the volumetric flow rate entering the system
volume
2
vb is the volumetric flow rate bypassing the reactor
vb
vSB
E( t )
( t 0)
et /
v0
Vv 0

The space time, SB, will be greater than that if there

were no bypassing. Because SB is greater than
there will be a slower decay of the transients C(t)
and E(t) than of perfect operation.

SB

Having an initial jump equal

to the fraction by-passed.

87

Dead Volume (DV)

V VD VSD

VSD V

SD

V is the total volume

VD is the dead volume
VSD is the system volume

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

Dead Volume (DV)

VSD V

SD

89

PFR/CSTR Series RTD

The reacting mixture may follow a somewhat tortuous

path either before entering or after leaving the perfectly
mixed zone-or even both. This tortuous path may be
modeled as a plug-flow reactor. Thus this type of tank
reactor may be modeled as a CSTR in series with a plugflow reactor, and the PFR may either precede or follow
the CSTR.
s is the residence time in the
CSTR
p is the residence time in the PFR

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

If the pulse of tracer is introduced into

the entrance of the plug-flow section,
then the same pulse will appear at
the entrance of the perfectly mixed
section p seconds later.

t p
0

E ( t ) e ( t ) /

t p

s
P

90

Models for Non-ideal Reactors-I

(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)

1.The model must be mathematically tractable.

The equations used to describe a chemical reactor can be solved without an inordinate
expenditure of human or computer time.

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

Dispersion model and Tanks-in-series model models

that consider a small deviation from PF.

These models apply to turbulent flow in pipes, laminar flow in very

long tubes, flow in packed beds, shaft kilns, long channels, screw
conveyers etc.

For laminar flow in short tubes or laminar flow of viscous materials,

(parabolic velocity profile) these models may not apply, in which
case we go for convection model.

Some molecules will diffuse forward

ahead of molar average velocity
while others will lag behind.

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.

Flow, Reaction, and Dispersion

Pe

Rate of transport by convection

UL

Rate of transport by diffusion or dispersion De

Rate of consumption ofA by reaction

Da
ktav (1st order rxn.)
Rate of transport ofA by convection
Da - Damkohler number
Pe - Peclet number

97

Material enters and

leaves the differential

section not only by bulk
flow but also by
dispersion

98

Analytical solution for

99

V = Volume of real
reactors (dispersed PF)
Vp = Volume of the
PFR

10
0

Comparison of performance of real reactors (dispersed PF)

with that of PFR
De
V
1 (k )
Vp
uL

for same C A out

CA
2 De
1 (k )
C Ap
uL

for same V or

10
1

10
2

Dispersion in a Tubular Reactor with Laminar Flow

The axial velocity varies in the radial direction according to the Hagen-Poiseuille equation:

r 2
u (r ) 2U 1
R

U is the average velocity

0t / 2

E( t ) 2

3 t / 2
2t

In arriving at this distribution E(t), it was assumed that

there are no transfer of molecules in the radial direction
between streamlines.

r 0u 2Ut
r 3R / 4u 7U / 8t

/ 2
8 / 7

In addition to the molecules diffusing between

streamlines, they can also move forward or
backward relative to the average fluid velocity
by molecular diffusion (Ficks law).
10
3

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

Dispersion in Packed Beds

dp is the particle diameter

is the porosity
dt is the tube diameter
Sc is the Schmidt number
10
5

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

Unsteady-State Tracer Balance

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

Mass of tracer injected, M is

M UA C CT (0 , t )dt

For a pulse input, CT0

is defined as the mass
of tracer injected, M,
divided by the vessel
volume, V.

10
6

Solution for a Closed-Closed System

At =0

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

Solution for a Open-Open System

At =0

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.

For long tubes (Pe>100) in

which the concentration
gradient at will be zero

(1 ) 2
CT (L, t )
1
(1, )

exp

CT 0
4

/
Pe
2 / Pe r
r

10
8

t m 1
Pe r

is based on the volume between z=0 and z=L (i.e., reactor

volume measured with a yardstick).

2
8

2 Pe r Pe 2r

The mean residence time for an open system is greater than

that for a closed-system. The reason is that the molecules can
diffuse back into the reactor after they exit.

Case 1~space time is known

RTD data
tm
2

2
2
8

2 Pe r Pe 2r

Per
check

t m 1
Pe r
tm

Case 2~space time is unknown

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

Sloppy Tracer Inputs

It is not always possible to inject a tracer pulse
cleanly as an input to a system because it takes a
finite time to inject the reactor.
When the injection does not approach a perfect
input (Figure 14-14), the differences in the variances
between the input and output tracer measurements
are used to calculate the Peclet number:
2
2 in2 out

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)

For an open-open system

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)

0 C(t)dt 50g min

t m tE ( t )dt 5.15min
0

2 ( t t m ) 2 E(t )dt t 2 E( t )dt t 2m 32.63 (5.15) 2 6.10min 2

2
2
2
Pe

(
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

Da k t m k (5.15min)( 0.25min 1 ) 1.29

q 1

4Da
4(1.29)
1
1.30
Pe r
7.5

Pe r q (7.5)(1.3)

4.87
2
2

X 1

4(1.30) exp( 7.5 / 2)

0.68
(1 1.3) 2 exp( 4.87) (1 1.3) 2 (4.87)
11
2

(b)

X 1 ek 1 eDa 1 e1.29 0.725

(c)

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

In order to study the residence time distribution in a CSTR operating at

steady state, a tracer is introduced in the feed stream. The tracer
concentration in the effluent stream is monitored as a function of time
and data is tabulated as shown below:
t(sec)
0 100 200 300
460 500 670 735 840 960
1100
1.

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

Models for Non-ideal Reactors-II

(Tanks-in-Series Model)

11
5

Tanks-in-Series Model
RTD

Model
Kinetic Data

Exit Concentration
Exit Conversion

Dispersion model and Tanks-in-series model models

that consider a small deviation from PF.

These models apply to turbulent flow in pipes, laminar flow in

very long tubes, flow in packed beds, shaft kilns, long
channels, screw conveyers etc.

For laminar flow in short tubes or laminar flow of viscous materials,

(parabolic velocity profile) these models may not apply, in which
case we go for convection model.

Some molecules will diffuse

forward ahead of molar average
velocity while others will lag behind.

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

Tanks-in-Series (T-I-S) Model

We are first going to develop the RTD equation for three tanks in series (Figure 142) and then generalize to n reactors in series to derive an equation that gives the
number of tanks in series that best fits the RTD data.
Considering a tracer pulse injected
into the first reactor of three equally
sized CSTRs in series

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

For a first order reaction,

X 1

1
(1 i k ) n

V
v0n

n may be a
noninteger.

For reactions other than first order,

an integer number of reactors must be used.

12
0

Tanks-in-Series Model Vs. Dispersion Model

For first-order reactions, the two models can be applied with equal
ease.

However, the tanks-in-series model is mathematically easier to use to

obtain the effluent concentration and conversion for reaction orders
other than one and for multiple reactions.
These two models are equivalent when the Bodenstein number is
related to the number of tanks in series (n) by the equation:
Bo = UL/De

Bo 2(n 1)

Bo
1
2

U is the superficial velocity

L is the reactor length

De is the dispersion coefficient

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.

These reactors employ the characteristics of laminar flow to achieve

various research purposes.

Used to study fluid dynamics in chemical reactors.

In LFR, the residence time of the chemicals in the reactor can be

varied by either changing the distance between the reactant
input point and the point at which the product/sample is taken,
or by adjusting the velocity of the gas/fluid.

Benefit of a LFR The factors affecting a reaction can be easily

controlled and adjusted throughout an experiment.

12
3

Laminar Flow Reactor (LFR)

For laminar flow in a tubular reactor, the velocity profile is parabolic, with the fluid in
the center of the tube spending the shorter time in the reactor.

r 2
r 2 2v0
U U max 1 2U avg 1 2
R
R R

r 2
1
R

Umax is the centerline velocity

Uavg is the average velocity
through the tube.

The time of passage of an element of fluid at a radius r

is:
L
R 2 L
1

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 )

The fraction of total fluid passing between r and (r+dr) is:

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 )

The complete RTD function for a LFR is:

E (t ) 2
3
2t

t / 2
t / 2

In the pure convection regime (negligible molecular diffusion) each

element of fluid follows its own streamline with no intermixing with
neighboring elements., i.e. it gives macrofluid behavior.

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

v0 is the total volumetric flow rate

vSB is the volumetric flow rate entering the system
volume
2
vb is the volumetric flow rate bypassing the reactor
vb
vSB
E( t )
( t 0)
et /
v0
Vv 0

The space time, SB, will be greater than that if there

were no bypassing. Because SB is greater than
there will be a slower decay of the transients C(t)
and E(t) than of perfect operation.

SB

Having an initial jump equal

to the fraction by-passed.

13
2

Dead Volume (DV)

V VD VSD

VSD V

SD

V is the total volume

VD is the dead volume
VSD is the system volume

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

Dead Volume (DV)

VSD V

SD

13
4

PFR/CSTR Series RTD

The reacting mixture may follow a somewhat tortuous

path either before entering or after leaving the perfectly
mixed zone-or even both. This tortuous path may be
modeled as a plug-flow reactor. Thus this type of tank
reactor may be modeled as a CSTR in series with a plugflow reactor, and the PFR may either precede or follow
the CSTR.
s is the residence time in the
CSTR
p is the residence time in the PFR

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

If the pulse of tracer is introduced into

the entrance of the plug-flow section,
then the same pulse will appear at
the entrance of the perfectly mixed
section p seconds later.

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.

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 on this reactor are shown in the
following table:

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

3. A tracer is introduced in a laminar flow reactor of

cylindrical cross-section. The first trace of tracer is
identified at reactor outlet after 50 sec. When a first order
reaction is carried out in the reactor with initial reactant
concentration of 0.1 mol/m3, 20% conversion is achieved.
Calculate the rate constant for the reaction.
4. Assuming plug flow, it was calculated that a tubular
reactor 12 m long gives 96% conversion of A for the 2nd
order reaction A->R. However, the fluid is very viscous,
and flow is strongly laminar. So, to closely represent the
flow, convection model was expected in stead of plug
flow model. Under the circumstance, how long should be
reactor to insure 96% conversion of A?

13
7

Earliness of Mixing, Segregation, and

the RTD

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 reactions other than first order, the

degree of mixing of molecules must be
known in addition to how long each molecule
spends in the reactor.

The conversion is independent of concentration

~Macromixing produces a distribution of residence times WITHOUT specifying

how molecules of different ages encounter one another in the reactor.
~Micromixing describes how molecules of different ages encounter one another
in the reactor.
~Complete segregation: all molecules of the same age group remain together as they
travel through the reactor and are not mixed with any other age until they exit the reactor.
~Complete micromixing: molecules of different age groups are completely mixed at the
molecular level as soon as they enter the reactor.

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.

Late mixing ~ complete segregation

Early mixing ~ maximum mixedness

A fluid in which molecules are not constrained to remain in the globule

and are free to move everywhere is called a microfluid.

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.

In the segregated flow model we visualize the

flow though the reactor to consist of a continuous
series of globules.

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).

The molecules removed near the entrance to the

reactor correspond to those molecules having
short residence times in the reactor.
This effluent would correspond to the molecules
that channel rapidly through the reactor.
The farther the molecules travel along the
reactor before being removed, the longer their
residence time.
The points at which the various groups or
batches of molecules are removed correspond
to the RTD function for the reactor.

14
3

Mixing of fluids during reaction is important for

extremely fast reactions in homogeneous systems,
as well as for all heterogeneous systems.
Problem associated with mixing has two aspects:
(i) Degree of segregation of the fluid, or whether
mixing occurs on the microscopic level (mixing of
individual molecules) or the macroscopic level
(mixing of clumps, groups, or aggregates of
molecules);
(ii) Earliness of mixing, or whether fluid mixes
early or late as it flows through the vessel.

14
4

State of aggregation of flowing stream

Microfluid fluid in which molecules are free to move

everywhere, collide, and intermix (e.g. gases, thin liquids)
Macrofluid fluid in which globules (each containing large
number of molecules) of a given age do not mix with other
globules (e.g. highly viscous liquids)

A macrofluid exhibits complete segregation and a microfluid exhibits no

segregation.

14
5

 Degree

of segregation

The normally accepted state of a liquid or gas is that

of a microfluid.
Let us consider a single reacting macrofluid being
processed
in batch, plug flow, and mixed flow
reactors to see how this state of aggregation can
result in behavior different from that of a microfluid.
Batch reactor:
Let the batch reactor be filled with a macrofluid
containing reactant A. Since each packet of
macrofluid acts as a little batch reactor, conversion is
same in all packets and is identical to what would be
obtained with a microfluid.
So, for batch operations the degree of segregation
does not affect conversion or product distribution.

Plug flow reactor:

Since plug flow can be visualized as a flow of small

batch reactors passing in succession through the
vessel, macro- and micro fluids act alike.
So, the degree of segregation does not influence
conversion or product distribution.

Mixed flow reactor-Microfluid:

When a microfluid is treated in a MFR, the reactant

concentration drops to the low value prevailing in the
reactor. No clump of molecules retains its high initial
concentration of A.
The conversion of the reactant can be found by the
same method as obtained for homogeneous
reactions:
XA=(-rA)V/FA0
With no density change (A=0), CA/CA0 =[1-{(-

14
8

Mixed flow reactor-Macrofluid:

When a macrofluid enters a MFR, the reactant

concentration in an aggregate does not drop
immediately to a low value but decreases in the same
way as it would in a batch reactor.
The performance equation for a macrofluid in a
mixed flow reactor is given by:

14
9

Difference in Performance: Early

or Late Mixing, Macro- or
Microfluids, PFR or MFR

A rise in segregation improves

reactor performance for reaction
orders greater than unity but
Lowers performance for reaction
orders smaller than unity.

15
0

15
2

Maximum Mixedness Model

We return again to the plug-flow reactor with side
entrances, only this time the fluid enters the reactor
along its length.
As soon as the fluid enters the reactor, it is
completely mixed radially (but not longitudinally)
with the other fluid already in the reactor.
The entering fluid is fed into the reactor through the
side entrances in such a manner that the RTD of
the plug-flow reactor with side entrances is identical
to the RTD of the real reactor.

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.

E() is the fraction of the total that has life

expectancy between and +.
v0E() is the volumetric rate of fluid entering through
the sides of volume V.

v v v0 E()

dv
v 0 E ( )
d

V is the volumetric flow rate at

V+ is the volumetric flow rate at +
15
4

v 0 at
v v at

v v0 E()d v0 [1 F()]

The volume of fluid with a life

expectancy between and +
is V v [1 F()]
0
The rate of generation of
substance A in this volume is

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

v0 [1 F()]CA v0CA0 E() v0 [1 F()]CA rA v0 [1 F()] 0

dividing by v0

0
C A 0 E ( )

d{[1 F()]C A ()}

rA [1 F()] 0
d
15
5

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()

The boundary condition is

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

Conversion if fluid is completely segregated.

The batch reactor equation for a second-order reaction of this type is

kC A 0 t
1 kC A 0 t

The conversion for a completely segregated fluid in a reactor

is

X X( t ) E( t )dt
0

The calculation for this integration are

c a r r i e d o u t i n Ta b l e E 1 3 - 7 . 2 . T h e
numerical integration uses the simple
trapezoid rule. The conversion for this
s y s t e m
i f
t h e
f l u i d
were complete segregated is 0.61 or 61%.

15
7

RTD and Multiple Reactions

Segregation Model

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

Maximum Mixedness Model

dC A
E ( )
riA (C A C A 0 )
d
1 F()
dC B
E ( )
riB (C B C B0 )
d
1 F()

RTD

CA ?
CB ?

at 0

15
8