DESIGN FOR MULTIPLE REACTIONS

REACTOR DESIGN FOR MULTIPLE REACTIONS

• Usually, more than one reaction occurs within a chemical reactor
• Minimization of undesired side reactions that occur with the desired
reaction contributes to the economic success of a chemical plant

• Goal: Determination of the reactor conditions and configuration

that maximizes product formation
• Reactor design for multiple reactions
• Parallel reactions
• Series reactions
• Independent reactions
• More complex reactions
• Use of selectivity factor to select the proper reactor that minimizes
unwanted side reactions
 1) Parallel or competing reactions

k1 B
A
k2 C
Desired product

The reactions in which the reactant is consumed by two different reactions to

form different products called Parallel reaction

2) Series reactions k1 k2
A B C
Desired product

The reactions in which the reactant first form an intermediate product which then
reacts further to form another product are called Series reaction
3) Independent reactions Crude oil cracking
k1 k2
A B C D

4) Complex reactions A + B ⎯⎯→

k1
C+D A + C ⎯⎯⎯
2 →E k
 rate of formation of D rD
instantaneous rate selectivity, SD/U SD U = =
rate of formation of U rU

overall rate selectivity, SD/U

 FD Exit molar flow rate of desired product

SD/U
DU = =
FU Exit molar flow rate of undesired product

ND Final moles of desired product

SD U = =
NU Final moles of undesired product

instantaneous yield,YD YD =
rate of formation of D r
= D
(at any point or time in reactor) rate of consumption of A −rA

overall yield,YD

FD Evaluate ND Evaluate
flow YD = batch YD =
FA0 − FA d at NA0 − NA d at tfinal
outlet
 Condition for maximizing the desired product or
Minimizing unwanted products for single reactants
for the parallel reaction
k1 D (Desired Product)
A
k2 U (Undesired Product)
D

Separator
A Reactor

rD = k1C aA1
The rate laws are:
rU = k 2C aA 2

(a1 & a2 are the positive constants. a1 is the order of desired reactions, a2 is
the order of undesired reaction)
 Condition for maximizing the desired product or Minimizing unwanted products for
two reactants
The rate of disappearance of A for the above reaction sequence is the sum
of the rates of formation of D & U
The rate laws are:

-rA = rD+rU

− rA = k1C aA1 + k 2C BAa 2

Taking the ratio of these rates be obtained, a rate selectivity parameter, S

can be maximized as follows:
rD k1 a1 −a 2
S DU = = CA
rU k 2
The only factor we can control is CA because, k1, k2, a1, a2 are constant
for specific system
 Minimizing unwanted products for Single reactant

Case I : If a1 > a2
Case II: If a1 < a2 ( i.e., a2 > a1)
Case III: If a1 = a2
Case III a : By Changing Temperature of the operation:
k D k1 AD −[( ED − EU ) / RT ]
= = e
kU k 2 AU
A: Temp independent constant of integration usually termed as
frequency factor
E: Activation Energy
Hence: a) If ED > EU : System should be operated at high temp.
b) If ED < EU : System should be operated at low temp.
Case III b : Use of Catalyst
(a1 & a2 are the positive constants. a1 is the order of desired reactions, a2 is the order of
undesired reaction)
 Maximizing the wanted products for single reactant (Case-1)

k1 D (Desired Product)
A
k2 U (Undesired Product)
Case I : If a1 > a2
If the reaction order of the desired reaction is greater than the reaction order of
the undesired reaction, let ‘a’ be a positive number; i.e., the difference between
these reaction order ; i.e., a1 - a2 = a
𝑟𝐷 𝐾
Rate selectivity parameter, SDU 𝑆𝐷𝑈 = = 𝐾𝐷 . 𝐶𝐴𝑎
𝑟𝑢 𝑈

To maximize the SDU, maintain the concentration of reactant ‘A’ as high as possible.
With high conc. of A, we see that the ratio of the desired product to undesired
product will also be high.
To achieve this, use of  a batch or plug flow reactor
 Maintaining the low conversions  Removing inert from feed;
 high pressures (if gas phase reaction);  Eliminating recycle system
 Using a minimum size reactor  Minimum Diluent use in liquid phase system
 Maximizing the wanted products for single reactant (Case-2)

k1 D (Desired Product)
A
k2 U (Undesired Product)
Case II : If a1 < a2
If the reaction order of the un-desired reaction is greater than the reaction order
of the desired reaction, let ‘a’ be a positive number; i.e., the difference between
these reaction order ; i.e., a2 – a1 = a
𝑟𝐷 𝐾𝐷 𝐶𝐴𝛼1 𝐾𝐷 1
Rate selectivity parameter, SDU 𝑆𝐷𝑈 = = . = .
𝑟𝑢 𝐾𝑈 𝐶𝐴𝑎2 𝐾𝑈 𝐶𝐴𝑎2−𝛼1

To maximize the SDU, maintain the concentration of reactant ‘A’ as low as possible.
To achieve this, use of  a backmix reactor
 Maintaining the high conversions  Increasing the inert in the feed;
 Decreasing pressure (if gas phase reaction);  Using large recycle system
 Using a large reactor  Maximizing the Diluent use in liquid phase system
 Minimizing unwanted products for Single reactant

Case III: If a1 = a2
If the reaction order of the desired reaction is equal to the reaction
order of the un-desired reaction, then the difference between these
reaction order ; i.e., a2 – a1 = 0
𝑟𝐷 𝐾𝐷 𝛼1−𝛼2 𝐾𝐷 0 𝐾𝐷
𝑆𝐷𝑈 = = .𝐶 = .𝐶 =
𝑟𝑢 𝐾𝑈 𝐴 𝐾𝑈 𝐴 𝐾𝑈

Hence, the product distribution is fixed by kD/kU alone and is unaffected by the
type of reactor use.

However, we may control the distribution by varying the kD/kU by two ways:

Case III a : By Changing Temperature level of the operation

Case III b : By using the Catalyst
 Minimizing unwanted products for Single reactant

i) Change of Temp.: If the activation energy of the two reactions are

different, kD/kU can be made to vary.
The selectivity of the rate selectivity parameter to temperature can be
determined from the ratio of the specific reaction rates:
k D k1 AD −[( ED − EU ) / RT ]
= = e
kU k 2 AU

Where, A: Temp independent constant of integration usually termed as frequency factor

E: Activation Energy
Hence: a) If ED > EU : System should be operated at high temp.
b) If ED < EU or AU > AD : System should be operated at low temp (but not
to low so that the desired reaction does not proceed to any significant extent

Case III b : Use of Catalyst, selectivity of the catalyst for accelerating the
desired product is important. This is the much more effective way of
controlling the product distribution than any other methods.
▪ When a reactant gives two product (desired, and
undesired) simultaneously with different rate constant
then this is called a parallel reaction.

▪ To keep maximum amount of desired product we can

take following steps.

▪ If a1>a2 or the desired reaction is of higher order then

keep reactant concentration high for high product
concentration.

▪ If a1<a2 than for desired reaction keep reactant

concentration low.

▪ For a1 = a2 change in reactant concentration will not

affect the product then, because rate constant k1 and k2
are different at different temperature so, we can keep
our temperature such that desired product will be high
or use of catalyst would be a option which are selective
in nature.
SUMMARY OF FINDING IN PARALLEL REACTION
OF SINGLE REACTANT
Summary:
# For reactions in parallel, the concentration level of reactants is the
key to proper control of product distribution.

# A high reactant concentration favors the reaction of higher order

# A low concentration favors the reaction of lower order

# The concentration level has no effect on the product distribution for

reactions of the same order.
Different reactors and schemes for maximizing the desired product
A B A
B
A
B A
B A B

(a) CSTR (b) tubular reactor (c ) batch (d) semi-batch 1 (e) semi-batch 2

A A
B B

(f) Tubular reactor with side streams (g) Tubular reactor with side streams

B
A

A
B

(i) Tubular reactor with recycle

(h) Series of small CSTRs
Different reactors and schemes for maximizing the desired product

A
B

(h-1) Series of small CSTRs

 Minimizing unwanted products for two reactants (Case-1)

for the parallel reaction

k1 D (Desired Product)
A+B
k2 U (Undesired Product)

Case I : a1 > a2, b1 > b2, a = a1-a2 > 0, b = b1-b2 > 0

(a1 & a2 are the positive constants. a1 is the order of desired reactions, a2 is the order of undesired
reaction)
rD k1 a b
the rate selectivity parameter, S DU = = C AC B
rU k 2

To maximize the SDU, maintain the concentration of both A and

B as high as possible.
How Could We Achieve This?????
Solution: Fogler page 293 (329)
Different reactors and schemes for maximizing the desired product

We could achieve high concentration of both A and B, using

 a tubular reactor (Figure-a)
 a batch reactor (Figure-b)
 high pressures (if gas phase), reduce inert

A A
B B

(a) tubular reactor (b ) batch reactor

 Minimizing unwanted products for two reactants (case 2)

for the parallel reaction

k1 D (Desired Product)
A+B
k2 U (Undesired Product)

Case II : a1 > a2, b1 < b2, a = a1-a2 > 0, b = b2-b1 > 0

rD k1C Aa
the rate selectivity parameter S DU = =
rU k 2C Bb

To maximize the SDU, maintain CA high and CB low.

How Could We Achieve This?????

Different reactors and schemes for maximizing the desired product

You can maintain high CA and low CB by using

 a semi-batch reactor in which B is fed slowly into A. (Fig: a)
 a tubular reactor with side stream of B continually ( Fig: b)
 a series of small CSTRs with A fed only to the first reactor & B feed to the
each reactors (Fig: c)
B
B A

A
A B

(a) semi-batch 1 (b) Tubular reactor with side streams

(c) Series of small CSTRs

 Minimizing unwanted products for two reactants Case-3)

for the parallel reaction

k1 D (Desired Product)
A+B
k2 U (Undesired Product)

Case III : a1 < a2, b1 < b2, a = a2-a1 > 0, b = b2-b1 > 0

rD k1
S DU = =
the rate selectivity parameter rU k 2C Aa C Bb

To maximize the SDU, maintain the concentration of

both A and B as low as possible
Different reactors and schemes for maximizing the desired product

The concentration of both A and B as low as possible using,

 a CSTR (Fig: a)
 a tubular reactor in which there is a large recycle ratio ( Fig: b)
 a feed diluted with inert material
 low pressures (if gas phase)

A A
B B

(a) CSTR (b) Tubular reactor with recycle

How Could We Achieve This?????

 Minimizing unwanted products for two reactants (case 4)

for the parallel reaction

k1 D (Desired Product)
A+B
k2 U (Undesired Product)

Case IV : a1 < a2, b1 > b2, a = a2-a1 > 0, b = b1-b2 > 0

rD k1C Bb
the rate selectivity parameter S DU = =
rU k 2C Aa

To maximize the SDU, maintain CB high and CA low.

How Could We Achieve This?????

 Different reactors and schemes for maximizing the desired product

To achieve (CB high and CA low this, use-

 a semi-batch reactor in which A is slowly feed to a large amount of B (Fig – a)
 a tubular reactor with side stream of A (Fig – b)
 a series of small CSTR with fresh A to each reactor (Fig: c)

A A
B

(a) semi-batch 2
A
B

(b) Tubular reactor with side streams (c) Series of small CSTRs
 REACTOR DESIGN TO MAXIMIZE DESIRED
PRODUCT FOR PARALLEL RXNS
Figure:
Contacting
patterns for
various
combinations of
high and low
concentration
of reactants in
non-continuous
operation

Figure: Contacting patterns for various combinations of high and low concentration of reactants in
continuous flow operation
How do these concentration requirements affect reactor selection?
kD
D How do concentration requirements play
A+B into reactor selection?
kU CA0u0 CAu0
U
CB0u0 CBu0
CSTR:
PFR concentration is
PFR (or PBR): concentration is always at its
high at the inlet & lowest value
progressively drops to the (that at outlet)
outlet concentration
Semi-batch: concentration
Batch: CBu0
of one reactant (A as
concentration is shown) is high at t=0 &
CA(t)
CB(t) high at t=0 & progressively drops with
progressively increasing time, whereas
drops with CA concentration of B can be
increasing time kept low at all times
 kD
D High CA favors undesired
High CA favors desired
A+B
a1 > a 2 a1 < a 2 product formation
product formation
kU (keep CA low)
U

PFR/PBR
b1 > b2 Batch reactor
Side streams feed low CA
High CB
When CA & CB are low (end time or Semi-batch reactor CA
favors slowly feed A to large
position), all rxns will be slow ←High CB
desired amt of B
product
PFR/PBR CA CA CA
formation
High P for gas-phase rxn, do not add inert CSTRs in
gas (dilutes reactants) series

CA0u0 CAu0
CB0u0 CBu0
b1 < b2 CSTR
PFR/PBR w/ side streams feeding low CB
High CB
CB
favors
Semi-batch reactor,
undesired ←High CA
slowly PFR/PBR w/
product high recycle
formation feed B to large amount of A PFR/PBR
(keep CB CB CB CB
CSTRs in
low) • Dilute feed with inerts that are easily
series
separated from product
B consumed before leaving CSTR • Low P if gas phase
Math:
Chapter 7: Design for Parallel Reactions, page: 155, Levenspinel
Example: 7.1
 −(ED −EU )
SD U =
AD
AU
e RT ( )
CAa1−a2 CB b1− b2

What reactor conditions and configuration maximizes the selectivity?

Start with temperature (affects k):
a) If ED > EU b) If ED < EU

−(ED −EU ) −(ED −EU )

ED − EU ED − EU
>0 → e RT <1 <0 → e RT >1
RT RT
Specific rate of desired reaction
Specific rate of desired reaction kD increases less rapidly with
kD increases more rapidly with increasing T
increasing T
Use lower T to favor desired
Use higher temperature to product formation (not so low that
favor desired product the reaction rate is tiny)
formation
 kD D
−(ED −EU )
A AD
SD U = e RT CAa1−a2
AU
kU
U
What reactor temperature maximizes the selectivity?
ED = 20 kcal/mol, EU = 10 kcal/mol, T = 25 ◦C (298K) or 100 ◦C (373K)
T = 25 ◦C 
− 20,000
cal
−10,000
cal  a) ED > EU
 
(298K):  mol mol 
 cal 

( )
A  1.987 298K A
SD U = D e  molK  CAa1−a2 → SD U = D 4.6  10−8 CAa1−a2
AU AU
 cal cal 
T = 100 ◦C − 20,000 −10,000  kD/U
(373K):  mol mol 
 cal 

( )
AD  1.987 373K AD
SD U = e  molK  CAa1−a2
→ SD U = 1.4  10−6 CAa1−a2
AU AU
SD/U is greater at 373K, higher temperature to favors desired product
formation
 kD −(ED −EU )
D
A+B
kU
SD U =
AD
AU
e RT ( )
CAa1−a2 CB b1− b2
U
What reactor conditions and configuration maximizes the selectivity?
Now evaluate concentration:
a) a1 > a2 → a1 − a2 > 0 b) a1 < a2 → a1 − a2 < 0

CAa1−a2 CAa1−a2
→ Use large CA → Use small CA

c) b1 > b2 → b1 − b2 > 0 d) b1 < b2 → b1 − b2 < 0

CBb1−b2 CBb1−b2
→ Use large CB → Use small CB
 ▪ In multiple reaction reactor design contacting pattern is most
important factor to get a particular product.
▪ In irreversible reaction in series like

the mixing of fluid of different composition is the key to formation of

intermediate. The maximum possible amount of intermediate is
obtained if fluid of different composition and different stage of
conversation are not allowed to mixed.

• In series of reaction if intermediate reactant is our desired product than

semi batch reactor will be used.
 The rate equation in series reactions

The rate equations for

rA = −k1C A

rR = k1C A − k 2C R
For irreversible reactions in series:
# The mixing of fluid of different composition is
rS = k 2C R the key to the formation of intermediate.

# The maximum possible amount of any and all

intermediates is obtained:
a) if fluids of different compositions and
b) at different stages of conversion are not
allowed to mix
FAVORABLE CONTACTING PATTERNS FOR ANY SET OF IRREVERSIBLE
REACTIONS IN SERIES, NOT JUST A→R→S
Which contacting pattern of Figs. E8.1, when properly operated, can give a higher concentration of any
intermediate, the contacting pattern on the left or the one on the right?

SOLUTION : Focusing on the mixing rule for reactions in series, that the extent of mixing of streams of different
composition should be minimized, we reason
for part (a): The left pattern is better; in fact it is the best possible flow scheme.
for part (b): Looking at Figs. 6.5,6.6, and 6.16,6.17 of Chapter 6 we see that the left is closer to plug flow for both first-
and for second-order reactions. So we generalize this to any positive order reaction.
for part (c): The right pattern is better because it is closer to plug flow.
for (d): Turbulent flow has less intermixing of fluids of different ages, less bypassing; hence, the right scheme is better.
Note. In the quantitative analysis that follows we verify this general and important rule.
Maximizing the desired product in series reaction

k1 k2
A B C

 In parallel rxns, maximize the desired product

 by adjusting the reaction conditions
 by choosing the proper reactor

 In series rxns, maximize the desired product

 by adjusting the space-time for a flow reactor
 by choosing real-time for a batch reactor
 Maximizing the desired product in series reaction

k1 k2
A B C
Desired Product

 If the first reaction is slow and second reaction is fast, it will be

extremely difficult to produce species B.

 If the first reaction (formation of B) is fast and the reaction to form C is

slow, a large yield of B can be achieved.

 However, if the reaction is allowed to proceed for a long time in a

batch reactor or if the tubular flow reactor is too long, the desired product
B will be converted to C.

 In no other type reaction is exactness in the calculation of the time

needed to carry out the reaction more important than in series reactions.
 k1 k2
A B C Time is the key factor here!!!
(desired) (undesired)

Space time t for a flow reactor Real time t for a batch reactor

To maximize the production of B, use:

Batch CSTRs in series

or PFR/PBR or
n

and carefully select the time (batch) or spacetime (flow)

Reaction paths for different ks in series reaction
k1 k2
A B C

For k1/k2>1, a
Large quantity of B
B k1
>1
Can be obtained k2

k1
~1
k2
For k1/k2<1, a
Little quantity of B t 2'
Can be obtained t 3' k1
<1
t ' 1st rxn is slow
1 k2 2nd rxn is fast

A C
Long rxn time in batch or long tubular reactor
-> B will be converted to C
 CONCENTRATIONS IN SERIES REACTIONS
k1 k2 -rA = k1CA
A B C rB,net = k1CA – k2CB
How does CA depend on t?
dFA dC A
= −k1C A → u0 = −k1C A → C A = C A0e −k1t
dV dV
How does CB depend on t?
dFB
dV
= k1C A − k 2CB → u0
dCB
dV
(
= k1 C A0e −k1t − k 2CB ) Substitute
V
u0
=t

→
dCB
dt
( )
= k1 CA0e−k1t − k 2CB →
dCB
dt
+ k 2CB = k1 CA0e−k1t ( )
Use integrating
factor (reviewed →
(
d CBek 2t ) =k C  e−k1t − e−k 2t
( k 2 −k1)t → CB = k1CA0 


1 A0 e  k 2 − k1
on Compass) dt  
CC = CA0 − CA − CB
 IRREVERSIBLE SERIES-PARALLEL REACTION

▪ Multiple reaction that consist of steps

in series and steps in parallel reaction. Halogenations of alkane is a
example of this kind of
▪ In these reaction proper contacting reaction where reaction is
pattern is very important. parallel with respect to
▪ The general representation of these halogen
reaction are

▪ Here the reaction is parallel with

respect to reactant B and in series with
A.
▪ We will discuss simpler example of

…………..(1)

With the assumption that the reaction is irreversible, bimolecular, and of

TWO STEP IRREVERSIBLE SERIES-PARALLEL REACTION

constant density, the rate expression can be written as
 PRODUCT DISTRIBUTION WITH RESPECT TO
CONTACTING PATTERN:

Or

CASE-1: Add A slowly to B

▪ By contacting A slowly in a beaker containing
B and stirring to consume all A added

STEP IRREVERSIBLE SERIES-PARALLEL REACTION

a) when A added slowly each time, it was make
sure that all the A used up and the reaction
stopped before the next bit is added.

b) With each addition, a bit of R is produced but

this R finds itself in an excess of B, it will react
further to form S)
▪ Finally, the mixer with very high
concentration in S (and poorer in B) can be Fig-1: Distribution of materials in the B
found. beaker for the method of mixing shown

TWO
 PRODUCT DISTRIBUTION WITH RESPECT TO
CONTACTING PATTERN, CONTINUE….:

Or

CASE-2: Add B slowly to A

▪ Now by contacting B slowly to a beaker
containing A, the concentration of R will
be build up inside
▪ This R cannot react further as there is no

STEP IRREVERSIBLE SERIES-PARALLEL REACTION

B present in mixture. With next addition
of B, both A and R will compete with
each other to react with B added. Since,
A is very large excess, it will react with
most of B and will form more R.
▪ This Process will repeated until the conc.
Of R is high enough. Then after reaching
a maxima R will convert in to S and the
process will be gradual.
Fig-2: Distribution of materials in the mixing
beaker for either of the methods of mixing shown
CASE-3: Add A and B together rapidly
# Reaction become slow enough so that it does not proceed to any appreciable extent before the
mixture becomes uniform. During first few reaction increments R find itself competing with a large
excess of A & B and hence it is disadvantageous. Carrying through the line of reasoning, the
distribution curve will be similar to case-2.

TWO
# In this case it will give the behavior of series reaction, R will increase first and after reaching a
maxima it will diminish and concentration of S will increase.
PRODUCT DISTRIBUTION WITH RESPECT TO CONTACTING PATTERN,
CONTINUE….:
Two observations from Figure-2:
1) As per as A, R and S are concerned, the equation can be viewed as:

2) The concentration level of B, whether low or high, has no effect on

the path of reaction and on the product distribution. (This is precisely
the behavior of the parallel reaction. Hence, the equation –(1) can be
written as:

So, For desired Product R, The best way of contacting A and B is

to react A uniformly, while adding B in any convenient way.
HENCE, A GENERAL RULE FOR IRREVERSIBLE SERIES – PARALLEL REACTION
IS:

Or
General Rule:
Irreversible series-parallel reactions can be analyzed in terms of their constituent
series reactions and parallel reactions in that optimum contacting for favorable
product distribution is the same as for the constituent reactions.
 BEST ARRANGEMENT OF A SET OF IDEAL REACTORS

For the most effective use of a given set of ideal reactors (for reactors
in series), the following general rules should be followed:
1. For a reaction whose rate-concentration curve rises monotonically (any nth-order
reaction, n > 0) the reactors should be connected in series. They should be ordered
so as to keep the concentration of reactant as high as possible if the rate-
concentration curve is concave (n > I), and as low as possible if the curve is convex
(n < 1). As an example, for the case of Fig. 6.12 the ordering of units should be
plug, small mixed, large mixed, for n > 1; the reverse order should be used when n
< 1.
2. For reactions where the rate-concentration curve passes through a maximum or
minimum the arrangement of units depends on the actual shape of curve, the
conversion level desired, and the units available. No simple rules can be suggested.
3. Whatever may be the kinetics and the reactor system, an examination of the l/(-rA)
vs. CA curve is a good way to find the best arrangement of units.
RESIDENCE TIME DISTRIBUTION
▪ RTD is important factor from the point of
view of real equipment .
▪ Element of fluid will take different route
through the reactor and may take different
length of time to pass through the reactor.
▪ Ideal reactor design are made by
considering volume of reactor or time
spend by all the reactant will be same
inside reactor.
▪ Completion of reaction will depend on time
of exposure inside the reactor.
▪ The distribution of time inside the reactor is
called exit age distribution E, have unite
time-1.
▪ According to RTD fraction of exit stream of
age between t and t+dt is E dt.
RESIDENCE TIME DISTRIBUTION DETERMINATION

▪ RTD can be determined by two

experimental method.(Pulse input
experiment, and step input experiment )
▪ In pulse experimental method in a steady
state system we will put a pulse input of
tracer and will plot the graph of this tracer
concentration with time at output.
▪ This graph will show time variation or age
distribution of tracer concentration with
time.
▪ Another method of determination of RTD is
by putting a step input (Preferably unite
step input) of tracer.
▪ Then we can plot the graph between the
concentration versus time graph of tracer.
▪ The slope versus time graph of this system
will give us residence time distribution .
▪ Step input method is more accurate than
pulse input method although impulse
input would give the perfect distribution.
HOLDING TIME AND RESIDENCE TIME
▪ Holding time is defined as time needed
to treat one reactor volume.
▪ Residence time or mean residence
time/ space time is defined as mean
residence time of flowing material in
the reactor.
▪ From fig when inside popcorn popper,
when popping occurs at back end of
popper then holding time and
residence time will be same.
▪ When popping occurs in midway or
every where inside the popper then
the two time will be different.
▪ For unchanging density system holding
time and residence time will be equal.
 RESIDENCE TIME DISTRIBUTION (RTD)
RTD ≡ E(t) ≡ “residence time distribution” function
RTD describes the amount of time molecules have spent in the reactor
RTD is experimentally determined by injecting an inert “tracer” at t=0
and measuring the tracer concentration C(t) at exit as a function of
time
Measurement of RTD The C curve
Reactor X C(t)
↑ ↓
Pulse injection Detection
t
C(t) tracer conc at exit between t & t+t
E(t) =  =
0 C ( t ) dt sum of tracer conc at exit for infinite time

 E(t)=0 for t<0 since no fluid can exit before it enters

 E ( t ) dt = 1 E(t)≥0 for t>0 since mass fractions are always positive
0

Fraction of material leaving reactor that has = t2 E ( t ) dt


been inside reactor for a time between t1 & t1
t2
E(t) E(t) E(t) E(t) Nice multiple
choice
question

t t t t t t
Nearly Nearly PBR with CSTR with
ideal PFR ideal CSTR dead zones dead zones

The fraction of the exit stream that has resided in the reactor for a
period of time shorter than a given value t:
F(t) is a cumulative distribution function
0 E ( t ) dt = F ( t )
t


t E ( t ) dt = 1 − F ( t ) 0.8
F ( t ) = 0 when t<0 80% of the molecules
spend 40 min or less in
F ( t )  0 when t  0 the reactor
F () = 1
40
 REVIEW: MEAN RESIDENCE TIME, TM
▪ For an ideal reactor, the space time t is defined as V/u0
▪ The mean residence time tm is equal to t in either ideal or nonideal
reactors

0 tE ( t ) dt  V
tm = 
= 0 tE ( t ) dt = t u0
= t = tm
0 E ( t ) dt
By calculating tm, the reactor V can be determined from a tracer
experiment

The spread of the distribution (variance):  = 0 ( t − tm ) E ( t ) dt
2 2

Space time t and mean residence time tm would be equal if the following
two conditions are satisfied:
• No density change
• No backmixing

In practical reactors the above two may not be valid, hence there will be a
difference between them
 REACTOR SELECTION & DESIGN FOR BURNING OF
COAL
Reaction type
Burning of coal is a exothermic reaction
C + O2 = CO2 + heat
Reactor selection
For burning of coal contact of air and coal is very important

Resistance to mass transfer will be

1. film above the coal
2. Ash layer with burning of coal
3. Resistance due to chemical reaction
So, very high mass transfer resistance

conti………
Ignition temperature
For burning of coal minimum
ignition required so, heat should
be recycled
Plug flow reactor with recycle
will be most suitable reactor for
this system

Mass Transfer resistance and

rate equation
Total resistance = film resistance + Plug flow reactor
ash resistance + reaction
resistance
▪ We know the rate of reaction by knowing all resistance
▪ We know the flow type and reactor type is plug flow
▪ We know feed rate from heat balance of burning of coal
▪ From performance equation we will get the volume of reactor
STRATEGIES FOR MULTIPHASE REACTOR
SELECTION

• Strategy level I: Catalyst design strategy

– gas-solid systems: catalyst particle size, shape, porous structure,
distribution of active material
– gas-liquid systems: choice of gas-dispersed or liquid-dispersed
systems, ratio between liquid-phase bulk volume and liquid-phase
diffusion layer volume
• Strategy level II: Injection and dispersion strategies
– (a) reactant and energy injection: batch, continuous, pulsed,
staged, flow reversal
– (b) state of mixedness of concentrations and temperature: well-
mixed or plug flow
– (c) separation of product or energy in situ
– (d) contacting flow pattern: co-, counter-, cross-current
• Strategy level III: Choice of hydrodynamic flow regime
– e.g., packed bed, bubbly flow, churn-turbulent regime, dense-
phase or dilute-phase riser transport
Chemical reaction engineering
(octave levinspeil)
Element of chemical reaction engineering
(H. scott fogler)
Chemical reaction design
(Peter harriott)
[Link]
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