DESIGN

FOR
MULTIPLE REACTIONS
Presented by:
C D BALAJI (216CH1095)
AMBIKA PRASAD BEHERA (216CH1096)
PRATEEK KUMAR DAS (216CH1097)

UNDER THE ABLE GUIDANCE OF

Prof. R.K. SINGH

DEPARTMENT OF CHEMICAL ENGINEERING

NIT ROURKELA, ROURKELA, ODISHA
 Contents
Types of Reactors
1. Plug flow and CSTR
Multiple Reactions
1. Types and definition
2. Design for parallel reactions
a) Selectivity and yield
b) Temperature dependence
c) Reactor selection for maximising product
3. Design for series reactions
a) Conc. And time dependent
b) Reactor selection for maximising product
4. Chemical Reaction Network
 Types of reactors
1.Batch- uniform composition everywhere in
reactor but changes with time
2. Semi batch- in semi-batch one reactant will
be added when reaction will proceed
3. Continuous reactor
a. Mixed flow- this is uniformly mixed ,
same composition everywhere, within the
reactor and at exit
b. Plug flow- flow of fluid through reactor with
order so that only lateral mixing is possible
 Reactor design parameter
Reactor design basically means which type and size of
reactor and method of operation we should employ for
a given conversion.
Parameters
Volume of reactor
Flow rate
Concentration of feed
Reaction kinetic
Temperature
pressure
Plug flow and mixed flow reactor design

Mixed flow reactor design

Applying mass balance performance
equation for mixed flow reactor

Plug flow reactor design

Performance equation for plug flow reactor
 Types of Multiple Reaction
Parallel reactions (competing reactions)
k1 B
A
k2 C
Series reactions (consecutive reactions)
k1 k2
A B C

Complex reactions(Parallel + Series)

k1
A+ B C+D
k2
A+ C E

Independent reactions
k1
A B+C
k2
D E+F
 Design for parallel reaction
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.
Ifa1>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.
 Reactor design for multiple reaction
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
conversion are not allowed to mixed.
In series of reaction if intermediate reactant is our desired product
than semi batch reactor will be used.
 Irreversible series-parallel reaction
Multiple reaction that consist of steps in
series and steps in parallel reaction.
Halogenations of alkane is a
In these reaction proper contacting
example of this kind of reaction
pattern is very important. where reaction is parallel with
respect to halogen
The general representation of these
reaction are

Here the reaction is parallel with respect

to reactant B and in series with A.
 Minimizing unwanted products for two reactants

for the parallel reaction

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

Case I : 1 > 2, 1 > 2, a = 1-2 > 0, b = 1-2 > 0

rD k1 a b
S DU C AC B
the rate selectivity parameter rU k 2

To maximize the SDU, maintain the concentration of both A and B as high as possible
a tubular reactor
a batch reactor
high pressures (if gas phase), reduce inert
 Minimizing unwanted products for two reactants

for the parallel reaction

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

Case II : 1 > 2, 1 < 2, a = 1-2 > 0, b = 2-1 > 0

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

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

a semibatch reactor in which B is fed slowly into A.
a tubular reactor with side stream of B continually
a series of small CSTRs with A fed only to the first reactor
 Minimizing unwanted products for two reactants

for the parallel reaction

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

Case III : 1 < 2, 1 < 2, a = 2-1 > 0, b = 2-1 > 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
a CSTR
a tubular reactor in which there is a large recycle ratio
a feed diluted with inert material
low pressures (if gas phase)
 Minimizing unwanted products for two reactants

for the parallel reaction

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

Case IV : 1 < 2, 1 > 2, a = 2-1 > 0, b = 1-2 > 0

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

To maximize the SDU, maintain the concentration of both A and B as high as possible
Maximizing SD/U for Parallel Reactions: Temperature Control

ED EU
SD U
AD
AU
e RT
CA1 2 CB 1 2

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

Use higher temperature to favor Use lower T to favor desired

desired product formation product formation
 Product Distribution of Reactants
instantaneous yield, YD rate of formation of D r
YD D
(at any point or time in reactor) rate of consumption of A rA

overall yield, Y%
D rate of formation of D rD
YD
rate of consumption of A rA

FD Evaluated at outlet
Y%
D
flow FA0 FA

ND
batch Y%
D Evaluated
NA0 NA
at tfi
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

 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.
 Series (Consecutive) Reactions

k1 k2
A D U Time is the key factor here!!!
(desired) (undesired)

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

To maximize the production of D, use:

Batch CSTRs in series

or PFR/PBR or
n
Concentrations in Series Reactions
k1 k2 -rA = k1CA
A B C rB,net = k1CA k2CB
How does CA depend on ?
dFA dC A
k1C A 0 k1C A C A C A0e k1
dV dV
How does CB depend on ?
dFB
dV
k1C A k 2CB 0
dCB
dV

k1 C A0e k1 k 2CB Substitute
V
0

dCB
d

k1 C A0ek1 k 2CB
dCB
d
k 2CB k1 CA0e k1
Use

d CBek 2
k
C e

k 2 k1 CB k1C A0
ek1 ek 2

integrating d 1 A0
k 2 k1


factor
(reviewed on CC CA0 CA CB
Compass)
 Reactions in Series
B CA CA0ek1
A C ek1 ek 2
CB k1CA0
k k
2 1

CC CA0 C A CB

The reactor V (for a given 0) and that maximizes CB occurs when dCB/dt=0
dCB k1C A0
d

k 2 k1

k1e k1
k 2 e
k 2
0

1 k
opt ln 1
k1 k 2 k 2

V
so Vopt 0 opt
0
Maximizing the desired product in series and parallel reaction

k1 k2
A B C

In parallel reactions, maximize the desired product

by adjusting the reaction conditions
by choosing the proper reactor

In series reactions, maximize the desired product

by adjusting the space-time for a flow reactor
by choosing real-time for a batch reactor
 CHEMICAL REACTION NETWORK

Chemical reaction network theory is an area of applied mathematics

that attempts to model the behaviour of real world chemical systems.

CRN comprises a set of reactants, a set of products and a set of

reactions.

The mathematical modeling of CRN usually focuses on what happens to

the concentration of various chemicals as time passes.
 CHEMICAL REACTION NETWORK CONTD
A kinetics for a reaction network is an assignment of a rate function to each reaction in the
network.
Suppose A,B,C,D,E are the chemical species.

Instantaneous rate of change of each reactant is given by:

 CHEMICAL REACTION NETWORK CONTD
Let , , , , and are positive rate constants for the corresponding
equations.
Assuming mass action kinetics we have for the network, the following
differential equations are obtained:
 REACTION KINETICS IN NETWORK THEORY

Within each reaction network three sets can be associated as:

i.The set of chemical species-{A,B,C,D,E}

ii.Set of objects that appear in the reaction-{A, A+2B, A+C, D, B+E}

These objects are called complexes and are represented by

iii. The set R of reactions - {A2B, 2BA, A+CD, DA+C,

DB+E, B+EA+C}

With each of these three sets a vector space can be associated as

a vector of species concentration or a vector of reaction rate constant
 TWO THEOREMS
THE DEFICIENCY ZERO THEOREM:
i. If the network isnt weakly reversible for arbitrary kinetics , the
differential equations for the reaction system { , ,,,,, , R, , }
cannot admit a positive equilibrium.
ii. If the network isnt weakly reversible for arbitrary kinetics, the
differential equations for the reaction system cannot admit a cyclic
composition trajectory positive composition.
iii. If the network is weakly reversible, for any mass kinetics the
differential equations for the mass action system have the following
properties:
a) Equilibrium is asymptotically stable.
b) There cannot exist a non-trivial cyclic composition trajectory.
c) There exists with each positive stoichiometric compatibility class
precisely one equilibrium.
 TWO THEOREMS CONTD
THE DEFICIENCY ONE THEOREM: Let { , , , R}be a reaction

network with l linkage classes. Let denotes the deficiency of the

network; let denotes the deficiency of th linkage class( = 1,2,,..,l)

and suppose that both of the following conditions are satisfied:

If the reaction is weakly reversible for any mass action kinetics the

differential equations for the mass action system admit precisely one

equilibrium in each positive stoichiometric compatibility class.

Problem
a)
b)

c)
d)

e)
 AN K YOU
TH