CH 6602 Chemical Reaction Engineering I

Dr. P. Senthil Kumar

Associate Professor
Department of Chemical Engineering
 Unit III

Design of reactors for multiple reactions,

Consecutive, parallel and mixed reactions,

Factors affecting choice

optimum yield and conversion

Selectivity, reactivity and yield
 Design of Reactors for Multiple Reactions

Types of multiple reactions

1. Parallel Reactions
2. Series Reactions
3. Independent Reactions
 Parallel Reactions
Qualitative discussion about product distribution
A
k1
R (desired product )
A
k2
S (undesired product )
with correspond ing rate eqn
dC R
rR = = k 1CnA1 (1)
dt
dC S
rS = = k 2CnA2 ( 2)
dt
(1) /( 2)
rR dC R k 1 n1 n 2
= = CA (3)
rS dC S k 2
From the above eqn C A is the only factor which we can adjust and control
(k 1 , k 2 , n1 and n 2 are all cons tan t for specific reaction system at a given temp )
We can keep C A low by any of the following means :

1. U sin g a MFR
2. Ma int aining high conversion
3. Increa sin g inerts in the feed
4. Decrea sin g the pressure in the gas phase reactions

We can keep C A high by any of the following means :

1. U sin g a batch or PFR

2. Ma int aining low conversion
3. Re moving inerts from the feed
4. Increa sin g the pressure in the gas phase reactions
If n1 > n 2 , desired order of reaction > undesired order of reaction
a batch or PFR used
n1 n 2 =
rR dC R k 1 n1 n 2
= = CA
rS dC S k 2
rR dC R k 1
= = CA
rS dC S k 2

If the ratio rR / rS to be high then

(i ). High concentration of A is desirable
(ii ). Carry any gas phase reaction without presence of inert
(iii ). Any liquid phase reaction u sin g a min imum amount of diluents
(iv ). batch reactor or PFR should be used (required min imum size )
If n1 < n 2 , desired order of reaction < undesired order of reaction
a l arg e MFR used
n 2 n1 = '
rR dC R k 1 n1 n 2
= = CA
rS dC S k 2
rR dC R k 1 1 k1 1
= = =
rS dC S k 2 CnA2 n1 k 2 C '
A
If the ratio rR / rS to be high then
(i ). The concentration of A should be as low as possible
(ii ). low concentration may be maintained successfully by diluting the feed
with inerts
(iii ). MFR should be used
(iv ). Re cycle reactor may be used (product stream acts as a diluent )
If n1 = n2 , desired order of reaction= undesiredorder of reaction
eqn (3) becomes

rR dCR k1
= = = constan t
rS dCS k 2

We also may control the the product distribution by k1 / k 2

1. by changingthe temperature level of operation
2. by u sin g a catalyst
Summarization of our qualitative findings
A + B
k1 R (desired product )
A + B
k
2 S (undesired product )
 Quantitative treatment of product distribution and of
reactor size

If the rate eqn are known for the individual reactions, we can quantitatively
determine the product distribution and reactor size requirements

Two important terms in product distribution

(i ). Instantaneous fractional yield of R ( )

moles R formed dC R
= =
moles A reacted dC A

(ii ). Overall fractional yield of R ( )

All R formed C Rf C Rf
= = = = in reactor
All A reacted C Ao C Af ( C A )
For PFR
C A progressively changes through the reactor along the length of the reactor

1 C Af
1 C Af
p = dC A = C dC A
C Ao C Af C Ao A C Ao

For MFR
C A is same everywhere, so is likewise constant throughout the reactor

m = evaluated at C Af
For MFR and PFR proces sin g A from C Ao to C Af , the overall fractional
yields are related by
d p 1 C Af
m = and p = m dC A
dC
A at C Af C A C Ao

For a series of 1, 2, . . . , N mixed flow reactors in which the concentration of

A is C A1 , C A2 , , , . . . , C AN , , the overall fractional yield is obtained by summing the
fractional yields in each of the N vessels and weighting these values by the
amount of reaction occurring in each vessel. Thus

1 (C Ao C A1 ) + ... + N (C A , N 1 C A , N ) = N mixed (C Ao C A , N )

N mixed =
[1 (C Ao C A1 ) + ... + N (C A , N 1 C A , N )]
(C Ao C A , N )
For any reactor type the exit concentration of R is obtained directly
from
C Rf = (C Ao C Af )

 Selectivity

moles of desired product formed

Selectivity =
moles of undesired material formed

Multiple Reactions
 Irreversible first order reactions in series

Consider the reaction

A
k1
R k
2 S
dC A
rA = = k1 CA (1)
dt
dC R
rR = = k 1 C A k 2 C R (net rate of formation of R ) ( 2)
dt
dC S
rS = = k 2 CR ( 3)
dt
Qualitative discussion about product distribution
From the above statement evaluate the effectiveness of var ious reactor systems

Example :
1. PFR and batch reactor should give a maximum R
2. CSTR / MFR should not give maximum R
Favorable contacting patterns for any set of
irreversible reactions
 Quantitative treatment, PFR or Batch Reactor
Irreversible reactions in series
Consider a unimolecular-type first order series reaction of the type
A
k1
R k
2 S
Rate equations for A, R and S

dC A
rA = = k1 CA (1)
dt
dC R
rR = = k 1 C A k 2 C R (net rate of formation of R ) (2)
dt
dC S
rS = = k 2 CR (3)
dt
Assume initially no R and S present and
let C Ao be the initial concentration of A
dC A
= k1 CA ( 4)
dt
rearranging and int egrating,
C
ln A = k 1 t
C Ao
C A = C Ao e ( k1 t ) (5)
In order to find the var iation in concentration of R , put the value of C A to rR
dC R
+ k 2 C R = k 1 C Ao e ( k1 t ) (6)
dt
The above eqn is a first order linear differential eqn of the form
dy
+ Py = Q (7)
dx
comparing the eqns (6) and (7)
y = C R ; x = t; P = k 2 ; Q = k 1 C Ao e ( k1 t )
The solution of the linear differential eqn
y e pdx = Q. e pdx . dx + C
y = C R ; x = t; P = k 2 ; Q = k 1 C Ao e ( k1 t )
The solution of the linear differential eqn
y e pdx = Q. e pdx . dx + C
C R e k 2dt = k 1 C Ao e ( k1 t ) e k 2dt . dt + C
C R e k 2t = k 1 C Ao e (k 2 k1 ) t dt + C
e ( k 2 k1 ) t
CRe k 2t
= k 1 C Ao +C (8)
(k 2 k 1 )
Initial condition, C Ro = 0 at t = 0
k 1 C Ao
0= +C
(k 2 k 1 )
k 1 C Ao
C= (9)
(k 2 k 1 )
substituting C in eqn (8)
e ( k 2 k1 ) t k C
CRe k 2t
= k 1 C Ao 1 Ao
(k 2 k 1 ) (k 2 k 1 )
 e k1t e k 2t
C R = k 1 C Ao (10)
(k 2 k 1 ) (k 2 k 1 )
e k1t e k 2t
C R = k 1 C Ao + (11)
(
2k k 1 ) (k 1 k )
2

No change in total number of moles (cons tan t density system)

C Ao = C A + C R + CS
CS = C Ao C A C R
putting the C A value from eqn (5) and C R from eqn (10) in the above eqn
( k1 t ) e k1t e k 2t
CS = C Ao C Ao e k 1 C Ao
(k
2 k 1 ) (k 2 k )
1

( k1 t ) k 1 k 1e k 2t
CS = C Ao 1 e 1 + +
k 2 k 1 k 2 k 1

( k1 t ) k 2 k 1e k 2t
CS = C Ao 1 e + (12)
k 2 k1 k 2 k1
If k 2 is much l arg er than k 1 , the eqn (12) reduced to
[
CS = C Ao 1 e ( k1 t ) ] (13)
If k 1 is much l arg er than k 2 , the eqn (12) reduced to
[
CS = C Ao 1 e ( k 2 t ) ]
Maximum concentration of R
e k1t e k 2t
C R = k 1 C Ao
(
2 k k 1 ) (k 2 k )
1

k C
[
C R = 1 Ao e k1t e k 2t
(k 2 k 1 )
]
dC R
dt
k C
[
= 1 Ao k 1e k1t + k 2e k 2t
(k 2 k 1 )
]
dC R
At max imum R formation condition =0
dt
k 1 C Ao
[
(k 2 k 1 )
]
k 1e k1t + k 2 e k 2t = 0
 k 1 C Ao
can not be zero
(k 2 k 1 )
k 1e k1t + k 2 e k 2t = 0
Taking log arithm, we get
ln k 2 k 2 t ln k 1 + k 1t = 0
ln(k 2 / k 1 ) = k 2 t k 1t
t (k 2 k 1 ) = ln(k 2 / k 1 )
ln(k 2 / k 1 ) 1
t= = (14)
(k 2 k 1 ) k log mean
By combining eqns (10) and (14) the max imum concentration of R is given by
k 2 /(k 2 k1 )
C R max k 1
=
C Ao k2
 Quantitative treatment, MFR
Irreversible reactions in series
First order followed by zero order reaction
Zero order followed by first order reaction
Two-step irreversible Series-Parallel reactions
Qualitative discussion about product distribution
Denbigh reactions and their special cases
Batch or Plug Flow Reactors
Mixed Flow Reactors
 Problems
1. Liquid reactant A decomposes as per the following reaction
scheme:
AR
AS
with rates
rR = k1 CA2 k1 = 0.4 m3/(mol. min)
rs = k 2 C A k2 = 2 (min)-1

An aqueous feed containing A with CAo= 40 mol/m3 enters a

reactor, decomposes, and a mixture of A, R and S leaves the
reactor. Find the operating condition (XA, and CR) which
maximizes CR in a MFR.
2. The desired liquid phase reaction:

dC R dC T
A + B R + T, = = k 1C1A.5CB0.3
dt dt
is accompanied by the undesired side reaction
dCS dC U
A + B S + U, = = k 2C0A.5C1B.8
dt dt

What contacting schemes (reactor types) would you use to

these reactions to minimize the concentration of undesired
products?
3. Reactant A in a liquid produces R and S by the following
scheme:
AR
AS
Both these reactions are first order. A feed with CAo =1, CRo =0
and CSo =0, enters in two MFRs in series (1 = 2 min; 2 = 5
min). The composition in the first reactor is CA1 =0.40, CR1
=0.40 and CS1 =0.20. Find the composition leaving the second
reactor.
4. Liquid reactant A produces R and S by the following reactions:
A R, rR = k 1C 2A , k 1 = 0.4 m 3 /(mol . min)
A S, rS = k 2C A , k 2 = 2 (min) 1
A feed of aqueous A with CAo =40 mol/m3, enters a reactor,
reacts to produce R and S, and a mixture of A, R and S leaves.
Find CR, CS and for 90% conversion of A in a MFR.
5. Consider the competitive liquid phase reaction
dC R
A + B
k1
R (desired), = 1.0 C ACB0.3 , mol /(l . min)
dt
dCS
A + B
k2
S (undesired ), = 1.0 C0A.5C1B.8 , mol /(l . min)
dt
Equal volumetric flow rates of A and B streams with each
stream of concentration of 20 mol/l of reactant are fed to the
reactor.
For 90% conversion of A, find the concentration of R in the
product stream if flow in the reactor follows:
(a). Plug flow and
(b). Mixed flow
6. In a reactive environment, reactant A decomposes as follows:
A
k1
R k
2 S
where k 1 = 0.1 (min) 1 and k 2 = 0.1 (min) 1

R is to be produced from 1000 l/h of feed (CAo = 1 mol/l, CRo =

CSo = 0).
(i). What size of PFR will maximize the concentration of R?
(ii). What size of MFR will maximize the concentration of R?
(iii). What is CR,max in the effluent stream from which each of
these reactors