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CHAPTER 7

MULTIPLE REACTIONS
7.1 Condition for maximizing yields and
selectivity for parallel reactions
7.2 Condition for maximizing yields and
selectivity in series reactions
INTRODUCTION
1. Seldom is the reaction of interest is the ONLY
ONE that occurs in a chemical reactor
2. Typically multiple reactions will occur some
desired and some undesired
3. One of the key factors is minimizing the
undesired side reactions that occur along with
the desired reaction
4. There are 3 basic types of multiple reactions:
A. Series
B. Parallel
C. Independent
TYPES OF REACTIONS

A. Series
B. Parallel
C. Independent
TYPES OF REACTIONS

A. PARALLEL REACTION/COMPETING REACTIONS


Reaction is consumed by 2 different
reaction pathways to form different
products:

Example: Oxidation of ethylene to ethylene oxide while


avoiding complete combustion to CO2 and H2O
TYPES OF REACTIONS

B.SERIES REACTIONS/CONSECUTIVE REACTIONS


The reactant forms an intermediate product which reacts
further to form another product:

Example: Ethylene oxide reaction with ammonia to form


mono-, di- , and triethanolamine:
TYPES OF REACTIONS

C. INDEPENDENT REACTIONS
Independent reactions are of the type

They occur at the same time but neither the products or


reactants react with themselves or one another

Example: Cracking of crude oil to form gasoline


7.1: Condition for maximizing yields and selectivity
for parallel reactions
1. For PARALLEL/COMPETING REACTIONS
Desired Product
Reactant A
Undesired Product

2. The rate laws for respective reactions,


Desired
separator

A α is the order
Reactor of the reaction

Undesired
7.1: Condition for maximizing yields and selectivity
for parallel reactions
1. We want the formation of D, rD to be high with respect to
the rate of formation of U, rU.

2. Taking the ratio of these rates, we obtain rates selectivity


parameter, SDU which is to be maximized

3. Next we will discuss ways to maximize SDU for different


reaction orders of the desired and undesired products
7.1: Condition for maximizing yields and selectivity
for parallel reactions

MAXIMIZING THE DESIRED PRODUCT


FOR ONE REACTANT
CASE 1: α1 > α2 (+)
CASE 2: α2 > α1 (-)
7.1: Condition for maximizing yields and selectivity for
parallel reactions
MAXIMIZING THE DESIRED PRODUCT FOR ONE REACTANT

CASE 1: α1 > α2
(REACTION ORDER OF DESIRED GREATER THEN UNDESIRED
a
rD k D 1  2 k DCA
SDU   CA 
ru ku ku
1. Let the reaction order be positive number, difference
between these reaction orders. Therefore (α1 – α2 = a).
2. SD/U must be kept as large as possible, thus reactant A
concentration must be as high as possible during the
reaction.
A. If reaction in gas phase, run without inert and at high
pressure
B. If in liquid phase, minimum use of diluents
7.1: Condition for maximizing yields and selectivity for
parallel reactions
MAXIMIZING THE DESIRED PRODUCT FOR ONE REACTANT
CASE 1: α1 > α2
(REACTION ORDER OF DESIRED GREATER THEN UNDESIRED

3. Hence, batch or PFR should be used because A (reactant)


concentration starts at high value and drop progressively
during reaction

4. For perfectly mixed CSTR, the A concentration is always at


its lowest value therefore should not be chosen for this
case
7.1: Condition for maximizing yields and selectivity for
parallel reactions
MAXIMIZING THE DESIRED PRODUCT FOR ONE REACTANT
CASE 2: α2 > α1
(REACTION ORDER OF UNDESIRED GREATER THEN DESIRED

rD k D 1   2 kD
SDU   CA  a
ru ku k uC A
1. Let the reaction order be positive number, difference
between these reaction orders. Therefore (α1 – α2 = -a).
2. For SD/U to be high, the concentration of A should be as
low as possible
A.Diluting the feed with inert and that running the reactor
at low concentration of A
3. Hence, a CSTR should be used because concentration of
reactant are maintained at low level
7.1: Condition for maximizing yields and selectivity
for parallel reactions

MAXIMIZING THE DESIRED PRODUCT


FOR TWO REACTANT
CASE 1: α1 > α2 (+), β1> β2 (+)
CASE 2: α1 > α2 (+), β1< β2 (-)
CASE 3: α1 < α2 (-), β1< β2 (-)
CASE 4: α1 < α2 (-), β1> β2(+)
7.1: Condition for maximizing yields and selectivity for
parallel reactions
MAXIMIZING THE DESIRED PRODUCT FOR TWO REACTANT
1. Consider 2 simultaneous reactions in which
2 reactants, A and B consumed to produce
A  B 
kD
D
desired product, D and an unwanted product, A  B 
kU
U
U from a side reaction.
α1 β1
2. The rate laws for the reactions
rD  k DC A CB
α2 β2
rU  k UC A CB
3. The rate selectivity parameter:
rD k D α1  α 2 β1 β 2
SDU   CA CB
r U kU
4. Next we will discuss ways to maximize SDU for different reaction
orders of the desired and undesired products
7.1: Condition for maximizing yields and selectivity for
parallel reactions
MAXIMIZING THE DESIRED PRODUCT FOR TWO REACTANT
CASE 1: α1 > α2 (+), β1> β2 (+)
kD α α β β
S DU  C A 1 2 CB 1 2
kU
a b
1. Let a = α1 - α2 and b = β1- β2, rD kDCA CB
where a and b are positive
S DU  
rU kU
constants.
2. To maximize the ratio, maintain the concentrations for
both A and B as high as possible. To do this, use:
A. Tubular reactor A and B concentration starts at high value
B. Batch Reactor and drop progressively during reaction

C. High pressure (if gas phase)


7.1: Condition for maximizing yields and selectivity for
parallel reactions
MAXIMIZING THE DESIRED PRODUCT FOR TWO REACTANT
CASE 2: α1 > α2 (+), β1< β2 (-)
kD α1  α 2 β1 β 2
SDU  CA CB
kU
1. Let a = α1 - α2 and -b = β1- β2, where a are
positive constant while b is negative constant.

a
rD k DC A
SDU  
r U k UCBb
7.1: Condition for maximizing yields and selectivity for
parallel reactions
MAXIMIZING THE DESIRED PRODUCT FOR TWO REACTANT
CASE 2: α1 > α2 (+), β1< β2 (-)
2. To maximize the ratio, concentration of A should be high &
concentration of B should be low. To achieve this, use
A. Semi batch reactor in which B is fed slowly into large
amount of A
B. Tubular reactor with side streams of B continually fed to
reactor
C. Series of small CSTRs with A fed only to the first
reactor and small amount of B fed to each reactor.
7.1: Condition for maximizing yields and selectivity for
parallel reactions
MAXIMIZING THE DESIRED PRODUCT FOR TWO REACTANT
CASE 3: α1 < α2 (-), β1< β2 (-)
kD α1  α 2 β1 β 2
SDU  CA CB
kU
1. Let -a = α1 – α2 and -b = β1- β2, where a and b are
negative constants.

rD kD
S DU   a b
r U k UC A CB
7.1: Condition for maximizing yields and selectivity for
parallel reactions
MAXIMIZING THE DESIRED PRODUCT FOR TWO REACTANT
CASE 3: α1 < α2 (-), β1< β2 (-)
2. To maximize the ratio, the reaction should be carried out at
low concentration of A and B. To achieve this, use
A. CSTR (For CSTR, the reactant concentration is always
at its lowest value)
B. Tubular reactor in which there is a large recycle ratio
C. Feed diluted with inerts
D. Low pressure (if gas phase)
7.1: Condition for maximizing yields and selectivity for
parallel reactions
MAXIMIZING THE DESIRED PRODUCT FOR TWO REACTANT
CASE 4: α1 < α2 (-), β1> β2(+)
kD α1  α 2 β1 β 2
SDU  CA CB
kU

1. Let -a = α1 – α2 and b = β1- β2, where a and b are positive


constants.
b
rD k DCB
SDU   a
r U k UC A
7.1: Condition for maximizing yields and selectivity for
parallel reactions
MAXIMIZING THE DESIRED PRODUCT FOR TWO REACTANT
CASE 4: α1 < α2 (-), β1> β2(+)

2. To maximize the ratio, the reaction should contain high


concentration of B and low concentration of A. Use:
A. Semibatch reactor in which A is slowly fed to a large
amount of B
B. Tubular reactor with side streams of A
C. Series of small CSTRs with fresh A to each reactor
7.1: Condition for maximizing yields and
selectivity for series reactions
• For series reaction, the most important variable is time:
space time for a flow reactor and real time for a batch
reactor

• If the 1st reaction is slow & 2nd reaction is fast, it will be


extremely difficult to produce species B
• If the 1st reaction is fast & the reaction to form C is
slow, a large yield of B can be achieved

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