CHAPTER 6

MULTIPLE REACTIONS: PART 1

 Topic Outcomes
Week Topic Topic Outcomes
8 Multiple reactions It is expected that students are able to:

• Maximizing the • Define selectively and yield

desired product in
parallel reactions • Choose the best reaction mode to
maximise the selectivity for complex
• Maximizing the reaction
desired product in
series reactions • Describe the algorithm used to design
reactors with multiple reactions
• Algorithm for solution
to complex reactions • Determine reactor size for highest
selectivity of multiple reactions.
 Contents

Describe 4 basic types of multiple

reactions

Define selectivity parameter

Algorithm to minimize the unwanted

product
Types of Multiple Reaction

3 basic types of multiple reactions

Parallel Series Independent

Complex
 1. Parallel Reactions
Also called COMPETING REACTIONS

The reactant is consumed by 2 different reaction

pathways to form different products

B
k1

A
k2 C

E.g, Oxidation of ethylene to ethylene oxide

 2. Series Reactions
Also called CONSECUTIVE REACTIONS

The reactant forms an intermediate product,

which react further to form another product.

A B C

E.g, Reaction between ethylene oxide and

ammonia to produce mono-, di-, and
triethanolamine.
Simultaneous series and parallel reactions

A+B C+D

A+C E

E.g, formation of butadiene from ethanol

3. Independent Reactions

Occur in feed stocks containing many reactants.

A B

C D+E

E.g, cracking of crude oil to form gasoline

 Example 1
Three species were found in a CSTR. The following concentration data were
obtained as a function of temperature. The initial concentration of the single
reactant, A, was the same at all temperatures. Both B and C are products.

CA0 = 2 moles/dm3

Run T (oC) CA (mole/dm3) CB (mole/dm3) CC (mole/dm3)

1 30 1.7 0.01 0.29
2 50 1.4 0.03 0.57
3 70 1.0 0.1 0.90
4 100 0.5 1.25 1.25
5 120 0.1 1.80 0.1
6 130 0.01 1.98 0.01

What type of reaction is taking place, independent, complex, series or

parallel ?

Chemical Reaction Engineering Group, Universiti Teknologi Malysia

Observations
• At low temperatures
1. Little conversion of A
2. Little B formed
3. Mostly C formed (but not too much
because of the low conversion - 15
to 30% - of A)

• At high temperatures
1. Virtually complete conversion of A
2. Mostly B formed

Data suggest 2 reactions

k1 E /RT
A B  r1A  k1C A  C A A 1e 1
 rB
k2 E 2 /RT
A C  r2A  k 2C A  C A A 2 e  rC
 Desired & Undesired Products
Parallel reaction Series reaction
kD
A D
A D U
kU
A U

D maximize

Separator
Reactor
A system

U minimize

Can quantify the formation of D with respect to U by defining

the SELECTIVITY and YIELD of the system

Note: D, desired product; U, undesired product

 Selectivity
Instantaneous selectivity of D with respect to U,

r rate of formationof D Will guide us to design

Selectivity S D/U   D  reactor system to max.
rU rate of formationU
the selectivity

~ FD
Overall selectivity, S DU 
FU

~ ND
Batch reactor, S DU 
NU

Note: F, exit flow rate

 Yield
1. Yield based on the ratio of reaction rates (instantaneous yield)

rD given product
YD 
 rA key reactant A

2. Yield based on the ratio of molar flow rates

Batch system
~ ND
YD 
NA0  NA
moles of product formed at the end
of the reaction
Flow system
number of moles of the key reactant,
~ FD A, that have been consumed
YD 
FA0  FA
Parallel Reactions

kD
A D

ku
A U
 Rate Laws

Consider competing reactions, Rate of disappearance of A

rA  rD  rU
kD
A D
kU
A U
rA  k DC αA1  k UC αA2

Rate laws Rate selectivity parameter

rD  kDC αA1 rU  k UC αA2 rD k D α1 α2

S D/U   CA
rU k U

Note: D, desired product; U, undesired product

 Max. Desired Product for 1 Reactant

Examine ways to maximize SD/U, for different reaction orders of the

D and U products.

Case 1: 1 > 2

Reaction order D product > reaction order U product

Let a be a +ve number, α1  α2  a

rD k D a
S D/U   CA Make CA as large
rU k U as possible

Note: D, desired product; U, undesired product; C, concentration

 Case 1: 1 > 2 (Cont.)

Gas phase: run without inerts & at high pressure

Liquid phase: use of diluents (minimum)

Reactor:
Start at a high value & drop
• Batch reactor
progressively during the course
• Plug-flow reactor of reaction

• DO NOT choose CSTR

− the C of reactant within the reactor is always at its lowest
value.

Note: D, desired product; U, undesired product; C, concentration

 Case 2: 2 > 1
Reaction order U product > reaction order D product

Let a be a +ve number, α2  α1  a

rD k
S D/U   Da Make CA as low
rU k UC A as possible and
run with inerts
Reactor:
• CSTR reactor
• A recycle reactor

Note: Case 1 and 2 ← Cannot determine whether the reaction should be

run at high or low T

Note: D, desired product; U, undesired product; C, concentration;

T, temperature
 SD/U  T
The sensitivity of the rate selectivity k D A D E D E U /RT 
S D/U ~  e
parameter to T
kU A U

Case 3 & 4: ED > EU & EU > ED

kD (and overall rate rD) increases more rapidly with

ED > EU
increasing T.

SD/U
Reaction system should be operated at the highest
possible T.
T

Reaction should be carried out at a low T, but not so

SD/U
EU > ED
low.

Note: D, desired product; U, undesired product; T, temperature; T

A, frequency factor; E, activation energy
Reactor Selection &
Operating Conditions
 Reactors for Minimizing U

Tubular reactor
CSTR Batch Semibatch

Tubular reactor
A membrane reactor or tubular with recycle
reactor with side streams

Series of small CSTRs

CSTR with recycle Membrane reactor Reactive distillation

Note: U, undesired product
Max. Desired Product for 2 Reactants
Consider competing reactions,

k1
A+B D
k2
A+B U

Rate laws

rD  kDC αA1C Bβ1 rU  k UC αA2 C Bβ 2

Rate selectivity parameter

rD k D α1 α2 β1 β 2
S D/U   C A CB
rU k U
 Case 1: 1 > 2, 1 >  2

Let a be a and b +ve number, α1  α2  a, β1  β2  b

rD k D a b
S D/U   C AC B Maintain CA & CB
rU k U as high as possible

Reactor:
• Tubular reactor
• Batch reactor

Conditions
• High P (if gas phase) & reduce inerts

Note: P, pressure; C, concentration

 Case 2: 1 > 2, 1 <  2

Let a and b a +ve number, α1  α2  a, β2  β1  b

rD k DC aA
S D/U   CA high & CB low
rU k UC Bb

Reactor:
• Semibatch reactor.
• Membrane or tubular reactor with side streams.
• Series of small CSTRs.

Note: C, concentration
 Case 3: 1 < 2, 1 <  2
Let a be a and b +ve number, α2  α1  a, β2  β1  b

rD kD
S D/U   CA & CB low
rU k UC aA C Bb

Reactor:
• A CSTR.
• A tubular reactor in which there is a large recycle ratio.

Conditions:
• A feed diluted with inerts.
• Low pressure (if gas-phase).

Note: C, concentration
 Case 4: 1 < 2, 1 >  2

Let a be a and b +ve number, α2  α1  a, β1  β2  b

rD k DC Bb
S D/U   High CB & low CA
rU k UC aA

Reactor:
• A semibatch reactor in which A is slowly fed to a large amount of B.
• A tubular reactor with side streams of A.
• A series of small CSTRs with fresh A fed to each reactor.

Note: C, concentration
Series Reactions

k1 k2
A B C
Maximizing the Desired Product
k1 k2
A B C
(D) (U)

The most important variable is TIME:  (flow) and t (batch)

Case 1: 1st reaction is slow & 2nd reaction is fast

 Difficult to produce B
Case 2: 1st reaction is fast & 2nd reaction is slow
 Large yield of B can be achieved.
Case 3: Reaction allowed to proceed for long time/to long in reactor
B→C

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

time needed to carry out the reaction more important than in
consecutive reactions.
 Example 3
Series reaction in a batch reactor

k1 k2
A  B  C

This series reaction could also be written as

k1
Reaction(1) A  B :  r1A  k1C A

k2
Reaction(2) B  C :  r2B  k 2C B