CHEE 321: Chemical Reaction Engineering

6. Multiple Reactions;
Reaction Networks and Pathways
6a. Multiple Reactions (Fogler Ch 6, Ch 8.8)

Course (Content) Organization

Isothermal, Ideal Reactor (Single Reaction) Design
Mole Balance
(Module-1,2)
In Out + Con = Acc
FA,in-FA,out+(rA)V = dCA/dt

Rate Law
(Module-1)
(rA) = kCAn

Design Algorithm
(Module-2)
1. GMBE, 2. Rate Law
3. Stoich 4.Combine

Output
Reactor Volume
Reaction Time
Rate Constant

Analysis of Rate law

(Module-5)
Kinetics: How to obtain k and rxn order

Conversion
Product Composition

Multiple Reactions
(Module-6)
Selectivity, Yield

Non-Isothermal Reactor Design

(Module-3)

Energy Balance
Heat Transfer Rate
Equilibrium Reactions
Multiple Steady State

dT/dz = ?
Tin-Tout =?

Output
Temperature Profile
Heat Removal
Heating Requirement

Topics to be covered in this Module

Algorithm for Reactor Design of Multiple Reactions

Mole Balance
Net Rates of Reactions
Stoichiometry
Energy balances

Introduction to selectivity and yield

Qualitative Analyses (Parallel and Series Reactions)
Maximizing the reactor operation for single reactant systems
Maximizing the reactor operation for two reactant systems

Multiple Reactions
Types of Multiple Reactions
1. Series Reactions
k1
k2
A

B
C

2. Parallel Reactions

Use molar flow rates and concentrations;

DO NOT use conversion!

k1
A

B
k2
A
C

3. Complex Reactions: Series and Parallel

VERY IMPORTANT!!!

k1
A

B+C
k2
A+C
D

4. Independent
k1
A

C
k2
B
D

Cannot use stoichiometric tables to relate

change in CB to change in CA

Why not Stoichiometric Tables?

Reaction:

A+ B C+ D

Define

i = Fi 0 / FA0

(Limiting reagent A)

Species

Feed Flow Rate

(mol/s)

Change within
Reactor
(mol/s)

Effluent Rate from

Reactor
(mol/s)

FA0

FB 0 = B FA0

FC 0 = C FA0

FD 0 = D FA0

( FA0 X A )
b
( FA0 X A )
a
c
( FA0 X A )
a
d
( FA0 X A )
a

FA = FA0 (1 X A )
b
FB = FA0 ( B X A )
a
c
FC = FA0 (C + X A )
a
d
FD = FA0 ( D + X A )
a
FI = FI 0

I (inert)
Total

FIIf
I Fhave
0 =
A0
you
multiple reactions:

A + B C
FA0 X A
FT 0 = FA0 (1 + B + C
and
+ D +A
I )+ C D
then the consumption/generation rates of
A, B, C and D are not simply coupled

FT = FT 0 + FA0 X A

d c b
+ 1
a a a

Fogler 3.6

Multiple Reactions: dont use Design Equations in

terms of Conversion
IDEAL
REACTOR

BATCH

DIFFERENTIAL
FORM

N A0

INTEGRAL
FORM

dXIfAyou have multiple reactions:

t = N A0
= ( rAA)V+ B C
dtand
A + C D
then the consumption/generation
FA0 ( X A ) rates of
A, B, C and DVare=not simply coupled

XA

dX
rAV

( rA )

CSTR

PFR

ALGEBRAIC
FORM

FA0

Therefore, we need to write individual

dX equations for all species in the system.
A

= (rA )

dVWrite these in terms of molar quantities,

V = FA0

XA

dX
rA

not fractional conversions

PBR

dX A
= ( rA' )
FA0
dW

W = FA0

XA

dX
rA'

Multiple Reactions: Use these Design Equations,

writing a balance for each species
Differential
Equation
Batch

(well-mixed)

dN j
dt

Algebraic
Equation

= (rj )V

t=

V=

dF j
dV

N j0

(well-mixed
at steady-state)

= rj

dN j

Nj

CSTR

PFR
(steady-state flow;
well-mixed radially)

Integral
Equation

(rj )V

Remarks
Conc. changes with time
but is uniform within the
reactor. Reaction rate
varies with time.
Conc. inside reactor is
uniform. (rj) is constant.
Exit conc = conc inside
reactor.

Fj 0 Fj
( rj )

Fj

V=

Fj 0

dFj
( rj )

Concentration and hence

reaction rates vary
spatially (with length).

Design Equation for Reactors Multiple Reactions

Gas-Phase
Batch

Liquid Phase

NOTE the design equations

are EXACTLY as for a
single reaction
but

Semi-Batch
(B fed)

CSTR
PFR
PBR

Balances must be written for

all components

Modification to the CRE Algorithm for Multiple Reactions

Fogler, 6.4

Mole balance on every species (not in terms of conversion)

Rate Law: Net Rate of reaction for each species,
e.g., rA = ri where subscript i indicates the ith reaction
Stoichiometry
a) Liquid Phase, incompressible: CA=NA/V=FA/v0
b) Gas Phase use
Variable
volumetric
flowrate;
ideal gas
Combine More difficult: set of algebraic or differential equations
for A, B,

Net Rate of Reaction

For N reactions, the net rate of formation of species A is:

For a given reaction i

ai A + bi B ci C + di D

This relationship is valid ONLY for reaction-i

(i.e., it does not couple the OVERALL consumption rates
of A, B, C and D)

Example: Net Rate of Reaction

The following reactions follow elementary rate law:

Write net rates of formation of A, B and C

Note that the rate coefficients are associated with a

particular component (-rA) for Rxn 1 and rD for Rxn 2
Fogler, 6.4.2; see Ex. 6-5

Example: Multiple Gas Phase Reactions in

an Isothermal PFR

The complex gas phase reactions take place in a PFR. The feed is equal molar in A
and B with FA0 = 10 mol/min and the volumetric flow rate is 100 dm3/min. The
reactor volume is 1,000 dm3, there is no pressure drop, the total entering
concentration is CT0 = 0.2 mol/dm3 and the rate constants are:

Plot FA, FB, FC, FD and SC/D as a function of V.

(We will formulate, but not solve the differential equations. SC/D is selectivity of
C relative to D, which we will talk about later.)

Gas Phase Multiple Reactions - Algorithm

1. Mole Balance
A
B

Remember, unlike single-reactions,

for multiple reactions
mole balance for each species
must be written

rA, rB, rC, rD are all NET rates of reactions

Example (contd)
2. Rate Laws

Species A

Species B
Species C
Species D

Example (contd)
3. Stoichiometry
4. Combine

Solution

Also, see example 6-10

Energy Balance with Multiple Reactions

Steady-state PFR, Single Reaction
dT U a (Ta T ) + (rA ) (H rxn (T ))
=
n
dV
Fi C pi
i =1

Steady-state PFR, Multiple Reaction (Nrxn)

Rxn-i rate and heat of

reaction specified in
terms of reactant-j

N rxn

dT
=
dV

U a (Ta T ) + (rij ) (H rxn ,ij (T ))

i =1
n

F C
i =1

See Example 8-10

pi

Fogler, 8.8.1

Energy Balance with Multiple Reactions

Steady-state CSTR, Single Reaction
n

UA(Ta T ) FA0 [ H Rxn (T ) ] X A = FA0 i C pi (T T0 )

i =1

UA(Ta T ) + [ H Rxn (T ) ] (rAV ) = FA0 i C pi (T T0 )

F (X )
but V = A 0 A
( rA )

i =1

Steady-state CSTR, Multiple Reaction (Nrxn)

N rxn

i =1

i =1

Rxn-i rate and heat of

reaction specified in
terms of reactant-j

UA(Ta T ) + V rij H Rxn ,ij (T ) = FA0 i C pi (T T0 )

See Example 8-11

Fogler, 8.8.2

Examples: Fogler Ex 6-5 and 6-6, 8-10 and 8-11

Know how to do set up this type of problem! Being

able to formulate a model for a multiple reaction
system is important. Usually they will be solved by
computer.

Selectivity and Yield

Desired Reaction:
kD
A
D
Undesired Reaction:
U
Ak
U and/or
U2
U
Dk

Instantaneous
Selectivity

SDU =

Yield

YD =

Global

~ F
SDU = D
FU

rD
rU

rD
rA

YD =

FD
ND
=
FA0 FA NA0 NA

What should be the criterion for designing the reactor ?

Is it necessary that reactor operates such that minimum amount of undesired
products are formed ?
FD

Reactor
System

FA
FD
FU

Fogler 6.1

Total Cost

FA

FU

Cost

FA0

S
E
P
A
R
A
T
O
R

Reactant Conversion

Instantaneous vs. Global Yield

For a CSTR:

SDU = SDU
Y =Y
D

For proof, see Fogler Ex. 6-1 (pg 308)

For a PFR, concentrations and rxn rates are changing along
reactor length:
instantaneous yield:
global yield
for v=v0:

rD dFD
=
rA dFA
FD
Dformed
YD =
=
Areacted (FA0 FA)

YD =

YD =

CA
1
YDdCA

C
(CA0 CA) A0

Series Reactions

Batch reactor, isothermal, incompressible

, t=0 CA=CA0

From Fogler website

http://www.engin.umich.edu/~cre/06chap/frames_learn.htm

Series Reactions

See Appendix A3

Series Reactions

What about byproduct C? This can be calculated by integration, or by stoichiometry

dC C
= k 2CB , t = 0 CC = 0
dt

You would have the same set of equations for an isothermal PFR, replacing t with
; see Fogler Ex. 6-4

Parallel Reactions:
Selectivity for Single Reactant Systems
Example (parallel reaction)
Desired Reaction:

kD
A
D

rD = kDCAD

Undesired Reaction:

kU
A
U

rU = kU CAU

What is the net rate of reaction of A ??

S DU

rD
k D C A D
k D ( D U )
=
=
=
CA
U
rU
kU
kU C A

Let us examine some reactor operating scenarios to maximize selectivity.

Fogler, 6.2

Parallel Reactions:
Selectivity for Single Reactant Systems
Case 1: D-U >0
rD kD (D U )
SDU = = CA
rU kU

High CA favors D

How can we accomplish this?

For gas phase reactions, maintain high pressures
For liquid-phase reactions, keep the diluent to a minimum
Batch or Plug Flow Reactors should be used
CSTR should NOT be chosen

Parallel Reactions:
Selectivity for Single Reactant Systems
Case 2: D-U < 0
rD
kD
SDU = =
rU kU CA(U D )

Low CA favors D

How can we accomplish this?

For gas phase reactions, operate at low pressures
For liquid-phase reactions, dilute the feed

CA0
CA

CSTR is preferred

CA
Reactant concentration
maintained at low level

Parallel Reactions:
Selectivity for Single Reactant Systems
Case 3: D-U = 0
Concentration cannot be used operating parameter for selectivity
maximization
What now?

rD kD
A D exp [ E D / RT ]
SDU = =
=
rU kU
AU exp [ E U / RT ]

AD
=
exp [ ( E D EU ) / RT ]
AU

(a) If ED > EU
Operate reactor at highest possible temperature
(b) If EU > ED
Operate reactor at lowest possible temperature

None of these discussions /

strategies examine yield.
Both must be considered in
reactor design!

Parallel Reactions:
Selectivity for Two Reactant Systems

Example
kD
A + B
D

rD = kD CA1 CB1

k
Undesired Reaction: A + B
U

rU = kU CA2 CB2

Desired Reaction:

rD kD (1 2 ) ( 1 2 )
SDU = = CA
CB
rU kU

Parallel Reactions:
Selectivity for Two Reactant Systems
Case 1: 1>2; 1 > 2
S DU

Let, a = 1-2; b = 1 - 2

rD k D a b
=
=
C AC B
rU kU

For high SDU, maintain both A & B as high as possible

How can we accomplish this?

Use Batch reactor
Use Plug Flow reactor

Parallel Reactions:
Selectivity for Two Reactant Systems
Case 2: 1>2; 1 < 2
S DU

rD k D C Aa
=
=
rU kU CBb

Let, a = 1-2; b = 2 - 1
kD
A + B
D

rD = kD CA1 CB1

kU
A + B
U

rU = kU CA2 CB2

For high SDU, maintain concentration of A high and of B low

How can we accomplish this? See Fogler Figure 6.3

Use semi-batch reactor where B is fed slowly
Use Tubular reactor with side streams of B being fed continuously
Use series of small CSTR with A fed only to first and B to each reactor

Parallel Reactions:
Selectivity for Two Reactant Systems
Case 3: 1<2; 1 < 2
S DU

Let, a = 2-1; b = 2 - 1

rD k D 1
=
=
rU kU C Aa CBb

For high SDU, maintain both concentration of A and B low

How can we accomplish this?

For gas phase reactions, operate at low pressures
For liquid-phase reactions, dilute the feed
CSTR is preferred

Parallel Reactions:
Selectivity for Two Reactant Systems
Case 4: 1<2; 1 > 2
S DU

Let, a = 2-1; b = 1 - 2

rD k D CBb
=
=
rU kU C Aa

For high SDU, maintain concentration of B high and of A low

How can we accomplish this?

Use semi-batch reactor where A is fed slowly
Use Tubular reactor with side streams of A being fed continuously
Use series of small CSTR with B fed only to first and A to each reactor
Same as Case 2, with A and B switched

Why Semi-Batch Reactors?

B
C

heat

B is slowly fed to A contained in

the reactor.
Unwanted products can be
minimized
exothermic reaction can be carried
out at controlled rate

A, B

Product C is continuously
removed
Higher conversion for reversible
reactions can be obtained

Semi-Batch Reactors - GMBE

1. GMBE on a molar basis
Input - Output + Gen = Accu.
For Species A (present in reactor at t=0)
dN A
Constant Density
0 0 + (rA ) V =
Systems
dt
For Species B

FB 0

dN B
0 + (rB ) V =
dt

V = V0 + v0t
Constant Flowrate

FB0
v0

Semi-Batch Reactors - GMBE

FB0
v0

2. GMBE on a concentration Basis

For Species A (no inflow)

[N A = V CA ]

dN A
0 0 + (rA ) V =
dt
(rA ) V =

d (V C A )
dC A
dV
=V
+ CA
dt
dt
dt

(rA ) V = V

dC A
+ v0C A
dt

Similarly for Species B

FB 0

dN B
0 + (rB ) V =
dt

v
dCB
= (rB ) 0 (CB CB 0 )
dt
V

v
dC A
= (rA ) 0 C A
dt
V

[ FB 0 = v0 CB 0 ]
[ N B = V CB ]

Constant flow
and density

dV
= v0
dt

What you should know

Qualitative Analyses (Parallel and Series Reactions)

Maximizing the reactor operation for single reactant systems
Maximizing the reactor operation for two reactant systems
Consideration of selectivity and yield

Algorithm for Reactor Design of Multiple Reactions

Mole Balance
Net Rates of Reactions
Stoichiometry
Energy Balances
Be able to derive the set of equations for the system
usually cannot be solved without computer programs
be able to sketch the expected qualitative behaviour