Chemical Reaction Engineering

Industrial reactors

Theory
(rxn mechanism)

Laboratory
expts

Reaction
kinetics

Mass
Transfer

Reactor Design
or simulation

Energy
Balance

Pressure
Drop

Non-ideal
Flow patterns
(RTD)
Momentum
Balance

Reaction Kinetics
A+B

rA = -k CA m CBn

mols/hr m3

(power law model: A simplest form possible!)

k = rate constant; m,n: orders with respect to A and B

Rate constant:
k = k0 exp (-E/RT)
E: Activation energy; T is absolute temperature; k0: frequency factor
Significance of E

ln(k)

It shows sensitivity w.r.t. temperature

Higher the reactivity lesser is the value of E

Slope = E

Energy

1/T
Arrhenius Plot

Progress of reaction

Reversible reactions
A+B

rA = -k CA m CBn kCCp
k = rate constant for forward reaction; k: rate constant for backward reaction

Equilibrium constant:
Keq= k/k = keq0 exp (-H/RT)= Ccp/ (CAm CBn);

H= E1-E2

H: Heat of reaction; E1 and E2: Activation energy for forward and backward reactions

Le Chateliers principle
1. Use one of the reactants in excess or
remove products during the course of the Rxn
2. Play with reaction pressure (non-equimolar reactions)
Increase pressure for reduction in number of moles
decrease pressure for increase in number of moles
3. Play with reaction temperature
increase T for endothermic rxn
and decrease T for exothermic rxn

Reactor Design/Simulation
Ideal Reactors

CSTR:
PFR:

Batch reactor:

FA o FA rAV 0

dFA
rA
dV

1 dN A
rA
V dt

Sulfuric acid converter with associated heat exchangers

Case study 1: Sulfuric Acid

manufacture
Reactions:
S + O2 = SO2 irreversible
SO2 + O2 = SO3 reversible
SO3 + H2O = H2SO4 irreversible
All the reactions are exothermic
First two reactions are vapor phase; last reaction is gasliquid
No side reactions
SO2 emission from the plant should be zero!
Sulfur is available in pure form
Air is used as oxidizing agent
Product is Aq. Solution of sulfuric acid (e.g. 98% w/w)

SO2 + O2
Cso2*(1-x)

K eq

= SO3

Cso2* (R - x/2)

CSO 3
C 1O/2 2CSO 2

K eq ( P1 / 2 )

Cso2* x

*
C SO
2

1/ 2

R x 1 / 2 1 x

R x 1 / 2 1 x

xe
conversion

As pressure increases conversion increases

As R increases conversion increases
As T increases.. What happens to the eqm conversion?
T

Reactor Design for SO2 to SO3

Further cooling
Does not help
much !

xe

conversion

Saw tooth Profile

T

Things to remember
The concentration changes due to
reaction
change in volumetric flow rate
separation

Volumetric flow rate can change (gas phase

reaction) due to the following:
change in pressure
change in total number of moles due to reaction
change in temperature

Ft T Po
v

v0 Fto To P

Platforming

Platforming

Feed (naphtha)

-H2

Catalyst

Endothermic Reaction
Regenerator

Product

N2

conversion

Temperature

Case study 2: Alkylation reaction (C4 upgradation to gasoline)

Isobutene + Isobutane = isooctane (highly exothermic)
Side reaction : Dimerization of isobutene to diisobutene
Reaction catalysed by sulfuric acid
Sulfuric acid forms a separate liquid phase:
Hence in the reactor one has two liquid phases
Reaction temp: 200C
Reaction type:
A+ B = C
2A= D
Selectivity factor = r1/ r2 =

k1C AC B k1C B

2
k 2C A
k 2C A

Reactor should be such that concentration of B is as high as

Possible and concentration of A is as low as possible.
Any guess?

Batch operation:

A
Reaction type:
A+ B
2A
D
B
Continuous operation:

A
How to remove heat of reaction?

Product

Isobutane vapors

H2SO4
Product
+H2SO4

isobutane
Isobutene

Since sulfuric acid forms a separate phase reaction rate is governed by

Mass transfer across L-L interface and mass transfer characteristics
of a plug flow are very poor. What to do?
Provide agitation but still avoid back-mixing !!!

Can we make stirred compartments?

Isobutane vapors

H2SO4
Product
+H2SO4

isobutane
Isobutene

Vaporised isobutane
What
To do
With this?

isobutane

Makeup H2SO4

Isobutene
Exxons Alkylator

Case study -3 Fluid Catalytic Cracking

Heat management
in packed bed reactors
condenser
jacket
Inter-stage-cooling/heating
In-situ vaporization
Increase HT area/vol
Think of performing
Reaction in a distillation
Column!

Multi-tubular reactors

Concept of Reactive Distillation

We can improve equilibrium conversion
by removing product in the reactor.
(Le Chteliers principle)

A+BC+D
If we remove C the equilibrium
conversion to product D increases

xDxC
K

x
A
x
B

If the volatilities are right,

we can remove a component by vaporization
C (A, B, D)

A
B

A+BC+D

A, B, D

Improved yield

Provide reflux to prevent loss of feed in vapor

A, B, D
A
B

A, B, D

We can strip the product and recycle the feeds

(if the volatilities are right)

C
C

A, B, D

B
A, B

this is starting to
look like a column !
D

RD Process for methyl acetate

methanol + Acetic Acid

methyl acetate + water

AcOH
MeOH
H2SO4

MeOAc
MeoAc

1
AcOH
H2SO4

To impurity removal
columns

Water

Return form impurity

removal columns
Heavies
Water + H2SO4

MeOH
4
H2O

Underground coal gasification

C + H2O = CO + H2

Highly non-ideal flow

18

14
RECYCLE

P1-RECYC

M1

M3

M2

15

13

M4
M5

10

11

P2-EXIT

12
16

17

MAIN+BPS
3
BYPASS

B3

B1

B5

B4

B2
5