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Chemical Reactor Design

An engineer seeks to design reaction


vessels, to carry out a particular chemical
reaction or set of reactions
This requires a knowledge of the reaction and
hence reaction kinetics
Questions relate to operating conditions, heat
release/absorption/ reaction rate/ reaction
order/phase change
A knowledge of the appropriate type of reactor
to achieve this goal
Scale, duration of reaction, conditions
CHG 3127: Reaction Engineering E.J. Anthony 2012 1
Contact Details
I have two e-mail accounts you can use
eanthony@uottawa.ca
or
banthony@nrcan.gc.ca

I can be contacted by telephone, but
this is not reliable
Tel: 613 996 2868
Course Marking Structure
Tutorials and Assignments will be worth
15% of the mark (5% Tutorials and 10%
Assignments)
6 Assignments remit in groups of 2
Mid-term 35% of the Mark
Final 50% of the Mark
CHG 3127: Reaction Engineering E.J. Anthony 2012 3
TA for Class Xue Wang
Email address: xwang173@uottawa.ca
Office: CBY D218
Office hours to be announced.
CHG 3127: Reaction Engineering E.J. Anthony, 2012 4
I. Reviewing the Basics
Introduction
basic definitions, industrial reactors

Mole Balances and Stoichiometry
fractional conversion & extent of reaction
mole balance equation
stoichiometric tables
systems with phase changes
CHG3127: Reaction Engineering E.J. Anthony 2012 6
Basic Definitions
Chemical Species
any chemical compound or element with a
given identity (determined by kind, number,
and configuration of atoms)


Chemical Reaction
said to occur when detectable number of
molecules of one or more species have lost
their identity and assumed a new one
There may be intermediates, which maintain a steady
concentration during the process of conversion
CHG 3127: Reaction Engineering EJ Anthony 2012 7
Basic Definitions
Decomposition Reaction



Combination Reaction


Isomerization Reaction
C H C H H
2 6 2 4 2
+
C H H C H
2 4 2 2 6
+
cis trans 2 butene 2 butene
CHG3127: Reaction Engineering E.J. Anthony 2012 8
Basic Definitions
Homogeneous Reaction

Reaction involving only one phase


Heterogeneous Reaction

Reaction involving more than one phase,
with the reaction usually occurring at or
near the interface between phases
CHG 3127: Reaction Engineering E.J. Anthony 2012 9
Basic Definitions
Series Reactions


Parallel Competitive Reactions



Independent Reactions
A B C
A B
A C

A B
C D

CHG 3127: Reaction Engineering E.J. Anthony 2012 10


Basic Definitions
Chemical Reaction Rate, r
j

rate of formation of species j, by chemical reaction,
per unit volume (mass of catalyst, surface area of
catalyst)

N.B. the reaction rate is not necessarily equal to
dC
j
/dt
This is true only for a constant volume batch
reactor
CHG3127: Reaction Engineering E.J. Anthony 2012 11
Basic Definitions
Elementary Reaction

a reaction in which the reaction order of each
species is identical with the stoichiometric coefficient
of that species within the reaction equation as
written





Note here that -r
A
is the rate of consumption of
species A
A B C
r k C C
A A B
+
=
2
2
CHG 3127: Reaction Engineering E.J. Anthony 2012 12
Basic Definitions
Non-elementary Reaction

reaction rate is not discernible directly from
overall stoichiometry of reaction


| || |
| | | |
2 2
2 1
2 2 1
2 2
2
Br HBr k
Br H k
r
HBr Br H
HBr
+
=
+
CHG 3127: Reaction Engineering E.J. Anthony 2012 13
Basic Definitions
Molecularity
the number of atoms, ions, or molecules involved
(colliding) in the rate-limiting step of the reaction

unimolecular: reaction involving one atom or
molecule (e.g., radioactive decay)
bimolecular: reaction involving two atoms or
molecules
termolecular: reaction involving three atoms or
molecules
CHG 3127: Reaction Engineering E.J. Anthony 2012 14
Basic Definitions
Reaction Order

relates to the exponents of the concentrations
in the reaction rate expression of the general
form

reaction is order with respect to A, order with
respect to B, order overall

N.B. some complex reaction rate expressions
yield meaningful orders under limiting
conditions only
= r kC C
A A B
o |
...
o
|
o | +
CHG 3127: Reaction Engineering E.J. Anthony 2012 15
Basic Definitions
The Arrhenius law
assume the rate law given by

specific reaction rate constant, k, accounts for
temperature dependence of reaction rate
(Arrhenius expression):

N.B. in some complex cases k and F functions
not separable:
( )
k T Ae
E RT
=
/
( )
( ) = r k T F C C
A A B
, ,...
2
2
2
*
1
O
O N
O N
C k
kC
r
+
=
CHG 3127: Reaction Engineering E.J. Anthony 2012 16
Classifying Industrial Reactors
Classification by Reactor Operation

Batch Reactor
all reactants enter at start
high conversions, high labour costs
limited scale-up potential

Continuous Reactor
reactants introduced while products removed
continuously
used extensively in large scale operations
reactor may be tank, tube or vertical tower

CHG 3127: Reaction Engineering E.J. Anthony 2012 17
Classifying Industrial Reactors
Classification by Reactor Operation

Semi-Continuous Reactor
either reactants or products removed
continuously
remaining components entered batch-wise
limitations of batch, except better control of
unwanted side reactions through control of
specific component concentrations
used in two-phase reactions where gas is
bubbled through liquid
CHG 3127: Reaction Engineering E.J. Anthony 2012 18
Classifying Industrial Reactors
Homogeneous batch reactor
hand holes for
recharging reactor
connection for
heating or cooling jacket
agitator
From Fogler, Elements of Chemical Reaction Engineering, 3rd Edition
CHG 3127: Reaction Engineering E.J. Anthony 2012 19
Classifying Industrial Reactors
Semi-batch reactor
reactant B
reactant A
and product
heater or cooler
CHG 3127: Reaction Engineering E.J. Anthony 2012 20
Classifying Industrial Reactors
Classification by Reactor Design
Features
Tank Reactor
most common reactor type; ideal: CSTR
operated in batch, continuous, or semi modes
frequently includes mixing devices and heat transfer
components

Tubular Reactor
common in gas phase reactions
can contain packing, catalysts
heat transfer jackets or shell and tube systems
ideal form: plug flow reactor

CHG 3127: Reaction Engineering E.J. Anthony 2012 21
Classifying Industrial Reactors
Classification by Reactor Design Features
Slurry Reactor
vertical tower containing fine catalyst particles
suspended in liquid slurry
gas phase reactant bubbled through
high heat capacity of slurry maintains temperature control
used in hydrocracking of fuel oils and in coal liquifaction



CHG 3127: Reaction Engineering E.J. Anthony 2012 22
Classifying Industrial Reactors
CSTR
. Courtesy of Pfaudler, Inc
CHG 3127: Reaction Engineering E.J. Anthony 2012 23
Classifying Industrial Reactors
Longitudinal tubular reactor
From Fogler, Elements of Chemical Reaction Engineering, 3rd Edition
CHG 3127: Reaction Engineering E.J. Anthony 2012 24
Classifying Industrial Reactors
Circulating fluidized bed reactor
feed
product
settling
hopper
riser
standpipe
CHG 3127: Reaction Engineering E.J. Anthony 2012 25
Mole Balances and
Stoichiometry
Consider the reaction


generalized stoichiometric equation


extent of reaction fractional conversion


0 = + + + + + v B v C v S v T
b c s t
... ...
v A
i i
i
=

0
=
n n
v
i i
i
0
X
n n
n
i i
i
=

0
0
CHG 3127: Reaction Engineering E.J. Anthony 2012 26
Mole Balances and
Stoichiometry
relationship between and X
=
Xn
v
lim,
lim
0
CHG 3127: Reaction Engineering E.J. Anthony 2012 27
Mole Balances and
Stoichiometry
Mole balance on species j in system of
volume V

well-mixed system


not well-mixed
F F G
dN
dt
j j j
j
0
+ =
G r V
j j
=
G r V r dV
j ji i
i
m
j
V
~ =
=

}
A
1
CHG 3127: Reaction Engineering E.J. Anthony 2012 28
Mole Balances and
Stoichiometry
General integral mole balance on
species j in system of volume V


F F r dV
dN
dt
j j j
V
j
0
+ =
}
CHG 3127: Reaction Engineering E.J. Anthony 2012 29
Stoichiometric Tables
Objective: to find expressions for r
j
and
N
j


Consider the reaction

A as basis:

Rate of formation of C:

In general:
aA bB cC dD + +
A
b
a
B
c
a
C
d
a
D + +
( )
A A C
r
a
c
r
a
c
r = =
= = =
r
a
r
b
r
c
r
d
A B C D
CHG 3127: Reaction Engineering E.J. Anthony 2012 30
Stoichiometric Tables
Consider the previous reaction with a batch
system



Moles A reacted at time t:


Moles A remaining at time t:



A
b
a
B
c
a
C
d
a
D + +
N X
A0
( ) ( )
N t N N X N X
A A A A
= =
0 0 0
1
CHG 3127: Reaction Engineering E.J. Anthony 2012 31
Stoichiometric Tables
Consider further the batch system with reaction



Moles B reacted at time t:



Moles B remaining at time t:



A
b
a
B
c
a
C
d
a
D + +
moles reacted
moles reacted
moles reacted =
B
A
A
b
a
N X
A

0
( )
N t N
b
a
N X
B B A
=
0 0
CHG 3127: Reaction Engineering E.J. Anthony 2012 32
Stoichiometric Tables
!"#$%#& '(%)%*+ ,-*(.# /#0*%(%(.
1
N
A0
N X
A0
N N X
A A 0 0

2 N
B0

b
a
N X
A0
N
b
a
N X
B A 0 0

, N
C0
c
a
N X
A0
N
c
a
N X
C A 0 0
+
3 N
D0
d
a
N X
A0
N
d
a
N X
D A 0 0
+
' N
I 0
N
I 0
45)*+ N
T0 ( ) ( )
N d c b a N X
T A 0 0
1 + +
CHG 3127: Reaction Engineering E.J. Anthony 2012 33
Stoichiometric Tables
Total change in number of moles:



Define parameter



represents change in total number of
moles per mole of A converted
o
N N
d
a
c
a
b
a
N X
T T A
= + +
|
\

|
.
|
0 0
1
o = +
d
a
c
a
b
a
1
o
CHG 3127: Reaction Engineering E.J. Anthony 2012 34
Stoichiometric Tables
Concentration of species j given by



For species B, for example,
C
N
V
j
j
=
C
N
b
a
N X
V
B
B A
=

0 0
CHG 3127: Reaction Engineering E.J. Anthony 2012 35
Stoichiometric Tables
Define new variable to represent the inlet
molar flow rate of species i relative to the inlet
flow rate of the reference (limiting) reactant



For species B, for example
O
i
i
A
N
N
=
0
0
C
N
b
a
X
V
B
A B
=

|
\

|
.
|
0
O
CHG 3127: Reaction Engineering E.J. Anthony 2012 36
Stoichiometric Tables
For a constant volume process




Cases of constant volume process:
dilute liquid phase reactions
organic liquid phase reactions (except
polymerization reactions)
gas phase reactions where number of reacting
molecules equals number of product ones,
operating at constant T, P
C
N
b
a
X
V
N
b
a
X
V
C
b
a
X
B
A B A B
A B
=

|
\

|
.
|
=

|
\

|
.
|
=
|
\

|
.
|
0 0
0
0
O O
O
CHG 3127: Reaction Engineering E.J. Anthony 2012 37
Stoichiometric Tables
For flow problems, replace


with




N N
j j
and
0
F F
j j
and
0
CHG 3127: Reaction Engineering E.J. Anthony 2012 38
Stoichiometric Tables
!"#$%#& '(%)%*+ ,-*(.# /#0*%(%(.
1
F
A0
F X
A0
( )
F X
A0
1
2 F
B0

b
a
F X
A0
F
b
a
X
A B 0
O
|
\

|
.
|
, F
C0
c
a
F X
A0
F
c
a
X
A C 0
O +
|
\

|
.
|
3 F
D0
d
a
F X
A0
F
d
a
X
A D 0
O +
|
\

|
.
|
' F
I 0
F
A I 0
O
45)*+ F
T0
o F X
A0
F F X
T A 0 0
+o
CHG 3127: Reaction Engineering E.J. Anthony 2012 39
Stoichiometric Tables
Local concentrations calculated from
local molar flow rates and total
volumetric flowrate


C
F
v
i
i
=
CHG 3127: Reaction Engineering E.J. Anthony 2012 40
Stoichiometric Tables
In the case of negligible volume
changes (most liquid phase reactions)



( )
( )
C
F
v
F
v
F X
v
C X
A
A A
A
A
= = =

=
0
0
0
0
1
1
CHG 3127: Reaction Engineering E.J. Anthony 2012 41
Stoichiometric Tables
In the case of significant volume
changes (most gas phase reactions)


or


Define a new symbol
N N N X
T T A
= +
0 0
o
N
N
y X
T
T
A
0
0
1 = +o
c o = y
A0
c
CHG 3127: Reaction Engineering E.J. Anthony 2012 42
Stoichiometric Tables
Calculate the volume (volumetric flow
rate) using the gas law:



or, in terms of fractional conversion
V V
P
P
T
T
z
z
N
N
T
T
=
|
\

|
.
|
|
\

|
.
|
|
\

|
.
|
0
0
0 0 0
| |
V V
P
P
T
T
z
z
X =
|
\

|
.
|
|
\

|
.
|
|
\

|
.
|
+
0
0
0 0
1 c
CHG 3127: Reaction Engineering E.J. Anthony 2012 43
Stoichiometric Tables
Concentration given by





or, neglecting compressibility effects





( )
| |
|
|
.
|

\
|
|
.
|

\
|
c +
+ O
=
0
0
0
1
/
P
P
T
T
X
X a v
C C
j j
A j
( ) ( )
( )( )| | X z z P P T T V
X a v N
V
X a v N
V
N
C
j j A j j A j
j
c +
+ O
=
+ O
= =
1
/ /
0 0 0 0
0 0
CHG 3127: Reaction Engineering E.J. Anthony 44
Stoichiometric Tables
For a flow system


Concentration given by




or, neglecting compressibility effects




| | v v
P
P
T
T
z
z
X =
|
\

|
.
|
|
\

|
.
|
|
\

|
.
| +
0
0
0 0
1 c
( )
| |
C C
v a X
X
T
T
P
P
j A
j j
=
+
+
|
\

|
.
|
|
\

|
.
|
0
0
0
1
O
c
( ) ( )
( )( )
| |
C
F
v
F v a X
v
F v a X
v T T P P z z X
j
j
A j j A j j
= =
+
=
+
+
0 0
0 0 0 0
1
O O
c
Stoichiometric Tables
In summary
For a batch system:



For a flow system:



For both:

CHG 3127: Reaction Engineering E.J, Anthony 2012 45
| |
V V
P
P
T
T
z
z
X =
|
\

|
.
|
|
\

|
.
|
|
\

|
.
|
+
0
0
0 0
1 c
| |
v v
P
P
T
T
z
z
X =
|
\

|
.
|
|
\

|
.
|
|
\

|
.
|
+
0
0
0 0
1 c
( )
| |
C C
v a X
X
T
T
z
z
P
P
j A
j j
=
+
+
|
\

|
.
|
|
\

|
.
|
|
\

|
.
|
0
0 0
0
1
O
c
CHG 3127: Reaction Engineering E.J. Anthony 2012 46
Alternatives to X
Fractional conversion not
appropriate for following situations:
membrane reactions
gas phase multiple reactions
unsteady-state flow reactors
CHG 3127: Reaction Engineering E.J. Anthony 2012 47
Alternatives to X
Express concentrations in terms of
molar flows in these cases

|
|
.
|

\
|
|
.
|

\
|
=
0
0
0
P
P
T
T
F
F
C C
T
j
T j
0 0
0
0
0
0
RT Z
P
v
F
C
T
T
= =
0
0
0
0
0
0
0
0
T
T
P
P
C
F
z
z
T
T
P
P
F
F
v
v
T
T
T
T
= =
(z=z
0
=1)
CHG 3127: Reaction Engineering E.J. Anthony 2012 48
Analysis of Reactions with
Phase Change
Consider the reaction


Condensation occurs when



beyond this point each mole of D produced in
the reaction condenses

( ) ( ) ( ) ( )
A g B g C g D g l + + 2 ,
y
P
P
D e
v
T
,
=
CHG 3127: Reaction Engineering E.J. Anthony 2012 49
Analysis of Reactions with
Phase Change
Create additional column in the stoichiometric
table to account for balances after
condensation begins
Let X
C
represent the conversion of A at which
condensation begins
Use definition of mole fraction of D at
condensation along with expressions for total
molar flow rate to calculate X
C


CHG 3127: Reaction Engineering E.J. Anthony 2012 50
Consider the example


Assume reactants only are introduced
into a flow reactor according to their
stoichiometric ratios:


( ) ( ) ( ) ( )
A g B g C g D g l + + 2 ,
F F
F F
B A
C D
0 0
0 0
2
0
=
= =
Analysis of Reactions with
Phase Change
CHG 3127: Reaction Engineering E.J. Anthony 2012 51
Analysis of Reactions with
Phase Change
!"#$%#& /#0*%(%(.
62#758# ,5(:;<
/#0*%(%(.
617)#8 ,5(:;<
1
( )
F X
A0
1
( )
F X
A0
1
2
( )
F X
A0
2 2
( )
F X
A0
2 2
,
F X
A0
F X
A0
3
F X
A0
y F
D e T ,
45)*+
( )
F F X
T A
=
0
3
( )
( )
F y F F F X
F F X y
T D e T A A
T A D e
= +
=
,
,
. /
3 2
2 15 1
0 0
0
CHG 4127: Reaction Engineering David G. Taylor, 2000 52
Calculate y
D,e
from operating conditions:



Equate total molar flow rates from two
columns at point of condensation and solve
for y
D,e
in terms of X
C
:



or


y
X
X
D e
C
C
,
=
3
y
P
P
D e
vD
T
,
=
( )
( )
( )
F X F
X
y
A C A
C
D e
0 0
3 2
15
1
=

.
,
Analysis of Reactions with
Phase Change
CHG 3127: Reaction Engineering E.J. Anthony 2012 53
Analysis of Reactions with
Phase Change
to calculate the concentrations after
condensation we note that, at constant
pressure and temperature
C C
T T
=
0
C
C
F
v
F
v
v
F
F
v
T
T
T
T
T
T 0
0
0
0
0
= =
CHG 3127: Reaction Engineering E.J. Anthony 2012 54
Analysis of Reactions with
Phase Change
Knowing F
T0
and F
T
, we can calculate
concentrations:



where
( )
T
T A A
A
F
F
X
v
F
v
F
C
0
0
0
1 = =
( )
( )
F F
X
y
F F
T A
D e
T A
=

= 2
15
1
3
0 0 0
.
,
,
CHG3127: Reaction Engineering E.J. Anthony 2012 55
Reversible Elementary
Reactions
Consider the reaction

assume rate constants written in terms of
benzene
rate of disappearance of benzene by forward
reaction:

rate of appearance due to reverse reaction:

2
6 6 12 10 2
1 2
C H C H H
k k ,
+
= r k C
B forward B , 1
2
r k C C
B reverse D H ,
=
2
CHG 3127: Reaction Engineering E.J. Anthony 2012 56
Reversible Elementary
Reactions
net rate of formation of benzene given by



net rate of consumption of benzene then


equilibrium constant :

r r r r
r k C k C C
B B net B forward B reverse
B B D H
= +
= +
, , ,
1
2
2
|
|
.
|

\
|
= =
H D B H D B B
C C
k
k
C k C C k C k r
1
2
2
1 2
2
1
K
k
k
c
=
1
2
CHG 3127: Reaction Engineering E.J. Anthony 2012 57
Summarizing So Far...
Basic definitions:
chemical species, and reaction; types of reactions
(e.g., decomposition, combination, etc.); reaction rate;
elementary and non-elementary reactions; molecularity
and reaction order; Arrhenius law

Characterizing industrial Reactors:
by operation
batch, continuous, and semi-batch
by design
tank , tubular, tower, fluidized bed, slurry
CHG 3127: Reaction Engineering E.J. Anthony 2012 58
Summarizing So Far...
generalized stoichiometric equation, extent of
reaction, and fractional conversion

generalized mole balance equation
well-mixed
not well-mixed
CHG 3127: Reaction Engineering E.J. Anthony 2012 59
Summarizing So Far...
relationships between reaction rates
stoichiometric tables for batch systems
tables for continuous (flow) systems
definitions for and
defining inlet moles (molar flow rates) in
terms of limiting reactant
constant and variable volume processes
c
o
CHG 3127: Reaction Engineering E.J. Anthony 2012 60
Summarizing So Far...
Use stoichiometric table to analyze phase
change
Calculate critical mole fraction from vapour
pressure and operating pressure
Add column for after condensation
Use two expressions for total moles (or proper
ratio of molar flows) to determine critical X
Expressions for reversible, elementary
reactions
Acknowledgement
Slides taken and modified from David
Taylor
CHG 3127: Reaction Engineering E.J. Anthony 2012 61