Intro Notes

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
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
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
Basic Definitions
Series Reactions

Parallel Competitive Reactions

Independent Reactions
A B C
A B
A C
A B
C D

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
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
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
+
=
+
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
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 | +
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
+
=
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

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
Homogeneous batch reactor
hand holes for
recharging reactor
connection for
heating or cooling jacket
agitator
From Fogler, Elements of Chemical Reaction Engineering, 3rd Edition
Semi-batch reactor
reactant B
reactant A
and product
heater or cooler
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

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

CSTR
. Courtesy of Pfaudler, Inc
Longitudinal tubular reactor
From Fogler, Elements of Chemical Reaction Engineering, 3rd Edition
Circulating fluidized bed reactor
feed
product
settling
hopper
riser
standpipe
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
Mole Balances and
Stoichiometry
relationship between and X
=
Xn
v
lim,
lim
0
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
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
+ =
}
Stoichiometric Tables
Objective: to find expressions for r
j
and
N
j


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
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
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
!"#$%#& '(%)%*+ ,-*(.# /#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 + +
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
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
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
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
For flow problems, replace

with

N N
j j
and
0
F F
j j
and
0
!"#$%#& '(%)%*+ ,-*(.# /#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
Local concentrations calculated from
local molar flow rates and total
volumetric flowrate

C
F
v
i
i
=
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
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
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
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
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
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
Alternatives to X
Fractional conversion not
appropriate for following situations:
membrane reactions
gas phase multiple reactions
unsteady-state flow reactors
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)
Analysis of Reactions with
Phase Change

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
,
=
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

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
=
= =
Phase Change
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
=

.
,
Phase Change
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
= =
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
.
,
,
Reversible Elementary
Reactions

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
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
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
generalized stoichiometric equation, extent of
reaction, and fractional conversion

generalized mole balance equation
well-mixed
not well-mixed
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
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

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Chemical Reactor Design

An engineer seeks to design reaction

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

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