Reactor Design Lectures Notes: Third Year

Dr.
Farah Talib Al-Sudani

Third Year
Reactor Design Lectures
Notes
Department of Chemical Engineering
University of Technology

[Introduction to Chemical Reaction Engineering ] | [Chapter-One]..University of Technology-Chemical Engineering Department-Dr.Farah Al-Sudani

1

.


2

Chemical kinetics is the study of chemical reaction rates and reaction mechanisms. The
study of chemical reaction engineering (CRE) combines the study of chemical kinetics
with the reactors in which the reactions occur. Chemical kinetics and reactor design are
at the heart of producing almost all industrial chemicals.
It is primarily a knowledge of chemical kinetics and reactor design that distinguishes
the chemical engineer from other engineers. The selection of a reaction system that
operates in the safest and most efficient manner can be the key to the economic
success or failure of n chemical plant.
Design of the reactor is no routine matter, and many alternatives can be proposed for a
process. In searching for the optimum it is not just the cost of the reactor that must be
minimized. One design may have low reactor cost, but the materials leaving the unit
may be such that their treatment requires a much higher cost than alternative designs.
Hence, the economics of the overall process must be considered. Reactor design uses
information, knowledge, and experience from a variety of areas-thermodynamics,
chemical kinetics, fluid mechanics, heat transfer, mass transfer, and economics.
Chemical reaction engineering is the synthesis of all these factors with the aim of
properly designing a chemical reactor.
To find what a reactor is able to do we need to know the kinetics, the contacting
pattern and the performance equation. We show this schematically in Figure (1).

Figure (1). Information needed to predict what a reactor can do.

Much of this lectures deals with finding the expression to relate input to
output for various kinetics and various contacting patterns, or
output = f [input, kinetics, contacting] (1)

This is called the performance equation. Why is this important? Because with
this expression we can compare different designs and conditions, find which is
best, and then scale up to larger units.
1.Introduction


3

In Uchemical engineeringU, chemical reactors are vessels designed to contain Uchemical
reactionsU. The design of a chemical reactor deals with multiple aspects of Uchemical
engineeringU. Chemical engineers design reactors to maximize net present value for the
given reaction. Designers ensure that the reaction proceeds with the highest efficiency
towards the desired output product, producing the highest yield of product while
requiring the least amount of money to purchase and operate. Normal operating
expenses include energy input, energy removal, raw material costs, labor, etc.
There are a couple main basic vessel types:
A tank
A pipe or tubular reactor (Ulaminar flow reactorU(LFR))
Both types can be used as continuous reactors or batch reactors. Most commonly,
reactors are run at Usteady-stateU, but can also be operated in a Utransient stateU. When a
reactor is first brought back into operation (after maintenance or inoperation) it would
be considered to be in a transient state, where key process variables change with time.
Both types of reactors may also accommodate one or more solids (UreagentsU, UcatalystU, or
inert materials), but the reagents and products are typically liquids and gases.
There are three main basic models used to estimate the most important process
variables of different chemical reactors:
UBatch ReactorU
UContinuous Stirred-Tank ReactorU U (CSTR)U
UPlug Flow ReactorU U (PFR)U

Key process variables include
Residence time () , Volume (V) , Temperature (T) , Pressure (P) , Concentrations
of chemical species (C
1
, C
2
, C
3
, ... C
n
) ,Heat transfer coefficients (h, U)
Chemical reactions occurring in a reactor may be UexothermicU, meaning giving off heat,
or UendothermicU, meaning absorbing heat. A chemical reactor vessel may have a cooling
or heating jacket or cooling or heating coils (tubes) wrapped around the outside of its
vessel wall to cool down or heat up the contents.

2.Type of Reactors.


4

2.1 Batch Reactor

Kinds of
Phases Present
Usage Advantages Disadvantages
1. Gas phase
2.Liquid
phase
3.Liquid Solid

1. Small scale production
2. Intermediate or one
shot production
3.Testing new process
that have not been fully
developed
4.Manufacture of
expensive products.
5.Pharmaceutical,
Fermentation
1. High conversion per
unit volume for one
pass
2.Flexibility of
operation-same reactor
can produce one
product one time and a
different product the
next
3. Easy to clean

1. High operating
cost
2. Product quality
more variable than
with continuous
operation
3.Difficalty of
large scale
production .

Figure(2) simple batch reactor .
Batch Reactor Type of Reactor
Reactor is charged (i.e., filled) through the holes
at the top ; while reaction is carried out.
Nothing else is put in or taken out until the
reaction is done; tank easily heated or cooled by
jacket
Characteristics


5
Semi-batch reactors operate much like Ubatch reactorsU in that they take place in a single stirred
tank with similar equipment . It modified allow reactant addition and/or product removal in time.
A semi-batch reactor, however, allows partial filling of reactants with the flexibility of adding more
as time progresses. Semi-batch reactors are used primarily for liquid-phase reactions , two-phase
reactions in which a gas usually is bubbled continuously through the liquid , and also for
biological and polymerization reaction.

2.2. Continuous-Flow Reactors
2.2.1 Continuous-Stirred Tank Reactor CSTR

Kinds of Phases
Present
1. Gas phase
2. Liquid phase
3. Liquid Solid

1. When agitation
is required
2. Series
configurations for
different
concentration
streams
1. Continuous operation
2. Good temperature control
3. Easily adapts to two phase
runs
4. Simplicity of construction
5.Low operating (labor) cost
6. Easy to clean
1. Lowest conversion
per unit volume, very
large reactors are
necessary to obtain
high conversions
2. By-passing and
channeling possible
with poor agitation

Continuous-Stirred Tank Reactor CSTR Type of Reactor
Run at steady state ,the flow rate in must equal the mass flow
rate out, otherwise the tank will overflow or go empty
(transient state).
The feed assumes a uniform composition throughout the
reactor, exit stream has the same composition as in the tank.
The reaction rate associated with the final (output)
concentration.
Reactor equipped with an impeller to ensure proper mixing.
Dividing the volume of the tank by the average volumetric flow
rate through the tank gives the residence time, or the average
amount of time a discrete quantity of reagent spends inside the
tank.
Characteristics


6
Some important aspects of the CSTR:
It is economically beneficial to operate several CSTRs in series. This allows, for
example, the first CSTR to operate at a higher reagent concentration and therefore a
higher reaction rate. In these cases, the sizes of the reactors may be varied in order
to minimize the total Ucapital investmentU required to implement the process.

Figure (3) Flow sheet for the manufacture of nitrobenzene from benzene using
a cascade of CSTR


7

2.2.3. Tubular Reactor (PFR)

Kinds of
Phases
Present
1.
Primarily
Gas
Phase
1. Large Scale
2. Fast Reactions
3. Homogeneous Reactions
4. Heterogeneous Reactions
5. Continuous Production
6. High Temperature
1. High Conversion
per Unit Volume
2. Low operating
(labor) cost)
3.Good heat
transfer
1. Undesired thermal
gradients may exist
2. Difficult temperature
control
3. Shutdown and
cleaning may be
expensive
4.Hot spot occur for
exothermic reaction
Tubular Reactor (PFR) Type of Reactor
Consists of a long cylindrical tube or many short reactors in a tube
bank.
Operated at steady state.
The rate is very high at the inlet to the PFR.
No radial variation in reaction rate (concentration) and the reactor is
referred to as a plug-fiow rcactor (PFR).
Concentration changes with length down the reactor
As the concentrations of the reagents decrease and the concentration
of the product(s) increases the reaction rate slows.
A PFR typically has a higher efficiency than a CSTR of the same
volume. That is, given the same space-time, a reaction will proceed to a
higher percentage completion in a PFR than in a CSTR.
Characteristics


8
Other types of reactors:- Catalytic reactors(packed bed and Fluidized-bed
Reactor

Kinds of Phases
Present
1. Gas-Soli phase
2. Liquid-Solid
phase
3. Gas-Liquid -
Solid

Heterogeneous
reaction
Most reaction gives
the highest conversion
per weight of catalyst
of any catalytic
reactor.
1. Difficulties with temperature
control.
2. Catalyst is usually troublesome to
replace
3. Channeling of the gas or liquid flow
occurs, resulting in ineffective use of
part of the reactor bed

Figure(4) Packed bed Reactors

Paced bed Reactor (fixed-bed,PBR) Type of Reactor
is essentially a tubular reactor that is packed with solid
catalyst particles.
Characteristics


9

Kinds of Phases
Present
1. Gas-Solid phase
2. Liquid-Solid
phase
3. Gas-Liquid
Solid phase

1.Heterogeneous
reaction
2. reactor can
handle large
amounts of feed
and solids
1.Good mixing
2. temperature is relatively
uniform throughout
3. Catalyst can be
continuously regenerated with
the use of an auxiliary loop
4. good temperature control
1. Bed-fluid mechanics
not well known
2. Severe agitation can
result in catalyst
destruction and dust
formation
3. Uncertain scale-up

Figure(5) Fluidized-bed
Reactors

Fluidized-bed Reactor Type of Reactor
Is analogous to the CSTR in that its contents.
Heterogeneous reactor, are well mixed.
Characteristics


10

it classify according to
Five traditional types of chemical reactions are
1. Decomposition reactions: single compound decomposes to two or more other
substances,decomposition of calcium carbonate by heating it.
CaCO
3
(s) ---> CaO(s) + CO
2
(g)
2. Combination reactions (Synthesis reactions)
3. Single-replacement reactions (Displacement reactions):copper displaces silver
from an aqueous solution of silver nitrate is an example of a single-replacement
reaction.
Cu(s) + 2 AgNO
3
(aq) ---> Cu(NO
3
)
2
(aq) + 2 Ag(s)
4. Double-replacement reactions (Metathesis reactions):Precipitation reactions are
one type of double-replacement reaction. An example is
AgNO
3
(aq) + NaCl(aq) ---> AgCl(s) + NaNO
3
(aq)
5. Combustion reactions: substance reacts with oxygen,butane burns in air as
follows.
2 C
4
H
10
(g) + 13 O
2
(g) ---> 8 CO
2
(g) + 10 H
2
O(l)

Also Oxidation-reduction reactions (Redox reactions).

phases involved:
o Homogeneous reaction : it takes place in one phase alone
o Heterogeneous reaction : multiple phases, reaction usually occurs at the interface
between phases.

Direction of reaction
o Irreversible Reaction: Proceeds in only one direction and continues in that
direction until the reactants are exhausted.
Example :
Heterogeneous reaction
Toluene-hydrogenation
6
3()
+
2()

6
6()
+
4()

3.Classification of Chemical Reaction


11
Homogeneous reaction
Decomposition N
2
O N
2
O (g)+2O
2
(g) 2 N
2
(g) + O
2
(g)
Water gas shift reaction H
2
O (g)+CO (g) H
2
(g) + CO
2
(g)

o Reversible Reaction: Can proceed in either direction, depending on the
concentrations of reactants and products present relative to the corresponding
equilibrium concentration.
Example :
Homogeneous reaction
Ammonia synthesis 2
2()
+ 3
2()
2
3()

Thermal cracking of ethane :
2
6()

2
4()
+
2()

Heterogeneous reaction
Ammonium chloride synthesis or decomposition
3()
+
()

4
()

[ [[ [Reaction Rate and Conceptes of Kinetics] Reaction Rate and Conceptes of Kinetics] Reaction Rate and Conceptes of Kinetics] Reaction Rate and Conceptes of Kinetics]

Reaction Rate and Conceptes of Kinetics] Reaction Rate and Conceptes of Kinetics] Reaction Rate and Conceptes of Kinetics] Reaction Rate and Conceptes of Kinetics][Chapter [Chapter [Chapter [Chapter- -- -Two].. Two].. Two].. Two]..University of Technology University of Technology University of Technology University of Technology- -- -Chemical Engineering Department Chemical Engineering Department Chemical Engineering Department Chemical Engineering Department

Chemical Engineering Department Chemical Engineering Department Chemical Engineering Department Chemical Engineering Department- -- -Dr.Farah Al Dr.Farah Al Dr.Farah Al Dr.Farah Al- -- -Sudani Sudani Sudani Sudani

12

[ [[ [Reaction Rate and Conceptes of Kinetics] Reaction Rate and Conceptes of Kinetics] Reaction Rate and Conceptes of Kinetics] Reaction Rate and Conceptes of Kinetics][Chapter [Chapter [Chapter [Chapter- -- -Two].. Two].. Two].. Two]..University of Technology University of Technology University of Technology University of Technology- -- -Chemical Engineering Department Chemical Engineering Department Chemical Engineering Department Chemical Engineering Department- -- -Dr.Farah Al Dr.Farah Al Dr.Farah Al Dr.Farah Al- -- -Sudani Sudani Sudani Sudani

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In homogeneous reaction , the reaction rate (r
A
) is defined as the change in
moles of component A(reactant consumed) or mole of product formed with
respect to time per unit volume of reaction mixture.

In solid-catalyzed reactions, the reaction rate ( r
A
) is defined as the change in

moles of component A with respect to time per unit reaction surface area or
catalyst weight.

o r
A
= rate of formation of A per unit volume
o -r
A
= rate of a disappearance of A per unit volume

Batch Reactor

r
A
=
JN
A
I Jt
=
molc o A uisappeai
:olumc o luiJ timc
homogeneous ieaction2a

r
A
|||| =
JN
A
I
Jt
=
molc o A uisappeai
:olumc o rcoctor timc
homogeneous ieaction2b

r
A
=
JN
A
w Jt
=
molc o A uisappeai
moss o cotolyst timc
heteiogeneous ieaction2c

r
A
|| =
JN
A
S Jt
=
molc o A uisappeai
surocc timc
heteiogeneous oi homogeneous ieaction
2d

r
A
||| =
JN
A
I
s
Jt
=
molc o A uisappeai
:olumc o Cotolyst timc
heteiogeneous ieaction2e

Ir
A
= wr
A
=Sr
A
||=I
s
r
A
|||=I
r
A
||||.3

The rate of reaction per unit weight catalyst, -r
A
, (e,g., -r
A
), and thi rate of reaction per unit
volume, -r
A
, , are related through the bulk density ,(mass of solid /volume) of the catalyst
particles in the fluid media:

1.Reaction Rate (Rate Law , r
A

Tubular Flow Reactor

Where N
A
is the molal rate of flow component A into the volume element

Rate of reaction r

o a function of concentration, temperature, pressure, and the type of
catalyst (if any)
o independent of the type of reaction system (batch, plug flow, etc.)
on the reaction chemistry
o an algebraic equation, not a differential equation
o Rate of reaction per unit weight of catalyst and rate of reaction per unit
volume is related
the fluid media

Rate of reaction r
A
is
(Concentration), and
the material mean the temperature (random kinetic
molecules), the light intensity within the system (this may affect the bond
energy between atoms), the ma
only need to consider the temperature

1. Stoichiometry.

Consider the general reaction;

on a per mole of A basis

where the Stoichiometric Coefficients
-r
A
= f {temperature dependent term,concetration dependent term}
= mole/m
3
.time
a
c
a
b
,
2.Conceptes of Kinetics
Tubular Flow Reactor
r
A
=
dN
A
dv
..4
is the molal rate of flow component A into the volume element
Rate of reaction rA is:
a function of concentration, temperature, pressure, and the type of
catalyst (if any)
independent of the type of reaction system (batch, plug flow, etc.)
on the reaction chemistry
an algebraic equation, not a differential equation
Rate of reaction per unit weight of catalyst and rate of reaction per unit
volume is related through the bulk density of the catalyst particle in
media
is an intensive quantity and depended on
(Concentration), and the energy of the material (Temperature
the material mean the temperature (random kinetic
energy between atoms), the magnetic field intensity, etc. Ordinarily
only need to consider the temperature

on a per mole of A basisi.e assume A is the limiting reactant
where the Stoichiometric Coefficients ,
temperature dependent term,concetration dependent term}
.time
dD cC bB aA + +
D
a
d
C
a
c
B
a
b
A
a
d
,
2.Conceptes of Kinetics


14

is the molal rate of flow component A into the volume element.
a function of concentration, temperature, pressure, and the type of
independent of the type of reaction system (batch, plug flow, etc.) but
Rate of reaction per unit weight of catalyst and rate of reaction per unit
through the bulk density of the catalyst particle in
an intensive quantity and depended on composition
Temperature) . Energy of
energy of the
gnetic field intensity, etc. Ordinarily we

limiting reactant :-

temperature dependent term,concetration dependent term}


15

Molecules are lost and formed by reaction , and mass conservation requires
that amounts of species are related by Stoichiometry as:-

1 mole of A and
a
b
of B consumed , while mole of C and
a
d

mole of D formed or appear

Rate of reaction or disappearance of A =r
A

moIc
m
3
.tmc

Rate of formation of C (r
C
) = (r
A
)
moIc
m
3
.tmc

Rate of formation of D (r
) =

a
d
(r
A
)
moIc
m
3
.tmc

Also, Rate of formation of C (r
C
) = [
C
d
(r
)
Rate of formation of D (r
) = [
d
C
(r
C
)

Then the reaction Stoichiometry ;
-
A
u
=
-
B
u
=
C
u
=
D
u

Examples (1),(2)

********************************************************************

2. Temperature Dependent Term of a Reaction Rate Law.

Reaction Rate Contestant.

Kinetic (reaction) Rate law (r
A
) gives relationship between reaction rate
and concentration (is an algebraic equation that relates (r
A
) to species
concentrations)

r
A
= {tcmpcroturc JcpcnJct tcrm, conccntrotion JcpcnJcnt tcrm]
moIc
m
3
.tmc

..5

a
c
a
c
( ) [ ] ( ) [ ] K , ,
B A A A
C C f T k r =
( ) T k
A
k
A
(T) is the reaction rate constant
Strongly dependent on temperature
Depends on whether
NOT really a constant, but

The rate constant

A Pre-exponential factor (frequency factor)
E Activation energy (J/mol)
R Gas constant (8.314 J/mol
T Absolute temperature

Activation Energy

Activation energy has been equated with minimum energy that must be
possessed by reacting molecules before the reaction will occur.

Figure(2.1)Activation energy for
reaction rate constant
trongly dependent on temperature
epends on whether or not a catalyst is present
NOT really a constant, but f(C
i
)
rate constant is described by Arrhenius equation :-
6
7
exponential factor (frequency factor)
ctivation energy (J/mol)
as constant (8.314 J/molK, 1.987 cal/mol K)
bsolute temperature (K)
Activation Energy

(2.1)Activation energy for exothermic and endothermic reaction.
( )
RT E
A
Ae T k

=
( ) ( )

=
T R
E
A k
1
ln ln


16
6
7
exothermic and endothermic reaction.
Heat
Absorbed
Heat
Released


17

At the same concentration but different two temperature Activation
Energy can be estimated as :

8

Figure (2.2) shows temperature dependency of the reaction rate

Example (4)
Example (5) =example 3.1 from elemental of chemical reaction
engineering , 4ed pag 95

*********************************************************************

( )
( )
( )
( )

= =
2 1 1
2
1
2
1 1
ln
ln
ln
ln
T T R
E
k
k
r
r


18

3. Concentration Dependent Term of a Reaction Rate Law.

.5

One of the most common general forms of this dependence is the product of
concentrations of the individual reacting species, each of which is raised to a power .

Reaction Order.

Elementary Reaction
A reaction order for which each specie is identical to its
Stoichiometric coefficient as shown :-

o a and b represent the reaction order with respect to the reactant
A and B respectively ,
over all reaction order( n ) = a + b

o Reaction rate constant, k will vary with the order of the reaction as
shown :-

( ) [ ] ( ) [ ] K , ,
B A A A
C C f T k r =
( ) K , ,
B A
C C f
dD cC bB aA + +
b
B
a
A A
C kC r =


19

A products
Order Rate Equation Units
Zero

mol.V
-1
.s
-1
First

s
-1
Second

V.mol
-1
.s
-1

Third

( V.mol
-1
)2.s
-1
nth order

(concentration)
1-n
.s
-1

o Another example of elementary reaction ; reversible second
order :-

where K
c
equilibrium constant
All reversible reaction rate laws must reduce to the thermodynamic
relationship relating reacting species concentrations at equilibrium.
At equilibrium, the net rate of reaction is zero for all species involved
in the reaction

Example (6)
k r
A
=
A A
kC r =
2
A A
kC r =
3
A A
kC r =
n
A A
kC r =
2 10 12 6 6
1
2 H H C H C
k
+
k2
=
c
H D
B B
K
C C
C k r
2 2
1
0 =
ie
r
C B A
A
A
k
k
+
2
2
A A A
C k r =
C B A A
C C k r

=
Forward rate law
Backward or reverse rate law
C B A A A A A net A
C C k C k r r r

+ = + =
2
,
net rate law
C B A A A net A
C C k C k r

+ = =
2
,
0
C B A A A
C C k C k

=
2
C
A
C B
A
A
K
C
C C
k
k
= =
2
Equilibrium condition
Equilibrium relationship
=
C
C B
A A A
K
C C
C k r
2
Rate law in term Equilibrium relationship


20

Non-Elementary Reaction
Do not follow the Stoichiometric coefficients for the overall
reaction
Homogeneous Reactions :
Gas-phase synthesis of phosgene,

n=5.5
Decomposition of nitrous oxide

n depended on CO2 concentration

Heterogeneous Reactions :
Heterogeneous reaction and corresponding rate law is the
hydrodemethylation of toluene (T) to form benzene (B) and methane (M)
carried out over a solid catalyst.

4. Molecularly Reaction.
The term molecularity refers to number of atoms, ions, or molecules
involved in the rate-limiting step of the reaction.
Unimolecular one reactant involved in reaction
Bimolecular two reactants must collide to react
Termolecular three reactants must interact for reaction to occur

2 2
COCl Cl CO +
2 / 3
2
Cl CO CO CO
C C k r =
2 2 2
2 2 O N O N +
2
2 2
2
1
O
O N O N
O N
C k
C k
r
+
=
4 6 2
.
2 3 5 6
CH H C H CH H C
cat
+ +
T T P B
T H
T
P K P K
P P k
r
+ +
=
1
2
2
. . kPa s kg
toluene mol
k
cat
=


21
5. Conversion , yield and selectivity
conversion, X, is defined as the fraction (or percentage) of the more
important or limiting reactant that is consumed. With two reactants A and
B and a nearly Stoichiometric feed, conversions based on each reactant
could be calculated.

.8

yield, Y, is the amount of desired product produced relative to the amount
that would have been formed if there were no byproducts and the main
reaction went to completion

9

6. Van't Hoff Equation.
Van't Hoff equation relates equilibrium composition to temperature:

..10

Van't Hoff equation can be integrated from 298K to any temperature T to
yield :
.11

Enthalpy change of reaction varies with temperature as:
( ) ( )

+ =
T
T
p
o
r r
dT C T H T H
298
298
....12
An approximate estimate of equilibrium constant at any time , ignore the second
term in equation 12, then equation 11 became :
..13

For endothermic reactions, the equilibrium constant, K
eq
, increases with increasing
temperature. While for exothermic reactions, K
eq
and X
eq
decreases with increasing
temperature.

fed A mole
reacted A mole
= X
1.0 x product, of moles maximum
formed product of moles
=
= Y
( )
dT
K d
RT
H
dT
RT G d
eq
o
r
o
R
ln
/
2
=

+ =
T
r
eq
dT
RT
H
K K
298
2
298
ln ln
=
298
1 1
ln ln
298
298
T R
H
K K
r
eq

Figure (2.3) show the
equilibrium conversion as a function of temperature for an exothermic reac
the variation of the concentration equilibrium constant
equilibrium conversion as a function of temperature for an exothermic reac


22
equilibrium constant and
equilibrium conversion as a function of temperature for an exothermic reaction.
[ [[ [Reactor Sizing and Design Reactor Sizing and Design Reactor Sizing and Design Reactor Sizing and Design] ]] ][Chapter [Chapter [Chapter [Chapter- -- -Four Four Four Four] ] ] ]

Four Four Four Four] ] ] ] .. .. .. ..University of Technology University of Technology University of Technology University of Technology- -- -Chemical Engineering Department Chemical Engineering Department Chemical Engineering Department Chemical Engineering Department


1. General Mole Balance Equation

Mole balance on species j at any instance in time t ;

F
j0
= Entering molar flow rate of
F
j
= Exiting molar flow rate of
G
j
= Rate(total rate)
r
j
= rate of generation(formation) of
N
j
= number of moles of

If r
j
varies with position in the system,

Then general mole balance:

From this general mole balance equation
the various types of industrial r
reactors.
+
(
of system into j of
flow of rate
jo
F
2
V
1
V
1
j
r
2
j
r
General Mole Balance Equation
lance on species j at any instance in time t ;
..4.1

= Entering molar flow rate of species j (mol/time)
= Exiting molar flow rate of species j (mol/time)
(total rate) of generation(formation) of species j (mol/time)
V = Volume (e.g. m
3
)
= rate of generation(formation) of species j (mole/time
= number of moles of species j inside the system Volume V (
varies with position in the system,

Then general mole balance:-
4.2
From this general mole balance equation we can develop the design equations
the various types of industrial reactors: batch, semi-batch. and continuous
=
(
(
of
rate
system of out j of
flow of rate
rxn by system in j of
generation of rate
dt
dN
j
j j jo
= + F G
6
V
5
V
4
V
3
V
3
j
r
4
j
r
5
j
r
6
j
r
=
=
=
m
i
j j
j j
G
r
1
1 , 1 ,
G
G
m Let
=
V
j
r G
dt
dN
dV r
j
j
V
j jo
= +
F F

V system Volumn


(mol/time)
(mol/time)
(mol/time)=r
j
.V
(mole/time.vol)
inside the system Volume V (mole)
4.2
design equations for
batch. and continuous-flow
(
(
system within j of
on accumulati of rate
=
=
m
i
i i j i j
V r
V
1
, ,
1
0 , V
j
dV r

o Operate under unsteady state
o Neither inflow nor outflow of reactants or products
If the reaction mixture
o Constant rate of reaction throughout
o Composition f
o Composition =f (time)
o Temperature f
o Temperature f

Mole Balance

REACTOR SIZING AND DESIGN
Batch Reactor
,
=
o j
F F
dV r
V
j jo
+
F
dV r
V
j

Operate under unsteady state
either inflow nor outflow of reactants or products
mixture is perfectly mixed so:
f reaction throughout the reactor volume
f (Position)
(time)
f (Position)
f (time)
...............................4.3
REACTOR SIZING AND DESIGN
PART ONE
Batch Reactor
0 =
j
F
dt
dN
dV
j
j
= F
dt
dN
dV
j
=
Isothermal Operation


ideal restrictions

[ [[ [Reactor Sizing and Design Reactor Sizing and Design Reactor Sizing and Design Reactor Sizing and Design] ]] ][Chapter [Chapter [Chapter [Chapter- -- -Four Four Four Four] ] ] ] .. .. .. ..University of Technology University of Technology University of Technology University of Technology- -- -Chemical Engineering Department Chemical Engineering Department Chemical Engineering Department Chemical Engineering Department- -- -Dr.Farah Al Dr.Farah Al Dr.Farah Al Dr.Farah Al- -- -Sudani Sudani Sudani Sudani

..4.4
Let's consider the isomerization of species A in a batch reactor

As the reaction proceeds. the number of moles of A decreases and the number of
moles of B increases, as shown in Figure below

The time t necessary to reduce the initial number of moles N
Ao
to a final number
of mole N
A
can be estimated as :
from equation 4.4

4.4

integrating with limits that at :
t = 0 N
A
= N
A0

stat of reaction and at
t = t N
A
= N
A
reaction time (end of reaction ) we obtain

..4.5

(
(
(
(
(
=
=
(
(
(
fed moles
reacted moles
moles
A of
A of
0 at t
fed initially
A of
consumed or reacted
A of moles
B A
dt
dN
V r
j
j
=
dt
dN
V r
A
A
=
V r
dN
dt
A
A
=
=
0 A
A
N
N A
A
V r
dN
t
[ ] [ ] X N
A
=
(
(
(
0
consumed or reacted
A of moles


number of mole N
A
remain un-reacted after time t ,

Sub in equation 4.5 and 4.4

.4.6 4.7

Differential form Integral form
Batch Reactor Design Equation Used in the Interpretation of
m Lab Rate Data

Space time or Mean Residence Time= is the time necessary to process one reactor
mmmmmmmmmmmmmmmmmmm volume of fluid based on entrance conditions.

t
B
=t+t
D

[ ] [ ] [ ] [ ] X N N N
A A A
=
0 0
(
(
(
(
(
(
=
=
(
(
(
consumed or reacted
A of moles
0 at t reactor the
to fed initially
A of
t time
at (remain) reacter in
A of moles moles
( ) X N N
Ao A
= 1
Ao
A Ao
N
N N
X

=
V r
dt
dX
N
A Ao
=
V r
dt
dN
A
A
=
=
0 A
A
N
N A
A
V r
dN
t
( ) X N N
Ao A
= 1
( )

=
t X
A
Ao
V r
dX
N t
0


At constant volume batch reactor
i.e constant density reaction mixture.
N
Ao
= C
Ao
* V then; equations 4.4 and 4.5 become ( ) :

..4.8.(Reaction Time)

Evaluation of Reaction Time Graphically:

From equation 4.7 plot vs. X and evaluate the area under the curve
to estimate reaction time

X1 X X

Or
From equation 4.7 plot vs. C
A
and evaluate the area under the curve
to estimate reaction time

CA CA CA
o

Example

dt
dC
r
A
A
=

=
A
Ao
C
C
A
A
r
dC
t
V
N
C
i
i
=
A
r
1
A
r
1
A
r
1
( )

=
t X
A
Ao
V r
dX
N t
0
Area
V
N
t
Ao
* =
Area
Area
A
r
1

=
A
Ao
C
C
A
A
r
dC
t
Area t =


Evaluation of Reaction Time Numerically:

Need to size reactors or calculate reaction time

o For the reactions in which the rate depends only on the concentration of
one species then

First order and Irreversible :-

,

Second order and Irreversible :-

,

,

nth order and Irreversible :-

,

Example
B A
A A
kC r =

=
=
A
Ao
A
Ao
C
C
A
A
C
C
A
A
C
dC
k kC
dC
t
1
|
|
\
|
=
Ao
A
C
C
k
t ln .
1
kt
Ao A
e C C

=
2
A A
kC r =
B A

=
=
A
Ao
A
Ao
C
C
A
A
C
C
A
A
C
dC
k kC
dC
t
2 2
1
|
|
\
|
=
Ao A
C C k
t
1 1 1
kt C
C
C
Ao
Ao
A
+
=
1
n
A A
kC r =
B A
( )
1 1
1
1
+ +
+
=
n
Ao
n
A
C C
n
kt
( ) [ ]
n
n
Ao Ao A
t kC n C C

+
+ =
1
1
1
1 1
) (
A A
C f r =
) (CA f r
A
=


Bimolecular Reactions

o when the rate law depends on more than one species , we must relate the
concentrations of the different species to eac2h other "as a function of
conversion ". This relationship is most easily established with
the aid of a Stoichiometric table.
In formulating our stoichiornetsic table, we shall take species A component as
our basis of calculation (i.e.. limiting reactant) and then divide through by the
stoichiometric coefficient of A , in order to put everything on a basis of "pet mole
of A ".

Stoichiornetsic table presents the following information
o Column I: the particular species
o Column 2: the number of moles of each species initially present
o Column 3: the change in the number of moles brought about by reaction
o Column 4: the number of moles remaining in the system at time t
o Column 5: concentrations as a function of conversion of each species


Stoichiometry set up of equations with A as basis

The rate law is :

D
a
d
C
a
c
B
a
b
A
|
\
|
+
|
\
|
\
|
+
|
|
\
|
=
C
d
D
c
C
b
B
a
A A A
K
C C
C C k r
) ( X f r
A
=


Constant Volume (Constant Density)

liquid-phase and some of gas phase reaction system fall into this category.
Stoichiometric Table Batch System
Specie Initial Change Remaining Concentration
A N
Ao

-N
Ao
X

N
A
= N
Ao
(1 X)

=
A
C ( ) X C
A
1
0

B N
Bo
= N
Ao

B

-(b/a)N
Ao
X

N
B
= N
Ao
[
B
(b/a)X]

=
B
C |
\
|
X
a
b
C
B A0

C N
Co
= N
Ao

C

+(c/a)N
Ao
X

N
C
= N
Ao
[
C
+(c/a)X]

=
C
C |
\
|
+ X
a
c
C
C A0

D N
Do
= N
Ao

D

+(d/a)N
Ao
X

N
D
= N
Ao
[
D
+(d/a)X]

=
D
C |
\
|
+ X
a
d
C
D A0

I N
I
= N
Ao

N
I
= N
Ao

I

Io
C
N
To
= N
Ao

i
N
T
= N
To
+ N
Ao
X

Where

i
= N
io
/N
Ao
= C
io
/C
Ao
= y
io
/y
Ao

= (d/a) + (c/a) (b/a) - 1

Express table in terms of concentrations
Concentration (batch):

Mole balance equation and the rate law are coupled and then solved
Example
V
N
C
i
i
=
0
V V =
( )
( )
|
\
|
=
|
\
|
= =
=
= =
X
a
b
C X
a
b
V
N
V
N
C
X C
V
X N
V
N
C
B A B
A B
B
A
A A
A
0
0
0
0
0
0
1
1
|
\
|
+ =
|
\
|
+ = =
|
\
|
+ =
|
\
|
+ = =
X
a
d
C X
a
d
V
N
V
N
C
X
a
c
C X
a
c
V
N
V
N
C
D A D
A D
D
C A C
A D
C
0
0
0
0
0
0


Variable Volume (Variable Density, but with Constant T and P )

Individual concentration can be determined by expressing the volume for
batch system as a function of conversion using the equation of state:

PV=ZNTRT..at any time in the reaction
PoVo=ZoNToRToat any time =0;when reaction is initiated
Then,
|
|
\
|
|
\
|
|
|
\
|
|
|
\
|
=
0
0
0 0
0
Z
Z
P
P
T
T
N
N
V V
T
T
.4.9
Change in the total number of moles during reaction in gas phase reaction system,
but with constant temperature and pressure, and the compressibility factor will not
change significantly during the course of the reaction ,

|
|
\
|
=
0
0
T
T
N
N
V V

Where N
T
= N
To
+ N
Ao
X

= (d/a) + (c/a) (b/a) 1
= (change in total number of mole)

/ (mole of A reacted)

X
N
N
N
N
T
Ao
T
T
0 0
1+ =

0 T
Ao
Ao
N
N
y =

Ao
T
Ao
y
N
N
= =
0
4.10a.
Then

X
N
N
T
T
+ =1
0

X N
N N
T
To T
0
=
..4.10b


At complete conversion i.e X=1 , N

T
= N
Tf
; therefore ,

0 T
To Tf
N
N N
=
.4.11
= (change in total number of mole for complete conversion )

/ (total moles fed)
Then the volume as a function of conversion :
( ) X V V + = 1
0
.4.12

Concentration at variable volume or density
Specie
|
\
|
=
V
N
C
A
A

( )
V
X N
A

=
1
0

( )
) 1 (
1
0
X V
X N
o
A
+
=

( )
) 1 (
1
0
X
X C
A
+
=
|
\
|
=
V
N
C
B
B

( )
V
X N
B
(b/a) -
B 0

=
( )
) 1 (
(b/a) -
B 0
X V
X N
o
B
+
=

( )
) 1 (
(b/a) -
B 0
X
X C
B
+
=
|
\
|
=
V
N
C
C
C

( )
V
X N
Co
(c/a)
C
+
=
( )
) 1 (
(c/a)
C
X V
X N
o
Co
+
+
=

( )
) 1 (
(c/a)
C
X
X C
Co
+
+
=
|
\
|
=
V
N
C
D
D

( )
V
X N
D
(d/a) -
D 0

=

( )
) 1 (
(d/a) -
D 0
X V
X N
o
D
+
=

( )
) 1 (
(d/a) -
D 0
X
X C
D
+
=
|
\
|
=
V
N
C
I
I

V
N
I Ao
=

) 1 ( X V
N
o
I Ao
+
=

) 1 ( X
C
I Ao
+
=

Example


Chemical reactors can liberate or absorb very large amounts of energy , and the handling of
this energy is a major concern in reaction engineering. It is important to estimate the
temperature increase or decrease in an adiabatic reactor in which no heat is add or
removed, and exothermic reactor and also the composition of the reaction mixture at any
time.
Energy Balance

+ =

( ) ) ( V r T H
A r

) ( T T UA Q
a
=
&

|
\
|
dt
dT
C C V
i i p,

T = reaction temperature K
Ta= wall temperature K
TR= reference temperature K
A = heat transfer area m
2

Cpi = specific heat KJ/Kmol
U = overall heat transfer KJ/s.m
2
.K
r
H =enthalpy change in the reaction per mole of Areacting
The number of moles of species i at any X is =
( ) X N N
i i A i
+ =
0

Then energy balance is :

( )

|
\
|
= +
dt
dT
N C T T UA V r T H
i i p a A r ,
) ( ) (

.4.13
Energy and mole balance equations with the rate law are coupled and then solved

Non-Isothermal Operation
Heat Generated by
Reaction
Heat Addition and
Removal by wall
Heat Accumulated by
Reaction
( ) ( )
dt
dT
CpX C N T T UA V r T H
i p i A a A r
+ = +
, 0
) ( ) (


Mole balance equation

r
H is calculated as
( ) ( )
+ =
T
T
p R
o
r r
R
dT C T H T H

The rate law is required as a function of temperature and composition

Variable Volume (Variable Density ,T and/or P)
"Variable T in non-isothermal"
The volume for batch system as a function of conversion as :-
|
|
\
|
|
\
|
|
|
\
|
|
|
\
|
=
0
0
0 0
0
Z
Z
P
P
T
T
N
N
V V
T
T

( )
|
|
\
|
|
\
|
|
|
\
|
+ =
0
0
0
0
1
Z
Z
P
P
T
T
X V V

If the compressibility factor will not change significantly during the course of the
reaction Z
o
=Z

( ) |
\
|
|
|
\
|
+ =
P
P
T
T
X V V
0
0
0
1

Concentration at variable volume (density , T and/or P )
Specie
|
\
|
=
V
N
C
A
A

( )
V
X N
A
1
0

( )
|
|
\
|
|
\
|
+
o
o
o
A
P
P
T
T
X V
X N
) 1 (
1
0

( )
|
|
\
|
|
\
|
+
o
o A
P
P
T
T
X
X C
) 1 (
1
0
\
|
=
V
N
C
B
B

( )
V
X N
B
(b/a) -
B 0

( )
|
|
\
|
|
\
|
+
o
o
o
B
P
P
T
T
X V
X N
) 1 (
(b/a) -
B 0

( )
|
|
\
|
|
\
|
+
o
o B
P
P
T
T
X
X C
) 1 (
(b/a) -
B 0
\
|
=
V
N
C
C
C

( )
V
X N
Co
(c/a)
C
+

( )
|
|
\
|
|
\
|
+
+
o
o
o
Co
P
P
T
T
X V
X N
) 1 (
(c/a)
C

( )
|
|
\
|
|
\
|
+
+
o
o Co
P
P
T
T
X
X C
) 1 (
(c/a)
C
\
|
=
V
N
C
D
D

( )
V
X N
D
(d/a) -
D 0

( )
|
|
\
|
|
\
|
+
o
o
o
D
P
P
T
T
X V
X N
) 1 (
(d/a) -
D 0

( )
|
|
\
|
|
\
|
+
o
o D
P
P
T
T
X
X C
) 1 (
(d/a) -
D 0
\
|
=
V
N
C
I
I

V
N
I Ao

|
|
\
|
|
\
|
+
o
o
o
I Ao
P
P
T
T
X V
N
) 1 (

|
|
\
|
|
\
|
+
o
o I Ao
P
P
T
T
X
C
) 1 (

Example
V r
dt
dX
N
A Ao
=


A batch reactor is usually well mixed, so that may neglect the special variation in
temperature and species concentration .
Batch reactors operated adiabatically are often used to determine the reaction
orders, activation energies, and specific reaction rates of exothermic reactions by
monitoring the temperature-time trajectories for different initial conditions.
In adiabatic operation of a batch reactor

0 = Q
&

( ) ( )
dt
dT
N C V r T H
i i p A r
=
,
) (

.4.14
Energy and mole balance equations with the rate law are coupled and then
solved:

;Where T
o
= initial temperature

Example

Adiabatic Operation of a Batch Reactor

( ) ( )
dt
dT
CpX C N V r T H
i p i A A r
+ =
, 0
) (

( ) T H
T T C
X
r
o i p i

=

) (
,

( )
CpX C
X T H
T T
i p i
r
o
+

+ =
,


The highest conversion that can be achieved in reversible reactions is the
equilibrium conversion X
EB
. For endothermic reactions, the equilibrium
conversion increases with increasing temperature up to a maximum of 1.0.
For exothermic reactions, the equilibrium conversion decreases with increasing
temperature
Figure ( ) show the variation of the concentration equilibrium constant as a
function of temperature for an exothermic reaction the corresponding equilibrium
conversion X
EB
as a function of temperature.

Figure ( ) show the variation of the concentration equilibrium constant and
equilibrium conversion as a function of temperature for an exothermic reaction.

To determine the maximum conversion that can be achieved in an exothermic
reaction carried out adiabatically, we find the intersection of the equilibrium
conversion as a function of temperature ,with temperature conversion
relationships from the energy balance

..4.15

Graphical solution of equilibriurn
and energy balance equations to
obtain the adiabatic temperature
and the adiabatic equilibriurn
conversion X
EB
.
Example
Equilibrium Conversion

( ) T H
T T C
X
r
o i p i
EB

=

) (
,

Reactor Design Lectures Notes: Third Year

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Reactor Design Lectures Notes: Third Year

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Dr.

Farah Talib Al-Sudani

) is defined as the change in

Constant Volume (Constant Density)

Variable Volume (Variable Density, but with Constant T and P )

At complete conversion i.e X=1 , N

Mole balance equation

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