Reactor Lecture 1

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 epartment Chemical Engineering epartment Chemical Engineering epartment Chemical Engineering epartment

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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 epartment Chemical Engineering epartment Chemical Engineering epartment Chemical Engineering epartment- -- -r.!arah "l r.!arah "l r.!arah "l r.!arah "l- -- -#$dani #$dani #$dani #$dani

13

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 ieaction.2a

r
A
|||| =
JN
A
I
Jt
=
molc o A uisappeai
:olumc o rcoctor timc
homogeneous ieaction.2b

r
A
=
JN
A
w Jt
=
molc o A uisappeai
moss o cotolyst timc
heteiogeneous ieaction.2c

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 ieaction.2e

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

he 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"

!Reaction Rate (Rate "a# , r
A

$ubular %lo# Reactor

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

Rate o& reaction r

o a function of concentration! temperature! pressure! and the type of
catalyst (if any)
o independent of the type of reaction system ($atch! plug flow! etc.)
on the reaction chemistry
o an alge$raic e%uation! not a differential e%uation
o &ate of reaction per unit weight of catalyst and rate of reaction per unit
volume is related
the fluid media

Rate o& reaction r
A
is
('oncentration), and
the material mean the temperature (random kinetic
molecules), the light intensity #ithin the system (this may a&&ect the bond
energy bet#een atoms), the ma
only need to consider the temperature

! (toichiometry!

'onsider the general reaction(

on a )per mole of A $asis*

where the +toichiometric 'oefficients
-r
A
) & *temperature dependent term,concetration dependent term+
) mole/m
,
!time
a
c
a
b
,
-!'onceptes o& .inetics
$ubular %lo# Reactor
r
A
=
dN
A
dv
..,
is the molal rate of flow component A into the volume element
Rate o& reaction rA is/
a function of concentration! temperature! pressure! and the type of
catalyst (if any)
independent of the type of reaction system ($atch! plug flow! etc.)
on the reaction chemistry
an alge$raic e%uation! not a differential e%uation
&ate of reaction per unit weight of catalyst and rate of reaction per unit
volume is related through the $ul- density of the catalyst particle in
media
is an intensive 0uantity and depended on
('oncentration), and the energy o& the material ($emperature
the material mean the temperature (random kinetic
energy bet#een atoms), the magnetic &ield intensity, etc! 1rdinarily
only need to consider the temperature

'onsider the general reaction(
on a )per mole of A $asis*i.e assume A is the limiting reactant
where the +toichiometric 'oefficients !
temperature dependent term,concetration dependent term+
!time
dD cC bB aA + +
D
a
d
C
a
c
B
a
b
A
a
d
,
-!'onceptes o& .inetics


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 ($atch! plug flow! etc.) $ut
&ate of reaction per unit weight of catalyst and rate of reaction per unit
through the $ul- density of the catalyst particle in
an intensive 0uantity and depended on composition
$emperature) ! 2nergy o&
energy o& the
gnetic &ield intensity, etc! 1rdinarily #e

limiting reactant "-

temperature dependent term,concetration dependent term+


15

.olecules are lost and formed $y reaction ! and mass conservation re%uires
that amounts of species are related $y +toichiometry as"-

/ mole of A and
a
b
of 0 consumed ! while mole of ' and
a
d

mole of 1 formed or appear

&ate of reaction or disappearance of A =r
A

moIc
m
3
.tmc

&ate of formation of ' (r
C
) = (r
A
)
moIc
m
3
.tmc

&ate of formation of 1 (r
) =

a
d
(r
A
)
moIc
m
3
.tmc

Also! &ate of formation of ' (r
C
) = [
C
d
(r
)
&ate of formation of 1 (r
) = [
d
C
(r
C
)

hen the reaction +toichiometry (
-
A
u
=
-
B
u
=
C
u
=
D
u

23amples (),(-)

22222222222222222222222222222222222222222222222222222222222222222222

-! $emperature 4 5ependent $erm o& a Reaction Rate "a#!

Reaction Rate 'ontestant!

3inetic (reaction) &ate law (r
A
) gives relationship $etween reaction rate
and concentration (is an alge$raic e%uation that relates (r
A
) to species
concentrations)

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

..4

a
c
a
c
( ) [ ] ( ) [ ] K , ,
B A A A
C C f T k r =
( ) T k
A
-
A
() is the reaction rate constant
+trongly dependent on temperature
1epends on whether
56 really a constant! $ut

he rate constant

A 7re-exponential factor (fre%uency factor)
8 Activation energy (9:mol)
& ;as constant (<.3/, 9:mol
A$solute temperature

Activation 2nergy

Activation energy has $een e%uated with minimum energy that must $e
possessed $y reacting molecules $efore the reaction will occur.

=igure(2./)Activation energy for
reaction rate constant
trongly dependent on temperature
epends on whether or not a catalyst is present
56 really a constant! $ut f('
i
)
rate constant is descri$ed $y Arrhenius e%uation "-
>
?
exponential factor (fre%uency factor)
ctivation energy (9:mol)
as constant (<.3/, 9:mol3! /.@<? cal:mol 3)
$solute temperature (3)
Activation 2nergy

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

=
( ) ( )

=
T R
E
A k
1
ln ln


16
>
?
exothermic and endothermic reaction.
Heat
Absorbed
Heat
Released


17

At the same concentration $ut different two temperature Activation
2nergy can $e estimated as "

<

=igure (2.2) shows temperature dependency of the reaction rate

23ample (6)
23ample (7) )e3ample ,! &rom elemental o& chemical reaction
engineering , 6ed pag 87

222222222222222222222222222222222222222222222222222222222222222222222

( )
( )
( )
( )

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


18

3. 'oncentration 4 5ependent $erm o& a Reaction Rate "a#!

.4

6ne 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 1rder!

2lementary Reaction
A reaction order for which each specie is identical to its
+toichiometric coefficient as shown "-

o a and b represent the reaction order #ith respect to the reactant
A and B respectively ,
over all reaction order( n ) ) a 9 b

o &eaction 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
1rder Rate 20uation :nits
;ero

mol.A
-/
.s
-/
%irst

s
-/
(econd

A.mol
-/
.s
-/

$hird

( A.mol
-/
)2.s
-/
nth order

(concentration)
/-n
.s
-/

o Another e3ample o& elementary reaction < reversible second
order /-

#here .
c
e0uilibrium constant
All reversible reaction rate la#s must reduce to the thermodynamic
relationship relating reacting species concentrations at e0uilibrium!
At e0uilibrium, the net rate o& reaction is zero &or all species involved
in the reaction

23ample (=)
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

>on-2lementary Reaction
5o not &ollo# the (toichiometric coe&&icients &or the overall
reaction
?omogeneous Reactions "
@as-phase synthesis o& phosgene,

n)7!7
5ecomposition o& nitrous o3ide

n depended on '1- concentration

?eterogeneous Reactions "
Beterogeneous reaction and corresponding rate la# is the
hydrodemethylation of toluene () to form $enCene (0) and methane (A)
carried out over a solid catalyst.

6! Aolecularly Reaction!
he term molecularity refers to num$er of atoms! ions! or molecules
involved in the rate-limiting step of the reaction.
Dnimolecular E one reactant involved in reaction
0imolecular E two reactants must collide to react
ermolecular E 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
7! 'onversion , yield and selectivity
conversion, B! is defined as the fraction (or percentage) of the more
important or limiting reactant that is consumed. #ith two reactants A and
0 and a nearly +toichiometric feed! conversions $ased on each reactant
could $e calculated.

.<

yield, C, is the amount of desired product produced relative to the amount
that would have $een formed if there were no $yproducts and the main
reaction went to completion

@

=! DanEt ?o&& 20uation!
AanFt Boff e%uation relates e%uili$rium composition to temperature"

../G

AanFt Boff e%uation can $e integrated from 2@<3 to any temperature to
yield "
.//

8nthalpy change of reaction varies with temperature as"
( ) ( )

+ =
T
T
p
o
r r
dT C T H T H
298
298
..../2
An approximate estimate of e%uili$rium constant at any time ! ignore the second
term in e%uation /2! then e%uation // $ecame "
../3

=or endothermic reactions! the e%uili$rium constant! K
eq
, increases with increasing
temperature. #hile for exothermic reactions! K
eq
and
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

=igure (2.3) show the
e%uili$rium conversion as a function of temperature for an exothermic reac
the variation of the concentration e%uili$rium constant
e%uili$rium conversion as a function of temperature for an exothermic reac


22
e%uili$rium constant and
e%uili$rium 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 Technoogy University of Technoogy University of Technoogy University of Technoogy- -- -Che!ica "ngineering Depart!ent Che!ica "ngineering Depart!ent Che!ica "ngineering Depart!ent Che!ica "ngineering Depart!ent

Che!ica "ngineering Depart!ent Che!ica "ngineering Depart!ent Che!ica "ngineering Depart!ent Che!ica "ngineering Depart!ent- -- -Dr.Farah # Dr.Farah # Dr.Farah # Dr.Farah #- -- -Sudani Sudani Sudani Sudani

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
= nmber of moles of

!f r
j
"aries wit# position in t#e system$

%#en general mole balance&

From t#is general mole balance e'ation
t#e "arios types of in(strial 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 ;
****))+),

= 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)
. = .olme (e)g) m
/
)
= rate of generation(formation) of species j (mole-time
= nmber of moles of species j insi(e t#e system .olme . (
"aries wit# position in t#e system$

%#en general mole balance&0
4.2
From t#is general mole balance e'ation we can (e"elop t#e (esign e'ations
t#e "arios types of in(strial reactors& batc#$ semi0batc#) an( continos
=
(
(
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
).
(mole-time)"ol)
insi(e t#e system .olme . (mole)
4.2
(esign e'ations for
batc#) an( continos0flow
(
(
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 mixtre
o Constant rate of reaction throughout
o Composition f
o Composition =f (time)
o Temperature f
o Temperature f

Mole alance

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
mixtre is perfectly mi!ed so"
f reaction throughout t#e reactor #olume
f ($osition)
(time)
f ($osition)
f (time)
)))))))))))))))))))))))))))))))+)/
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 Technoogy University of Technoogy University of Technoogy University of Technoogy- -- -Che!ica "ngineering Depart!ent Che!ica "ngineering Depart!ent Che!ica "ngineering Depart!ent Che!ica "ngineering Depart!ent- -- -Dr.Farah # Dr.Farah # Dr.Farah # Dr.Farah #- -- -Sudani Sudani Sudani Sudani

*********))+)+
1et2s consi(er t#e isomeri3ation of species % in a batc# reactor

%s the reaction proceeds. the nmber of moles of % decreases and the num&er of
moles of increases' as s#own in (igure &elow

%#e time t necessary to re(ce t#e initial nmber of moles N
%o
to a final nmber
of mole N
%
can &e estimated as "
from e'ation +)+

******+)+

integrating wit# limits t#at at &
t = 0 N
%
= N
%)

stat of reaction an( at
t = t N
%
= N
%
reaction time (en( of reaction ) we obtain

****))+)4

(
(
(
(
(
=
=
(
(
(
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


nmber of mole N
%
remain n0reacte( after time t $

5b in e'ation +)4 an( +)+

***)+)6 *+)7

*ifferential form Integral form
atch +eactor *esign ,-uation .sed in the Interpretation of
m /a& +ate *ata

0pace time or Mean +esidence Time1 is the time necessary to process one reactor
mmmmmmmmmmmmmmmmmmm #olume of fluid &ased on entrance conditions.

t
8
=t9t
:

[ ] [ ] [ ] [ ] 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


%t constant #olume &atch reactor
i.e constant density reaction mi!ture.
N
%o
1 C
%o
2 3 t#en; e'ations +)+ an( +)4 become ( ) &

*)***)+);*)(Reaction %ime)

,#aluation of +eaction Time 4raphically"

(rom e-uation 5.6 plot #s. 7 and e#aluate the area under the cur#e
to estimate reaction time

71 7 7

Or
(rom e-uation 5.6 plot #s. C
%
and e#aluate the area under the cur#e
to estimate reaction time

C% C% C%
o

,!ample

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 =


,#aluation of +eaction Time Numerically"

Need to si8e reactors or calculate reaction time

o For t#e reactions in w#ic# t#e rate (epen(s only on t#e concentration of
one species t#en

(irst order and Irre#ersi&le &0

$

0econd order and Irre#ersi&le &0

'

'

nth order and Irre#ersi&le "9

'

,!ample
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
=


imolecular +eactions

o w#en t#e rate law (epen(s on more t#an one species $ we mst relate t#e
concentrations of t#e (ifferent species to eac<# ot#er :as a function of
con#ersion :) %#is relations#ip is most easily establis#e( wit#
t#e ai( of a 5toic#iometric table)
!n formlating or stoic#iornetsic table$ we s#all ta=e species % component as
or basis of calclation (i)e)) limiting reactant) an( t#en (i"i(e t#rog# by t#e
stoic#iometric coefficient of > $ in or(er to pt e"eryt#ing on a basis of ?pet mole
of % :)

0toichiornetsic ta&le presents the following information
o Column I" the particular species
o Column ;" the num&er of moles of each species initially present
o Column <" the change in the num&er of moles &rought a&out &y reaction
o Column 5" the num&er of moles remaining in the system at time t
o Column =" concentrations as a function of con#ersion of each species

@onsi(er t#e general reaction;

5toic#iometry set p of e'ations wit# > 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 3olume (Constant *ensity)

li'i(0p#ase an( some of gas p#ase reaction system fall into t#is category)
Stoichiometric Table Batch System
0pecie Initial Change +emaining Concentration
A N
Ao

-N
Ao

N
A
! N
Ao
"# $ %

=
A
C ( ) X C
A
1
0

B N
Bo
! N
Ao

B

-"b&a%N
Ao

N
B
! N
Ao
'
B
$"b&a%(

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

C N
Co
! N
Ao

C

)"c&a%N
Ao

N
C
! N
Ao
'
C
)"c&a%(

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

D N
Do
! N
Ao

D

)"*&a%N
Ao

N
D
! N
Ao
'
D
)"*&a%(

=
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

+here

i
! N
io
&N
Ao
= C
io
&C
Ao
= y
io
&y
Ao

! "*&a% ) "c&a% $ "b&a% - #

,!press ta&le in terms of concentrations
Concentration (&atch)"

Mole balance e'ation an( t#e rate law are cople( an( t#en sol"e(
,!ample
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


3aria&le 3olume (3aria&le *ensity' &ut with Constant T and $ )

Indi#idual concentration can &e determined &y e!pressing the #olume for
&atch system as a function of con#ersion using the e-uation of state"

A.=BN%R%***))at any time in t#e reaction
Ao.o=BoN%oR%o**at any time =0;w#en reaction is initiate(
%#en$
|
|
\
|
|
\
|
|
|
\
|
|
|
\
|
=
0
0
0 0
0
Z
Z
P
P
T
T
N
N
V V
T
T
>>>>>>>.5.?
Change in t#e total num&er of moles (ring reaction in gas p#ase reaction system$
bt wit# constant temperatre an( pressre$ an( t#e compressibility factor will not
c#ange significantly (ring t#e corse of t#e reaction $

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

C#ere N
T
! N
To
) N
Ao

! "*&a% ) "c&a% $ "b&a% $ #
! (change in total num&er of mole)

@ (mole of % 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
**********+),0a)
%#en

X
N
N
T
T
+ =1
0

X N
N N
T
To T
0
=
*******)*****)+),0b


>t complete con"ersion i)e D=, $ N

%
= N
%f
; t#erefore $

0 T
To Tf
N
N N
=
*************)+),,
! (change in total num&er of mole for complete con#ersion )

@ (total moles fed)
%#en t#e "olme as a fnction of con"ersion &
( ) X V V + = 1
0
**************)+),<

Concentration at #aria&le #olume or density
0pecie
|
\
|
=
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
+
=

,!ample


@#emical reactors can liberate or absorb "ery large amonts of energy $ an( t#e #an(ling of
t#is energy is a major concern in reaction engineering) !t is important to estimate t#e
temperatre increase or (ecrease in an a(iabatic reactor in w#ic# no #eat is a(( or
remo"e($ an( exot#ermic reactor an( also t#e composition of t#e reaction mixtre at any
time)
,nergy alance

A 1

( ) ) ( V r T H
A r

) ( T T UA Q
a
=
&

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

% = reaction temperatre E
%a= wall temperatre E
%R= reference temperatre E
> = #eat transfer area m
<

@pi = specific #eat EF-Emol
G = o"erall #eat transfer EF-s)m
<
)E
r
H =ent#alpy c#ange in t#e reaction per mole of >reacting
%#e nmber of moles of species i at any X is =
( ) X N N
i i A i
+ =
0

%#en energy balance is &

( )

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

*******)+),/
Energy an( mole balance e'ations wit# t#e rate law are cople( an( t#en sol"e(

Non-Isothermal Operation
,eat Generate* by
Reaction
,eat A**ition an*
Remo-al by .all
,eat Acc/m/late* by
Reaction
( ) ( )
dt
dT
CpX C N T T UA V r T H
i p i A a A r
+ = +
, 0
) ( ) (


Mole &alance e-uation

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

The rate law is re-uired as a function of temperature and composition

3aria&le 3olume (3aria&le *ensity 'T and@or $)
?.ariable % in non0isot#ermal?
%#e "olme for batc# system as a fnction of con"ersion as &0
|
|
\
|
|
\
|
|
|
\
|
|
|
\
|
=
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

!f t#e compressibility factor will not c#ange significantly (ring t#e corse of t#e
reaction B
o
=B

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

Concentration at #aria&le #olume (density ' T and@or $ )
0pecie
|
\
|
=
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 (

,!ample
V r
dt
dX
N
A Ao
=


> batc# reactor is sally well mixe($ so t#at may neglect t#e special "ariation in
temperatre an( species concentration )
8atc# reactors operate( a(iabatically are often se( to (etermine t#e reaction
or(ers$ acti"ation energies$ an( specific reaction rates of exot#ermic reactions by
monitoring t#e temperatre0time trajectories for (ifferent initial con(itions)
In adia&atic operation of a &atch reactor

0 = Q
&

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

**********)+),+
Energy an( mole balance e'ations wit# t#e rate law are cople( an( t#en
sol"e("

;C#ere %
o
= initial temperatre

,!ample

%dia&atic Operation of a atch +eactor

( ) ( )
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 #ig#est con"ersion t#at can be achie#ed in re"ersible reactions is t#e
e-uili&rium con"ersion X
EB
) For en(ot#ermic reactions$ t#e e-uili&rium
con#ersion increases with increasing temperature up to a ma!imum of ,)0)
For exot#ermic reactions$ t#e e-uili&rium con"ersion (ecreases wit# increasing
temperature
Figre ( ) s#ow t#e "ariation of t#e concentration e'ilibrim constant as a
fnction of temperatre for an exot#ermic reaction t#e correspon(ing e'ilibrim
con"ersion X
EB
as a fnction of temperatre)

Figre ( ) s#ow t#e "ariation of t#e concentration e'ilibrim constant an(
e'ilibrim con"ersion as a fnction of temperatre for an exot#ermic reaction)

%o (etermine t#e maximm con"ersion t#at can be ac#ie"e( in an exot#ermic
reaction carrie( ot a(iabatically$ we fin( t#e intersection of t#e e'ilibrim
con"ersion as a fnction of temperatre $wit# temperatre Hcon"ersion
relations#ips from t#e energy balance

*****))+),4

Grap#ical soltion of e'ilibrirn
an( energy balance e'ations to
obtain t#e a(iabatic temperatre
an( t#e a(iabatic e'ilibrirn
con"ersion X
EB
.
,!ample
,-uili&rium Con#ersion

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

=

) (
,

Reactor Lecture 1

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Dr.

Farah Talib Al-Sudani

) is defined as the change in

Constant 3olume (Constant *ensity)

3aria&le 3olume (3aria&le *ensity' &ut with Constant T and $ )

>t complete con"ersion i)e D=, $ N

Mole &alance e-uation

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