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Reactor Lecture 1 PDF
Reactor Lecture 1 PDF
Third Year
1
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).
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) 2
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.
[Introduction to Chemical Reaction Engineering ] | [Chapter-One]…..University of Technology-Chemical Engineering Department-Dr.Farah Al-Sudani
2.Type of Reactors.
reactions. The design of a chemical reactor deals with multiple aspects of chemical
U U
engineering. Chemical engineers design reactors to maximize net present value for the
U
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.
A tank
A pipe or tubular reactor (laminar flow reactor(LFR))
U U
Both types can be used as continuous reactors or batch reactors. Most commonly,
reactors are run at steady-state, but can also be operated in a transient state. When a
U U U U
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 (reagents, catalyst, or U U U U
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:
Batch Reactor
U U
Residence time (τ) , Volume (V) , Temperature (T) , Pressure (P) , Concentrations
of chemical species (C1, C2, C3, ... Cn) ,Heat transfer coefficients (h, U)
Chemical reactions occurring in a reactor may be exothermic, meaning giving off heat,
U U
or endothermic, meaning absorbing heat. A chemical reactor vessel may have a cooling
U U
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.
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.
•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)
Characteristics
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.
Figure (3) Flow sheet for the manufacture of nitrobenzene from benzene using
a cascade of CSTR
Figure(5) Fluidized-bed
Reactors
it classify according to
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 : 10
Heterogeneous reaction
𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐𝑐
Toluene-hydrogenation 𝐶𝐶6 𝐻𝐻5 𝐶𝐶𝐶𝐶3(𝐿𝐿) + 𝐻𝐻2(𝑔𝑔) �⎯⎯⎯⎯� 𝐶𝐶6 𝐻𝐻6(𝑔𝑔) + 𝐶𝐶𝐻𝐻4(𝑔𝑔)
Example :
Homogeneous reaction
Ammonia synthesis 2𝑁𝑁2(𝑔𝑔) + 3𝐻𝐻2(𝑔𝑔) ⇔ 2𝑁𝑁𝐻𝐻3(𝑔𝑔)
Heterogeneous reaction
Ammonium chloride synthesis or decomposition
𝑁𝑁𝐻𝐻3(𝑔𝑔) + 𝐻𝐻𝐻𝐻𝐿𝐿(𝑔𝑔) ⇔ 𝑁𝑁𝐻𝐻4 𝐶𝐶𝐶𝐶(𝑠𝑠)
11
Batch Reactor
disappear
− =− = homogeneous reaction … 2a
×
disappear
− %%%% =− = homogeneous reaction … 2b
&
'( ×
disappear
− * =− = heterogeneous reaction … 2(
+ ',, (' ' -, ×
− %% =−
.
disappear
= heterogeneous or homogeneous reaction
, '( ×
…2d
disappear
− %%% =− = heterogeneous reaction … 2e
/
0' ' -, ×
The rate of reaction per unit weight catalyst, -rA, (e,g., -rA), and thi rate of reaction per unit
volume, -rA, , are related through the bulk density ρ,(mass of solid /volume) of the catalyst
particles in the fluid media:
13
Where * is the molal rate of flow component A into the volume element.
element
-rA= f {temperature
temperature dependent term,concetration dependent term}
= mole/m3.time
2.Conceptes of Kinetics
1. Stoichiometry.
b d
1 mole of A and of B consumed , while
c
mole of C and
a a a
mole of D formed or appear
789:
Rate of reaction or disappearance of A =−
7; .=>7:
c 789:
Rate of formation of C ? @ A = ?− A ; .=>7:
a 7
d 789:
Rate of formation of D ? B A = ?− A 7; .=>7:
a
@
Also, Rate of formation of C ? @ A = C3D ? B A
3
Rate of formation of D ? B A = C D ? @ A
@
Examples (1),(2)
********************************************************************
789:
− = J K ' K L , ( L( L ' L K L L N
7; .=>7:
k A (T ) = Ae − E RT ……………………………6
E1
ln (k ) = ln ( A) − ………………………7
R T
A ≡ Pre-exponential
exponential factor (frequency factor)
E ≡ Activation
ctivation energy (J/mol)
R ≡ Gas J/mol 1.987 cal/mol ⋅K)
as constant (8.314 J/mol⋅K,
T ≡ Absolute
bsolute temperature (K)
Activation Energy
Activation energy has been equated with minimum energy that must be
possessed by reacting molecules before the reaction will occur.
Heat
Absorbed
Heat
Released
16
(2.1)Activation energy for exothermic and endothermic reaction.
Figure(2.1)Activation
ln (r2 ) ln(k 2 ) E 1 1
= = −
ln(r1 ) ln (k1 ) R T1 T2 ……………8
Example (4)
Example (5) =example 3.1 from elemental of chemical reaction
engineering , 4ed pag 95
*********************************************************************
17
− rA = [k A (T )]⋅ [ f (C A , C B ,K)]……………….5
f (C A , C B ,K)
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 :-
aA + bB → cC + dD
− rA = kC Aa C Bb
o Reaction rate constant, k will vary with the order of the reaction as
shown :-
18
First s-1
− rA = kC A
Second V.mol-1.s-1
− rA = kC A2
Third ( V.mol-1 )2.s-1
− rA = kC A3
nth order (concentration)1-n.s-1
− rA = kC An
CDCH2
2C 6 H 6 ←→
k1
C12 H 10 + H 2 − rB = k1 C B2 −
k2
Kc
where Kc equilibrium constant
rA,net = 0 = − k AC A2 + k − AC B CC
Equilibrium condition k AC A2 = k − AC B CC
k A C B CC
Equilibrium relationship = = KC
k− A C A2
2 C B CC
Rate law in term Equilibrium relationship − rA = k A C A −
KC
19
Example (6)
[Reaction Rate and Conceptes of Kinetics][Chapter
Kinetics][Chapter-
[Chapter-Two]…..University
Two]…..University of Technology-
Technology-Chemical Engineering Department-
Department-Dr.Farah Al-
Al-Sudani
– Non-Elementary Reaction
Do not follow the Stoichiometric coefficients for the overall
reaction
Homogeneous Reactions :
Gas-phase synthesis of phosgene,
CO + Cl 2
→ COCl 2 − rCO = k CO CCO CCl3 /22 n=5.5
Decomposition of nitrous oxide
2N 2O
→ 2N 2 + O2
k N 2 O C N 2O
− rN2O = n depended on CO2 concentration
1 + k ′CO2
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.
C6 H 5CH3 + H 2 cat
→ .
C2 H 6 + CH4
k PH 2 PT
− rT′ =
1 + K B PP + K T PT
mol toluene
k=
kg cat .s.kPa 2
4. Molecularly Reaction.
The term molecularity refers to number of atoms, ions, or molecules
involved in the rate-limiting step of the reaction.
(
d − ∆GRo / RT
=
)
∆H ro d ln K eq ……………..10
=
dT RT 2 dT
∆H r (T ) = ∆H ro (T298 ) + ∫ ∆C p dT
T
……..…………………..12
T298
∆H r 298 1 1 ……..13
ln K eq = ln K 298 − −
R T 298
For endothermic reactions, the equilibrium constant, Keq, increases with increasing
temperature. While for exothermic reactions, Keq and Xeq decreases with increasing
temperature.
21
22
Mole balance
lance on species j at any instance in time t ;
Volumn system V
dN j
Fjo + G j − Fj = …………..4.1
dt
Fj0 = Entering molar flow rate of species j (mol/time)
Fj = Exiting molar flow rate of species j (mol/time)
Gj = Rate(total
(total rate) of generation(formation) of species j (mol/time)=r
(mol/time) j .V
V = Volume (e.g. m3)
rj = rate of generation(formation) of species j (mole/time.vol)
(mole/time
Nj = number of moles of species j inside the system Volume V (mole)
(
∆V2 rj 6
rj 4 rj 5
rj 2 rj 3 ∆V6
∆V5 ∆G j ,1 = r j ,1∆V1
∆V4
rj1
m m
∆V3
G j = ∑ ∆G j ,i = ∑ r j ,i ∆Vi
∆V1
i =1 i =1
Let m → ∞, ∆V → 0
V
G j = ∫ rj dV
Then general mole balance:-
balance:
V
dN j
Fjo + ∫ r j dV − Fj =
dt …………4.2
From this general mole balance equation we can develop the design equations for ٢
the various types of industrial reactors:
r batch, semi-batch.
batch. and continuous-flow
continuous
reactors.
[Reactor Sizing and Design]
Design][Chapter-
[Chapter-Four]…
Four]…………………
]…………………..
………………..University
..University of Technology-
Technology-Chemical Engineering Department-
Department-Dr.Farah Al-
Al-Sudani
REACTOR SIZING AND DESIGN
PART ONE
Batch Reactor
Isothermal Operation
Mole Balance
F j ,o = F j = 0
V dN j
Fjo + ∫ rj dV − Fj =
dt
V dN j
∫ r j dV =
dt
...............................4.3 ٣
A → B
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 NAo to a final number
of mole NA can be estimated as :
from equation 4.4
dN A
rAV = ………………4.4
dt
dN A
dt =
rAV
integrating with limits that at :
t = 0 NA = NA0 ← stat of reaction and at
t = t NA = NA reaction time (end of reaction ) we obtain
N A0
dN A
t= ∫
NA
rAV
…………..4.5
moles of A moles of A
reacted or consumed = initially fed • moles of A reacted
moles of A fed
at t = 0
moles of A
reacted or consumed = [N ] • [ X ]
A0
٤
[N A ] = [N A0 ] − [N A0 ]• [X ]
N Ao − N A
X=
N Ao
dN A N A = N Ao (1 − X ) N A0
dN A
dt
= rAV t= ∫
NA
r AV
dX X (t ) dX
N Ao = −rAV ……….4.6 t = N Ao ∫ …4.7
dt 0 − rAV
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
CA dC A
t=∫ ….……….4.8….(Reaction Time)
C Ao − r
A
1 X (t ) dX
− rA t = N Ao ∫
0 − rAV
Area
X1 X X N Ao
t= * Area
V
Or 1
From equation 4.7 plot vs. CA and evaluate the area under the curve
− rA
to estimate reaction time
CA dC A
1 t=∫
C Ao − r
A
− rA
t = Area
Area
CA CA CAo
Example
٦
o For the reactions in which the rate depends only on the concentration of
one species then − rA = f (CA)
A → B , − rA = kC A
CA dC A 1 C A dC A
t=∫ =− ∫
C Ao − kC k C Ao C A
A
1 C
t = − . ln A
k C Ao
C A = C Ao e − kt
A → B , − rA = kC A2
CA dC A 1 C A dC A
t=∫
k ∫C Ao C A2
= −
C Ao − kC 2
A
1 1 1 C Ao
t = − − CA =
k C A C Ao
,
1 + C Ao kt
A → B , − rA = kC An
1
− kt =
− n +1
(
C A−n +1 − C Ao
− n +1
)
1
[
C A = C Ao 1 + (n − 1)kC ]
− n +1 1− n
Ao t
٧
Example
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 − rA = f ( X ) ". This relationship is most easily established with
the aid of a Stoichiometric table.
b c d
A + B ⇔ C + D
a a a
The rate law is :
a b CCc C Dd
− rA = k A C AC B −
K C
Where
N A N A0 (1 − X )
CA = = = C A0 (1 − X )
V V0
N B N A0 b b
CB = = Θ B − X = C A0 Θ B − X
V V0 a a
N D N A0 c c
CC = = Θ C + X = C A0 Θ C + X
V V0 a a
N N d d
C D = D = A0 Θ D + X = C A0 Θ D + X
V V0 a a
Mole balance equation and the rate law are coupled and then solved
٩
Example
N T P0 Z
V = V0 T ………………….4.9
NT 0 T0 P Z 0
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 ,
N
V = V0 T
NT 0
Where NT = NTo +δ
δNAoX
NT N
= 1+ Ao δ X
NT 0 NT 0
N Ao
y Ao =
NT 0
N Ao
ε= δ = y Aoδ …………………………4.10a.
NT 0
Then
NT
= 1 +ε X
NT 0
N T − N To
ε= ………………….…………….4.10b
NT 0 X
١٠
N Tf − N To
ε= ………………………………….4.11
NT 0
= (change in total number of mole for complete conversion ) / (total moles fed)
V = V0 (1 + ε X ) …………………………………….4.12
Specie
N N A0 (1 − X ) N A0 (1 − X ) C A0 (1 − X )
CA = A = = =
V V Vo (1 + εX ) (1 + εX )
N N D 0 ( Θ D - (d/a) X ) C D 0 ( Θ D - (d/a)X )
CD = D = N D 0 ( Θ D - (d/a)X ) =
V V = (1 + εX )
Vo (1 + εX )
N N Ao Θ I N Ao Θ I C Ao Θ I
CI = I = = =
V V Vo (1 + εX ) (1 + εX )
Example
١١
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
dT
− ∆H r (T ) ⋅ (−rAV ) Q& = UA(Ta − T ) V ∑ C p,i Ci
dt
T = reaction temperature K
Ta= wall temperature K
TR= reference temperature K
A = heat transfer area m2
Cpi = specific heat KJ/Kmol
U = overall heat transfer KJ/s.m2.K
∆H r =enthalpy change in the reaction per mole of Areacting
dT
− ∆H r (T ) ⋅ (− rAV ) + UA(Ta − T ) = ∑ C p ,i N i
dt
dT
− ∆H r (T ) ⋅ ( − rAV ) + UA(Ta − T ) = N A 0 (∑ Θ i C p ,i + ∆CpX )
dt
………………….4.13
Energy and mole balance equations with the rate law are coupled and then solved ١٢
N T P0 Z
V = V0 T
NT 0 T0 P Z 0
T P Z
V = V0 (1 + ε X ) 0
T0 P Z 0
If the compressibility factor will not change significantly during the course of the
T P
reaction Zo=Z V = V0 (1 + ε X ) 0
T0 P
Concentration at variable volume (density , T and/or P )
Specie
N N A0 (1 − X ) N A 0 (1 − X ) To P C A0 (1 − X ) To P
CA = A
V V V o (1 + εX ) T Po (1 + εX ) T Po
N N Ao Θ I N Ao Θ I To P C Ao Θ I To P
CI = I
V V V o (1 + εX ) T Po (1 + εX ) T Po
١٣
Example
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 Q& = 0
dT
− ∆H r (T ) ⋅ ( − rAV ) = ∑ (C p ,i N i )
dt
dT
− ∆H r (T ) ⋅ ( −rAV ) = N A0 (∑ Θ i C p ,i + ∆CpX )
dt
………………………….4.14
Energy and mole balance equations with the rate law are coupled and then
solved:
X =
∑Θ C i p ,i (T − To ) T = To +
− ∆H r (T )X
− ∆H r (T ) ∑ Θ i C p,i + ∆CpX
Example
١٤
X EB =
∑Θ C i p ,i (T − To ) ……………..4.15
− ∆H r (T )
conversion XEB. ١٥
Example