1

Chemical Reaction Engineering g g

By Asst.Prof.Dr.Sirirat Wacharawichanant
Introduction, Mole Balances
By Asst.Prof.Dr.Sirirat Wacharawichanant
Objectives
Define the rate of chemical reaction.
Apply the mole balance equations to a batch
reactor, CSTR, PFR, and PBR.
Text books
Elements of Reaction Engineering, 4
th
Edition,
H.Scott Fogler, Prentice Hall.
Chemical Reaction Engineering, 2
nd
or 3
rd
Edition, Octave Levenspiel, John Wiley and
Sons.
Rate of Reaction
A number of moles of one chemical species are
being consumed to form another chemical
i
Chemical species refers to any chemical
component or element with a given identity.
species.
The identity of a chemical species is determined
by the kind number and configuration of that by the kind, number, and configuration of that
species' atoms.
2
Rate of Reaction (cont.)
Chemical reaction -> a detectable number of
molecules of one or more species reacted have lost
th i h i l id tit their chemical identity.
Assumed a new form by a change in the kind or
number of atoms in the compound and/or by a
change in structure or configuration of these atoms
A d th t th t t l i ith t d Assumed that the total mass is neither created nor
destroyed when a chemical reaction occurs.
Rate of Reaction (cont.)
The mass referred to is the total collective mass of
all the different species in the system.
The rate of disappearance of a species is the
number of A molecules that lose their chemical
identity per unit time per unit volume through the
breaking and subsequent re-forming of chemical
bonds during the course of the reaction.
The rate of a reaction can be expressed as the
rate of disappearance of a reactant or as the
rate of appearance of a product.
Rate of Reaction (cont.)
Consider reaction (species A)
A + 2B C + D
The numerical value of the rate of disappearance
of reactant A, -r
A
is a positive number
(-r
A
= 4 mol A/dm
3
s, r
A
= -4 mol A/dm
3
s
-r
B
= 8 mol A/dm
3
s, r
C
= 4 mol A/dm
3
s)
Whats -r
A
?
The rate of reaction, -r
A
is the number of moles of A
reacting (disappearing) per unit time per unit volume
(mol/dm
3
s)
Rate of Reaction (cont.)
Consider species j
r
j
is the rate of formation of species j per unit
j
s e a e o o a o o spec es j pe u
volume [e.g. mol/dm
3
s]
r
j
is a function of concentration, temperature,
pressure, and the type of catalyst
r
j
is independent of the type of reaction system
(batch, plug flow, etc.)
r is an algebraic equation not a differential r
j
is an algebraic equation, not a differential
equation (-r
A
= kC
A
)
is not the rate of reaction
dt
dC
A
3
Example of Rate of Reaction
Consider reaction
A B
If B is being created 0.2 mole/dm
3
s
r
B
= 0.2 mol /dm3/s
Then A is disappearing at the same rate:
-r
A
= 0 2 mol /dm
3
s r
A
0.2 mol /dm s
The rate of formation of A (Generation of A) :
r
A
= 0.2 mol /dm
3
s
General Mole Balance Equation
Mole balance on species j in a system volume (V),
where species j represents the particular chemical
species of interest (such as NaOH, water)
G
j
F
j
F
j
V
General Mole Balance Equation (cont.)
Equation of mole balance on species j at any time (t)
Rate of flow
of j into
system
(moles/time)
-
Rate of flow
of j out of
system
(moles/time)
Rate of
generation of j
by chemical
reaction within
system
(moles/time)
+
Rate of
accumulation of
j within system
(moles/time)
=
In Out + Generation = Accumulation In Out + Generation = Accumulation
(1-1)
Where N
j
= the number of moles of species j in system at t.
dt
dN
G F F
j
j j j
= +
0
General Mole Balance Equation (cont.)
The rate of generation of species j, G
j
is the
product of the reaction volume (V) and the rate of
formation of species j, r
jj
G
j
= r
j
V
volume
volume time
moles
time
moles

=
4
General Mole Balance Equation (cont.)
The rate of formation of species j for the reaction
various position in system volume
VV
AV
1
AV
2
r
j1
r
j2
The rate of generation, AG
j1
in terms of r
j1
and
subvolume AV
1
is
AG
j1
=r
j1
AV
1
General Mole Balance Equation (cont.)
The total rate of generation is the sum of all the
rates of generation in each of the subvolumes

= =
A = A =
M
i
i ji
M
i
ji j
V r G G
1 1
By taking limits (M and AV0) and use of
definition of integral, the equation can rewrite in g , q
}
=
V
j j
dV r G
General Mole Balance Equation (cont.)
Replace G
j
in the mole balance equation
dN
G F F
j
(1 3)
}
= +
V
j
j j j
dt
dN
dV r F F
0
dt
G F F
j
j j j
= +
0
(1-3)
(1-4)
This is the general mole balance equation, we can
develop the design equations for the various types
of reactors: batch, semibatch and continuous-flow.
Types of Ideal Reactors
Perfectly mixed batch reactor (Batch)
Continuous stirred tank reactor (CSTR) or
Backmix reactor
Plug flow reactor (PFR)
Packed bed reactor (PBR)
5
Mole Balance for Batch Reactor
A batch reactor has neither inflow nor outflow of
reactants or products while the reaction is being
carried out: F
j0
= F
j
= 0. The resulting general
mole balance on species j is
dt
dN
G F F
j
j j j
= +
0
}
= =
V
j
j j
dt
dN
dV r G
Mole Balance for Batch Reactor (cont.)
The reaction mixture is perfectly mixed so that
there is no variation in the rate of reaction
throughout the reactor volume, we can take r
j
out
of the integral, integrate, and write the mole
balance in the form.
V r
dt
dN
j
j
=
(1-5)
dt
Consider the reaction of species A in batch reactor
A B
Mole Balance for Batch Reactor (cont.)
As the reaction proceeds, the number of moles of
A (N
A
) decreases and the number of moles of B
(N
B
) increases as shown in Figure
N
A0
N
A
N
A1
N
B1
N
B
0
t
t
1
0
t
t
1
Mole-time trajectories
Mole Balance for Batch Reactor (continue)
Consider time t
1
to reduce N
A0
to N
A1
. Applying the
mole balance equation
dN
V r
dN
dt
A
A
= V r
dt
dN
A
A
=
1 A
N
dN
Integrating with limits that t = 0, then N
A
= N
A0
and
t = t
1
, then N
A
= N
A1
}
=
1
0
1
A
A
N
N A
A
V r
dN
t
This equation is the integral form of the mole
balance on a batch reactor.
(1-6)
6
Usage of Batch Reactor
Testing new processes
Small scale operation
Production of expensive products
Testing new processes
Processes that are difficult to convert to
ti ti continuous operations
Used for liquid phase reactions that require a fairly
long reaction time.
Advantage of Batch Reactor
High conversions can be obtained by leaving
reactants in the reactor for long periods of time.
Low capital cost.
Versatile, can be used to make many
products consecutively.
Good for producing small amounts of Good for producing small amounts of
products while still in testing phase.
Easy to clean
Disadvantage of Batch Reactor
High labour cost.
Difficult for large-scale production.
Long downtime for cleaning leads to
periods of no production.
Ideal CSTR
Normally operated at steady state, therefore
reaction rate is the same at every point, and time
independent.
Assumed to be perfectly mixed.
depe de t
No time dependence or position dependence of
temperature, concentration, or reaction rate inside
CSTR (no spatial variations).
F
CSTR (no spatial variations).
F
j0
V
7
Mole Balance for CSTR
CSTR operated at steady state or conditions do
not change with time.
dN
V
}
=
V
Vr dV r
0
0
= = +
}
dt
dN
dV r F F
j
V
j j j
No spatial variation in the rate of reaction
}
=
j j
Vr dV r
The design equation for CSTR
j
j j
r
F F
V

=
0
(1-7)
Mole Balance for CSTR (cont.)
The CSTR design equation gives the reactor
volume V necessary to reduce the entering flow
rate of species j, from F
jo
to the exit flow rate F
j
,
j j
when species j is disappearing at a rate of r
j
.
C F
The molar flow rate F
j
is the product of the
concentration of species j and the volumetric flow
rate v
v C F
j j
=
time
volume
volume
moles
time
moles
=
(1-8)
Mole Balance for CSTR (cont.)
Rewrite the design equation for CSTR on species
j as
j
j j
j
j j
r
vC C v
r
F F
V

=
0 0 0
F
j0
(1-9)
F
j
V
Usage of CSTR
Usually employed for liquid phase
reactions.
Use for two-phase reactions in
which a gas is bubbled
continuously through the liquid.
Use when intense agitation is
required.
8
Advantage & Disadvantage of CSTR
Relatively easy to maintain good temperature
control with a CSTR because it is well mixed.
Advantage
Cheap to construct.
Interior of reactor is easily accessed.
Disadvantage
Conversion of reactant per volume of reactor is the
smallest of the flow reactors - very large reactors
are necessary to obtain high conversions
sad a tage
Ideal PFR
Normally operated at steady state
The reactants are continuously consumed as
they flow down the length of the reactor.
The concentration various continuously in the
axial direction through the reactor.
No radial variation in reaction rate and the reactor
is referred to as a plug-flow reactor (PFR)
Mole Balance for PFR
From the general mole balance equation
dN
dV r F F
j
V
= +
}
dt
dV r F F
j j j
= +
}
0
The design equation of PFR at steady state can
be developed 2 ways: (1) directly form the general
equation or (2) form a mole balance on species j
in a differential segment of reactor volume AV.
Mole Balance for PFR (cont.)
The differential volume, AV, shown in Figure
F
j0
F
j
F
j
F
j
V V+AV
AV
No spatial variations in reaction rate within this
volume. Thus the generation term, AG
j
is
V r dV r G
j
V
j j
A = = A
}
9
Mole Balance for PFR (continue)
Molar flow
rate of j
In at V
-
Molar flow
rate of j
Out at V+ AV
Molar rate of
Generation of j
within AV
+
Molar rate of
Accumulation of
j within AV
=
In Out + Generation = Accumulation
F
j
|
V
F
j
|
V+AV
+ r
j
AV = 0
Dividing by AV and rearranging
(1-10)
Dividing by AV and rearranging
j
V j V V j
r
V
F F
=
(

A

A +
Mole Balance for PFR (cont.)
The term in brackets resembles the definition
of the derivative
Taking the limit as AV approaches zero, we
obtain the differential form of steady state mole
( ) ( )
dx
df
x
x f x x f
x
=
(

A
A +
A 0
lim
obtain the differential form of steady state mole
balance on a PFR.
j
j
r
dV
dF
=
(1-11)
Mole Balance for PFR (cont.)
Consider the reaction of species A in PFR
A B
F
A0
F
A
F
A1
F
B1
F
B
0
V
V
1
0
V
V
1
Profiles of molar flow rates in a PFR.
Mole Balance for PFR (cont.)
What is the reactor volume (V) to reduce F
A0
to
F
A1
. Applying the mole balance equation
d
A
A
r
dF
dV =
F F
Integrating with limits that V = 0, then F
A
= F
A0
and
V = V
1
, then F
A
= F
A1
} }

= =
0
1 0
1
A
A
A
A
F
F A
A
F
F A
A
r
dF
r
dF
V
This equation is the integral form of the mole
balance on a PFR
(1-13)
10
Usage of PFR
A wide variety of applications in either gas or
liquid phase systems.
Use for produces the highest conversion per
reactor volume of any of the flow reactors.
Common industrial uses of tubular reactors are in
gasoline production, oil cracking, synthesis of
ammonia from its elements ammonia from its elements.
Used as bioreactor.
Advantage of PFR
Hi h i t t l
Relatively easy to maintain since there are no
moving parts.
High conversion rate per reactor volume.
Mechanically simple.
Unvarying product quality. y g p q y
Good for large capacity processes.
Disadvantage of PFR
Reactor temperature difficult to control.
Hot spots may occur within reactor when used
for exothermic reactions.
Difficult to control due to temperature and
composition variations composition variations.
Packed-Bed Reactor (PBR)
The reaction takes place on the surface of the
catalyst.
The reaction is based on mass of solid catalyst
(W) rather than on reactor volume.
The rate of reaction of a substance A is defined as
-r
A
= mol A reacted / sg catalyst r
A
mol A reacted / s g catalyst
11
Mole Balance for PBR
The derivation of the design equation for PBR will
be carried out in a manner analogous to the
development of PFR, replace the volume
coordinate in equation with the catalyst weight (W)
F
A0
F
A
F
A
F
A
W W+AW
In Out + Generation = Accumulation
F
A
|
W
F
A
|
W+AW
+ r
A
'AW = 0
No radial gradients in concentration, temperature,
or reaction rate. The general mole balance as
(1-14)
Mole Balance for PBR (continue)
Differential with respect to W and rearrange
' A
r
dF
= (1 15)
A
r
dW
=
0 A A
F F
dF dF
Integral form of PBR design equation
(1-15)
} }

= =
0
1 0
' '
A
A A
A
A A
F
F
A
F
F
A
r
dF
r
dF
W (1-16)
Summary of Reactor Mole Balances
Reactor Comment Mole Balance
Differential
Form
Algebraic
Form
Integral form
Batch No spatial dN
}
0 A
N
dN
Batch No spatial
variations
CSTR No spatial
variations,
steady state
- -
PFR Steady state
V r
dt
dN
A
A
=
A
A A
r
F F
V

=
0
A
A
r
dV
dF
=
}

=
1
1
A
N A
A
V r
dN
t
}
=
0
1
A
F
A
dF
V
PBR Steady state
A
dV
'
A
r
dV
dF
A
=
}

1
1
A
F A
r
V
}

=
0
1
' 1
A
A A
F
F
A
r
dF
W
Industrial Reactor
12
Equipment of Batch Reactor
The movie to the left shows the basic
operation of a batch reactor.
The reactants are placed into the p
reactor and then allowed to react, and
products form inside the reactor.
The products and unreacted
reactants are then removed and the
process is repeated.
Equipment design
(Fogler, 2006 )
Equipment of CSTR
The movie to the left shows the
operation of a CSTR.
Reactants are fed continuously into y
the reactor through ports at the top.
The contents of the tank are well
mixed by unit's stirring device.
Products are removal continuously.
Equipment design
(Fogler, 2006 )
Equipment of PFR
The movie to the left shows the
operation of a plug flow reactor.
Plugs of reactants are g
continuously fed into the reactor
from the left.
As the plug flows down the
reactor the reaction takes place,
resulting in an axial
concentration gradient
Equipment design
(Fogler, 2006 )
concentration gradient.
The products and unreacted
reactants flow out of the reactor
continuously.
Equipment of PBR
The animation on the left shows the
operation of a packed bed reactor.
The reactants (green) enter the reactor (g )
on the top, then flow through.
Upon entering the reactor the reactants
flow through the packed bed of catalyst.
By contacting with the catalyst pellets,
the reactants react to form products
Equipment design
(Fogler, 2006 )
the reactants react to form products
(blue), which the exit the reactor on the
bottom.