Ch E 441: Chemical Kinetics

and Reaction Engineering

Mole Balances in Reacting Systems &
Reactor Design Equations
David A. Rockstraw, Ph.D., P.E.
New Mexico State University
Chemical Engineering
Objectives
Describe photos of real reactors.
Define the rate of chemical reaction.
Apply a general mole balance to
a batch reactor,
a continuous stirred tank reactor (CSTR),
a plug flow reactor (PFR), and
a packed bed reactor (PBR).
Industrial Reactors
Industrial Reactors
Industrial Reactors
Spherical Reactors
Industrial Reactors
Industrial Reactors
Industrial Reactors
Industrial Reactors
Industrial Reactors
Industrial Reactors
Industrial Reactors
Packed Bed Reactor
Packed Bed Reactor in use for a
Fisher-Tropsch synthesis reaction at
Sasol Limited Chemical.
Moving Bed Reactor
This photo is of a catalytic
cracker moving bed reactor. Only
the disengager section of the
reactor is visible in the picture -
the reaction section is hidden
behind the stair structure
beneath the disengager.

The cracker is used for the
catalytic cracking of gas oil into
light aromatics and straight chain
hydrocarbons, which are then
separated in the distillation tower
to the right of the photo.
The white unit to the left of the cat cracker is the catalyst regenerator,where coke
deposits are burned off the catalyst. This is a highly exothermic operation,
(1400F), and so the boiler unit at the far left recovers the sensible heat of the
regenerator exhaust to produce steam.
boiler
disengager
still regenerator
Straight Through
Transport Reactor
Straight Through Transport Reactor (STTR) in
use for a Fisher-Tropsch synthesis reaction at
Sasol Limited Chemical.
Industrial Reactors
Automotive Catalytic Converter
Industrial Reactors
Glass Lined Reactors
General Reactor Construction
Fluidized-Bed
Reactor
Trickle-Bed
Reactor
Wetlands

Chemical Vapor Deposition Reactor
reacting gas flows through annulus between outer edges of
cylindrical wafers and the tube wall
Laboratory CSTR/Batch Reactor
Laboratory CSTR
RC1e Reaction Calorimeter
React IR 1000 (FTIR)
Which of the following is probably
NOT a chemical reactor?
A. a pan of boiling water containing pasta
B. a jar of medication in the bathroom cabinet
C. a public swimming pool
D. a cup of coffee with cream and sugar
E. a cows stomach and contents
Chemical Identity
A chemical species has reacted when it
has lost its chemical identity. The
identity of a chemical species is
determined by the kind, number, and
configuration of that species' atoms.
Loss of Chemical Identity
Decomposition; AB A + B
Combination; A + B AB
Isomerization; A B
single displacement (substitution);
A + BC AC + B
double displacement (metathesis);
AB + CD AD + CB
Reaction Rate
The reaction rate is the rate at which a species
looses its chemical identity per unit volume.
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.
Reaction rates are associated with reaction
stoichiometry, which describe molar
relationships
Reaction Rate
Consider species A:
r
A
= rate of formation of A per unit vol
-r
A
= rate of a disappearance of A per unit vol
For a catalytic reaction, -r
A
' is the rate of
disappearance of species A on a per mass of
catalyst basis.
NOTE: dC
A
/dt is not the rate of reaction
Reaction Rate
Consider in general terms, species j
The rate, r
j
is
the rate of formation of species j per unit volume
a function of concentration, temperature, pressure,
and the type of catalyst (if any)
independent of the type of reaction system (batch,
plug flow, etc.)
an algebraic equation, not a differential equation
Which reaction type characterizes the
combusion of ethane?
2 C
2
H
6
+ 7 O
2
4 CO
2
+ 6 H
2
O

A. combination
B. isomerization
C. decomposition
D. single displacement
E. double displacement
Which statement is always false?
A.

B.

C.

D.

E.
- r
A
= f temperature
( )
- r
A
= f reactant concentration
( )
- r
A
= f pressure
( )
- r
A
= f reactor type
( )
- r
A
= f catalyst
( )
What are the units of reaction rate?
A. mass / length / time

B. moles / volume / time

C. moles / catalyst mass / time

D. both A and B

E. both B and C
General Mole Balance Equation
G
j

F
jo
F
j
(

=
(

+
(

system within j of
on accumulati of rate
system of out j of
flow of rate

rxn by system in j of
generation of rate
system into j of
flow of rate
dt
dN
F G F
j
j j j o
= +
where N is the moles of j
in the system at time t.
General Mole Balance Equation
G
j

F
jo
F
j
(

=
(

+
(

system within j of
on accumulati of rate
system of out j of
flow of rate

rxn by system in j of
generation of rate
system into j of
flow of rate
dt
dN
F G F
j
j j j o
= +
V r G
j j
=
if all variables are spatially uniform
General Mole Balance Equation
If r
j
varies with position in the system,
r
j,1

AV
1
r
j,2
AV
2

= =
A = A =
A = A
m
1 i
i i , j
m
1 i
i , j j
1 1 , j 1 , j
V r G G
V r G
0 V , m Let A
}
=
V
j j
dV r G
General Mole Balance Equation
dt
dN
F G F
j
j j j o
= +
}
=
V
j j
dV r G
dt
dN
F dV r F
j
j
V
j j o
= +
}
G
j

F
jo
F
j
GMBE Applied to Batch Reactors
For a batch reactor (no flows):


GMBE reduces to:
0 F F
j o , j
= =
dt
dN
F dV r F
j
j
V
j j o
= +
}
dt
dN
dV r
j
V
j
=
}
0 0
GMBE Applied to Batch Reactors
Assuming perfect mixing:
dt
dN
dV r
j
V
j
=
}
dt
dN
dV r
j
V
j
=
}
V r
dt
dN
j
j
=
Batch Reactor
Design Equation
GMBE Applied to Batch Reactors
For the simple reaction A products:



In a constant volume reactor,
dt
dN
V
1
r
A
A
=
( )
dt
dC
dt
V N d
dt
dN
V
1
r
A A A
A
= = =
GMBE Applied to Batch Reactors
For the simple reaction A products:


In a constant pressure reactor,
( )
|
.
|

\
|
+ = + =
= =
dt
V ln d
C
dt
dC
dt
dV
V
C
dt
dC
dt
V C d
V
1
dt
dN
V
1
r
A
A A A
A A
A
dt
dN
V
1
r
A
A
=
Which is NOT a characteristic
of an ideal batch reactor ?
A. Absence of concentration gradients
(i.e., perfect mixing)
B. Steady state operation
C. No material crosses system boundary
(i.e., no flows)
D. Derivative with respect to time

GMBE Applied to Flow Reactors
Continuous Stirred-Tank Reactor (CSTR):
reactants
products
dt
dN
F dV r F
j
j
V
j j o
= +
}
0
steady
state
0 F V r F
j j jo
= +
perfect
mixing
j
j j o
r
F F
V

=
v =
j j
C F
volumetric
flow rate
GMBE Applied to Flow Reactors
Continuous Stirred-Tank Reactor (CSTR):
CSTR
Design
Equation
reactants
products
j
j j o
r
F F
V

=
dt
dN
F dV r F
j
j
V
j j o
= +
}
0
steady
state
0 F V r F
j j jo
= +
perfect
mixing
Which is NOT a characteristic
of an ideal CSTR?
A. Absence of concentration gradients
(i.e., perfect mixing)
B. Steady state operation
C. Material crosses system boundary
(i.e., flows in and out)
D. Derivative with respect to time

GMBE Applied to Flow Reactors
Tubular (Plug Flow) Reactor (PFR):
reactants products
Ay
y+Ay y
AV F
j
(y) F
j
(y+Ay)
GMBE Applied to Flow Reactors
Tubular (Plug Flow) Reactor (PFR):
dt
dN
F dV r F
j
j
V
j j o
= +
}
A
0
steady
state
0 F V r F
j j j o
= A +
spatially
uniform AV
AV F
j
(y) F
j
(y+Ay)
GMBE Applied to Flow Reactors
Tubular (Plug Flow) Reactor (PFR):
( ) ( ) ( ) 0 y A r y y F y F
j j j
= A + A +
uniform
cross-section
dt
dN
F dV r F
j
j
V
j j o
= +
}
A
0
steady
state
0 F V r F
j j j o
= A +
spatially
uniform AV
GMBE Applied to Flow Reactors
Tubular (Plug Flow) Reactor (PFR):
j
j
r
dV
F d
=
PFR
Design
Equation
dy
dV
r A r
dy
F d
j j
j
= =
( ) ( )
A r
y
y F - y y F
j
j j
=
(

A
A +

( ) ( )
dx
df
x
x f - x x f
lim
0 x
=
(

A
A +
A
Which IS a characteristic
of an ideal Plug Flow Reactor?
A. Absence of concentration gradients
(i.e., perfect mixing)
B. Steady state operation
C. Material crosses system boundary
(i.e., flows in and out)
D. Derivative with respect to time

GMBE Applied to Packed Bed Reactors
PBR used for fluid/solid catalytic reaction:
F
Ao
F
A

AW
W+AW W
AW F
A
(W) F
A
(W+AW)
GMBE Applied to Packed Bed Reactors
PBR used for fluid/solid catalytic reaction:
( ) ( ) 0 W r W W F W F
'
A A
A
= A + A +
( )
( )( )
( ) catalyst mass
catalyst mass time
A moles
W r
'
A

(

= A
dimensions of
generation term
AW F
A
(W) F
A
(W+AW)
GMBE Applied to Packed Bed Reactors
PBR used for fluid/solid catalytic reaction:
'
A
A
r
dW
F d
=
PBR
Design
Equation
( ) ( )
'
A A
A
r
W
W F - W W F
=
(

A
A +
( ) ( )
dx
df
x
x f - x x f
lim
0 x
=
(

A
A +
A
When pressure drop and catalyst decay can
be neglected, integral form can be used:
}
=
A
Ao
A
F
F
'
A
r
F d
W
Which IS a characteristic
of an ideal Packed Bed Reactor?
A. Absence of concentration gradients
(i.e., perfect mixing)
B. Steady state operation
C. No material crosses system boundary
(i.e., no flows)
D. Derivative with respect to position

Design Equation Summary
Batch
V r
dt
dN
A
A
=
CSTR
PFR
PBR
'
A
A
r
dW
F d
=
}
=
A
Ao
A
F
F
'
A
r
F d
W
j
j
r
dV
F d
=
j
j j o
r
F F
V

=
}
=
A
Ao
F
F
A
A
r
F d
V
}
=
A
Ao
N
N
A
A
V r
N d
t
Next Session
Define conversion and space time.
Write the mole balances in terms of conversion
for a batch reactor, CSTR, PFR, and PBR.
Size reactors either alone or in series once given
the molar flow rate of A, and the rate of reaction,
-r
A
, as a function of conversion, X.