Chemical Reactor Modeling - Lecture 7

Vinod M. Janardhanan
Department of Chemical Engineering
Indian Institute of Technology Hyderabad, Yeddumailaram 502 205
Catalytic xed bed reactors
The easiest way to carry out heterogeneously catalysed gas phase reaction is by passing it over a xed catalyst. In
chemical industry xed bed reactors are used as a standard for heterogeneously catalyzed gas phase reactions. Different
particle shapes can be used for packing. The mean diameters of these packings vary from 2 to 10 mm. The minimum
diameter is limited by pressure drop considerations and maximum diameter by mass and heat transfer limitation. The
reactors can be operated adiabatically or non adiabatically. Since temperature can affect the reaction signicantly,
adiabatic xed bed reactors are used only when the heat of reaction is low, or when there is only one reaction pathway.
Reactions having large heat of reactions are carried out in isothermal xed bed reactors where a heat transfer medium
is circulated around the xed bed reactor to maintain the temperature at desired level. The overall transport and kinetic
processes are
diffusion of the reactants from the owing gas through the outer gas-particle boundary layer, macropores, and
micropores
chemisorption on active sites
surface reactions
desorption of the products
back-diffusion of the products into the owing gas.
Inorder to keep the construction volume of the reactor low catalyst should be available in high concentration. The
specic surface area of the catalyst must be high for reactions controlled by external mass transfer.
Pressure drop considerations
Industrial catalyst differ considerably with respect to the pressure drop loss. For same mean dimensions and void
fraction, random packings offer signicantly higher pressure loss than regular packings. External catalyst mass and
heat transfer are strongly correlated with pressure loss. This means that the benets of low pressure loss are partly
compensated by increased heat and mass transfer resistance. The pressure drop of randomly packed tubes are described
by
p =

g
2
v
2
g
, (1)
where is pressure loss coefcient and v
g
is the channel velocity. Erguns equation may also be used for the calculation
of pressure loss
p = f
1
v
g
+ f
2
v
2
g
(2)
where,
f
1
= 150
(1)
2

2
d
2
p
f
1
= 1.75
g
(1)
d
p
(3)
Thus the pressure drop depends very strongly on the pellet diameter d
p
and void fraction of the packing. The pres-
sure loss coefcient depends on the form of packing. For good operation, the ow must be evenly distributed over
the entire packing, which can be easily obtained if the pressure drop in the bed section is substantially larger than that
in the entrance or exit.
Modeling packed bed reactors
The 1D model of packed bed reactors assumes that there are no gradients in the radial direction. For adiabatic reactors
this is a good assumption. The lack of heat transfer through the wall combined with at velocity prole does not create
any mechanism for the radial gradients of temperature and concentration. The situation is different in the case of
non-adiabatic reactors. The thermal conductivity of typical packed bed is low and hence the removal of heat through
the wall will cause radial gradients in temperature. Since the reaction rates are exponential functions of temperature,
signicant variations can occur in the radial direction. If the thermal conductivity of the packing is high compared
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to the heat transfer coefcient at the wall, most of the heat transfer resistance will be located at the reactor wall and
the temperature prole within in the bed will be at. The models can be classied into pseudo-homogeneous or
heterogeneous. The pseudo-homogeneous model considers the reactor bed as a continuous phase and assumes that the
solid and uid temperatures are the same at any given point within the reactor. The heterogeneous model treats the
solid and gas phase separately.
Pseudo homogeneous 1D model
Species transport
Accumumation = A
c
dx
d(Y
k
)
dt
(4)
In = uA
c
Y
k,in
(5)
Out = uA
c
Y
k,in
+uA
c
dY
k
dx
dx (6)
Genetation =
k
W
k
A
c
dx + s
k
W
k
A
s
(7)
At steady state
d(uY
k
)
dx
=
k
W
k
+ s
k
W
k
(A
s
/A
c
dx) =
k
W
k
+ s
k
W
k
A
v
(8)
where A
v
is the surface area available per unit volume. The total continuity is obtained by summing up the above
equation over all species
d(u)
dx
=
N
g

k=1
s
k
W
k
A
v
(9)
The right hand side will vanish if there is no addition of depletion of mass on the packing surface.
Energy balance
Accumulation = A
c
dx
d(h)
dt
(10)
In = A
c
uh (11)
Out = A
c

uh+
d(uh)
dx
dx

(12)
At steady state for an adiabatic reactor
d(uh)
dx
= 0 (13)
If there is heat transfer at the walls of the reactor
d(uh)
dx
= Q (14)
If one wishes to write the balance equation in terms of temperature, then one may proceed as follows
Accumulation = A
c
dxc
p
dT
dt
(15)
In = A
c
uc
p
(T T
ref
) (16)
Out = A
c

uc
p
(T T
ref
) +
uc
p
d(T T
ref
)
dx
dx

+Q (17)
Generation =
N
g

k=1
( s
k
A
s
+ g
k
A
c
)h
k
(18)
2
At steady state this leads to
uc
p
dT
dx
=
N
g

k=1
( s
k
A
v
+ g
k
)h
k
Q (19)
The pressure drop along the reactor may be calculated according to
dp
dx
= f
u
2
d
p
, (20)
where d
p
is the characteristic dimension of the packing. The density can be calculated from the ideal gas equation.
Heterogeneous model
The heterogeneous model treats the solid and gas phase separately. For calculating the concentrations on the surface,
the mass transfer resistance between the bulk of the uid and catalyst surface needs to be considered. The homoge-
neous gas-phase transport equation becomes
d(uY
k
)
dx
=
k
W
k
+ s
k
W
k
(A
s
/A
c
dx) =
k
W
k
+ s
k
W
k
A
v
k = 1, . . . , N
g
(21)
At the surface the following condition takes care of the mass transfer resistance
k
m
C
tot
(X
k,b
X
k,s
) = s
k
k = N
g
+1, . . . N
g
+N
s
(22)
The gas-phase energy balance equation is
uc
p
dT
dx
=
N
g

k=1
g
k
h
k
h
f
A
v
(T
s
T) (23)
The steady state energy balance equation for the solid catalyst is
h
f
A
v
(T
s
T) =
N
g

k=1
s
k
h
k
(24)
Derivation of the above equations is left as an exercise.
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