Diffusion in a Catalyst Pellet

BGHiggins ê UCDavis ê May_ 08 HDraftL

Background
We consider steady state diffusion in a spherical catalyst pellet. We write the species balance within the porous pellet as

“ ÿ Nj = Rj (1)

Here R j represents the rate of production of species j due to heterogeneous reaction and N j is the molar flux of species j. This
form of the species balance can be derived from the volume average form of the point form of the species balance equations- see
notes on averaging.

If we take the process to have azimuthal and polar symmetry, then the species balance in terms of spherical coordinates becomes

Ir2 Njr M = Rj
1 „
(2)
r2 „r
For notational convenience we will suppress the subscript r. The molar flux of species j is given by

Nj = Cj vj (3)

where v j is the species velocity which can be expressed as

vj = v* + uj (4)

where v* is molar average velocity and u is the diffusional velocity. Because of the imposed symmetry we suppress the subscript r
for notational convenience and write the vector quantities as
vj = vjr er ª vj

v* = v*r er ª v* (5)

u = ur er ª uj

Within the pores of the pellet we assume the diffusion in Fickian with a suitable effective diffusivity for species j:  j . Thus the
diffusion velocity becomes
uj = -j “ Cj (6)

In terms of the radial component we write

uj ÿ er = -j “ Cj ÿ er

∂ Cj (7)
ur = -j
∂r
Within the catalyst pores we assume that convective effects are unimportant and so the species velocity is approximated by

vj = v* + uj º uj (8)

Invoking the approximation given by Eq. 8 and inserting Eq. 7 into Eq. 2 and taking the effective diffusivity to be constant we get
2 ReactionIsothermalPellets.nb

1 „ „ Cj
-j r2 = Rj (9)
r2 „ r „r

Let us suppose that species A undergoes a first order reaction

k
A Ø B, RA = -k CA (10)

Thus our species balance for reactant A becomes

1 „ „ CA
A r2 - k CA = 0 (11)
r2 „ r „r
We will take the following boundary conditions to be imposed on CA

BC1 : CA = C0A at r=R

(12)
„ CA
BC2 : =0 at r=0
„r

Dimensionless Variables
As our length scale we use the pellet‘s volume to surface ratio
4
Vp 3
p R3 R
a= = = (13)
SP 4 p r2 3

As our concentration scale we take C0A . Thus our dimensionless variables are
r CA
x= , = (14)
a C0A
In terms of these variables, the diffusion problem becomes

1 „ „
x2 - F2  = 0
x 2 „x „x

BC1 : =1 at x=3 (15)

„
BC2 : =0 at x=0
„x

where F= k a2 ë A is called the Thiele modulus and represents the ration of the rate of reaction to the rate of molecular
diffusion.

Solution
To solve Eq. 15 we introduce the following transformation
u HxL
 HxL = (16)
x
then our ODE becomes
 ReactionIsothermalPellets.nb 3

„2 u
- F2 u = 0 (17)
„ x2
The general solution is

u HxL = a Cosh HF xL + b Sinh HF xL (18)

Applying the BCs we get

u H0L = 0, u H3L = 3 (19)

The final result is

3 Sinh HF xL
 HxL =
x Sinh H3 FL
(20)

Here is a plot of the concentration profile for select values of F

1.0
F =0.2

0.8
F =0.5

0.6


0.4
F =2

0.2

F =1
0.0
0.0 0.5 1.0 1.5 2.0 2.5 3.0
x

For large values of F , the reaction rate is large compared with the rate of molecular diffusion, and hence the reactant species is
converted to product before it can penetrate the pellet. For small values of F, the opposite is true. Now the reactant can penetrate
the pellet before it has a chance to react and thus the concentration of  is almost uniform across the pellet.

Now ar the surface of the pellet, the rate of production of the reactant within the pellet must be balanced by the flux of reactant
through the outer surface of the pellet. If  is the volume of the pellet, then the total rate of production of reactant in a pellet of
radius R is given by

XRAs \  ª ‡ RA HrL 4 p r2 „ r
R
(21)
0

But at the surface of the pellet

XRAs \  = -S A
„ CA
(22)
„r r=R

Thus

XRAs \ = -
3 „ CA
A
R „r r=R

(23)
3 A C0A „
=-
aR „x x=3

But
4 ReactionIsothermalPellets.nb

But

„ 3 F Cosh@F xD 3 Sinh@F xD
= -
„x x=3 x Sinh@3 FD x2 Sinh@3 FD x=3
(24)
1 1
=F -
Tanh@3 FD 3F
Substituting this result into Eq. 23 gives

XRAs \ = -
9 A C0A 1 1
F - (25)
R 2 Tanh@3 FD 3F

Then using the fact that F= k a2 ë A , we can eliminate A to get

XRAs \ = -
k C0A 1 1
- (26)
F Tanh@3 FD 3F

Limiting Case
Consider the case when FØ 0. Then Tanh@3 FD º 3 F so that

XRAs \0 = limit :- >

k C0A 1 1
-
FØ0 F Tanh@3 FD 3F
(27)

limit :-k C0A >

0
FØ0 0
If we use L‘Hopital‘s rule to evaluate

„ 1 1 1
- = - 3 Csch@3 FD2
„x Tanh@3 FD 3F 3 F2 (28)

= 1 as F Ø 0
as

1 9 F2
3 Csch@3 FD2 º -1+ + O@FD3 as F Ø 0 (29)
3 F2 5

Thus the limit is

XRAs \0 = limit :-k C0A > = -k C0A

0
(30)
FØ0 0

Effectiveness Factor
We define the effectiveness factor for the catalyst to be

XRAs \
XRAs \0
1 1 1
h= = - (31)
F Tanh@3 FD 3F

Thus when h º 1, the entire volume of the catalyst pellet is subject to a reaction rate at the concentration C0A because the reactant is
able to duffuse quickly through the pellet. In contrast when h<<1, only the region near the surface of the pellet achieves the high
reaction rate. In the interior of the pellet, the reactant concentration is effectively zero and is thus the catalyst not being utilized
fully. In short the pellet‘s diffusional resistance is large and this resistance lowers the overall production rate.
 ReactionIsothermalPellets.nb 5

Thus when h º 1, the entire volume of the catalyst pellet is subject to a reaction rate at the concentration C0A because the reactant is
able to duffuse quickly through the pellet. In contrast when h<<1, only the region near the surface of the pellet achieves the high
reaction rate. In the interior of the pellet, the reactant concentration is effectively zero and is thus the catalyst not being utilized
fully. In short the pellet‘s diffusional resistance is large and this resistance lowers the overall production rate.

1.00

0.50

0.20

0.10
h

0.05

0.02

0.01
0.01 0.1 1 10 100
F

In summary when the Thiele Modulus is large, A is small relative to k and therefore the diffusional resistance is large and thus
the pellet is diffusion limited. The catalytic potential of the pellet is not being utilized. When the Thiele modulus is small (k is
small relative to ), the pellet is said to be reaction limited.

Calculation using Thiele Modulus

Suppose we have a pellet with radius R=0.3 cm and a reaction temperature T=450K. We are told that at a partial pressure
PA = 0.7 atm for A , the rate of production of A is given by

XRA \c = -2.5 ä 10-5 mol ê gcat ÿ s (32)

are told further that the density of the catalyst pellet is rc = 0.85 g ë cm3 and A = 0.007 cm2 ë s .
where the unit gcat is gram catalyst. Can we determine the production rate for A at T=450 K in a pellet with radius 0.15 cm? We

From the information given we can calculate the molar concentration of the reactant at the surface of the pellet

= 1.896 ä 10-5 mol ë cm3

0.7 atm
C0A = 3 (33)
82.06 ä 106 cmmolatm
K
450 K

The molar rate of production per unit volume of catalyst particle is

XRAs \ = XRA \c rc = I-2.5 10-5 mol ê g ê sM I0.85 g ë cm3 M

(34)
mol
= -2.125 ä 10-5
cm3 ÿ s
From the definition of the effectiveness factor we have
6 ReactionIsothermalPellets.nb

XRAs \
XRAs \0
1 1 1
= -
F Tanh@3 FD 3F

XRAs \
(35)
1 1 1
= -
k C0A F Tanh@3 FD 3F

We use the definition of F to determine k

k = F2 A ë a2 (36)

Thus Eq. 35 becomes

XRAs \ a2 1 1
=F - (37)
A C0A Tanh@3 FD 3F

Based on the data given we can evaluate the LHS of Eq. 37

XRAs \ a2 2.125 10-5 0.01

= = 1.6062 (38)
A C0A 7 10-3 1.89 10-5
Thus we need to determine F such that

1 1
F - = 1.6062 (39)
Tanh@3 FD 3F

A calculation gives F=1.94 and from this value we can determine the rate constant from Eq. 36

k = F2 A ë a2 =
1.942 0.007
= 2.63452 s-1 (40)
2
0.1
If we have a catalyst pellet that is half the radius, then the Thiele modulus will be half as large. The effectiveness factor would be

ê. F Ø 1.94 ê 2
1 1 1
-
F Tanh@3 FD 3F
0.682794

Thus the production rate in the smaller pellet is

XRAs \
= h ï XRAs \ = h k C0A = H0.683L H2.634L I1.896 ä 10-5 M
C0A
mol ë cm ÿ s
k (41)
-5 3
h = 3.41 10

Hence by reducing the size of the pellet we get a 60% increase in the production rate. This is possible because the pellet is in the
diffusion limited regime so not all of the pellet‘s catalyst potential is being utilized and thus by reducing the radius of the pellet
one achieves better effectiveness.