ChE 512: Topic 2

Reactions in a porous catalyst

Pore Diffusion and Implications

P.A. Ramachandran
rama@wustl.edu
 Outline
Pore diffusion, Effect of pore structure
Diffusion + Reaction in a porous catalyst
Effectiveness factor
Multiple Reactions; Effect of diffusion on
rate, selectivity, temperature rise etc
Numerical Methods
 Internal Transport
C CAS

0 r R
Typical concentration profiles
Schematic of a porous catalyst
within the catalyst
dC
Diffusive flux in the catalyst = DeA
dr
DeA = effective or intraparticle diffusion coefficient of species A
in the catalyst.
A medium property; not a unique species property
 Catalyst Properties
Mean Diameter = dp
= 6Volume/External area
Surface area (internal) per unit mass, Sint
Solid density, s
Bulk density, B
Average porosity, P = 1- B/s
Pore volume, m3/kg. catalyst
 Pore Size Distribution
Distribution function F(r) defines the pore volume and
can be measured by techniques such as Hg
porosimetry.
Volume of pores (per unit mass) in the size r to r + dr
is F( r )dr.
Units of F (r ) is volume/mass / length
Total volume and average pore radius can be
calculated from this distribution function.
 Pore Size (Unimodal Case)
Integral under the curve = Pore volume
F(r)
per unit mass of catalyst
m3/gm-m

r r, m
Mean Radius:

r = rF ( r )dr F ( r )dr Surface area per unit mass = 2V/ r
(assuming cylindrical pores)
Bulk Density:
1 B =1 s +V
 Pore sizes (Bimodal Case)
Macro-pore volume, Vmacro
Micro-pore volume, Vmicro F(r)
Micropore average size, r
Macropore average size, r m
Bulk density, 1 B = 1 s + V macro + V micro r rm r

Surface area (Total)

2V macro 2V micro
S = + = S macro + S micro
r macro r micro
 Diffusion Mechanisms
Pore radius > > mean free path
of molecules.
Molecular diffusion within the
pores
Diffusion takes place by
molecule to molecule collisions
(Ordinary diffusion)
No collision with the pore walls
Diffusivity in a single pore
same as the (pseudo-binary)
molecular diffusivity of A in
the mixture,
DM = DAmix
Pore radius comparable to mean
free path
Collision with the pore walls
predominant mode of transport
Knudsen diffusivity in a single
pore is given as:
2
D K = reV A
3
V A = Average speed of A
= (8 RT M 1 )1 / 2
D K = 97 re (T / M 1 ) 1 / 2
 Models based on pore size
distribution
Unimodal pore
1 1 1
= +
D A ,e D M , eff D K , eff

D M , eff = D M ; D K , eff = D K P

1
= Tortuosity
P

Bimodal pore (macro+micro pores) Wakao-Smith Model

(1 + 3 M )
De = M
2
D M + 2 D
(1 M )
Dm D K
D M or =
( Dm + D K )
 Governing Differential Equation
Consider a spherical shell located between r and r + dr
dr
r
In Out = - Generation
dC dC r=R
4r 2
De 4r 2
De = 4r 2
rkv C
dr r dr r + r

De d 2 dC
2 r = kvC
r dr dr
kv = volumetric reaction rate constant
Rate based on catalyst volume.
Solution for concentration profiles
Transformation y = cr reduces D.E. to a simpler form

B.C. at r = 0
dC
dr
=0
CA
=
(
sinh 3 r
R
)
C AS r sinh (3 )
B.C. at r = R C = C AS
R

1
R kv 2
= = Thiele modulus
3 DeA
A measure of relative ratio of particle diffusion time to reaction time.
Concentration profiles within the catalyst
Catalyst Effectiveness
1 1
Catalyst effectiveness factor c = coth (3 )
3

Rate per unit volume of catalyst = k v C ASc

actual rate
c =
rate based on surface concentration

kvCdr = An integral average rate

2
Actual rate = 4 r
0

dc
Actual rate from flux = 4R De
2

dr r = R
 Slab Model: General Kinetics
d2A
De , A 2
= k v A ( First order reaction )
As dx
k tanh
Center Surface Thiele Modulus = L ; c =
De , A

0 x General Kinetics:
L d2A
L = Half slab thickness = VP/SP De , A = k v A m or f ( A)
dx 2
Numerical Solutions or approximate assymptotic solution

Multiple Reactions:
nr
d 2 Ai
D e ,i
dx 2
=
j=1
ji rj
Shape Normalization
Vp R 0
10

L= = Slab
Sphere

Sp 3
For a sphere

Thiele Modulus = Effectiveness factor, c

-1
10
k
L
De

tanh
c =
-2
10
-1
10
0
10
1
10
2
10
Thiele modulus,
Problem 1: Rate for larger size given kinetics

Rate of reaction over a finely crushed catalyst of radius of 0.5 mm was

measured as 10.0 mole/sm3 catalyst.

Temperature is 400 K and

pressure is 105 Pa and
mole fraction of reactant in the gas is 0.1.

Find the rate for a catalyst of pellet radius of 3mm.

Solution to Problem 1
Assume c = 1 for small catalyst.

yP 0.1 105 mol

C Ag = = = 3.007 3
RT 8.314 400 m
Rate 10 mol / m 3 s 1
Rate = kC Ag Hence k = k = = 3.3256 s
C Ag 3.007 mol / m 3
To find rate for larger catalyst, we need an estimate of intraparticle
diffusion coefficient.
Let De = 4x10-6 m2/s (a reasonable estimate)
Then

=
R k
= 0.9118 c = 0.7051
3 De
Rate = c kC Ag = 7.05 mole / m s 3
Diagnostics: The Weisz Modulus
Given the measured rate, establish if there is significant pore
diffusion resistance.
L2 ( RA )obs
M W = Weisz Modulus =
C Ag De
where L = R / 3 = characteristic length scale
If Weisz modulus (Wagner modules) < 0.15, then the
concentration profile in the pellet is nearly uniform.

Note M W = c 2
Problem 2: Test for pore resistance
A rate of 105 mole/hr m3 cat is observed for a gas concentration of A
of 20 mole/m3. The catalyst particle diameter is 2.4 mm.

An independently measured value is needed to solve this problem.

Let us assume effective diffusivity is 5x10-5 m2/hr.

Is there a strong pore diffusion resistance?

Solution to Problem 2
L = R / 3 = 4 x 10-4 mm

L2 ( RA )
Wagner modulus = M T = = 16
DeC Ag

Strong pore resistance

The measured data are not representative of true or intrinsic kinetics.

Problem 3: Intrinsic kinetics
In Problem 2, find the effectiveness factor and the true rate constant.

Solution
rate
rate = kC Ag k = = 5000 hr 1
C Ag
Since depends on k, we used a trial and error solution. We expect
to be small. Let us assume some value, say 0.01.
5000 k
Then k= = 5 10 5
Thiele mod ulus = L = 40
De

tanh
= = 0.025

Solution to Problem 3 cont

assumed k=5000/ Thiele equation

0.01 5x105 40 0.025
0.03 1.67x105 23 0.0433
0.063 7.93x104 15.9 0.0627
External + Internal Transport
CAG

CAS
External gas film

( RA ) = 4R 2
k m (C AG C AS )
= 4R kc C AS
3

Overall effectiveness factor

actual rate
o =
rate based on bulk conditions
Overall effectiveness factor
C AS
First order reaction o = c
C AG
C AS 1
= where BiM = k m R = Biot number
C AG 1 + 2 c De for mass transfer
BiM

c BiM
o = Addition of resistances.
BiM + 2c
More complex for other orders (nonlinear
kinetics) but the concept is the same.
1 1 2 Thiele modulus is a function of surface
= +
o c BiM concentration for non-linear kinetics.