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Chemical Engineering Science, 1962, Vol. 17, pp. 825-834. Pergamon Press Ltd., London.

Printed in Great Britain.

Difhsion in catalyst pellets


N. WAKAOand J. M. SMITH
University of California, Davis, California
(Received 10 April 1962)
Abstract-A
theory is proposed for predicting diffusion rates at constant pressure through bi-disperse
porous media. The total rate is the sum of separate contributions for diffusion through macropores,

micropores and a series path. To apply the theory requires a knowledge of the pore volume-pore
radius distribution for the porous material.
Experimental diffusion measurements are reported for five high-area alumina pellets of different
densities made from the same Boehmite powder. The results show that for the least dense pellets
macropore diffusion is dominant. In contrast the micropore contribution controls the diffusion rate
in the most dense pellet. The theory predicts rates in good agreement with the data over the pressure
range investigated, 1-12 atm. Comparison with other diffusion data is hindered by the lack of porevolume-distribution information. However, such data are available for a silver catalyst and for a lowarea alumina. For these different materials the theory also predicts reliable diffusion rates.

DIFFUSIONIN CATALYST
PELLETS
importance of pore diffusion resistance in
some gas-solid catalytic reactions (for example
cumene cracking [l] and o&o-hydrogen conversion
[2]) has resulted in several studies of pore diffusion
rates [3-71. Because of the range of pore sizes that
exist in many solid catalysts, both Knudsen and bulk
diffusion processes may be significant. The interpretation of diffusion data in terms of the appropriate diffusivities in such cases lead to some
confusion in the early work. However, correct
and equivalent interpretations have been developed recently by SCOTT and DULLIEN [8], MASON et
al. [9] and ROTHFELD and WATSON[lo].
For optimum rates of reaction the pore-size
distribution should be such that the total of
diffusion and reaction resistances are a minimum.
One can anticipate the time when catalysts can be
prepared specifically to give a pore-size and area
relationship for optimum performance.
Before
this can be done, it is necessary to develop a means
of predicting diffusion rates as a function of the
physical properties of the porous material. The
objective of the present study is to propose a method
for correlating and predicting diffusion rates in
terms of the porosity and pore size-distribution
data. The work is restricted to pelleted type
materials prepared by compressing particles of

THE

catalyst powder, which themselves are porous.


Thus the resulting pellet has two pore systems:
micropores within the powder particles and macropore space between the powder particles. To
evaluate the proposed method experimental diffusion measurements were made on high-surface
alumina pellets over a range of pressure and
macropore sizes. These data constitute the only
results that cover a broad enough range of variables
and include sufficient pore size-distribution information to evaluate the method critically. However,
partial comparisons can be made with published
data on silver [5] and low-surface alumina [IO]
catalysts.
MECHANISMOF DIFFUSION IN CATALYSTPELLETS
In a bi-disperse porous system at constant pressure
the mass transport will be a combination of diffusion
through (1) macro- and (2) micropores,
the relationship
between the two depending
upon the
bulk density (macropore volume). Fig. 1 is proposed
to represent the system as far as diffusion is concerned.
The dotted squares identify the powder
particles containing
micropores
and the spaces
between them represent the macropores.
It will
be assumed that the area void fractions are the
same as the volume void fractions.
Then the
probability
that a given location
(on a plane

825

N. WAKAO and J. M. SMITH

This expression accounts for bulk diffusion according to the molecular diffusivity D,, and Knudsen
diffusion with a diffusivity D, determined by the
pore radius a
D, = 2ijAa/3

FIG. 1.

Diffusion

Equation (2) is now applied to the model of Fig. 1,


adding the contributions to mass transfer of A for
each of the three mechanisms. The resulting
diffusion rate per unit cross-sectional area of the
pellet is

mechanisms in b&disperse porous


materials.

RT- -s,zD, 2

(Mechanism 1)

(&2

Da = (1 - ay,+)/DA, + I/&,,
$I(1 - &,)2
Di = (1 -

(1 - &,)2

RT (1 - uyJIDAB + l/D,

(4)

(3) Through the macropores and micropores in


series. The area for this contribution is 1 - E: (1 - &a)2or 2~,(1 - EJ.
The general equation for the rate of diffusion of
A in a circular capillary per unit area at constant
pressure in a binary system of gaseous A and B
[8-lo] is

NAYP

(Mechanism 2)

In formulating this expression the unit cell that is


repeated to make up the pellet has a length Ax,
from the centre of one powder particle to that of its
neighbour (Fig. 1). The composition change across
the element is AyA. The diffusivities Da and D,
apply for the macro- and micro-regions respectively, and are given by the equations

6
Or

2
*A
- 2E(1 - s) (l/D,) + (l/Di) Ax
(Mechanism 3)

(1)

Suppose the sample is cut at the plane and the two


surfaces are rejoined. Then the void area per unit
total area on the rejoined plane will be the probability of two successive events, or (E)(E) = E.
The diffusion through the plane can be divided
into three additive parts (parallel mechanisms):
(1) Through the macro-pores with an area of E:
and an average pore radius Z,,.
(2) Through the particles having an area (1 - 8,)
and an average pore radius L&. The effective void
area of micropores per unit area in the particles is
2

- (1 - Q2Di 2

N AT-

perpendicular to the direction of diffusion) will


be in a void space is E. If E,,,.si, and E, represent the
volume fractions of macropores, micropores and
solid,
E, + Ei + Es =

(3)

(2)

(6)
~YAYDAB

(l/h,)

Here Bkti and Dk, are the Knudsen diffusivities for


component A in the macro- and micropore regions.
Since the pores cover a range of sizes, mean values
of the diffusivity based upon mean macro- and
micropore sizes should be used.
Equation (4) applies to the unit cell of Fig. 1.
If it is summed to include the whole pellet of thickness L, and if equations (5) and (6) are introduced
for D, and Di, the diffusion flux NA can be expressed
in terms of L and the end compositions yA, and
yA,.

826

Diffusion in catalyst pellets

1-aYA2

+(DA~/Dki)

1 -

+(DAB/%,>

aYAl

ayA

+I [tl - Ea)2/si21
+ @k,/k.)

I
2

4sLl(I - e3
+ 1 + [(i - &,)2/E;]

1 _

ayA,

1 + [(l -

Dki
: +

cc1

RTLa
_=E21n
A PDAB

1-

aYA2

+cDAdBk)

1 -

"YA,

+ (D.&k)

aYAz

1 - aYAl

@)

+ @?&/p~k.)

a(yA,

+ <&/pDk,>

4%0
+

qJ2/$J

%~)~/~iZl +
[(l

(7)

@k#k.)

qJ2jEiZ1

pressures on the two ends of the pellet, contained


in a stainless steel chamber [7], were maintained by
slowly bubbling streams of each gas (helium and
nitrogen) into a surge tank [3] containing water.
The lines containing the two gases extended to
the same depth in the surge tank. The pure gases
(nitrogen 99.97 per cent pure and helium 99.99
per cent) were directed tangentially into the chamber
near the end surfaces of the pellet. The exit streams
from the chamber were analysed in calibrated,
thermal conductivity cells (Gow-Mac Co., Type
30s) immersed in a constant temperature bath
maintained at 25C. The entire flow rates of each

In most bi-disperse porous catalysts the macropore radius Za is much larger than the micropore
value, &. Then Dki/Ljko is small with respect to
(1 - &a)2/&i2. Also the ratio DAB/nki iS large enough
for the arithmetic mean to approach closely the
logarithmic mean. Hence, equation (7) is closely
represented by a simpler result:
1-

1 +

Dk,

If either the macro- or micropores do not exist,


i.e. E, = 0 or ~~ = 0, equation (7) reduces to the
simple integrated form of equation (2);

1 -

d(YA,

- 80)

YAz)

YA,)/21 + (%/p~k,)
a(YAt - J)AI)

1 + [(l - &J2/&l

(9)

.
l-a[(YA~

+ YA2)/21

1 +z$(

-a

)2]

Here D.&, = PD,, and is independent of pressure.


Equation (9) predicts the effect of macro- and
microporosities and mean pore sizes (through
9, and 9, and equation 3) on the diffusion rate.
The result is based upon the model of Fig. 1 which
includes the assumption that the three contributions
are independent of each other. Of particular
significance is the simple result that in a random
distribution of pores the effect of porosity is proportional to s2.
EXPERIMENTAL
WORK AND RESULTS

The diffusion apparatus shown schematically in


Fig. 2 is similar to that used and described by
HENRY et al. [3]. It is based upon the original procedure by WICKE[ 111, for measuring counter-current
diffusion rates through porous materials under
constant pressure conditions.
Equal and constant

827

FIG. 2.
1,2
3
4
5
6
7
8
9
10

Experimental apparatus.
He, Na cylinders
Surgetank
Manometer
Pressuregauge
Porous pellet
Pellet container
He, NZ reference gases
Thermal conductivity cell
Soap-film meter.

N.

WAKAOand J. M. SMITH

sented elsewhere [13]. The distribution curves for


the micropores were essentially the same for all the
pellets with a narrow peak at about 20 A. This result
indicates that the pelleting process did not destroy
the powder particles. The minimum in the volume
distribution vs. pore-radius curves occurred at
about 100 A, and this was taken as the boundary
between micro- and macropores for determining
void fractions. The densities of the six pellets were

stream were passed through the cells. Soap film


meters were employed to measure the rates which
varied from O-5 to 2 cma/min (S.T.P.).
Data were obtained for the nitrogen (component
A) and helium (component B) system, at pressures
from 1 to 12 atm and at 24C.
The pellets consisted of cylindrical disks of
Al,OZ - lHzO (Boehmite) 1 in. in diameter and
about 4 in. in thickness (see Table 1). They were
Table 1.

Pellet *

A
B
C
D
E

Thickness
(mm.)
12.6
12.6
13.0
12.7
12.6

Total
pore volume
Vt (cm3/g)t
2.14
l-39
1.10
0.728
O-560

Physical Properties of Boehmite pellets


Density
Total
Wm3)

Total
void
fraction

0.488
0.679
0.800
1.041
l-206

O-80
O-72
0.67
0.57
0.51

Micropores

Macropores

Voidfraction
.%

$1

Voidfraction
ea

&

0.17
0.27
0.33
0.39
0.42

25
24
23
23
23

0.63
0.45
0.34
0.18
0.09

15,000
2300
1100
460
370

* Pellets are disks with a diameter of 1 in.


t Pore volume is per gramme of AlaOs; i.e. per gramme of pellet weighed after ignition.

made by compressing the Boehmite powder in a


Carver Model-B Press without adding lubricant or
other contaminant. The powder was contained in
a stainless steel ring, 1 in. I.D., and the ring and
powder together placed in the press to form the
pellet. The ring and pellet as a unit were then
installed in the stainless steel chamber using
flanges with O-rings to obtain a tight seal. This
arrangement allowed operation up to 15 atm
pressure without leakage. The powder used was
spray dried alumina from the American Cyanamid
Company and had an average particle size of about
90 F. Pellets (A to E) of five different densities,
and hence different macropore sizes and void
fractions, were obtained by using different masses
of alumina in the press.
The total pore-volume data and volume distribution vs. pore-radius calculations were obtained by
Mr. Marvin F. L. Johnson of the Sinclair Research
Laboratories, Harvey, Illinois, by nitrogen adsorption and mercury penetration
measurements.
Measurements were made on six pellets, each of a
different density but all made from the same
Boehmite powder.
Examples of the volume
distribution-pore-radius
curves have been pre828

in the same range as that of pellets A-D studied


in this investigation. Hence, the void volume for
samples A-D were obtained by interpolation and E
by extrapolation, The resulting physical properties
for the five samples are summarized in Table 1.
The measured diffusion rates, related data and
calculated results are given in Table 2. It has been
shown (9) that the ratio - Na/N, should be inversely
proportional to the square roots of the molecularweight ratio, regardless of type of diffusion. For
helium and nitrogen this result is -N,,/N, = 2.64.
The measured rates given in Table 2 indicate ratios
close to this value.
ANALYSIS OF DATA AND THEORY

1. Evaluation of mean pore radii


In using equation (9) to calculate the diffusion rate
the mean micro- and macropore radii are necessary
in order to evaluate i&, and &,. This requires
data on the distribution of micro- and macropore
sizes. The distribution curves [13] for the micropores are narrow with a very sharp peak at 20 A,
so that cj will be close to this value. Since the mean
radii are used to evaluate the Knudsen diffusion

Diffusion in catalyst pellets

Table 2.

Experimental data and the comparison with theoretical values.

Diffusion rate
mole fraction of
(mol/sec)
Na in Helium Nitrogen
Run PresHe in
no. sure Na-side
He-side-SNB
S.NA
x 10-4
x 10-4
P
1 - YAI
YAz
A 1

1GO
1.92
3.25
4.81

0.353
0402

0.127
0.133

0.333
0.302

0.273
0.326

0.124
0.0915

B 1 1.26
2 5.05
3 12.0

0.358
0.391
0.372

c 1 1.92
2 4.23
3 7.80
4 12.4

RTLNA
--

(JJA, -

NB

YA#%B

RTLNA
@A,

YA,)~~B

observed

NA

Calculated from Eq. [9]


Contribution of
series
macromicro-

0.125

2.66

o-209

O-228

0.226

o+MO293 0~00200

0.410
0.397

0.119
0,162
0.169

2.54
2.53
2.35

0.222
0.234
0.252

0.248
0.247
0.271

0.244
0.240
0.261

oGoO555 0.00377
O+MlO938 0.00620
oMI134
oGO9Oo

0.115
0.106
0.109

0.1264
0.1622
0.2198

0.0485
0.0655
0.0845

260
2.54
260

0.0800
0.114
0.142

OG90
0.133
0.155

0.086
0.118
0.124

o+loO929 0GO301
0.00351
0.0113
0.00754
0.0237

0.154
0.240
0.321
0.320

0*0500
0.0620
0.0931
OWI80

0.1044
0.1297
0.1258
0.1507

OWO8
0.0498
0.0484
0.0584

2-56
2.61
2.60
2.58

OGKO
0.0641
0.0740
0.0900

0.0584
0.0697
0.0862
0.101

0.0428
0.0553
0.0629
0.0663

OW132
0.00443
o+IO777
0.0115

0.00425
0.00896
0.0155
0.0228

D 1 1.05
2 2.70
3 3.28
4 5.18
5 6.58
6 11.5

0.0387
0.0560
0.147
0.180
0.202
0.197

0.0203
0.0298
0.0335
0.0483
0.0640
0.0641

0.0281
0.0473
0.0523
0.0648
0.0604
0.0872

0.0107
0.0184
0.0200
0.0249
0.0241
0.0352

2.63
2.57
2.62
260
2.51
2.48

0.00996
0.0176
0.0214
0.0282
0.0287
0.0418

0.00889
0.0182
0.0210
0.0285
0.0335
0+473

OGO571
0.0103
0.0115
0.0139
0.0154
0.0180

0+0170
OGO424
o+IO511
0.00785
0.00975
0.0159

OGO148
0.00367
oGo441
OGO671
0.00832
0.0134

E 1 1.68
2 3.56
3 6.25
4 9.30
5 10.86

0.0451
0.0582
0.140
0.0853
0.147

0.0127
0.0149
0.0890
0.0375
0.0522

0.0184
0.0321
0.0390
0.0630
0.0564

0.00714
0.0122
0.0147
0.0237
0.0233

2.58
2.63
2.65
2*66
2.42

O+IO659
0.0114
0.0166
0.0235
0.0253

003566
0.0108
0.0171
0.0233
0.0267

OGO154
0.00239
0GO303
ow343
0.00377

0.00296
OTlO605
0.0102
0.0144
0.0166

O+KU16
0.00236
oGO393
oGO553
0.00637

2
3
4

All runs are at 24C,

A = Nitrogen,

B = Helium,

S = Cross-sectional

Combining equations (10) and (11) and solving


for pi gives
6%

contributions in equation (9), the averaging procedure should be for this type of mass transfer.
The total rate of Knudsen diffusion through the
micropores, using equation (3) is
QA = - &

Oba(xa2)n(a)da

ai

i&

=B

---a,

RT3Ax

ab
so

na2n(a)da

s0

axa2n(a)da

(12

ali

7ca2n(a)da
s 0

The quantity za2n(a)da is the volume of micropores


between a and a + da, per unit length of pore.
Hence, equation (12) can be written in terms of the
known pore volume per gramme of alumina.
Vi
ai=vi

*kz2n(a)da
s0

P 2vA by, _

(10)

s0

The function n(a)& represents the number of pores


with a radius between a and a + da, and a, the
upper limit of the microradius, in this case 100 A.
In terms of the mean diffusivity &, the total
diffusion rate is
QA = - ;

area of end of pellets = 5.07 cm2.

s0

adVi

(13)

This expression was used to calculate ai from the

(11)

pore-volume-pore-radius
distribution curves and
found to be 23-25 A. The integral is applied over
the microvolume region, 0 to Vi. The result

829

N. WAKAO

and J. M. SMITH

depends upon the somewhat arbitrary separation


of the distribution data into separate curves for
the micro- and macroregions. Since the micropore
distribution was the same for all the pellets, this
value of pi is applicable for pellets A-E.
The diffusion data for the most dense pellets
also can be used to obtain a value of Zi. Thus as
s,, + 0, equation (9) reduces to the micropore term
only. Under these conditions,

The intercept, obtained by extrapolation to s,, = 0,


should be equal to EF&/D~~.From Fig. 3(a) this is
EiD
2

D"
AR

The value of the


can be estimated
in Table 1. The
Fig. 3(b), is (E~)_~
(15)
&, =

RTL
NA
P(YAi - YA&%S

=P{l

-a[(yA,

Furthermore, at low pressures (l-3 atm), the term


involving the pressure in the denominator of the
right-hand side of equation (14) becomes small with
respect to D;iB/bki.
Fig. 3(a) is a plot of

RTL
vs. E,.

NA

O+M20atm-

(YAl - YA,P&

micropore void fraction at .sll= 0


by extrapolating the sl data given
result, illustrated by the graph in
=
O-44. Then from equation
0~0020(0~697)~(044)2

00
8

c
i

0.4

.;o
8
it

0.3

0
9

0.2

e
.o
r
0.001

0.2

0.4

0.1
0

Estimation

0.2

0.4

Macro void

FIG. 3.

(15)

= 0.0072 cm/sec
(16)
where DiB = 0.697 atm(cm)/sec is the value of
DA,obtained from the Chapman-Euskog expression
[12] for the N,-He system at 1 atm pressure and
24C. Using this result for & in equation (3)
gives Z, = 23 A assuming circular pores. The
excellent agreement between the two results is
probably due to the narrow distribution of micropore radii.
Equation (13) can also be used to evaluate Z,,
for the macropores by changing the limits of

(14)

yAz)/21) + @%/~d

of Knudsen

830

diffusion

fractlan

c-6

, r,

in micropores.

Diffusion in catalyst pellets

2.
oa

IO'

r
IO'
0

Total pore
FIG. 4.

volume, V,,

Mean macropore

cdh

radii for Boehmite pellets.

integration to cover the macropore region V, =


V, - Vi. The values of (z, SO calculated for the
original six pellets are plotted vs. total pore volume
V, in Fig. 4. Values of Za for pellets A-E were
obtained by using the V, data in Table 1 and Fig. 4.
The values of (5, so evaluated are given in the last
column of Table 1. These were used to determine
the corresponding
mean Knudsen diffusivities

Dk,.

pressure,
Exp data of

Total
o

P.

atm

pellet

Comparison

with data for high-area alumina

Knowing i& (OGO720 cm2/sec) and &._ equation (9) can be used to predict diffusion rates through
the pellets as a function of density and gas pressure.
The porosities a. and ai are available from the porevolume measurements. The observed and predicted
total rates are compared in Fig. 5 for three of the
pellets by plotting N,R7X/(yA, - vA,)D& vs.
pressure. Experimental and calculated results for
all the pellets are given in Table 2. Also included
in Fig. 5 are curves for the separate contributions
to the total rate, corresponding to the separate terms
in equation (9). For the low-density pellets, illustrated by the results for pellet B in Fig. 5, diffusion
through the macropores is dominant. The contributions of the micro- and series mechanisms are
10 per cent or less of the total. For the most dense
pellet E, this is reversed and the contribution of the
macropore diffusion is least signitkant. The total
rate decreases sharply as the density increases.
The agreement between the predicted and experimental result lends confidence to the proposed
theory, particularly since thereare no arbitrary constants involved in equation (9).
Evaluation of equation (9) requires data (a) for
pellets of different densities to test the validity of
the porosity functions in each term, and (b) for

P,
o Pellet

FIG. 5.

atm
D

P,
o Pellet

Comparison of experimental data for high-area alumina with theory.


1: Macro contribution.
2: Micro contribution.
3 : Series contribution.

831

atm
E

N. WAKAOand J. M. SMITH

different pressures to test the validity of the functions giving the relative significance of bulk and
Knudsen diffusion. Complete data of this nature
do not appear to be available except for that presented here. However, some information has been
published which permits partial evaluation of
equation (9).
3.

I.0 _
8

II

IL
n

Comparison with silver-pellet data

MASAMUNE and SMWH [5] measured diffusion


rates through silver catalyst pellets of different
densities at 1 atm pressure. Void-fraction data
were obtained but not volume pore size-distribution
information.
Hence, the appropriate values of
D,. and Dkkiare not available. However, for lowdensity pellets under conditions where Knudsen
diffusion is negligible, such information is not
needed to apply equation (9).
The results of most prior investigators have been
reported in terms of an effective diffusivity, D,,
defined by the expression

De

dYA

FIG. 6.

restricted conditions, equation (19) reduces to the


simple form
D
e=E
DAB

If this is integrated at constant pressure conditions,


there results

1 - aYA

= D,P In

(18)

l- MyA,
Equation (18) can be combined with Equation (9)
to give an expression for D, in terms of the properties of the porous material. Expressed as the
diffusibility, De/DAB, the result is
D

DAB

ln[(l - ayAz)/(l - ayAl)l

e=

dyA,
+ "

(20)

The experimental results for silver-catalyst pellets


are shown in Fig. 6 plotted as D,/DAB VS. ~2.
The dotted line on the Fig. represents equation (20).
The results for the least-dense pellet (si = O-57)
agree reasonably well with Equation (20). The
data for the higher-density pellets show large
deviations for equation (20). This is expected, from

1 -RYAN

+(D~B/P&.)

- YAz)

1 - @[(YA, + YAJPI

+ (KBIP~,,)

4%(1 - %)
+ 1 + [(l - &,)/S] *

of silver and alumina data with


theory.

(17)

1 - ay, dx

N,RTLu

Comparison

dYA, - YAz)
1 - a[(YA, + YAz)/~~ + 1 +;$$fe
I

For low-density pellets only the macropore contribution should be signmcant (see Fig. 5). Also if
the macropores are large enough, or the pressure
high enough, the Knudsen part of the diffusion in
the macropores should be negligible. Under these

(19)

121
cl

equation (19), because of the increasing importance


of Knudsen diffusion in the macropores and
increasing importance of the micropore and series
contributions.

832

Diffusion in catalyst pellets

4.

Comparison with low-area alumina


ROTHFELD and WATSON [lo] measured diffusion

rates through Q in. cylindrical pellets of alumina


(Type Al-0104-T,
Harshaw Chemical Co.) and
presented data for the isobutane (A)-helium
(B)
system at pressures of 200 to 700 mm Hg. This

material corresponded approximately to the more


dense pellets D or E in Table 1 with respect to void
fractions. The values of E, and Ei were 0.18 and
0.34 respectively. However, the micro- and macropores were much larger and the surface area much
smaller (76 m2/g vs. 350 m2/g for pellets A-E).
The pore volume vs. pore-radius distribution data
did not show a sharp minimum between macro- and
microregions in contrast to the high-area alumina.
There was a signi6cant volume in pores of intermediate radii. Therefore, taking the minimum in
the distribution curve as the boundary between
micro- and macropores introduces errors in calculating ii and Cr,. This difficulty was circumvented by
extrapolating the micro- and macrosections to give
separate distribution curves. From these curves,
using equation (13), the mean pore radii were found
to be Zi = 84 A and & = 4800 A. Composition
information was not available so that yA1 and Ye,
were unknown. This prevents an exact comparison
of theory and experimental data. However, most
diffusion measurements of this type are made with
nearly pure gases on the opposite faces of the pellet
so that yA, = 1 and yA2 = 0, is probably a good
approximation. Using these results diffusion rates
were calculated from equation (9). The experi-

FIG.

7. Theoretical and experimental results for lowarea lumina [lo].

mental and calculated values are shown in Fig. 7


based upon the same co-ordinates as Fig. 5. The
agreement suggests that the theory is also applicable
to this different type of porous material.
In summary a model has been proposed for
diffusion in bi-disperse porous catalysts. The
development gives a relationship between diffusion
rate, porosity and pore-size characteristics, that
agrees well with available data. To predict diffusion
rates from the equations it is necessary to know
the pore-volume-pore-radii
distribution in the
porous material.
study was sponsored by the
United States Army Research Office (Durham) through
Grani #DA-ARO(@-31-124-Gl91.

Acknowledgement-This

NOTATION

a Pore radius
li, Mean radius for diffusion in the macropores
CZb
tit

DAB
D'AB
De
DC2

cm
cm
cm
Upper limit of radius of micropores
Mean radius for diffusion in the micropores
cm
cm2/sec
Binary bulk diffusivity for system A-B
cn+/sec
DABP atm
Effective diffusivity defined by equation (17) cm2/sec
Composite diffusivity, defined by equation (5)
cm2/sec
Composite diffusivity, defined by Equation (6)
CllG/StZC

Mean Knudsen diffusivity of gas A in the micropores,


cm2/sec
defined by equation (11)
Mean Knudsen diffusivity of gas A in the macropores
cm2/sec
cm
Geometrical length of porous pellet
Molecular weight
g/g mole
Diffusion rate per unit area of gas A (nitrogen)
g mole/(cm2)sec
cm-
Number distribution of pores
atm
Total pressure
g mole/set
Diffusion rate
Gas constant
cm3(atm)/(K)g mole
cm2
Cross-sectional area of pellet
SNA = total diffusion rate through pellet
K
T Temperature
V Pore volume per g (ignited,
cm3/g
Vt = total pore volume,
Vt = micropore volume
Average molecular velocity of gas A
Cm/SeC
BA
Distance in the direction of diffusion
X
cm
Mole fraction of gas A in the system;
YA
y_Q = mole fraction nitrogen on nitrogen side of
pellet ;
yA2 = mole fraction nitrogen on helium side of
pellet
OL Ratio of diffusion rates 1 + NBINA
E
Void fraction
Subscripts
a, i Macro- and micropores, respectively
A, B Nitrogen and helium, respectively
1,2 Nitrogen and helium sides of pellet

833

N. WAKAOand J. M. Surrn
RFFERENCES

[l] PRAYERC. D. and LAGOR. M., Advances in Catalysis Vol. VIII, p. 294. Academic Press, New York 1956.
[2] WAKAON., SELWOOD
P. W. and SETH 5. M., Amer. Inst. Chem. Engrs. .I. To be published.
[3] HENRYJ. P., CHENNAKF..SAVAN
B. and SMITHJ. M., Amer. Inst. Chem. Engrs. J. 1961 7 10.
[4] HOOGSCHAGEN
J., Industr. Engng. Chem. 1955 47 906.
[5] MASAMUNE
S. and %rrrr J. M., Amer. Inst. Chem. Engrs. J. 1962 8 217.
[6] Scorr D. S. and Cox K. E., J. Chim. Phys. 1960 57 1010.
[7] WEISZ P. B.,Z. Phys. Chem. 1957 11 1.
[8] Scorr D. S. and DULLIENF. A. L., Amer. inst. Chem. Engrs. J. 1962 8 293.
[9] EVANSR. B., WATSONG. M. and MACONE. A., Gaseous Diffusion in Porous Media at Uniform Pressure, IMP-AEC-15.
Institute for Molecular Physics, University of Maryland, 1 June 1961.
[IO] ROTHFELD
L. B. and WATSONC. C., Gaseous Counter Diffusion in Catalyst Pellets. Paper presented at the 54th Ann.
Meeting Amer. Inst. Chem. Engrs., New York, 3-7 December 1961.
[ll]
WICKEE. and RALLENBACH
R., KoNoidZ. 1941 97 135.
[12] HIRXHFELDER
J. O., CURT~SSC. F. and BIRD R. B., Molecular Theory of Gases andliquids, Chap. 8. John Wiley, New
York 19.54.
[13] MISCHKER. A. and Sm
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Ind. & Eng. Chem., Fundamentals Quarterly.

R&urn&La
auteurs proposent une theorie pour ltvaluation des vitesses de diffusion a pression
constante a travers un milieu poreux ;i double dispersion.
La vitesse totale est la rtkultante des vitesses de diffusion a travers les macro et micropores et
diverses voies. Lapplication de la theorie nkcessite la connaissance de la repartition des volumes
et rayons des pores du mat&au.
Des mesures experimentales de diffusion sont effectukes pour cinq sortes de granules dalumine
a grande surface active de differentes densites, obtenues a partir de la m&me poudre de Boehmite. Les
r&hats montrent que la diffusion par les macropores est predominante pour les plus faibles densites.
Inversement, la diffusion par les micropores correspond aux plus grandes densitb.
Les vitesses
prevues theoriquement dans lintervalle 1-12 atm correspondent bien aux r&hats
experimentaux.
Le manque dinformation sur les distributions des volumes des pores concemant dautres rksultats
de diffusion empkhe toute comparaison.
Cependant ces donnks sont valables pour un catalyseur dargent et pour une alumine a faible
surface spkcifique.
La theorie donne aussi des evaluations de vitesses de diffusion correctes pour ces differents
mattriaux.

834