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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
825
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
RT- -s,zD, 2
(Mechanism 1)
(&2
Da = (1 - ay,+)/DA, + I/&,,
$I(1 - &,)2
Di = (1 -
(1 - &,)2
RT (1 - uyJIDAB + l/D,
(4)
NAYP
(Mechanism 2)
6
Or
2
*A
- 2E(1 - s) (l/D,) + (l/Di) Ax
(Mechanism 3)
(1)
- (1 - Q2Di 2
N AT-
(3)
(2)
(6)
~YAYDAB
(l/h,)
826
1-aYA2
+(DA~/Dki)
1 -
+(DAB/%,>
aYAl
ayA
+I [tl - Ea)2/si21
+ @k,/k.)
I
2
4sLl(I - e3
+ 1 + [(i - &,)2/E;]
1 _
ayA,
1 + [(l -
Dki
: +
cc1
RTLa
_=E21n
A PDAB
1-
aYA2
+cDAdBk)
1 -
"YA,
+ (D.&k)
aYAz
1 - aYAl
@)
+ @?&/p~k.)
a(yA,
+ <&/pDk,>
4%0
+
qJ2/$J
%~)~/~iZl +
[(l
(7)
@k#k.)
qJ2jEiZ1
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,
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]
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
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
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
Table 2.
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
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
A = Nitrogen,
B = Helium,
S = Cross-sectional
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
*kz2n(a)da
s0
P 2vA by, _
(10)
s0
s0
adVi
(13)
(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
D"
AR
RTL
NA
P(YAi - YA&%S
=P{l
-a[(yA,
RTL
vs. E,.
NA
O+M20atm-
(YAl - YA,P&
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.
2.
oa
IO'
r
IO'
0
Total pore
FIG. 4.
volume, V,,
Mean macropore
cdh
Dk,.
pressure,
Exp data of
Total
o
P.
atm
pellet
Comparison
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
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
De
dYA
FIG. 6.
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
e=
dyA,
+ "
(20)
1 -RYAN
+(D~B/P&.)
- YAz)
1 - @[(YA, + YAJPI
+ (KBIP~,,)
4%(1 - %)
+ 1 + [(l - &,)/S] *
(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
832
4.
FIG.
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
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
J. M., Thermal Conductivity of Alumina Catalyst Pellets. Submitted for publication to
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