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Gen Spin 8 03 Catalytic Part I by Barth in Joc V 2 Iss 6 PP 485 497 y 1963
Gen Spin 8 03 Catalytic Part I by Barth in Joc V 2 Iss 6 PP 485 497 y 1963
OF
Catalytic
CATALYSIS
2,
Aluminas
&i-&t7
(1963)
I. Surface
D. S. MACIVER,,
Chemistry
H. H. TOBIN,
Alumina
AND R. T. BARTH
Pennsylvania
INTRODUCTION
Because alumina has been widely employed as a catalyst or as a catalyst support,
a considerable amount of research has been
devoted to elucidating the nature of its
catalytic properties. In general, alumina
has been regarded as an acid-type catalyst,
and, recently, Pines and Haag (1) have
shown how these acid properties serve as a
basis for explaining the role of alumina in a
number of catalytic applications. However,
despite a general agreement as to the acidic
nature of alumina surfaces, an exact chemical
description of this acidity has not been
achieved, and it seems clear that additional
research will be required before a thorough
understanding of the catalytic chemistry of
alumina can be realized.
It is well known (2) that there are two
general classes of aluminas, the low surface
area, alpha alumina, or corundum, and the
highly porous aluminas, which are of catalytic interest. These latter exist in several
forms (2), of which the so-called eta and
gamma modifications
are perhaps the
most common. Both eta alumina, which is
obtained by the thermal decomposition of
bayerite (2, 3, 4), and gamma alumina, the
decomposition product of boehmite (4, 6),
485
486
MACIVER,
TOBIN,
EXPERIMEXTAL
Materials.
Gamma alumina was obtained by the thermal decomposition of
boehmite at 500C. The boehmite was prepared by slowly adding an aqueous solution
of aluminum nitrate to a solution of ammonium hydroxide, with constant stirring.
The resulting precipitate was immediately
filtered, washed, and dried at 120C for
50 hr. X-ray diffraction showed that this
dried precipitate
consisted entirely of a
gelatinous boehmite, which, when calcined
for 24 hr at 5OOC, yielded a white solid
having an X-ray diffraction pattern characteristic of gamma alumina.
Eta alumina was obtained by the thermal
decomposition of bayerite at 500C. The
bayerite was prepared by slowly adding a
water solution of aluminum nitrate to a
solution of ammonium hydroxide with constant stirring, and with the continuous
addition of sufficient ammonium hydroxide
so as to maintain the pH above 9. After the
precipitation
was completed, the mixture
was allowed to stand for 4 hr, after which
it was filtered. The precipitate was then
contacted with water for 12 hr, refiltered,
and dried for 72 hr at 120C. The X-ray
diffraction pattern of this material indicated
that it was well-crystallized
bayerite. This
was then dehydrated to eta alumina by
heating for 16 hr at 250C and for 24 hr at
500C.
The two aluminas, after final calcination,
were examined for chemical impurities by
emission analysis. Both were quite pure and
had total impurity
contents of 500-700
ppm, the principal
contaminants
being
MgUOO ppm), JW200 mm), NaO00 ppm),
and Si(100 ppm). The aluminas were
ground to 50-140 mesh powders and used
in this form for all subsequent experimental
purposes.
American Cyanamid
Triple A silicaalumina having a surface of 445 m/g and
Davison silica-magnesia (16 wt y0 Mg) with
an area of 568 m/g were ground to 50-140
mesh and then calcined at 500C for 24 hr.
The sources of the various gases employed
in this work, and the techniques by which
they were purified, have been described in
earlier publications (6, ?). Water and metha-
AND
BARTH
CATALYTIC ALUMINAS I.
487
488
MACIVER,
TABLE
SURFACE
PROPERTIES
OF ALUMINA
DRIED
11-Al208
(d)
TOBIN,
240
21.6
0.33
AT 500C
yAlt0~
204
29.4
0.35
070Pore volume
37.4
29.2
5.6
4.4
6.8
9.2
7.4
0.0
54.1
41.4
2.0
1.0
0.7
0.8
AND
BARTH
CATALYTIC
ALUMINAS
489
I.
- 0.06
220 -
100
200
300
7)-A1203
y-Al203
SURFACE
H,O
AREA
LOSS
400
590
TEMPERATURE,C
600
700
so0
FIQ.
OF ALUMINA
AT 25%
IN WATER
Heat-of-Immersion
(Erdom)
Evacuation
$A%
9PAlSO~
-Y-AM):
25
75
100
150
250
350
450
199
310
406
470
548
648
270
328
354
412
500
698
530
635
761
787
heats and, as such, may represent a summation of several energetic processes. Further, it has been shown by other workers (15)
that when alumina is immersed in water
there may be, in addition to the rapid initial
heat effect, a slow evolution of heat which
can be appreciable over a period of several
hours. The nature of the calorimeter employed in the present work did not permit
detection of this later thermal process. The
values reported in Table 2 and Fig. 2 are,
therefore, those for the rapid initial process
alone. In general, they agree quite well with
the data reported by Wade and Hackerman
(16). As can be seen from Fig. 2 the heat of
immersion of eta alumina in water was
approximately proportional to the amount
of water removed at elevated temperatures.
In the case of gamma alumina, however, the
initial stages of dehydration did not cause
as large an increase in the heat of immersion,
and it was not until some 3 to 4 wt (o of
water had been removed that the rate of
heat increase with water loss approached
that of eta alumina. It might be noted that
the fact that the heats of immersion of eta
490
MACIVER,
0.01
0.02
FIG. 2. Heat
TOBIN,
0.03
AND
BARTH
0.04
0.05
0.06
Hz0 LOSS,g H20/g
of immersion
of alumina
in water
0.07
0.00
at 25C.
ALUMINA
Adsorbate
Eta
Eta
Gamma
Gamma
TABLE 3
OF Hz0 AND
SURF.4CES
Vm
[cc(STP)/m?l
Hz0
CH,OH
Hz0
CHsOH
0.198
0.122
0.226
0.133
AT
CHaOH
250
c
26
157
25
177
0.59
0.68
0.67
0.75
a v, = BET monolayer
volume;
C = BET C value8 = fraction of totalsurface
covered by V,.
CATALYTIC
ALUMINAS
PRETREATMENT
I.
491
TEMPERATUREfC
492
BIACIVER,
TOBIN,
AND
BARTH
; 0.06 Iv)
3
yo.05 it
m
g 0.04 ::
a
g 0.03 2
0.02-
0.01 -
PRETREATMENT
TEMPERATUREfC
CATALYTIC
TABLE
SURFACE
. .
(meq$%yg
Evacuation
Adsorbent
SiOdzO8
SiOt-MgO
r-AlsOa
T-408
7-&O,
&I802
r-&Ox
dhO8
y?$j*
500
500
500
500
700
700
900
900
ACIDITIES
10)
Strong
Medium
Weak
Total
3.7
0.5
0.4
1.3
2.9
6.5
0
7.6
3.8
6.3
11.8
20.5
19.4
10.0
15.3
14.7
3.4
9.0
27.2
11.7
15.9
27.0
27.6
13.5
10.9
15.8
39.4
33.5
38.2
43.5
32.9
35.8
ALUMINAS
I.
493
494
MACIVER,
TOBIN,
AND
BARTH
CATALYTIC
ALUMINAS
I.
495
496
MACIVER,
5.0
10.0
H20
FIG. 5. Effect
TOBIN,
AND
BARTH
15.0
20.0
LOSS.MOLS./g
of water
loss on ammonia
25.0
X10
30.0
35.0
chemisorption.
CATALYTIC
3.
4.
6.
6.
7.
8.
9.
10.
11.
Id.
13.
14.
ALUMINAS
I.
497
16. GUDEFUAHN, C. A., PAYNTER, D. A., BERQHAUSEN, P. E., AND GOOD, R. J., J. Phys.
Chem. 63, 2066 (1959).
16. W.OE, W. H., AND HACKERMAN, N., J. Phys.
Chem. 64, 1196 (1960).
17. YOUNQ, G. J., J. Colloid Sci. 13, 67 (1958).
18. PAULINE, L., The Nature of the Chemical
Bond. Cornell Univ. Press, Ithaca, New
York, 1944.
19. FRIPIAT, J. J., AND U~RHOEVEN,
J., J. Phys.
Chem. 66, 800 (1962).
20. FRIPUT, J. J., GAST~CHE, M. C., AND BmmABD, R., J. Phys. Chem. 66, 805 (1962).
81. GLEMSER, O., AND RIECK, G., 2. Angew. Chem.
67, 652 (1955) ; 68, 182 (1956).
.%. FORTUIN, J. M. H., Thesis, Univ. of Deift, The
Netherlands, 1955.
23. MEIJS, W. H., Thesis, Univ. of Delft, The
Netherlands, 1961.
94. DEBOER, J. H., AND HOUBEN, G. M. M., Proc.
Intern. Symp. Reactivity of Solids (Giithenborg) I, 237 (1952).
,666.KORDES, E., Z. Krist. 91, 193 (1935).
86. DEBoER, J. H., Chemisorption
(W. E. Garner, ed.), p. 85. Academic Press, New York,
1955.
27. U-v,
A. V., Zhur. Fiz. Khem. 36, 1346
(1962).
68. PRIU, J. B., AND HANNAN, R. B., J. Phys.
Chem. 64, 1526 (1960).
29. BALLOU, E. V., BARTH, R. T., AND FLINN, R. A.,
J. Phys. Chem. 65, 1639 (1961).
30. HALL, W. K., private communication.
31. DEBOER, J. H., FORTIJIN, J. M. H., LIPPENS,
B. C., AND MEIJS, W. H., J. Catalysis 2, 1
(1963).