Applied Catalysis A: General 177 (1999) 85±97

Characterization and infrared study of the effect of Cr,

Mo and W on carbon deposition on platinum/alumina
Zenon Sarbak
Faculty of Chemistry, Adam Mickiewicz University, Grunwaldzka 6, 60-780 Poznan, Poland

Received 21 July 1997; received in revised form 20 July 1998; accepted 20 July 1998

Abstract

Deposition of increasing amount of Cr, Mo and W ions on g-Al2O3 leads to a decrease of the surface area on the catalysts.
Additional introduction of Pt leads to the increase of the latter except for 0.3 wt% Pt±2 wt% Cr/Al2O3 sample.
Low-loaded Pt±Cr/Al2O3 samples have the surface CrOOH groups and Pt6‡ ions. However, high-loaded sample show
evidence of the presence of a- and g-Cr2O3 as well as hydrous chromium oxide.
Both high- and low-loaded Pt±Mo/Al2O3 samples contain Pt6‡±Mo surface species. High-loaded samples are characterized
by high thermal stability of surface species.
High-loaded Pt±W/Al2O3 samples contain W6‡ surface species but evidence for the presence of Pt6‡ ions is ambiguous.
The results show that ethylene deposition on low-loaded samples yield two strong bands with maxima near 1580 and
1460 cmÿ1 in the FT-IR spectra. These bands, identical to those observed for chemisorbed acetic acid were assigned to the
asymmetric and symmetric stretching vibrations of C±O bonds in carboxylate structure. Moreover, for Pt 2 wt% Mo/Al2O3
sample the bands assigned to the conventional coke were also noticed.
For high-loaded samples the bands attributed to carboxylate were only observed for Pt±Cr/Al2O3. However, the FT-IR
spectra of all samples from this series showed bands assigned to alkylnaphthalenes and polyphenylenes.
In conclusion, we can suggest that in low-loaded Pt±Me/Al2O3 samples coke has a more carboxylate character whereas for
high-loaded samples coke is more aromatic. # 1999 Elsevier Science B.V. All rights reserved.

Keywords: Pt±Cr; Pt±Mo; Pt±W catalysts; Coke deposition

1. Introduction expensive Re or Ir metals as a second one. For this

Alumina supported bimetallic catalysts show high
activity and selectivity in many reactions such as
naphtha reforming, hydrogenolysis of alkanes and
cycloalkanes, as well as in the removal of pollutants
from engine exhaust.
In general, these catalysts contain Pt at low
concentrations as the ®rst component and rare
reason Pt has been applied with Sn and very seldom
with such transition metals as Cr, Mo and W. Such
bimetallic catalysts were tested in reactions of nitric
oxide reduction [1,2] butane hydrogenolysis [3],
hydrocarbon hydroconversions [4,5] benzene hydro-
genation [6,7], and reforming [8,9]. Moreover, the
Pt±W system has been mentioned as an attractive
alternative for decreasing Pt content and it was also

0926-860X/99/$ ± see front matter # 1999 Elsevier Science B.V. All rights reserved.
PII: S0926-860X(98)00249-X
86 Z. Sarbak / Applied Catalysis A: General 177 (1999) 85±97

found to have signi®cantly longer life than a 0.3Pt Differential thermal analysis (DTA) was performed
catalyst1. on an OD-102 apparatus (Hungary). Samples were
However, a limiting factor in processing hydrocar- heated to 10008C in a ceramic crucible at a rate of
bon-containing feeds is deactivation due to coke 108C/min in nitrogen atmosphere.
deposition.
In order to investigate coke deposition, low (2 wt%) 2.3. Infrared study of coke deposition
and high (20 wt%) loaded Pt±Me/Al2O3 samples with
MeˆCr, Mo, W were prepared. Coke was deposited The infrared spectra of deposits formed by the in
on reduced samples by exposure to ethylene at 3508C situ decomposition of ethylene were measured with an
and examined using high vacuum cell and FT-IR Analect FX-6160 FT-IR spectrometer at a resolution
method. of 2 cmÿ1.
Samples were pressed at a low pressure into
25.4 mm diameter disks with an area of about
2. Experimental 2.6 cm2. A self-supporting wafer of about 50 mg
was placed in a glass cell with NaCl windows. The
2.1. Catalyst preparation cell was attached to a high vacuum system and the
wafer was outgassed at 3508C and 10ÿ5 Torr for 1 h
All samples were prepared by the incipient wetness and then reduced under 300 Torr of hydrogen for 1 h at
impregnation technique using water solution which 3508C. After evacuation of hydrogen, ethylene vapour
contained the desired amounts of chloroplatinic acid, was introduced to the cell. Coke deposition was
chromium nitrate and ammonium heptamolybdate or carried out by annealing the sample at 3508C for
ammonium tungstate. The catalysts were prepared in a 4 h. After deposition, the cell was cooled to room
two-stage procedure. In the ®rst stage one metal from temperature and IR spectra of 200 scans were
the sixth group (Cr, Mo or W) was deposited on an recorded.
alumina support (Alumina oxide-C, Degussa, USA) of
surface area equal to 100 m2/g, which was left to
equilibrate for 3 h at room temperature and then dried 3. Results and discussion
at 1108C for 3 h and ®nally calcined in air for 5 h. Pt
was deposited during the second stage, then dried and By applying the incipient wetness method, samples
calcined in air at 5008C. containing a low (2 wt%) and high (20 wt%) amount
A 0.3Pt/Al2O3 catalyst was prepared by impregna- of chromium, molybdena or tungsten were obtained.
tion of the alumina support with chloroplatinic acid by Moreover, some of the studied samples contained
the incipient wetness method followed by drying and 0.3 wt% of platinum. The nominal composition,
calcination under the same conditions as above. nomenclature, and the surface areas of two catalyst
series are shown in Table 1.
2.2. Catalyst characterization
Table 1
X-ray diffraction (XRD) patterns were obtained in a Nomenclature, nominal composition and surface area of catalysts
TUR±M62 diffractometer using Ni-®ltered Cu K
Ê ). Low loaded Surface High loaded Surface
radiation (ˆ1.5418 A catalysts area (m2/g) catalysts area (m2/g)
The IR measurements were made in the range
3700±400 cmÿ1 on a Perkin-Elmer 180 spectro- 2Cr/Al2O3a 92 20Cr/Al2O3 76
0.3Pt±2Cr/Al2O3 90 0.3Pt±20Cr/Al2O3 77
meter using 1.5 mg of the sample mixed with 2Mo/Al2O3 93 20Mo/Al2O3 69
30 mg KBr. 0.3Pt±2Mo/Al2O3 95 0.3Pt±20Mo/Al2O3 77
2W/Al2O3 87 20W/Al2O3 70
0.3Pt±2W/Al2O3 95 0.3Pt±20W/Al2O3 74
1 a
The number preceding the catalyst component represents its The number preceeding the catalyst component represents its
composition in wt%. composition in wt%.
 Z. Sarbak / Applied Catalysis A: General 177 (1999) 85±97
3.1. Surface area
Deposition of chromium ions on g-alumina oxide
support results in a reduction of the speci®c surface
area relative to that of pure oxide. The changes in
surface area are small for the low-loaded samples, but
signi®cant for the high-loaded samples.
For samples containing molybdena it was found that
small amounts of this metal cause only small changes
in the speci®c surface area, while deposition of
20 wt% of Mo ions on g-Al2O3 brings about 30%
decrease in the speci®c surface area. Similar results
were obtained for modi®cations with tungsten ions.
As a result of deposition of 0.3 wt% of platinum on
g-Al2O3 modi®ed with metal ions from the sixth
group, the surface area of the samples increases,
except for the sample of 0.3Pt±2Cr/Al2O3 for which
Fig. 1. X-ray diffraction patterns of alumina and alumina supported catalysts: (a) Al2O3, (b) 2Cr/Al2O3 (1108C), (c) 2Cr/Al2O3 (5008C) and
(d) 0.3Pt/2Cr/Al2O3.
87
the surface area decreases relative to that for the
samples without platinum.
The results provide grounds for a conclusion that
the increase of the concentration of ions from the sixth
group is responsible for a signi®cant decrease in the
speci®c surface area, whereas additional introduction
of platinum leads to its increase (except for the sample
of 0.3Pt±2Cr/g-Al2O3). Interestingly enough a direct
introduction of 0.3 wt% of Pt on g-Al2O3 does not
bring about any change in the speci®c surface area.
3.2. Characterization of Pt±Cr/Al2O3 samples
Besides changes in the texture of the samples,
also their structure changes, which can be seen in
the diffractograms. Fig. 1 shows diffractograms
of g-alumina oxide and the samples modi®ed with
88 Z. Sarbak / Applied Catalysis A: General 177 (1999) 85±97
Fig. 2. X-ray diffraction patterns of alumina supported catalysts: (a) 20Cr/Al2O3 (5008C) and (b) 0.3Pt/20Cr/Al2O3.
2 wt% of chromium and platinum. Deposition of
chromium on g-Al2O3 and drying of the sample
at 1108C causes an insigni®cant decrease in the
intensity of all crystallographic re¯exes relative to
the spectrum of pure g-Al2O3 (Fig. 1(b)). On the other
hand, calcination of this sample at 5008C leads to the
appearance of a new, quite distinct, re¯ex at dˆ4.62
(Fig. 1(c)). According to literature data [7±10], this
re¯ex is related to the CrOOH phase. The re¯ex,
however, is not clearly seen for the sample of
0.3Pt±2Cr/Al2O3 (Fig. 1(d)), yet instead a new one
appears at dˆ5.04 which is attributed to the newly
added Pt6‡ ions.
X-ray patterns of high chromium content samples
are given in Fig. 2. For 20Cr/Al2O3 (Fig. 2(a)), and
0.3Pt±20Cr/Al2O3 (Fig. 2(b)) many new distinct
re¯exes are observed, while the intensities of the
re¯exes characteristic of g-Al2O3 are either signi®-
cantly (dˆ1.40, 1.98) or totally reduced (2.28, 2.39).
The new re¯exes are related to a-Cr2O3 (dˆ2.66 and
2.46) [11] as well as to g-Cr2O3 (dˆ2.03, 1.67, 1.46)
[10], while the others can be attributed to hydrous
chromium(III) oxides [10] which undergo decom-
position into oxides at temperatures above 5008C.
The presence of these hydroxyoxides is con®rmed
by the thermal analysis DTA curves (Fig. 3) showing
two endothermic effects with minima at 1808C and
2208C. They are related to abstraction of water
molecules adsorbed on Al3‡ (the former) and on
Cr3‡ (the latter) ions. The second endothermic effect
characterizes abstraction of water molecules related
to two different groups containing Cr3‡, which is
indicated by the bipartite effect on the DTG curve
with the maximum of water loss at 2008C and 2208C.
A wide exothermic effect in the temperature range
350±6208C, which is accompanied by a small mass
loss (TG curve), may suggest transformation of the
Cr3‡±O groups.
Samples containing 2 and 20 wt% of Cr calcined at
5008C and the Pt±Cr/Al2O3 samples dried at 1108C
have similar IR spectra re¯ecting vibrations of the
crystalline lattice (Fig. 4). Only for samples contain-
ing Cr6‡ dried at 1108C an additional band appeared at
1375 and 1620 cmÿ1 for 2Cr/Al2O3, and at 1050,
1370, 1620, 1830 and 2400 cmÿ1 for 20 Cr/Al2O3.
In this case the bands at 1050 and 1370±1375 cmÿ1
are assigned to nitrate ions introduced upon prepara-
tion. During calcination, at 5008C these ions undergo a
 Z. Sarbak / Applied Catalysis A: General 177 (1999) 85±97 89

Fig. 3. Thermal analysis of 20Cr/Al2O3 (1108C) catalyst.

total decomposition. The other bands at 1620, 1830
and 2400 cmÿ1 are attributed to hydroxyl groups
associated with Cr3‡ ions occurring in different envir-
onments. There is also a broad band at 3400 cmÿ1
which is characteristic of vibrations of hydroxyl
groups. After calcination all these bands disappear,
the only one remaining is the weak 1620±1630 cmÿ1
band. The above described changes are fully con-
®rmed by the previously discussed DTA/DTG studies
(Fig. 3).
3.3. Characterization of Pt±Mo/Al2O3 samples
For the series of samples containing molybdenum in
low loading, all re¯exes characteristic of alumina
oxide occur (Fig. 5(a) and (b), yet there are no
re¯exes typical of the molybdena species. How-
ever, for samples containing molybdenum in high
loading (Fig. 5(c) and (d)), two distinct, sharp
re¯exes appear at dˆ3.23 and 3.77 and weak ones
at dˆ2.64 and 3.48 A Ê ± for samples free of platinum
90 Z. Sarbak / Applied Catalysis A: General 177 (1999) 85±97

Fig. 4. IR spectra of alumina and alumina supported catalysts: (a) Al2O3, (b) 2Cr/Al2O3 (1108C), (c) 2Cr/Al2O3 (5008C), (d) 0.3Pt/2Cr/Al2O3,
(e) 20Cr/Al2O3 (1108C), (f) 20Cr/Al2O3 (5008C) and (g) 0.3Pt/20Cr/Al2O3.

ions, and at dˆ3.25, 4.72 and 4.93 for samples with
platinum. For this reason we can suggest that the last
two re¯exes characterize surface species containing
Pt6‡ ions.
For the 0.3Pt±20Mo/Al2O3 samples (Fig. 5(d)), the
disappearance of re¯exes at dˆ2.64, 3.48, and 3.77
and a signi®cant reduction of re¯exes at dˆ3.25
suggest a coverage of molybdena phase with a layer
of platinum phase. These species have a relatively
high thermal stability (Fig. 6) and only after heating to
about 8508C decomposition involving most probable
cleavage of bonds between the molybdenum species
 Z. Sarbak / Applied Catalysis A: General 177 (1999) 85±97
Fig. 5. X-ray diffraction patterns of alumina supported catalysts: (a) 2Mo/Al2O3, (b) 0.3Pt/2Mo/Al2O3, (c) 20Mo/Al2O3 and (d) 0.3Pt/20Mo/
Al2O3.
and carriers may take place, which is related to mass
loss and appearance of the endothermic effect with the
minimum at 9608C. A similar phenomenon was
observed for the oxide species of the Co±Mo/Al2O3
catalyst [12]. Fig. 6 shows DTA curves for high-
loaded samples. In the temperature range RT±
4008C, only endothermic effects related to water
cleavage are found. For the 20Mo/Al2O3 sample a
quite broad symmetrical effect with the minimum at
1308C and a small one in the temperature range 300±
4008C are observed. The ®rst one is due to desorption
of weakly adsorbed water molecules, while the second
one might be related to dehydroxylation in the molyb-
dena species since the effect was not detected for
alumina oxide. Similar endothermic effects were
observed for the 0.3Pt±20Mo/Al2O3 catalysts, yet
the ®rst one was a bipartite effect with two distinct
minima at 1208C and 1608C. The second minimum in
the bipartite effect seems to be associated with
abstraction of water molecules bonded with molyb-
denum species.
91
3.4. Characterization of Pt±W/Al2O3 samples
Deposition of tungsten in low concentration on the
surface of alumina oxide does not bring about any
signi®cant structural changes, as con®rmed by the
X-ray diffraction patterns of 2W/Al2O3 and 0.3Pt±
2W/Al2O3 (Fig. 7(a) and (b)). On the other hand, the
structure of the samples undergoes considerable
changes upon introduction of tungsten ions in high
concentration (Fig. 7(c) and (d)). The XRD studies
testify to a formation of new tungsten species, which
is evidenced by the appearance of distinct, intense
crystallographic re¯exes at dˆ4.04, 2.64, 1.71, and
1.66. At the same time it is observed that many
re¯exes characteristic of alumina oxide (dˆ2.73,
2.45, and 2.28) disappear while the re¯exes at
dˆ1.39 and 1.98 markedly diminish. This suggests
that a considerable part of the alumina surface is
covered with tungsten and platinum±tungsten species.
Iannibello et al. [13] proved that only 19±20% of
W6‡ ions (as WO3) is chemisorbed on the surface
92 Z. Sarbak / Applied Catalysis A: General 177 (1999) 85±97

Fig. 6. DTA curves of catalysts: 20Mo/Al2O3 and 0.3Pt/20Mo/Al2O3.

of g-Al2O3. When the amount of these ions is higher, it
can be expected that after calcination they may occur
as WO3. In our studies this oxide is not observed to be
formed, as the DTA (Fig. 8) curves for the studied
samples reveal only endothermic effects attributed to
desorption of water molecules upon heating in the
temperature range RT±4208C. Moreover, it is known
that in the experimental conditions heating of the
samples in the temperature range RT±4208C does
not cause a signi®cant mass loss related to, for exam-
ple, WO3 volatization (TG curve is not shown in
Fig. 8).
According to Regalbuto and Wolf [14] all
the aforementioned crystallographic effects are
associated with the formation of the W6‡±O surface
phase.
3.5. Coke deposition
Fig. 9 shows a spectrum of a gaseous ethylene prior
to chemisorption on oxide species of the Pt±Me/Al2O3
catalysts (where MeˆCr, Mo, W). This spectrum
reveals three intense absorption bands at 1465,
1448, and 1412 cmÿ1 typical of alkene. As a result
of thermal activation of the samples and then their
reduction with hydrogen, ethylene at 3508C takes part
in a reaction leading to a formation of the so-called
coal deposit on the surface of these catalysts.
3.6. Coke deposition on Pt±Cr/Al2O3 samples
Fig. 10 presents FT-IR spectra, which characterize
the coke deposit on the 0.3Pt±XCr/Al2O3 catalysts
 Z. Sarbak / Applied Catalysis A: General 177 (1999) 85±97
Fig. 7. X-ray diffraction patterns of alumina supported catalysts: (a) 2W/Al2O3, (b) 0.3Pt/2W/Al2O3, (c) 20W/Al2O3 and (d) 0.3Pt/20W/
Al2O3.
(Xˆ2 and 20 wt%). The spectrum represented by
curve (a) in Fig. 10 refers to a low-loaded sample
and it reveals bands at 1570 and 1454 cmÿ1 which are
assigned, respectively, to asymmetrical and symme-
trical stretching carbon±oxygen vibrations in the car-
boxylate structure [15]. Curve (b) in Fig. 10 represents
a spectrum containing two bands characteristic of
carboxylate structure (1568, 1447 cmÿ1) and two
additional bands at 1548 cmÿ1. The two latter bands
also suggest formation of carbon deposit, but of a
different character than the previous one. The band at
1548 and 1350 cmÿ1 was also found by Fetting et al.
[16], Karge [17] and Novakova et al. [18] and it has
been assigned to alkylnaphthalenes, however, it is also
typical of polyphenylene structures [19]. According to
Blackmond et al. [20,21], the band at 1350 cmÿ1
represents a ±CH bond of a tertiary carbon, indicating
that the branching of the linear hydrocarbon reactant
may be taking place. These compounds could be
formed by successive polymerization and hydrogen
elimination reactions on the catalyst surface, as these
reactions proceed more easily than cyclization and
93
aromatization reactions. Gosh and Kydd [22],
Galuszka and Amenomiya [23] observed a similar
band at about 1340 cmÿ1. The band at ca.
1360 cmÿ1 was also observed in ground graphites,
carbon black and activated carbons [24].
3.7. Coke deposition on Pt±Mo/Al2O3 samples
For the 0.3Pt±Mo/Al2O3 catalysts in the case of a
low-loaded sample (Fig. 11(a)) bands revealing max-
ima at 1586, 1571, 1468 and 1408 cmÿ1 are observed.
On the basis of the description of bands presented for
the series of a sample containing chromium, for the
case under investigation we can differentiate bands
assigned to the formation of carboxylate species (1571
and 1468 cmÿ1) and bands assigned to the conven-
tional coke (1586, 1468, and 1408 cmÿ1). Similar
spectra were observed for coke deposited on HY
zeolite for acetylene at 2508C [25].
According to Heldeman and Botty [26], the carbo-
naceous species to which the band at 1586 cmÿ1 is
attributed, have microcrystalline graphitic carbon
94 Z. Sarbak / Applied Catalysis A: General 177 (1999) 85±97

Fig. 8. DTA curves of catalysts: 20W/Al2O3 and 0.3Pt/20W/Al2O3.

structures, which are present in polycyclic aromatic
compounds and carbonaceous more disorganized
materials.
The absorption band at 1468 cmÿ1 can be also
assigned to ±CH2± deformation on the oligomer itself
[27]. This band was also found in coke on zeolites by
Blackmond et al. [20,21], Karge [17], Gosh and Kydd
[22].
In the case of high-loaded samples (0.3Pt±20Mo/
Al2O3), their IR spectra reveal small and broadened
bands (Fig. 11(b)). Among the observed bands, none
are characteristic of carboxylate species, but one can
notice bands characteristic of different types of coke
deposits.
The bands at 1360 and 1447 cmÿ1 may characterize
deformation vibrations of ±CH2- and ±CH3-groups,
while the band at 1538 cmÿ1 was assigned to alkyl-
naphthalenes and polyphonylene species. The band at
1447 cmÿ1 may also arise from aliphatic groups
attacked to the aromatic rings [22].
3.8. Coke deposition on Pt±W/Al2O3 samples
The infrared spectra of 0.3Pt±W/Al2O3 catalyst
samples (low and high loading) are shown in
Fig. 12(a) and (b).
Fig. 12(a) shows intense carboxylate bands at 1575
and 1466 cmÿ1 observed in the spectrum of coke
deposited on 0.3Pt±W/Al2O3 sample as a result of
exposure to ethylene. Similar bands are observed
when alumina is used [27].
 Z. Sarbak / Applied Catalysis A: General 177 (1999) 85±97 95

Fig. 9. FT-IR spectrum of ethylene.

Fig. 10. FT-IR spectrum of coke deposition on 0.3Pt/20Cr/Al2O3 and 0.3Pt/2Cr/Al2O3 catalysts.
96 Z. Sarbak / Applied Catalysis A: General 177 (1999) 85±97

Fig. 11. FT-IR spectrum of coke deposition on (a) 0.3Pt/20Mo/Al2O3 and (b) 0.3Pt/2Cr/Al2O3 catalysts.

Fig. 12. FT-IR spectrum of coke deposition on (a) 0.3Pt/20W/Al2O3 and (b) 0.3Pt/2W/Al2O3 catalysts.
 Z. Sarbak / Applied Catalysis A: General 177 (1999) 85±97
However, for high-loaded sample (0.3Pt±W/Al2O3)
the spectrum of coke deposit (Fig. 12(b)) is much
more complex and very similar to the spectrum of that
on 0.3Pt±Mo/Al2O3. The only difference is the band at
1592 cmÿ1 which appeared for samples containing
tungsten. This band is attributed to conventional coke
and was found in microcrystalline graphitic carbon
structures which are present in polycyclic aromatic
compounds, and which also make up the carbonaceous
deposit on catalysts [26].
The bands at 1529, 1501, 1462, 1414, 1398 and
1363 cmÿ1 were already observed for high-loaded
0.3Pt±Mo/Al2O3 catalysts which characterize conven-
tional coke.
4. Conclusion
The increase of the concentration of metal ions from
sixth group is responsible for a signi®cant decrease in
surface area. However, additional introduction of Pt
leads to its increase.
The low-loaded Pt±Cr/Al2O3 samples contain sur-
face CrOOH groups and Pt6‡ ions. However, the high-
loaded samples show evidence of the presence of a-
and g-Cr2O3 as well as hydrous chromium oxides.
Both high- and low-loaded Pt±Mo/Al2O3 samples
contain Pt6‡±Mo surface species. High-loaded sam-
ples show high thermal stability of the surface species.
High-loaded Pt±W/Al2O3 samples contain W6‡
surface species but the evidence for Pt6‡ ions presence
is not clear.
Ethylene deposition on low-loaded 0.3Pt±2Me/
Al2O3 samples show bands typical of carboxylate
structure. However, in the case of Mo containing
sample conventional coke were also detected.
High-loaded sample contain mainly conventional
coke but in the case of Cr containing sample coke has
carboxylate character.
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