Applied Catalysis A: General 206 (2001) 221229

Iron molybdate catalysts for methanol to formaldehyde oxidation:

effects of Mo excess on catalytic behaviour
A.P.V. Soares a , M. Farinha Portela a, , A. Kiennemann b , L. Hilaire b , J.M.M. Millet c
a GRECAT Grupo de Estudos de Catlise Heterognea, Instituto Superior Tcnico,
Lisbon Technical University, Avenida Rovisco Pais, 1049-001 Lisbon, Portugal
b ECPM LERCSI, UMR CNRS 7515, 25, Rue Becquerel, BP08, 67087 Strasbourg Cedex 2, France
c Institut de Recherches sur la Catalyse, CNRS, 2 Avenue Albert Einstein, 69626 Villeurbanne Cedex, France
Received 10 June 1999; received in revised form 28 April 2000; accepted 28 April 2000

Abstract
Two iron molybdate catalysts have been prepared by coprecipitation, one stoichiometric (Mo/Fe atomic ratio=1.5) and the
other with a typical industrial composition (Mo/Fe atomic ratio=3). Physicochemical characterisation shows that Mo excess
brings about an increase in the surface area and deconvolution of NH3 TPD curves evidences some changes in acidity. On
the other hand, surprisingly, Mo excess does not cause significant changes in the activity for methanol oxidation per unit
surface area. This provides evidence that Fe2 (MoO4 )3 is in fact the active phase of the catalyst. The catalyst with Mo excess
leads to higher selectivity for HCHO to the detriment of dimethyl ether selectivity. This result is attributable to larger oxygen
availability at the catalyst surface and changes in acidity. The catalytic behaviour of the prepared catalysts was compared with
that of an industrial catalyst. It was found that the prepared catalyst with an Mo/Fe composition similar to the industrial one
is more active due to larger surface area. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Iron molybdates; Methanol oxidation; Formaldehyde

1. Introduction Nowadays, both processes are still in use [3] and

Formaldehyde is one of the most important basic
chemicals and is required for the manufacture of a
large number of industrial and consumer products.
It is the most important industrially produced alde-
hyde [1]. Two processes are generally used in the in-
dustry to produce formaldehyde, both using methanol
as the starting material [2]: (i) dehydrogenation of
methanol-rich air mixture over silver catalysts and (ii)
direct oxidation of methanol-poor air mixture over iron
molybdate catalysts.
Corresponding author. Fax: +351-21-8477695.
E-mail address: mportela@alfa.ist.utl.pt (M. Farinha Portela).
the choice between silver and iron molybdate cata-
lysts must be based not only on economic aspects
but should also take into account the product end-use,
size of plant and type of operation [4]. In comparison
with catalysis over Ag, the oxidation of methanol over
Fe2 O3 MoO3 is carried out at lower temperatures, the
catalyst is less sensitive to contamination by normal
methanol impurities and also provides 95% selectivity
to formaldehyde [1,2].
Since the pioneering work of Adkins and Peter-
son [5], the growing industrial importance of FeMo
oxide catalysts has led to a large number of inves-
tigations, but important aspects of their catalytic
behaviour are still controversial. Several researchers

0926-860X/01/$ see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 9 2 6 - 8 6 0 X ( 0 0 ) 0 0 6 0 0 - 1
222 A.P.V. Soares et al. / Applied Catalysis A: General 206 (2001) 221229
have found that the catalytic behaviour of iron molyb-
dates is mainly dependent on their Mo/Fe atomic
ratio [613]. MoO3 exhibits high selectivity (nearly
100%), but has poor activity, whereas Fe2 O3 has
poor selectivity for HCHO. The addition of Fe2 O3 to
MoO3 leads to an increase in activity, proportional
to the iron content, up to an Mo/Fe atomic ratio=1.7
[7]. Further enrichment with iron leads to progres-
sive decrease in activity. Normal iron molybdate
(Fe2 (MoO4 )3 ) is likely to be the active component
of the catalyst [7,12,14]. However, some researchers
associate active sites with surface Mo atoms in oc-
tahedral coordination and such coordination is only
achieved in Fe-defective iron molybdates [10,13].
This result agrees with the fact that maximum activity
is found for catalysts with an Mo/Fe ratio greater than
the stoichiometric value. The presence of two termi-
nal oxygen atoms double-bonded to Mo in such a
coordination allows the reacting methanol molecules
to be bonded simultaneously at two points to the
surface. The hydrogen abstraction of the methanol
hydroxyl group produces metoxy species that are in-
termediates in formaldehyde formation. The role of
Fe in iron molybdate catalysts would be to favour
the transfer of O2 and H2 O between the surface and
the gas phase and to facilitate reoxidation of reduced
Mo [13,15]. Furthermore, Fagherazzi and Pernicone
[8] admitted that the presence of Fe3+ ions increases
the concentration of methanol adsorption sites, con-
sisting of an anion vacancy (acid sites) and an O2
(basic sites).
According to Alessandrini et al. [14], the active
phase of iron molybdate catalysts is the stoichiomet-
ric mixed oxide. However, these researchers recognise
the need for Mo excess to maintain the structural co-
herence of the catalyst, to increase the surface area
and to prevent the formation of iron rich phases during
reaction.
Several studies on catalyst deactivation [1620]
show that, during reaction, the catalyst loses Mo and
Mo excess is required to maintain the Mo-rich com-
position. This would be the reason why industrial cat-
alysts always have Mo/Fe atomic ratios greater than
the stoichiometric value. In fact, an Mo/Fe atomic
ratio=3 is frequent in industrial catalysts [2].
In order to clarify the role of Mo excess in catalytic
systems based on MoFe mixed oxides for methanol
selective oxidation to formaldehyde, stoichiometric
and Mo-rich (Mo/Fe=3) catalysts were compared in
this work.
2. Experimental
2.1. Preparation of catalysts
Iron molybdates with Mo/Fe atomic ratios of 1.5
(stoichiometric mixed oxide) and 3 (industrial-like
catalyst) were prepared by coprecipitation from an
aqueous solution of Fe(NO3 )3 9H2 O and (NH4 )6 Mo7
O24 . Iron nitrate solution was slowly added to the
ammonium heptamolybdate solution under vigorous
stirring. For preparation of the stoichiometric mixed
oxide, Mo solution was first acidified (pH2) with
HNO3 . After total addition of Fe solution, the precip-
itates were ripened in contact with mother liquors at
373 K for 3 h under stirring. During this period, the
Mo/Fe=1.5 yellowish precipitate changes in colour
to pale green, whereas the Mo/Fe=3 precipitate only
undergoes a slight intensification of its initial yellow
colour.
After ripening, the precipitates were filtered, dried
at 393 K overnight, and finally calcined. Calcination
was performed at 648 K for 10 h in air flow.
2.2. Characterisation of catalysts
The BET surface areas were measured with a
Perkin-Elmer Shell 212 C sorptometer by N2 ph-
ysisorption. The bulk elemental compositions were
determined by atomic absorption. X-ray diffrac-
tion (XRD) patterns were recorded with a D5000
Siemens diffractometer with a primary beam quartz
monochromator (Co K1 =1.78897 ) at 40 kV and
25 mA. The morphology, chemical analysis and ho-
mogeneity of the prepared catalysts were examined
with a scanning electron microscope JEOL JSM 840
with a Delta Kevex energy dispersive X-ray analyser.
FT-IR spectra were recorded with a Perkin-Elmer
1600 spectrometer in the range of 4000400 cm1 ,
with a resolution of 4 cm1 . For each analysis, 1 mg
of the product was ground with 100 mg of KBr
and then pelleted (2000 kg cm2 ) to a disc 13 mm
in diameter. Sixty-four scans were used for each
spectrum.
 A.P.V. Soares et al. / Applied Catalysis A: General 206 (2001) 221229
X-ray photoelectron spectroscopy (XPS) was used
to investigate the chemical analysis and reduction state
of the surface of the fresh catalysts. The analyses
were performed with a VG ESCA 3 apparatus. The
kinetic energy of the emitted photoelectron was given
by EKin =1486.6EBcor , where 1486.6 eV is the en-
ergy of the incident radiation (Al K) and EBcor the
corrected binding energy of the electron. The binding
energy of the electron, corrected from charge effects,
was calibrated with respect to the signal for adventi-
tious carbon (binding energy: 284.8 eV). The corrected
intensity for an element A is given by [21]:
IAmeas
IAcor = p
nA A EKinA
where IAmeas is the measured intensity (experimen-
tal), nA the scan number (experimental), and A the
cross-section (tabulated [22]). The ratio of the cor-
rected intensities of two elements A and B directly
accounts for the A/B atomic ratio at the surface of the
analysed sample. Curve fitting analysis was performed
using a DoniachSunjic line shape with no asymmetry
parameter and a Shirley background correction. Due
to the small energy separation between Fe2+ and Fe3+
species, the spectra of pure reference compounds con-
taining either Fe2+ or Fe3+ were recorded under the
same conditions. In addition to the binding energies,
the parameters, which represent the half width at half
maximum of the peaks, were extracted from reference
spectra. Their values were used in the curve fitting
procedure for the catalysts and it was obvious that the
parameters of two species, and not one, had to be in-
troduced to get a reasonable fit. Moreover, the binding
energies found in such a way were in good agreement,
within 0.2 eV, with those of reference samples.
The bulk composition of iron phases was studied
by Mssbauer spectroscopy at room temperature with
a time mode spectrometer and a constant acceleration
drive. 57 Co in an Rh matrix was used as a radiation
source. The isomer shifts () were given with respect
to -Fe and calculated, as the quadrupolar splittings
(1) and the line width (W) with a precision of about
0.02 mm s1 .
The study of the surface acidity of the prepared
catalysts was performed by ammonia TPD. The
catalyst sample was previously submitted to a pre-
treatment involving heating (5 K min1 ) under He
223
(30.0 cm3 min1 ). After reaching 723 K, the sample
was cooled to 323 K and ammonia adsorption was
performed by NH3 pulses (1 cm3 ). The sample was
then flushed with He for 2 h to remove ammonia ex-
cess. Ammonia was thermally desorbed (5 K min1 )
in an He flow from 323 to 723 K. The amount of
desorbed NH3 was measured by TCD detector.
2.3. Catalytic tests
Methanol oxidation was carried out in a con-
ventional flow apparatus at atmospheric pressure.
Catalytic behaviour was studied in steady-state con-
ditions. Feed mixtures were prepared by injecting
liquid methanol into air flow with a precise Gilson
302 pump. The catalyst was diluted with inert SiC
(1:7 mass ratio), to avoid adverse thermal effects, and
charged into a tubular Pyrex reactor with thermocou-
ple in a coaxial centred thermowell. The reactor outlet
was kept at 403 K, to prevent condensation of liquid
products and formaldehyde polymerisation, and was
connected to a Shimadzu GC-8A gas chromatograph
with a thermal conductivity detector. Two in-parallel
columns, one at room temperature (Hayesep D) for
N2 +O2 , CO and CO2 , and the other in the oven
of the chromatograph (porapak T) at 443 K for
HCHO, CH3 OCH3 (DME), H2 O, CH3 OH (MeOH),
HCOOCH3 (MF) and CH2 (OCH3 )2 (DMM), allowed
the separation of the reactor effluents. Formic acid
was never detected.
3. Results and discussion
3.1. Characterisation of catalysts
The results presented in Table 1 show that the sur-
face area of the prepared catalysts increases with Mo
content in the bulk. For the same Mo/Fe atomic ra-
tio, the industrial catalyst has a lower surface area
Table 1
BET surface areas
Catalyst Mo/Fe Surface
(atomic ratio) (atomic ratio) area (m2 g1 )
Industrial 3 5
Coprecipitated 3 8.3
Coprecipitated 1.5 2.8
224 A.P.V. Soares et al. / Applied Catalysis A: General 206 (2001) 221229

Table 2
Mo and Fe composition and surface reduction of studied fresh
catalysts
Catalyst (preparation Mo/Fe (atomic ratio) Fe2+ /Fe3+
Mo/Fe atomic ratio) (atomic ratio)
Atomic EDX XPS XPS
absorption
1.5 1.5 2.1 1.89 0.24
3 2.9 4.3 2.35 0.19
Industrial 3.1

than the prepared catalyst, which can be attributed to

a more severe thermal treatment during the activation
step (773 K instead of 648 K).
Several authors have prepared iron molybdates with
different Mo/Fe atomic ratios, but the study of the
variation of their surface areas as a function of the
ironmolybdenum content has never been reported.
However, Sun-Kuo et al. [13] present, for equivalent
Mo/Fe compositions, higher surface areas than those
found in the present work. This disagreement can be
attributed to a shorter thermal treatment: 2 h instead
of the 10 h used here.
The results of the bulk and surface chemical anal-
ysis of the catalysts are summarised in Table 2.
The Mo/Fe bulk ratios of the coprecipitated solids
determined by atomic absorption are in good agree- Fig. 1. Scanning electron micrographs of prepared catalysts.
ment with those of the parent solutions used for the
precipitations. The noted differences are within the
experimental error range. EDX analysis shows an Mo ratio and pH during the precipitation step and the age-
enrichment of the surface of the prepared catalysts. ing period. But the conditions reported by the authors
The same is observed by XPS for a stoichiometric to favour the formation of ordered lamellae structure
catalyst but not for the Mo/Fe=3 catalyst. It is well (low pH and Mo/Fe atomic ratios with long ageing pe-
known that XPS is more surface-sensitive than EDX riods) correspond to those used for the precipitation of
and a profile of Mo contents would be established in the stoichiometric phase in the present work. In con-
the catalyst particles by the balance of the rates of Mo clusion, the morphology exhibited by this last phase
migration from the bulk and Mo loss from the surface. is in accordance with the results of these authors.
The scanning electron micrographs (Fig. 1) show No fibre-like material, usually assignable to the
that the catalysts with stoichiometric composition dis- MoO3 phase [13,18], was found in the prepared
play an ordered lamellae morphology, whereas cata- catalysts, which is a good indication that no phase
lysts with Mo excess show a sponge-like morphology. segregation occurred during the preparation and cal-
The morphological appearance is thus well in accor- cination steps. The segregation of MoO3 is a frequent
dance with surface areas of the catalysts. However, and adverse occurrence during the preparation of iron
this finding seems to disagree with recent results of molybdenum mixed oxides. In fact, such an occur-
Sun-Kuo et al. [13] who found that samples with or- rence must be prevented because the MoO3 phase
dered lamellae have larger surface areas and that the is much less active for the selective oxidation of
morphology of iron molybdates depends on the Mo/Fe methanol than iron molybdate. Moreover, segregation
 A.P.V. Soares et al. / Applied Catalysis A: General 206 (2001) 221229 225

Table 3
X-ray diffraction (XRD) results of the prepared catalysts
Mo/Fe=1.5 Mo/Fe=3

d () I/I0 (%) d () I/I0 (%)

3.884 100 3.248 100

3.481 38.6 3.854 85.4
3.583 29.5 3.447 71.3
4.098 23.3 3.791 45.0
4.357 22.2 2.306 33.7
3.249 22.2 2.649 33.0
3.207 21.6 4.064 26.4
2.966 19.3 1.845 25.2
2.629 18.8 6.935 23.8
6.436 16.5 3.549 20.5
5.809 14.2 2.948 18.8

in the 700900 cm1 range can be ascribed to tetra-

Fig. 2. X-ray diffraction (XRD) patterns of prepared catalysts: (a)
Mo/Fe atomic ratio=1.5 and (b) Mo/Fe atomic ratio=3.
hedric species of Mo in Fe2 (MoO4 )3 [10].
Iron-containing phases were also analysed by
Mssbauer spectroscopy. The significant spectral
parameters of industrial and prepared catalysts are
summarised in Table 4. The values were obtained by
fitting the experimental spectra with pure Lorentzian

of MoO3 can lead to an Fe-rich phase that promotes

total oxidation of methanol [6].
Stoichiometric mixed oxide displays a higher crys-
tallinity than mixed oxides with Mo excess. This
result agrees with the fact that Mo excess retards the
crystallisation of Fe2 (MoO4 )3 [7]. X-ray patterns of
fresh catalysts presented in Fig. 2 confirm that the sto-
ichiometric phase is better crystallised than the phase
with Mo excess. The indexed XRD patterns (Table 3)
show that the Mo/Fe=1.5 catalyst corresponds only
to the orthorhombic ferric molybdate [23], while the
Mo/Fe=3 catalyst presents, in addition, MoO3 (peaks
at 3.248 and 6.935 ) [10]. The absence of MoO3
peaks in the Mo/Fe=1.5 X-ray patterns does not totally
rule out the existence of free MoO3 because Deltch-
eff et al. [24] have demonstrated that MoO3 is only
detected by XRD when its content is higher than 7%.
Mo excess in the prepared Mo/Fe=3 catalyst and
industrial catalyst were confirmed by the presence in
IR spectra (Fig. 3) of a narrow band for all catalysts
at 990 cm1 and a broad one at 624 cm1 character-
istic of MoO3 [10,13,25]. The weak and narrow band
that appears at 960 cm1 can be assigned to FeOMo Fig. 3. IR spectra of catalysts: (a) Mo/Fe atomic ratio=1.5; (b)
bond vibrations [25]. Finally, the broad band observed Mo/Fe atomic ratio=3; (c) industrial catalyst.
226 A.P.V. Soares et al. / Applied Catalysis A: General 206 (2001) 221229

Table 4
Mssbauer parameters of fresh catalystsa
Catalyst Fe species (mm s1 ) W (mm s1 ) 1 (mm s1 ) Relative intensity (%) Phase attribution

Industrial Fe3+ 0.41 0.32 0.21 100 Fe2 (MoO4 )3

Mo/Fe=3 Fe3+ 0.44 0.26 0.19 99 Fe2 (MoO4 )3
Fe2+ 0.89 0.28 2.34 <1
Mo/Fe=1.5 Fe3+ 0.44 0.27 0.20 100 Fe2 (MoO4 )3
a : isomeric shift; W: band width; 1: quadrupolar splitting.

curves. The identification of the phases was based on stoichiometric catalyst. The Mo/Fe=1.5 catalyst has
the published results of previous investigations of iron a broader desorption peak of chemisorbed NH3 at the
molybdates [26,27,33]. The results show that iron in lower temperature. For the strongest acid sites, the
all catalysts is present only in the Fe2 (MoO4 )3 phase. peak was higher for the Mo/Fe=3 catalyst (Fig. 5).
Mssbauer parameters of ferric cations in the cat-
alysts with Mo excesses are comparable to those of 3.2. Catalytic behaviour
ferric cation in the stoichiometric catalyst. This result
shows well that MoO3 excess does not form a solid Only formaldehyde, DME, MF, H2 O and small
solution with the Fe2 (MoO4 )3 phase, which is in amounts of CO2 were found as reaction products in
agreement with the results of Abaulina et al. [10]. The all catalytic tests.
prepared catalyst with Mo excess additionally presents In Fig. 6, conversion of methanol versus reaction
a small amount of ferrous cations (<1%) that cannot temperature is plotted for the same contact time for
be identified with ferrous cations in - or -FeMoO4 . all catalysts. As expected, conversion increases with
The surface reduction state was checked by XPS. temperature and this effect seems to be more intense
Iron-reduced species were found in the studied cata- at low conversions. On a weight basis, it is seen that
lysts. The results in Table 2 show a noticeable sur- the industrial catalyst and the Mo/Fe=3 catalyst are
face reduction. This result agrees with the Mssbauer much more active than the Mo/Fe=1.5 one (Fig. 6a),
findings. Mo excess seems to make the iron reduction
difficult.
Characterisation of the surface acidity of the pre-
pared catalysts has been carried out by NH3 TPD.
Both the stoichiometric catalyst and the catalyst pre-
pared with Mo excess display a desorption spectrum
with two distinct desorption peaks (Fig. 4). Both pre-
sented thermograms were normalised to the same sur-
face area. Deconvolution of experimental curves by
symmetrical Gaussian curves [28] reveals a third des-
orption peak for both catalysts (Fig. 5). Stoichiometric
mixed oxide display desorption peaks with maxima
at 400, 520 and 600 K, whereas for the Mo/Fe=3
catalyst, the maxima are at 400, 480 and 580 K. For
both catalysts, the low-temperature peak has its max-
imum at the same temperature. It can be assigned to
physisorbed NH3 . The Mo/Fe=3 catalyst physisorbs
more NH3 than the stoichiometric one. The other des-
orption maxima of chemisorbed NH3 are at lower tem-
peratures for Mo/Fe=3 catalysts than for Mo/Fe=1.5 Fig. 4. TPD of NH3 : () Mo/Fe atomic ratio=3; () Mo/Fe
ones. This means that acid sites are stronger for the atomic ratio=1.5. Lines correspond to the deconvoluted curves.
 A.P.V. Soares et al. / Applied Catalysis A: General 206 (2001) 221229 227

Fig. 5. Deconvolution of experimental TPD of NH3 curves with symmetrical Gaussian curves.

but on a surface basis, they are comparable (Fig. 6b).
The results show that the surface Mo/Fe atomic ra-
tio does not significantly affect methanol conversion
since the specific activity of catalysts is almost in-
dependent of the Mo content. This finding disagrees
with the majority of previously published results that
reported an optimum activity for a catalyst composi-
tion corresponding to an Mo/Fe atomic ratio of 1.7
[7], but is consonant with those of Alessandrini et al.
[14] that reported no effect of Mo excess on the spe-
cific activity of iron molybdates. One explanation for
our finding is that, due to the rate of loss of Mo from
the surface, the composition and structure of the top
layers of the catalyst with Mo excess are identical to
the ones of the stoichiometric molybdate. The data of
Table 2 do not disagree with such a hypothesis taking
into account that XPS is sensitive to the composition
in a layer of a few nanometres.
In Fig. 7 are plotted changes in the products
selectivities with the reaction temperature. As re-
ported previously [29,30], formaldehyde selectivity
increases with methanol conversion, except for a

Fig. 6. Oxidation of methanol in an air feed with 4.4% of methanol. Steady-state conversion vs. temperature at the same contact time: (a)
weight basis W/F=4.9 gcat h mol1 2 1
MeOH ; (b) surface area basis S/F=40.7 mcat h molMeOH .
228 A.P.V. Soares et al. / Applied Catalysis A: General 206 (2001) 221229
Fig. 7. Oxidation of methanol: steady-state conversion and selec-
tivities (sel.) vs. temperatures (4.4% of methanol in air feed and
W/F=4.9 gcat h mol1 MeOH ).
high conversion level when the consecutive formalde-
hyde oxidation is not negligible. At a low conversion
level, catalysts with Mo excess are more selective for
HCHO than stoichiometric ones that produce high
amounts of DME, even at low contact time [31]. In
principle, this result would be explainable on the
basis of acidity differences. In fact, it is well known
that the formation of ethers occurs by an SN 2 mecha-
nism with one molecule of the alcohol acting as the
nucleophile and with the other, protonated molecule
of the alcohol acting as the substrate. NH3 TPD for
both catalysts shows differences in the position of the
central desorption peak at around 500 K and peak ar-
eas. For the stoichiometric catalyst, the maximum of
the peak is positioned at 520 K instead of 480 K for
the Fe-defective catalyst and its area its also larger,
evidencing stronger acidity of such a type. However,
Edwards et al. [32] have ascribed the high forma-
tion of DME to the low availability of oxygen at the
catalyst surface. Furthermore, Ai [33,34] stated that
dehydration of methanol to ether occurs over acidic
oxides with no oxidising potential. This would allow
to conclude that Mo in excess increases the amount
of available oxygen at the surface and enhances the
oxidation potential of mixed oxide.
4. Conclusions
The present investigation has shown that the intro-
duction of Mo excess in MoFe mixed oxide, with
respect to stoichiometry, leads to an increase in the
surface area of the catalysts.
The characterisation results agree with the litera-
ture pointing out that Mo in excess is embedded in the
interstices of the crystalline network without substitu-
tion of Fe3+ ions by Mo6+ ions.
In spite of the acidic character of the Mo oxide,
the prepared catalysts (Mo/Fe=1.5 and Mo/Fe=3) do
not present very significant differences of acidity, as
determined by NH3 TPD.
The results of the catalytic tests evidence that the
intrinsic activity (per unit surface area) is not af-
fected by Mo excess, suggesting that the Fe2 (MoO4 )3
stoichiometric phase would be the active phase
of the catalyst. However, Mo excess increases the
HCHO selectivity to the detriment of DME selec-
tivity. The differences in DME selectivity found
 A.P.V. Soares et al. / Applied Catalysis A: General 206 (2001) 221229
with stoichiometric and Mo-rich catalysts can be
attributable to differences in acidity and oxidising po-
tential. Mo excess in bulk seems to increase surface
reoxidability.
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