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Evaluation of different methods to prepare the Fe 2O 3/MoO 3 catalyst used for

selective oxidation of methanol to formaldehyde

Article  in  Studies in surface science and catalysis · December 2010

DOI: 10.1016/S0167-2991(10)75088-6

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10th International Symposium “Scientific Bases for the Preparation of Heterogeneous Catalysts”
E.M. Gaigneaux, M. Devillers, S. Hermans, P. Jacobs, J. Martens and P. Ruiz (Editors)
© 2010 Elsevier B.V. All rights reserved.

Evaluation of different methods to prepare

the Fe2O3/MoO3 catalyst used for selective
oxidation of methanol to formaldehyde
Karim H. Hassana,*, Philip C.H. Mitchellb
a
Department of Chemistry, College of Science, University of Diyala, Baqubq, Iraq
b
School of Chemistry, University of Reading, Reading, RG6 6AD, UK

Abstract
Different Fe2O3/MoO3 catalysts were prepared by kneading, precipitation and
co-precipitation methods. Their activities and selectivities in the oxidation of methanol
to formaldehyde were compared with those of a commercial catalyst. The iron(III)
molybdate catalyst prepared by co-precipitation and filtration had a selectivity towards
formaldehyde in methanol oxidation comparable with a commercial catalyst; maximum
selectivity (82.3%) was obtained at 573 K when the conversion was 59.7%. Catalysts
prepared by reacting iron(III) and molybdate by kneading or precipitation followed by
evaporation, omitting a filtration stage, were less active and less selective.

Keywords: Iron molybdate catalyst, Selective catalytic oxidation, Catalysts preparation

1. Introduction
Formaldehyde, CH2O, is manufactured by the selective oxidation of methanol over a
silver [1,2] or iron molybdate catalyst [3,,4]. Iron molybdate catalyst is a combination of
the two oxides that produces the desired active and selective catalyst. Iron(III) oxide by
itself is unselective producing carbon dioxide and water; molybdenum trioxide is
selective but with low activity [5].
The overall reaction is
CH3OH + 0.5O2 = CH2O + H2O.
The oxidation reaction is exothermic (∆H=-159 kJ mol–1) and proceeds through
reaction of methanol with the molybdate surface [6].
The technical catalyst composition is ca.(80% MoO3 and 20% Fe2O3), equivalent to
an iron mole fraction 0.31. Iron may be partially replaced by a promoter, e.g. chromium.
The active catalyst is considered to be Fe2(MoO4)3. The excess of MoO3 is said
variously to be required to ensure the stability of the catalyst towards loss of MoO3, to
maintain the active species and to enhance the surface area. It should be stressed that
catalyst structure depends also on other parameters such as metal loading, and drying
and calcination temperatures. The method of preparation appears to have a significant
impact on the activity and selectivity of the catalyst. There are some studies of different
preparations, for example sol-gel catalysts vs co-precipitated catalysts [7].
The aim of the present work is to evaluate different methods of preparation of the
iron molybdate catalysts and test the activities and selectivities in the oxidation of
methanol to formaldehyde by comparing with those of a commercial catalyst.
476 K. Hassan and P.C.H. Mitchell

2. Experimental
2.1. Catalyst preparation
Ammonium heptamolybdate, (NH4)6Mo7O24.4H2O; and iron(III) nitrate nonahydrate,
Fe(NO3)3 .9H2O, analytical grade (>99% purity), were used.
2.1.1. Kneading and evaporation: catalyst 1
Ammonium molybdate was added to the amount of water that is sufficient to obtain a
homogeneous paste when added gradually to iron nitrate powder with continuous
stirring. The paste was heated in an oven at 110oC for 2 h to evaporate water and
calcined at 400–500°C in a current of air for 4 h.
2.1.2. Precipitation and concentration: catalyst 2
Solutions of ammonium heptamolybdate and iron (III) nitrate were mixed at pH of
about 2. The precipitate formed was left to settle overnight at room temperature, the
supernatant was decanted off and the precipitate dried and calcined as for catalyst 2.
2.1.3. Coprecipitation and filtration: catalyst 3
Solutions of ammonium heptamolybdate and iron(III) nitrate were prepared and mixed
as in the preparation of catalyst 2. The precipitate was filtered off and washed several
times with distilled water until the pH of the filtrate reached 7. The solid was dried and
calcined as before. Pellets (or tablets) (7 mm diameter, 4 mm thick) were prepared in a
tablet press at 2 atm. Using polyvinyl alcohol as binder and were calcined at 500oC .
2.2. Catalyst characterization and testing
Iron and molybdenum were determined by standard atomic absorption methods. Pore
volume, densities and hardness values were determined by the usual methods used in
catalysts characterization. Activities and selectivities of the catalysts in the conversion
of methanol to formaldehyde were determined in a continuous flow pilot plant described
by Karim and Hummadi [8]. Test conditions were: reactor temperature 200 to 350°C
(473–623 K); pressure, 10 atm (1013 kPa); flow rate, 15.858 cm3/s; methanol, 5.5% by
volume in oxygen.
Analysis of the reaction products was carried out periodically [9] after two hours of
collection of the samples.

3. Results and discussion

3.1. Chemical composition and physical properties of the catalysts
Catalyst 3 in its composition and physical properties is closest to the commercial
catalyst. The most obvious difference between the different preparations is the excess
MoO3, which is greatest for catalyst 3 (Table 1). Excess molybdenum (over the
stoichiometric composition) appears to have little effect on the catalyst density.
However, the two catalysts with the highest molybdenum (catalyst 3 and the
commercial catalyst) have the greatest pore volumes and hardness.
Evaluation of different methods to prepare the Fe2O3/MoO3 catalyst 477

Table 1. Chemical composition and physical properties of the catalysts.

Composition Catalyst
and Property
Catalyst 1 Catalyst 2 Catalyst 3 Commerciala
Kneading and Precipitation and Coprecipitation
evaporation concentration and filtration
Composition/wt.
%
Fe 17.2 15.6 13.8 14.0
Mo 50.2 51.7 53.4 53.0
Fe2O3 24.6 22.3 19.7 20.0
MoO3 75.4 77.7 80.2 80.0
MoO3 2.32 4.57 7.12 6.52
excess/wt.%
Mo/Fe atomic 1.70 1.93 2.25 2.20
ratio
Fe/(Fe + Mo) 0.371 0.341 0.308 0.312
mole fraction
Colour Yellow green Yellow green Yellow Yellow
Pellet size/cm 0.9×0.9 0.9×0.9 0.9×0.9 0.45×0.4
Pore volume/ 0.28 0.30 0.40 0.35
cm3 g-1
Solid density/g 0.53 0.50 0.52 0.50
cm-3
Bulk density/g 1.05 1.05 1.05 1.10
cm-3
Hardness/105 1.70 1.63 2.1 2.3
dyne
a
Received from the Ministry of Industry of Iraq.

3.2. Catalytic properties: activities and selectivities in the oxidation of methanol

to formaldehyde
Activities and selectivities are shown plotted vs temperature in Fig. 1.
The behavior of our co-precipitated catalyst (catalyst 3) is similar to that of the
commercial catalyst. The activities of all catalysts rise with rising temperature and
converge to roughly the same conversion at 598 K. The significant distinction between
the catalysts is in the selectivity which passes through a maximum at 573 K with the
commercial and the co-precipitated catalysts having the highest selectivities.
Our catalytic results are consistent with the literature [3,4], with activities tending
to the same value independently of the iron (or molybdenum) content of the catalyst and
selectivities passing through a maximum with increasing reaction temperature.
We discuss now how the activity and selectivity depend on the composition of the
catalyst with reference to our results and literature data [10]. Generally the effect of
composition has been discussed in terms of excess of MoO3. However, since MoO3 is in
excess it would seem logical to express the variation of catalyst composition in terms of
iron added (or not) to molybdenum, i.e. the Fe/Mo ratio or the Fe/(Fe+Mo) mole
fraction as for other two-component catalysts, for example, the cobalt-promoted
molybdenum disulfide based hydrodesulphurization catalyst.
Unfortunately most researchers have not studied a wide range of Fe/Mo
compositions (and we are no exception). However, we can combine certain patent
literature data [10] with our data and thereby examine a wider range of compositions.
Activities and selectivities values (figure and data can be obtained from authors). For
 478 K. Hassan and P.C.H. Mitchell

the activities we see a typical volcano curve, the activity rising to a maximum value as
iron is added to MoO3 and then dropping off. This behavior demonstrates synergy
between iron and molybdenum. Beyond an iron mole fraction of 0.4 the activity begins
to increase as Fe2O3 takes over. The selectivity to formaldehyde is more or less constant
until an iron mole fraction of ca 0.3 is reached. The selectivity then drops as Fe2O3
becomes dominant. This behavior tells us that the selective catalyst is MoO3 and iron is
an activity promoter.

65 0.85

60
0.75

55
conversion/%

0.65
50 selectivity
0.55
45
commercial catalyst
0.45
40 catalyst 1 kneading
catalyst 2 precipitation
catalyst 3 co-precipitation
35 0.35
450 500 550 600 650 450 500 550 600 650
T /K T /K

Fig. 1. Conversion (left) and selectivity (right) in conversion of methanol to formaldehyde.

References
[1] J.L. Li, W.L. Dai, K. Dong and J.F. Domg, (2000) “A new silver–containing ceramics for
catalytic oxidation of methanol to formaldehyde”, Materials Letters,44 (3-4), 233-236.
[2] I.E. Wachs, (2003) “Extending surface science studies to industrial reaction conditions;
mechanism and kinetics of methanol oxidation over silver surface”, Surface Science, 544, 1-4.
[3] A.P.V. Soares, M.F. Portela, A. Kiennemann, L. Hilaire and J.M.M. Millet (2001) “Iron
molybdate catalysts for methanol to formaldehyde oxidation; effect of Mo excess on
catalystic behaviour”, Applied catalysis, 206, 221-229.
[4] K. Ivanov and I. Mitov, (2000) “Selective oxidation of methanol on Fe-Mo-W catalysts”,
Journal of Alloys and Compounds, 309(14) 57-60.
[5] C.T. Wang and R.J. Willey, (2001) “Mechanistic aspects of methanol partial oxidation over
supported iron oxide aerogel”, Journal of Catalysis, 202(2)211-219.
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and Uses of Molybdenum, Proceedings of the Climax Fifth International Conference,
Polyhedron Symposia-, Number 2, Pergamon Press, Oxford, 1986, p.129.
[7] A.P.V. Soares, M.F. Portela, and A. Kiennemann, Third World Congress on Oxidation
Catalysis, By Grasselli, R.K; Oyama, S.T; Gaffney, A.M, Published by Elsevier, (1997),
110, 807-816.
[8] K.H. Hassan and K.K. Hummadi, (2004), “Production of formaldehyde by catalytic
conversion of methanol”, Iraqi Journal of Chemical and Petroleum Engineering, 5, 33-39.
[9] D. Monti ,A. Reller and A. Baiker ,(1985) “Methanol oxidation on K2SO4- promoted
vanadium pentoxide catalysts”, Journal of Catalysis, 93, 360-367.
[10] I.E. Wachs and L.E. Briand, US Patent 6037290 (2000) to Lehigh University, Bethlehem,
PA, USA.

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