Applied Catalysis A: General 345 (2008) 185194

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Applied Catalysis A: General

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New Mo-Fe-O silica supported catalysts for methanol to formaldehyde oxidation

o Carlos Bentes Waerenborgh c, Manuel Farinha Portela a Ana Paula Soares Dias a,*, V.V. Rozanov b,1, Joa
a

cnico, Avenida Rovisco Pais, s/n, 1049-001 Lisboa, Portugal ICEMS-GRECAT, Technical University of Lisbon, Instituto Superior Te N. N. Semenov Institute of Chemical Physics, Russian Academy of Sciences, Kosygin St., 4, Moscow 117977, Russia c gico e Nuclear, Departamento de Qumica/CFMC-UL, Estrada Nacional 10, 2686-953 Sacave m, Portugal Instituto Tecnolo
b

A R T I C L E I N F O

A B S T R A C T

Article history: Received 17 December 2007 Received in revised form 28 April 2008 Accepted 29 April 2008 Available online 3 May 2008 Keywords: Supported catalysts Iron molybdates Silica Methanol oxidation Formaldehyde Iron phosphates

Silica supported Mo-Fe and Mo-Fe-P mixed oxides (Mo/Fe = 3 atomic ratio) were prepared in the presence of citric acid as chelating agent to obtain a uniform distribution of the active phase. Loading of 23.1% (w/w) of MoO3 was used exceeding the monolayer content (around 2.2 monolayers of MoO3). The low interaction between the silica and the mixed oxide in addition to the high content of the active phase led to a three-dimensional distribution of the active phase, conrmed by SEM. Several iron (Fe3+) precursors (nitrate, chloride, sulfate, phosphate and pyrophosphate) were used in order to assess their effect on the catalysts performances. Some elements (N, Cl, S and P) from the iron precursors remained in the catalyst. Samples prepared ssbauer spectra from phosphate and pyrophosphate had phosphorus in their compositions and Mo revealed the presence of iron phosphate. Nevertheless, due to lack of crystallinity, these phases (iron phosphates) are probably inactive. All the prepared catalysts display high activity and selectivity towards formaldehyde, even for low and high methanol conversions. The catalyst prepared from iron pyrophosphate was the most active. The presence of heteropolymolybdates, containing phosphorus, or its Mo rich surface can perhaps explain its enhanced catalytic behavior. For temperatures lower than 625 K this sample (merely 26.2% (w/w) of active phase) presented higher formaldehyde yields than one unsupported industrial catalyst. Such a catalyst prepared from iron pyrophosphate presents promising catalytic performances for use in uidized bed reactors. The loss of Mo during reaction was observed for all the prepared catalysts. Micrographs for post reaction samples displayed MoO3 needles (or plates) formed during the redox cycle, which are easily sublimated. Conversely, for the sample prepared from iron pyrophosphate the MoO3 needles are absent, which is probably indicative of a different reaction mechanism. 2008 Elsevier B.V. All rights reserved.

1. Introduction Formaldehyde is an important building block for complex chemicals that is produced from methanol by two main processes [1,2]: (1) Dehydrogenation of methanol rich air mixture over silver catalysts. (2) Oxidation of methanol over iron molybdate (Mo-Fe-O) based catalysts.

* Corresponding author. Tel.: +351 21 8417873; fax: +351 21 8499242. E-mail addresses: apsoares@ist.utl.pt (A.P.S. Dias), jcarlos@itn.pt (J.C.B. Waerenborgh), mfportela@ist.utl.pt (M.F. Portela). 1 Deceased. 0926-860X/$ see front matter 2008 Elsevier B.V. All rights reserved. doi:10.1016/j.apcata.2008.04.040

Hybrid processes are also used in industry. The Mo-Fe-O catalysts based process is advantageous because the reaction can be carried out at comparatively lower temperatures (350375 8C). The high exothermicity (159 kJ/mol [3]) of the main reaction leads to the formation of hot spots in the catalyst bed, which contributes to the fast deactivation of the catalyst by MoO3 sublimation [47]. Methanol oxidation over Mo-Fe-O catalysts is carried out using xed bed reactors. Some authors proposed the use of uidized bed reactors because such reactors present the advantage of minimization of the hot spots of the catalytic bed [8]. Additionally, other advantages such as decrease of the explosion risk, handling of the catalyst deactivation without interrupting the operation, and increase of production capacity are also referred. Due to weak resistance to mechanical abrasion, unsupported Mo-Fe-O catalysts cannot be used in uidized bed reactors [8]. Thus, some authors have studied Mo-Fe-O mixed oxides supported

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over materials (Al2O3, SiO2) with satisfactory mechanical resistance. Published results showed that supported catalysts are less active than unsupported catalysts [812]. The interaction between the support material and the active phase (Mo-Fe-O) is pointed out as the major reason. The reported results show that the increase of support material surface area has a negative effect on the catalytic behavior of the supported iron molybdate catalyst. This effect is more pronounced for alumina than for silica. This result led Cairati et al. [9] to conclude that silica and alumina interact differently with Mo-Fe-O phase. An analogous result was reported by Hill and Wilson [12]. They observed different Raman spectra for iron molybdates supported over silica and over alumina. For silica the spectra were more similar to that of the unsupported Mo-Fe-O mixed oxide. The same authors concluded that the interaction support/ Mo-Fe-O was stronger for alumina. In fact, the formation of [Al(OH)6Mo6O18]3 Anderson type ions during impregnation of alumina with Mo solution was reported [13]. Also Carbucicchio [14] reported the formation of Al2(MoO4)3, with iron in interstitial positions, when alumina was used as the support material. This occurrence would be responsible for catalysts with Fe rich surfaces. ` et al. [15] reported the formation of two types More recently Triro of interfacial compounds (Fe(III) dissolved in alumina and FeAl Mo heteromolybdate), which would contribute to lowering of catalytic performances, when alumina was used as the support o-Dias et al. [16] studied several Mo-Fe-O material. Castela ssbauer spectroscopy. For SiO2, SiC and TiO2 catalysts using Mo support materials they concluded that the Mo-Fe-O phase reacts with the support material and that the occurrence of such reaction depends mainly on the surface area of the support material and is reinforced for higher surface areas. In order to contribute to a better knowledge on the supported Mo-Fe-O catalysts, for possible uidized bed reactor operation, the inuence of the nature of the Fe3+ precursor, used in the catalyst preparation, was investigated. Silica was chosen as support material due to its lower interaction with the Mo-Fe-O active phase, its availability and low price. Relative high surface area silica was used but with a high content of the active phase in order to minimize the interaction support/active phase. The most used synthesis route for supported catalysts involves the impregnation of the support material with a solution of the metal (or oxide) precursor, followed by evaporation until dry and a nal thermal treatment. Usually a poor dispersion of the active phase is obtained. Alternative approaches leading to a high dispersion of the active phase, involve either the increase of the viscosity, or very high (or low) evaporation rates of the impregnation solution. A more effective technique is to use aqueous solutions of multidentate chelated metal complexes [17]. The use of chelating ligands, such as citric acid, to prepare supported catalysts with a more uniform distribution of the active phase is a widely accepted practice [18]. Additionally, it is reported [19] that the introduction of organic additives during preparation steps, namely citric acid as dispersant, can inuence the catalyst morphology and thus the catalyst performance. A brief survey of the literature on the preparation of supported Mo-Fe-O catalysts is given by Hill and Wilson [12]. Two preparation techniques are generally used: 1. incipient wetness; 2. spraying the support material with a solution of both Mo and Fe precursors in the presence of citric acid. In order to avoid the problem related to the degree of impregnation of Mo and Fe, the second technique was adopted in the present work. Citric acid avoids the precipitation of Mo and

Fe during the impregnation step, producing a homogenous solution and uniform distribution of both metal ions over the support material. This results from the formation of complexes (citrate type) with the metal ions. Furthermore the gases and the heat generated when burning the organic molecule (citric acid) in the calcination step lead to the increase of surface area and enhancement of the interaction between the active phase and the support material. Some modications to the preparation protocol, referred by Hill and Wilson [12], were introduced. 2. Experimental 2.1. Preparation of the catalysts The silica supported catalysts were prepared by contacting the support material (10 g of Sipernat 22 from DEGUSSA) with a hot (353 K) aqueous solution (300 cm3) of both Mo and Fe precursors and citric acid (citric acid/(Mo + Fe) = 1 molar ratio). Ammonium heptamolybdate was used as molybdenum precursor. Nitrate, chloride, sulfate, phosphate and pyrophosphate Fe3+ salts were used as iron precursors. All the catalysts were prepared with an atomic ratio Mo/Fe = 3, similar to the unsupported industrial Mo-Fe-O catalysts [2]. All the prepared samples were loaded with 23.1% (w/w) of MoO3. According to previously published results this loading corresponds approximately to 2.2 MoO3 theoretical monolayers [20]. Such loading was selected in order to avoid the presence of silanol groups on the catalyst surface. In fact, published results [21] showed that commercial silica can, depending on the reaction conditions, oxidize methanol to CO, methyl formate, formaldehyde and CO2. Moreover, this amount of MoO3 is expected to avoid the formation of Fe rich catalysts surfaces since iron oxide catalyzes the total combustion of methanol [22]. The slurry containing the support material, both Mo and Fe precursors and citric acid was heated (around 373 K) under vigorous stirring until dry. No precipitation occurred during this step. In fact citric acid prevents the precipitation of both Fe3+ and Mo6+ ions. The cake obtained after total evaporation of water was dried overnight at 393 K and then calcined (750 K) in a slow ow of dry air for 5 h. The calcination temperature was chosen in agreement with the results of activation studies by thermogravimetry. Before calcinations the samples were crushed in a pyrex mortar. For comparison of catalytic behavior, data from an industrial catalyst were used. Such unsupported ferric molybdate catalyst with atomic ratio Mo/Fe = 3 has characteristics similar to those of coprecipitated iron molybdate as reported before [23]. 2.2. Characterization of the catalysts In order to select the calcination temperature, the activation under air of the prepared samples after the drying step was studied by thermogravimetry in TG-DTA-DSC equipment (LabSysSETARAM). A few milligrams (<30 mg) of powder were used for each TG-DTA test. Alumina crucibles of 100 ml and a heating rate of 10 K/min were used. The weight loss and the heat ow were recorded for each sample from 320 K to 825 K. The BET surface areas of the catalysts were measured with a Coulter SA 3100 apparatus. Before BET measurements the samples were kept at 250 8C, under primary vacuum, for 120 min. The bulk content of molybdenum of fresh and post reaction samples was assessed by induced coupled plasma (ICP) with a PerkinElmer plasma 400.

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X-ray diffraction (XRD) patterns were recorded (0.58/min; step 0.028) at room temperature with a Rigaku equipment using Cu Ka radiation (Ni lter) at 40 kV and 30 mA. The bulk compositions of iron phases, for fresh and post ssreaction catalysts samples were studied by transmission Mo bauer spectroscopy at room temperature with a time mode spectrometer, a constant acceleration drive and a 57Co in a Rh matrix source. The isomer shifts (d) were given with respect to aFe at room temperature and calculated as the quadrupole splittings (D) and the line widths (W) with a precision of 0.02 mm s1. The spectra were tted to Lorentzian lines using a non-linear leastsquares method. The relative areas and widths of both peaks in a quadrupole doublet were kept equal during renement. The micro Raman spectra were collected with a Spex 1877 triplemate spectrometer using the 514.5 nm line as exciting radiation. Fresh and post reaction samples were characterized by SEMEDX using a HITACHI S2400 scanning electron microscope equipped with a RONTEC energy dispersive X-ray high vacuum detector (W lament, E = 25 kV). Samples were analyzed from a 15 mm working distance, with a resolution of 12 nm. The acid properties of the catalysts were examined by NH3 thermodesorption (TPD-NH3). The experiments were performed with a gaseous mixture of NH3 (5% (v/v)) in He. Before surface saturation with the probe molecule, each sample (200300 mg) was kept under helium ow at 823 K until complete removal of the adsorbed impurities. Then the sample was cooled down to 297 K and pulses of the adsorbing gas (NH3 + He) were introduced until saturation of the surface. The physisorbed species were removed by ushing with He for 30 min. The thermodesorption was then performed by heating the sample up to 700 K, at 10 K/min, under He ow (1 cm3/s). The desorption process was monitored using a thermal conductivity detector (TCD) of a Shimadzu gas chromatograph. 2.3. Catalytic tests Methanol oxidation was carried out in a conventional continuous ow apparatus at atmospheric pressure. Catalytic behavior was studied in steady state conditions. Feed mixtures (6%, v/v) were prepared by injecting liquid methanol into the air ow with a precise Gilson 302 pump. The catalyst (0.5 g; W/F = 10 g h/ molMeOH) was diluted with inert SiC (1:4, w/w) to avoid adverse thermal effects and charged into a tubular pyrex reactor with a thermocouple in a coaxial centered thermowell. Catalyst particles of diameter dp < 125 mm (115 mesh sieve) were used in order to minimize the effects of internal diffusion limitations on the mass and heat transfer. 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 thermal conductivity detector. Two in-parallel columns, one at room temperature (molecular sieve 13) for N2, O2, CO and CO2, and the other in the oven of the chromatograph (porapak T) at 443 K for HCHO, CH3OCH3 (DME), H2O, CH3OH (MeOH), HCOOCH3 (MF) and CH2(OCH3)2 (DMM), performed the separation of the reactor efuents. Formic acid was never detected. The average rate of methanol conversion (r MeOH ) was computed considering plug ow: F MeOH X r MeOH W where FMeOH is the molar ow of methanol in the reactor fed, W the weight of the active phase (26.2% of catalyst weight), and X the methanol conversion at the reactor outlet.

3. Results and discussion 3.1. Characterization of the catalysts 3.1.1. Morphology and chemical composition The DTG (rate of weight loss versus temperature) data of catalyst precursors are in Fig. 1. For all samples two main weight loss processes can be identied. They are complex because citric acid can form citrates with metals and chelates with others ligands, depending on the metal and the used precursor. In order to avoid molybdenum loss by sublimation and decrease of specic surface, all the prepared catalysts were calcined at 750 K. In fact, for samples prepared from iron nitrate, chloride, sulfate and phosphate the weight is almost stable for this temperature. Conversely for the sample prepared from Fe pyrophosphate the last weight loss process is still in progress at 750 K. Data in Table 1 show that the iron precursor inuences the surface area of the catalysts. The sample prepared with chloride precursor displays the lower surface area. The morphology of the fresh and post reaction catalysts was assessed by SEM. According to the silica supplier (DEGUSSA), the bare support material consists of small spheroids under 100 mm. Representative micrographs, for fresh samples, are presented in Fig. 2A. For all samples the morphology was similar to that of the silica support. However, this support was studded with the supported phase. Small (<10 mm) aggregates of the Mo-Fe-O studded over the silica spheres were discernible for all the samples. Additionally, samples revealed plate-like crystallites that seem to be stuck on the silica surface. Usually plate-like crystals forming small rosaceous aggregates are observable for stoichiometric unsupported Fe2(MoO4)3 [23]. A recent work on the 3D architectures of the iron molybdate phase conrms the attribution of plate-like crystallites (akes) to the Fe2(MoO4)3 phase [24].

Fig. 1. Rate of weight loss versus temperature (DTG) of the precursors of the catalysts (under air; heating rate 5 K/min).

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Table 1 BET surface area of fresh catalysts and Mo content, by ICP, for fresh and post reaction catalysts Catalyst Surface areaa (m2/g) Mo content (%, w/w) Fresh Fe3+ precursor Nitrate Chloride Sulfate Phosphate Pyrophosphate
a

Schematically the structure of the active phase, fresh and post reaction, can be represented by:

Post reaction

90 65 95 86 91

22.4 20.6 21.8 20.9 19.4

20.8 19.8 21.5 17.4 16.3

Support material Sipernat 22 (DEGUSSA) 190 m2/g.

Micrographs of the prepared samples clearly showed the formation of three-dimensional structures for the supported active phase. The absence of monolayer-like dispersion was expectable due to the large loading. Additionally, the monolayer dispersion of the active phase over the support material is believed to occur when there is a strong interaction between the active phase and the support material. Taking into account that there is no such interaction between silica and the MoFeO active phase, a monolayer dispersion was unlikely for the prepared samples, even using a solgel like procedure. The post reaction catalysts without phosphorus (Fig. 2B) exhibit MoO3 needles or/and plates representative of the molybdenum segregation usually reported for unsupported iron molybdate catalysts [2].

After calcination the prepared catalyst samples exhibit colours varying from yellow-green, characteristic of the unsupported iron molybdates [23], to blue, attributable to molybdenum phosphorus compounds [25]. The samples prepared with iron phosphate and iron pyrophosphate were blue, showing that phosphorus remained in the catalysts after calcinations. The post reaction samples prepared from nitrate, chloride and sulfate iron precursors displayed red/brown shades indicating the presence of Fe3+ species on the surface. This occurrence and the presence of molybdenum blues in the reactor bottom, for all the samples tested, point to the loss of molybdenum. In order to quantify the Mo loss, the molybdenum content was evaluated by ICP for fresh and post reaction samples (Table 1). Actually ICP measurements conrm the loss of molybdenum during reaction. Samples with phosphorus (from iron phosphate

Fig. 2. (A) SEM micrographs of fresh catalysts. (B) SEM micrographs of post reaction catalysts.

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Fig. 2. (Continued ).

and pyrophosphate) lose more Mo than the other samples. This result is ascribable to the fact that these two samples were tested for higher reaction temperatures than the other samples, 750 K instead of 725 K. In addition they remained 3 h longer on the stream. The sublimation of Mo species increases with temperature and this process is usually identied as the major deactivation process [47,26]. The content of molybdenum in the near surface layers, for fresh and post reaction samples, was also measured by EDX during SEM. Furthermore EDX analyses were also performed for other elements present at the catalysts surfaces. The main results are displayed in Table 2. The results show that during reaction the molybdenum migrates to the catalyst surface. In fact, methanol oxidation proceeds via a partial reduction followed by reoxidation of the active phase which segregates MoO3 [23,27]. The segregated MoO3 can be sublimated from the catalyst surface in reaction conditions. The corresponding Mo loss is compensated by Mo coming from the catalyst bulk. This result is corroborated by the presence of MoO3 needles in SEM micrographs for post reaction catalysts (Fig. 2). The MoO3 needles are only absent in the sample prepared from iron pyrophosphate, even though this sample shows the largest Mo loss. The lack of MoO3 needles suggests the absence of the above mentioned reduction process. Results in Table 3 show that

phosphorus remains at the catalyst surface prepared from both phosphorus-containing iron precursors. Both samples display similar P/Mo atomic ratios according to SEM-EDX. The sample prepared from iron pyrophosphate has a Mo-richer surface, and displays a lower Mo/Fe ratio after reaction as a consequence of Mo loss. The sample prepared with iron phosphate exhibits a Mo surface enrichment after reaction caused by Mo segregation during reaction.

Table 2 Mo/Si, Mo/Fe atomic ratios by SEM-EDX of fresh and post reaction catalysts Catalyst Atomic ratio Mo/Si Fresh Fe3+ precursor Nitrate Chloride Sulfate Phosphate Pyrophosphate Post reaction Mo/Fe Fresh Post reaction

0.3 0.2 0.6 0.3 0.3

0.5 0.5 0.5 0.7 0.5

2.8 2.6 2.6 2.5 10.4

4.0 2.0 4.3 3.6 7.6

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Table 3 P/Mo, Mo/Si and Mo/Fe atomic ratios by SEM-EDX for fresh and post reaction catalysts prepared with iron phosphate and pyrophosphate Atomic ratios P/Mo Phosphate Fresh Post reaction Pyrophosphate Fresh Post reaction Mo/Si Mo/Fe

0.4 0.3

0.3 0.7

2.5 3.6

0.3 0.3

0.3 0.5

10.4 7.6

3.1.2. Raman spectroscopy The fresh samples of supported catalysts were characterized by micro Raman spectroscopy. Micro Raman spectra are presented in Fig. 3 for Raman shifts in the range 1250200 cm1. The recorded spectra were compared with that of the unsupported mixed oxide (Mo/Fe = 3 atomic ratio). As reported before [2,6] the Raman spectrum of the Mo/Fe = 3 unsupported sample has bands ascribed to Mo-rich iron molybdate. The most intense band at 820 cm1 and the bands at 668 cm1and 291 cm1 are attributable to MoO3 whereas the band at 787 cm1 and the triplet around 995 cm1 are due to Fe2(MoO4)3 [11,12,28]. For all the prepared supported catalysts the main features of MoO3 are visible. In fact, the strong Raman signals at 996, 819, 668 cm1 and the low intensity ones at 380, 339, 291, 246 cm1 [22] are present. Only the sample prepared with FeCl3 presents scattering properties similar to those of the unsupported mixed oxide sample. Moreover this sample displays the Raman bands attributable to Fe2(MoO4)3 in addition to those of MoO3. The samples prepared from iron nitrate and iron sulfate have similar Raman features, showing a very small band characteristic of Fe2(MoO4)3. On the other hand the band at 787 cm1 is absent for samples prepared from iron precursors containing phosphorus, indicating that both these samples do not contain Fe2(MoO4)3 phase. The two characteristic bands of FePO4 [28] centered at 1015 cm1 and 1059 cm1 are also missing. Additionally, none of the spectral features can be attributable to heteropolymolybdate species. ssbauer spectroscopy 3.1.3. Mo In order to elucidate the phase distribution (iron-containing phases), the prepared samples before and after catalytic tests were ssbauer spectroscopy. The estimated hypercharacterized by Mo ne parameters resulting from curves tting (Lorentzian type) are summarized in Table 4. For samples prepared with iron nitrate and ssbauer spectra are characteristic of high spin iron chloride, the Mo ferric ions in octahedral coordination, thus indicating that Fe2(MoO4)3 is present [29]. These spectra are similar to those presented by the unsupported Mo/Fe = 3 mixed oxide [23]. Contrary to published results [16], the formation of FeSi containing compounds was not detected, probably because those samples were prepared with high loading of the active phase. The results of Table 4 corroborate the absence of Fe2(MoO4)3 phase in the samples prepared from iron phosphate and iron pyrophosphate. Hyperne parameters for both fresh samples are characteristic of two different Fe3+coordinations. The quadrupole doublets with lower isomer shifts (d) and quadrupole splittings (D) indicate the presence of Fe3+ with relatively low coordination. Within the experimental error these hyperne parameters are similar to those of unsupported FePO4 [30]. The doublet with higher isomer shift and quadrupole splitting indicates the presence of Fe3+ in sites with higher coordination. According to McCormik et al. [30] analogous hyperne parameters suggest Fe3+ in trigonal

Fig. 3. Micro Raman spectra of fresh catalysts.

bipyramidal coordination resulting from interaction of iron species with the support material. The increase of the estimated relative area, suggests that the latter iron species is enhanced in post reaction samples. The presence of the Fe2+ doublet shows that the sample prepared from iron phosphate undergoes reduction during reaction. The hyperne parameters estimated for this Fe2+species preclude the presence of any of the three FeMoO4 phases [2]. This Fe2+ contribution to the spectrum can neither be identied with
Table 4 ssbauer parameters (room temperature) of fresh and post reaction catalysts Mo Fe species Nitrate Fresh Post reaction Chloride Fresh Post reaction Sulfate Fresh Post reaction Phosphate Fresh

d (mm/s)
0.41 0.41

D (mm/s)
0.21 0.20

W (mm/s)

I (%)

Fe2(MoO4)3 Fe2(MoO4)3 Fe2(MoO4)3 Fe2(MoO4)3 Fe3+ Fe2(MoO4)3 Fe3+ Fe3+ Fe3+ Fe3+ Fe2+ Fe3+ Fe3+ Fe3+ Fe3+

0.38 0.36

100 100

0.42 0.42

0.19 0.18

0.31 0.34

100 100

0.42 0.42

0.24 0.21

0.46 0.38

100 100

Post reaction

0.36 0.40 0.36 0.39 1.17

0.61 1.10 0.56 1.01 2.60

0.52 0.40 0.48 0.40 0.46

74 26 61 32 7

Pyrophosphate Fresh Post reaction

0.33 0.39 0.31 0.39

0.60 1.02 0.60 0.99

0.42 0.36 0.43 0.38

71 29 69 31

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Fig. 5. XRD patterns of fresh and post reaction catalyst prepared from iron phosphate.

Fig. 4. XRD patterns of fresh catalysts prepared from chloride and phosphorus containing precursors and unsupported industrial like catalyst (Mo/Fe = 3 atomic ratio).

the mixed valence iron (Fe2+ + Fe3+) containing phase found by Millet et al. [31] in iron phosphate catalysts after dehydrogenation of isobutyric acid. This Fe2+ may be rather related with the fact that the prepared supported Fe-P-O phase was amorphous. Amorphous and crystalline FePO4 catalysts present different reduction behaviors [32]. On the other hand hyperne parameters for those Fe2+ species are analogous to those presented by Huynh and Millet [33] for iron substituted Keggin type phosphomolybdic compounds. However, the same is not observed for the Fe3+ species. For the remaining samples the reduction of iron phases during ssbauer spectroscopy. Furtherreaction was not detected by Mo more hyperne parameters for the sample prepared from iron sulfate seems to reveal an increase of crystallinity of the Fe2(MoO4)3 phase during reaction. 3.1.4. X-ray diffraction The main features of XRD patterns for fresh catalysts are presented in Fig. 4. The samples prepared from iron nitrate, chloride and sulfate show XRD patterns characteristic of poorly crystallized Mo-rich iron molybdate (unsupported MoFeO pattern of Fig. 4). The sample prepared from iron chloride displays the highest crystallinity. XRD lines for these samples are broader than those of the unsupported phase probably due to the crystallites size. The XRD data for fresh catalysts (Fig. 4) show that phosphorus (from iron precursor) prevents the formation of Fe2(MoO4)3. The samples prepared from iron phosphate and iron pyrophosphate only display XRD lines characteristic of MoO3 [2]. The XRD patterns recorded for these samples are similar to those reported by Said and El-Wahab [34] for silica supported MoO3 samples. An analogous effect was reported by Demdivod et al. [35]. They found that the introduction of phosphate ions into stoichiometric ferric molybdate leads to the formation of a proportional amount of MoO3 detectable by XRD. None of the ve phases (tridymite and quartz FePO4, FePO42H2O, Fe2P2O7 and a-Fe2O3) reported by Ren et al. [36] for silica supported FePO4 catalysts has been found. Additionally

no crystalline heteropolymolybdates [25] could be identied. The XRD pattern of the post reaction sample prepared from iron phosphate did not reveal the presence of Fe2+ crystalline phases. The XRD patterns for fresh and post reaction samples were similar ssbauer (Fig. 5). Thus, the phase containing Fe2+ evidenced by Mo spectroscopy could not be identied by XRD probably due to the detection limit of XRD technique. 3.1.5. Surface acidity by NH3 TPD The surface acidity of the prepared samples was assessed by NH3 TPD. The recorded desorptograms are presented in Fig. 6. The desorptograms were normalized to the same surface area. The desorptogram for the silica support was included since silanol groups have acidic character [37]. The NH3 desorption prole for this sample shows a maximum at 390 K. Published results [23] for unsupported Mo-Fe-O mixed oxides showed three desorption maxima (400 K, 480 K, 580 K) for samples having Mo/Fe = 3 atomic ratio. This study also showed that NH3 desorption prole was almost independent of the bulk Mo/Fe atomic ratio because the surface of the catalysts always

Fig. 6. NH3 TPD of fresh catalysts and support.

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presented an atomic ratio similar to that of the stoichiometric mixed oxide (Fe2(MoO4)3). The NH3 desorption proles of silica supported and unsupported mixed Mo-Fe-O samples were distinguishable. This may be attributed to the fact that the iron molybdate phase over the support material present Mo/Fe atomic ratios different from those

of the unsupported Mo-Fe-O mixed oxide. For the samples prepared from nitrate, sulfate and chloride the differences among them can be due to the contamination of surfaces by strange elements from the iron precursors. Unpublished XPS results revealed the presence of N for the sample prepared from iron nitrate and S for the sample prepared from iron sulfate. The

Fig. 7. Catalytic activity versus reaction temperature of the catalysts (6% (v/v) methanol in air; W/F = 10 g h/molMeOH, W = 0.5 g).

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samples prepared from iron phosphate and iron pyrophosphate have surface compounds that are different from iron molybdate, which changes the adsorption behavior of NH3. In fact the sample prepared from pyrophosphate has the highest acidity, whereas the sample prepared from iron phosphate displays the lowest surface acidity. This result can arise from the fact that the pyrophosphate sample has a Mo rich surface (Table 2). 3.2. Catalytic behavior Data on the catalytic behavior of the catalysts are presented in Fig. 7. For the conditions tested the major reaction product was formaldehyde. Low amounts of methyl formate (MF), CO and CO2 were observed as byproducts. Dimethyl ether (DME) and dimethoxymethane usually referred as byproducts for the methanol oxidation over metal oxides catalysts [2] were observed with residual selectivities (<0.5). The overoxidation byproducts (CO and CO2) were only produced with considerable selectivities for high temperature and high methanol conversion. This result seems to indicate that overoxidation products result from the consecutive oxidation of formaldehyde that remains adsorbed, or is readsorbed on the catalyst surface. The relatively large catalysts surfaces would contribute to this result. The plot of conversion versus reaction temperature, in Fig. 7, shows that the catalyst prepared from iron pyrophosphate was more active than the others for the same reaction conditions. This effect was noticeable even for the lower reaction temperatures. The average rate of methanol conversion, in Fig. 9, also conrms this result. The best catalytic behavior for the sample prepared from iron pyrophosphate can be ascribable to the presence of some kind of heteropolymolybdates compounds on the catalyst surface. In fact this sample presented a Mo surface enrichment (Table 2). This sample has also the highest NH3 adsorption, which substantiates the presence of such surface species. On the other hand the improved catalyst behavior of this catalyst can be ascribed to the effect of its Mo rich surface recently reported by Andersson et al. [26]. The methanol to formaldehyde oxidation over unsupported FePO4 catalysts was briey reported by Klissurski et al. [38]. They emphasized that taking into account the similar nature of MoO and PO bonds, theoretically FePO4 and Fe2(MoO4)3 must lead to

Fig. 9. Average rate of methanol conversion (reaction conditions of Fig. 7).

analogous performances. Their main result was high formaldehyde selectivity even for high reaction temperatures. In Fig. 8 the formaldehyde yields of the prepared samples were compared with those obtained using an industrial catalyst with the same Mo/Fe atomic ratio (Mo/Fe = 3). The industrial catalyst had physico-chemical characteristics similar to those of the above mentioned sample prepared by coprecipitation [23]. For temperatures lower than 600 K the catalyst samples prepared from iron sulfate, phosphate and pyrophosphate display higher formaldehyde yield than the industrial sample. This result is very important since supported samples merely contain 26.2% of active phase (basis Mo-Fe-O over inert silica) (Fig. 8). 4. Conclusions SEM micrographs clearly showed the formation of threedimensional structures for the supported active phase, instead of the monolayer type spreading. This result indicates that the interaction between the support and the active phase is weak, as previously reported. EDX results during SEM underline the fact that the iron source strongly inuences the Mo and Fe distribution in the surface layers of the catalysts. Additionally, for the samples prepared from iron phosphate and pyrophosphate they showed that phosphorus remains in the catalysts. The sample prepared from iron pyrophosphate showed a remarkable Mo surface enrichment. The iron (ferric) precursor inuences the catalytic performances of the prepared samples since some elements (N, Cl, S, and P), from the iron precursors, remain in the catalyst. Samples prepared from phosphate and pyrophosphate, have phosphorus in ssbauer spectra indicated the presence their compositions and Mo of iron phosphate. The lack of crystallinity probably makes these iron phosphate phases inactive. All the prepared catalysts display high activity and selectivity towards formaldehyde, both for low and high methanol conversions. The computed average rate of methanol conversion shows that the catalyst prepared from iron pyrophosphate was the most active. The presence of heteropolymolybdates, containing phosphorus, can perhaps explain the best catalytic behavior of this sample. Unfortunately no experimental evidence for the formation of such compounds was obtained. Only the blue color of the catalysts suggests its existence. In addition, the enhanced performances of the pyrophosphate derived sample can be related with its Mo-rich surface. For temperatures lower than 625 K this

Fig. 8. Formaldehyde yield versus reaction temperature for prepared catalysts and unsupported Mo-Fe-O industrial catalyst (reaction conditions of Fig. 7).

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