Gallium oxide promoted zeolite catalysts for oxidehydrogenation of propane

Novel gallium-containing catalysts for oxidehydrogenation of propane, based on zeolite Beta, ZSM-5 and ferrierite, have been prepared and characterised by scanning electron microscopy, IR, MAS NMR and Raman spectroscopies. The catalytic properties of zeolitic matrixes with B, Al, and both ions at tetrahedral sites have been studied. Transformation of propane on pure zeolites and promoted with gallium (III) oxide depended on the structure of the matrix, its morphology and the type of cations occupying zeolite framework sites. Formation of new hydroxyl groups has been evidenced for some MFI zeolites promoted with Ga₂O₃.     

Selective oxidation of propane over alkali-doped Mo–V–Sb–O catalysts

Alkali metal-doped MoVSbO catalysts have been prepared by impregnation of a MoVSbO-mixed oxide (prepared previously by a hydrothermal synthesis) and finally activated at 500 or 600 °C in N₂. The catalysts have been characterized and tested for the selective oxidation of propane and propylene. Alkali-doped catalysts improved in general the catalytic performance of MoVSbO, resulting more selective to acrylic acid and less selective to acetic acid than the corresponding alkali-free MoVSbO catalysts. However, the specific behaviour strongly depends on both the alkali metal added and/or the final activation temperature. At isoconversion conditions, catalysts activated at 600 °C present selectivity to acrylic acid higher than that achieved on those activated at 500 °C, both K-doped catalysts presenting the highest yield to acrylic acid. The changes in the number of acid sites as well as the nature of crystalline phases can explain the catalytic behaviour of alkali-doped MoVSbO catalysts.     

Aerogel VOx/MgO catalysts for oxidative dehydrogenation of propane

VO_x/MgO aerogel catalysts were synthesized using three different preparation methods: by mixing the aerogel MgO support with dry ammonium vanadate, by vanadium deposition from a precursor solution in toluene, and by hydrolysis of a mixture of vanadium and magnesium alkoxides followed by co-gelation and supercritical drying. The latter aerogel technique allowed us to synthesize mixed vanadium–magnesium hydroxides with the surface areas exceeding 1300 m²/g. The synthesized catalysts were studied by a number of physicochemical methods (XRD, Raman spectroscopy, XANES and TEM). A common feature of all synthesized samples is the lack of V₂O₅ phase. In all cases vanadium was found to be a part of a surface mixed V–Mg oxide (magnesium vanadate), its structure depending on the synthesis method. The VO_x/MgO mixed aerogel sample had the highest surface area 340 m²/g, showed higher catalytic activity and selectivity in oxidative dehydrogenation of propane compared to the catalysts prepared by impregnation and dry mixing. The addition of iodine vapor to the feed in 0.1–0.25 vol.% concentrations was found to increase to propylene yield by 40–70%.     

Effect of the oxide support on the propane ammoxidation with Sb–V–O-based catalysts

The role of Nb₂O₅ and γ-Al₂O₃ oxide supports on the ammoxidation of propane on supported mixed Sb–V oxide at different Sb+V surface coverages is studied. Sb and V oxide species on alumina and on niobia support show different structural features that reflect in different performance during the ammoxidation of propane to acrylonitrile. Niobia-supported catalysts are much more selective to acrylonitrile than alumina-supported ones. Alumina interacts weakly with the supported oxides while niobia forms new phases through solid state reactions with the supported oxides during catalytic operation that must account for its higher selectivity values towards acrylonitrile and higher specific rate of acrylonitrile formation per vanadium site.     

Structure–activity relationships in alumina-supported molybdena–vanadia catalysts for propane oxidative dehydrogenation

The interactions between Mo and V on alumina are studied for the oxidative dehydrogenation (ODH) of propane. Dispersed surface molybdena and vanadia species share alumina support but show no interaction below Mo + V monolayer coverage. Vanadia and molybdena species react on alumina into mixed Mo–V–(Al)–O above Mo + V monolayer coverage, which nature depends on environmental conditions. Molybdena sites may form Al₂(MoO₄)₃ or Mo–V–O phases depending on loading and temperature. The Mo–V–O phases spread on the support as separate surface oxides at lower coverage, such trend appears promoted by ODH reaction conditions.     

V–Al–O catalysts prepared by flame pyrolysis for the oxidative dehydrogenation of propane to propylene

A flame pyrolysis (FP) procedure has been set up for the preparation of V/Al/O catalysts to be employed for the oxidative dehydrogenation of propane to propylene. The samples have been characterised by means of various techniques (FT-IR, Raman, EPR, ICP-MS, TGA, XRD, SEM) and their catalytic activity has been evaluated in two different operating modes, i.e. under anaerobic conditions and by co-feeding oxygen. The particle size distribution became progressively more homogeneous with increasing V concentration, due to the catalytic effect of the V ions during the FP synthesis. Some V₂O₅ segregation was observed even at low V loading. However, higher V dispersion was attained with respect to a reference sample prepared by impregnation of the FP-prepared alumina support.The increase of V concentration always led to an improvement of propane conversion, though selectivity showed different trends depending on the operating conditions. The comparison with the sample prepared by impregnation showed similar catalytic activity, with a bit higher selectivity for the FP-prepared sample under anaerobic conditions.     

Alumina supported Mo–V–Te–O catalysts for the ammoxidation of propane to acrylonitrile

The effect of Te addition over Mo–V–O catalysts supported on alumina is discussed for the ammoxidation of propane to acrylonitrile. Catalyst composition and atmosphere of activation are evaluated. Catalysts are characterized before and after catalytic reaction by XPS, XRD and in situ Raman spectroscopies. The absence of Te in catalysts formulation and the presence of a high amount of vanadium induce the presence of V⁵⁺ species and the formation of V₂O₅ oxide; associated with a decrease in acrylonitrile selectivity. The presence of Mo-based polyacids structures decreases the selectivity to acrylonitrile. V⁵⁺ sites are responsible of propane activation and of the subsequent -H abstraction to form the intermediate propylene. Then, a Mo–V rutile-like structure in which vanadium species are reduced as V⁴⁺, is responsible for nitrogen insertion and acrylonitrile formation. The formation of such structure is favoured when Te is added to catalysts and is promoted during propane ammoxidation.     

Rutile-type metal (Cr, V) niobates as catalysts for propane ammoxidation to nitriles: In situ characterization and operando reactivity

Rutile-type Cr/Nb and V/Nb mixed oxides were prepared by co-precipitation from ethanolic solutions, and calcination at 700 °C. The development of the rutile structure during the thermal treatment of the precursor was investigated by in situ TP–Raman spectroscopy. It was found that graphite-like carbon deposits build-up during calcinations in inert. Their decomposition provides the reducing agent that leads to the formation of rutile VNbO₄ at relatively mild conditions. Rutile Cr and V niobates were tested as catalysts for the ammoxidation of propane, under both hydrocarbon-rich and hydrocarbon-lean conditions. Catalysts were active but non-selective to acrylonitrile. The catalyst modifications occurring during reaction were followed by operando Raman–GC methodology. VNbO₄ transforms into a catalyst active and selective for acetonitrile under leaner hydrocarbon feed.     

K–V–Ca catalysts supported on porous alumina ceramic substrate for soot combustion: Preparation and characterization

The KCl, KNO₃, CaCl₂, Ca(NO₃)₂, V–Ca and K–V–Ca catalysts supported on alumina ceramic substrates have been prepared. X-ray diffraction and thermogravimetry/differential scanning calorimetry were used to characterize the catalysts, and their catalytic activities were evaluated by a soot oxidation reaction using the temperature-programmed reaction system. The catalytic activity of KNO₃ is higher than KCl, and the catalytic activity of Ca(NO₃)₂ is as much as that of CaCl₂. The catalyst containing a higher KNO₃ content exhibits CO₂ adsorption, whereas higher CaCl₂ and Ca(NO₃)₂ content can restrain the adsorption of CO₂. The K–V–Ca catalyst with a molar ratio of 6:1:1 had the lowest soot onset combustion temperature. The melting and oxidation–reduction of KNO₃, oxygen content of catalyst surface, and formation of some eutectic phase may be the key factors in improving catalytic activity of catalysts.     

V–Mg–O catalysts for oxidative dehydrogenation of alkylpyridines and alkylthiophenes

Vanadium appears to be the element that is most frequent (along with molybdenum) used in the catalyst formulations for oxidative dehydrogenation (ODH) of hydrocarbons and alcohols. In the present work the employment of ODH reaction in the presence of air has been extended for the preparation of vinyl substituted pyridines and thiophenes using vanadium (and for comparison molybdenum) oxide catalysts.The efficiency of vanadium–magnesium oxide catalysts in the production of vinylpyridines and vinylthiophenes has been evaluated. A strong dependence of the yield and selectivity of the latter upon the vanadium (molybdenum) oxide loading and the conditions of heat treatment were observed. In optimized reaction conditions V–Mg–O catalysts at the temperature approximate 450 °C ensured the formation of vinylpyridines and vinylthiophenes with the yield of 40–60% at the selectivity of 90%. In prolonged runs no visible changes in the performance of the catalyst were observed. DTA–DTG, XRD, IR ESR, NMR methods have been used detecting the formation of species of V–Mg–O catalysts that appear to be responsible for the catalyst efficiency in the reactions under consideration.     

Selective oxidation of propane and ethane on diluted Mo–V–Nb–Te mixed-oxide catalysts

Te-free and Te-containing Mo–V–Nb mixed oxide catalysts were diluted with several metal oxides (SiO₂, γ-Al₂O₃, α-Al₂O₃, Nb₂O₅, or ZrO₂), characterized, and tested in the oxidation of ethane and propane. Bulk and diluted Mo–V–Nb–Te catalysts exhibited high selectivity to ethylene (up to 96%) at ethane conversions <10%, whereas the corresponding Te-free catalysts exhibited lower selectivity to ethylene. The selectivity to ethylene decreased with the ethane conversion, with this effect depending strongly on the diluter and the catalyst composition. For propane oxidation, the presence of diluter exerted a negative effect on catalytic performance (decreasing the formation of acrylic acid), and α-Al₂O₃ can be considered only a relatively efficient diluter. The higher or lower interaction between diluter and active-phase precursors, promoting or hindering an unfavorable formation of the active and selective crystalline phase [i.e., Te₂M₂₀O₅₇ (M = Mo, V, and Nb)], determines the catalytic performance of these materials.     

Selective oxidation of methanol to formaldehyde over V–Mg–O catalysts

The results of a complex investigation of V–Mg–O catalysts for oxidative dehydrogenation (ODH) of methanol are presented. The efficiency of vanadium–magnesium oxide catalysts in production of formaldehyde has been evaluated. Strong dependence of the formaldehyde yield and selectivity upon vanadium oxide loading and the conditions of heat treatment of the catalyst were observed. The parameters of the preparation mode for the efficient catalyst were identified. In optimised reaction conditions the V–Mg–O catalysts at the temperature approximate 450 °C ensured the formation of formaldehyde with the yield of 94% at the selectivity of 97%.

No visible changes in the performance of the catalyst (methanol conversion, formaldehyde yield and selectivity) were detected during the 60 h of operation in prolonged runs. Characterization of the catalyst by XRD, IR, and UV methods suggests the formation of species of the pyrovanadate type (Mg₂V₂O₇) with irregular structure on the surface of a V–Mg–O catalyst. These species make the catalyst efficient for methanol ODH.     

Selective oxidation and ammoxidation of propane on a Mo–V–Te–Nb–O mixed metal oxide catalyst: a comparative study

A comparative study on the selective oxidation and the ammoxidation of propane on a Mo–V–Te–Nb–O mixed oxide catalyst is presented. The catalyst has been prepared hydrothermally at 175 °C and heat-treated in N₂ at 600 °C for 2 h. Catalyst characterization results suggest the presence mainly of the orthorhombic Te₂M₂₀O₅₇ (M = Mo, V and Nb) bronze in samples before and after use in oxidation and ammoxidation, although some little modifications have been observed after its use in ammoxidation reaction. Propane has been selectively oxidized to acrylic acid (AA) in the 340–380 °C temperature range while the ammoxidation of propane to acrylonitrile (ACN) has been carried out in the 360–420 °C temperature interval. The steam/propane and the ammonia/propane molar ratios have an important influence on the activity and the selectivity to acrylic acid and acrylonitrile, respectively. The reaction network in both oxidation and ammoxidation reactions as well as the nature of active and selective sites is also discussed. The catalytic results presented here show that the formation of both ACN and AA goes through the intermediate formation of propene.     

Effect of preparation and reaction condition on the catalytic performance of Mo–V–Te–Nb catalysts for selective oxidation of propane to acrylic acid by high-throughput methodology

Combinatorial screening technique has been applied to investigate the catalytic activity and selectivity of quaternary Mo–V–Te–Nb mixed oxide catalysts treated with various chemicals during preparation for selective oxidation of propane to acrylic acid. The catalyst libraries were prepared by the slurry method and catalytic activities were examined in 32-channel high-throughput screening reactor system coupled with a mass spectrometer and/or gas chromatograph.The obtained results provided substantial evidence that the sample preparation condition would have strong effect on the catalytic performance for propane selective oxidation. Among screened samples, Mo–V–Te–Nb treated with HIO₃ solution presented a better performance. The reaction results of promising catalysts selected from the libraries were applied to further scale-up of the system and confirmed catalytic performance. Quantification of the result of Mo–V–Te–Nb treated with HIO₃ solution was realized by combination of GC and MS and relationship between the MS data and the GC results can be established.     

Nanoparticles of vanadia–zirconia catalysts synthesized by polyol-mediated route: Enhanced selectivity for the oxidative dehydrogenation of propane to propene

A polyol-mediated route was employed to obtain nanoparticles of vanadia–zirconia (10 nm) and Ti⁴⁺-modified zirconia catalyst for the selective oxidative dehydrogenation reaction of propane to propene. The catalytic activity and selectivity of samples thus prepared were compared with the values for the sample synthesized by the conventional impregnation method. More dispersed amorphous vanadia species on zirconia support could be obtained by polyol method compared to those obtained by conventional impregnation route, as discerned from transmission electron microscopy (TEM) and Raman studies. Raman spectra of samples prepared by polyol method indicated the presence of monovanadate and polyvanadate species on the zirconia support surface, whereas the impregnated sample showed the existence of aggregated vanadia besides mono and polyvanadate species though the vanadia loading was the same on all samples. XPS studies revealed that vanadia existed as both V⁵⁺ and V⁴⁺ in the samples prepared by the polyol method, whereas only V⁵⁺ state was seen in the impregnated sample. The catalysts prepared by polyol method exhibited enhanced selectivity for propene formation compared to the sample prepared by impregnation method. The enhanced selectivity is attributed to the presence of dispersed vanadia species with lower valence state of vanadium. The present results demonstrate that the polyol-mediated synthesis is an efficient method for the preparation of supported vanadia catalysts containing such active species.     

The synthesis of acrolein and acrylic acid by direct propane oxidation with Ni–Mo–Te–P–O catalysts

Ni–Mo–Te–P–O systems were tested for the synthesis of acrolein and acrylic acid by direct oxidation of propane. The effects of the reaction variables and of the water vapour on the catalytic performances were examined. The addition of dopants, such as Te and P, improved the yields and selectivities of acrolein and acrylic acid.     

Catalytic behaviour of M1, M2, and M1/M2 physical mixtures of the Mo–V–Nb–Te–oxide system in propane and propene ammoxidation

Essentially pure orthorhombic M1 and pseudo-hexagonal M2 phases were prepared using the precursor method. Consistent with literature the M1 phase was shown to be effective for propane ammoxidation to acrylonitrile while the M2 phase was essentially inert for propane activation. Both phases convert propene efficiently to acrylonitrile. Both phases show a significant selectivity dependence on the ammonia and oxygen concentrations in the feed, revealing thereby additional insights into the reaction mechanism.

Physical mixtures of the two separately prepared phases exhibited symbiosis in the ammoxidation of propane when finally divided (5 μm), thoroughly mixed and brought into intimate contact with each other. Acrylonitrile yields significantly higher than those obtained with the M1 phase alone were demonstrated with a 50 wt.% M1/50 wt.% M2 physical mixture having a corresponding surface area ratio of about 4:1. The phase cooperation effect is particularly large at high propane conversions and non-existent when the particle size of the phases is too large (e.g. >250 μm) and the inter-particle contact is poor.     

High surface area Mo–V–Te–Nb–O catalysts: Preparation, characterization and catalytic behaviour in ammoxidation of propane

Mo–V–Te–Nb mixed oxides with a molar ratio of 1:0.30:0.20:0.15 were prepared by citrate and dry-up method, both associated with hydrothermal treatments in the presence of a cationic surfactant (cetyl trimethylammonium bromide, CTAB), and tested in the ammoxidation of propane. The catalysts were characterized by adsorption–desorption isotherms of nitrogen at 77 K, particle size measurements, XRD, and XPS. By using the surfactant, the surface area increased significantly, and samples with surface area between 110 and 239 m²/g were obtained. These catalysts exhibited a propane conversion near 48% with selectivity to acrylonitrile of about 32% for a space velocity 30 times higher than generally reported.     

The role of V in rutile-type Sn/V/Nb/Sb mixed oxides, catalysts for propane ammoxidation to acrylonitrile

Rutile-type Sn/V/Nb/Sb mixed oxides of composition Sn/V/Nb/Sb 1/x/1/3 (atomic ratios) were prepared by co-precipitation from an alcoholic medium, characterized and tested as catalysts for the ammoxidation of propane to acrylonitrile. Vanadium had a relevant effect on chemical–physical and reactivity properties of catalysts. The latter consisted of Sn oxide incorporating Sb and Nb cations, of defective rutile-type V/Nb/Sb mixed oxide and of Sb oxide. Increasing amounts of V in samples caused an increase of the crystallinity and a corresponding decrease of the specific surface area. However, a relevant enhancement of the catalyst activity (rate of propane conversion per unit surface area) was observed. This was attributed to the generation of cationic vacancies, formed in the rutile-type V/Nb/Sb mixed oxide, that enhanced the intrinsic activity of V ions in the activation of the alkane. On the other hand, the selectivity to acrylonitrile declined considerably when the content of V in samples was increased, whereas the selectivity to carbon monoxide and that to cyanhydric acid increased.     

Effect of doping of TiO2 support with altervalent ions on physicochemical and catalytic properties in oxidative dehydrogenation of propane of vanadia–titania catalysts

Vanadia phase (one monolayer) was deposited on TiO₂ anatase doped with Ca²⁺, Al³⁺, Fe³⁺ and W⁶⁺ ions and the catalysts thus obtained (VMeTi) were characterized by XPS, work function technique, decomposition of isopropanol (a probe reaction for acido–basic properties) and tested in oxidative dehydrogenation of propane. The doping of the TiO₂ support modifies physicochemical and catalytic properties of the active vanadia phase with respect to the undoped TiO₂. The specific activity in the propane oxydehydrogenation decreases in the order: VFeTi>VWTi>VTi>VAlTi>VCaTi (3), whereas the selectivity to propene follows the sequence: VWTiVTi>VFeTi>VAlTi>VCaTi. This implies that the lower is the surface energy barrier for transfer of electrons from the catalyst to the reacting molecules the higher is the selectivity to the partial oxidation product. It is argued that owing to the decrease in this energy barrier the reoxidation step in the catalytic reaction, involving such a transfer: O₂+4e→2O²⁻ is fast, thus, preventing the presence of intermediate non-selective electrophilic oxygen species on the surface.