0000000000011335
AUTHOR
J.m. López Nieto
Selective Oxidation of n-Butane and Butenes over Vanadium-Containing Catalysts
Abstract The oxidative dehydrogenation (OXDH) of n-butane, 1-butene, and trans-2-butene on different vanadia catalysts has been compared. MgO, alumina, and Mg–Al mixed oxides with Mg/(Al+Mg) ratios of 0.25 and 0.75 were used as supports. The catalytic data indicate that the higher the acid character of catalysts the lower is both the selectivity to C4-olefins from n-butane and the selectivity to butadiene from both 1-butene or trans-2-butene. Thus, OXDH reactions are mainly observed from n-butane and butenes on basic catalysts. The different catalytic performance of both types of catalysts is a consequence of the isomerization of olefins on acid sites, which appears to be a competitive reac…
Total oxidation of VOCs on mesoporous iron oxide catalysts: Soft chemistry route versus hard template method
9 figures, 3 tables.-- Supplemantary information available
Insights into the catalytic production of hydrogen from propane in the presence of oxygen: Cooperative presence of vanadium and gold catalysts
7 figures.-- © 2015. This manuscript version is made available under the CC-BY-NC-ND 4.0 license http://creativecommons.org/licenses/by-nc-nd/4.0/
Redox and Catalytic Properties of Promoted NiO Catalysts for the Oxidative Dehydrogenation of Ethane
[EN] NiO and metal-promoted NiO catalysts (M-NiO, with a M/(M+Ni) atomic ratio of 0.08, with M = Nb, Sn, or La) have been prepared, tested in the oxidative dehydrogenation (ODH) of ethane, and characterized by means of XRD, TPR, HRTEM, Raman, XPS, and in situ XAS (using H-2/He, air or C2H6/He mixtures). The selectivity to ethylene during the ODH of ethane decreases according to the following trend: Nb NiO Sn NiO > La NiO > NiO, whereas the catalyst reducibility (determined by both TPR and XAS using H-2/He mixtures) shows the opposite trend. However, different reducibility and catalytic behavior in the absence of oxygen (ethane/He mixtures) have been observed, especially when comparing Nb- a…
Selective oxidation of C3–C4 olefins over Mo-containing catalysts with tetragonal tungsten bronze structure
Abstract Mo–V–Nb–P–O-based catalysts with a tetragonal tungsten bronze-type (TTB) structure have been prepared hydrothemally from a H 3 PMo 12 O 40 Keggin-type heteropolyacid. These catalysts have been tested in the oxidation of C 3 –C 4 olefins (propene, isobutene and 1-butene). Although the catalytic performance depends on the nature of the olefin fed the TTB-type catalysts prepared in the presence of elements of the V and VI groups such as Te, Sb and Bi have shown a high selectivity to partial oxidation products, especially that with Te. However, in the absence of these elements the TTB-catalysts present a high catalytic activity to deep oxidation. The selectivity to partial oxidation pr…
Selective oxidation of ethane: Developing an orthorhombic phase in Mo–V–X (X=Nb, Sb, Te) mixed oxides
Abstract Mo–V–X (X = Nb, Sb and/or Te) mixed oxides have been prepared by hydrothermal synthesis and heat-treated in N2 at 450 °C or 600 °C for 2 h. The calcination temperature and the presence or absence of Nb determines the nature of crystalline phases in the catalyst. Nb-containing catalysts heat-treated at 450 °C are mostly amorphous solids, while Nb-free catalysts heat-treated at 450 °C and samples treated at 600 °C clearly contain crystalline phases. TPR-H2 experiments show higher H2-consumption on catalysts with amorphous phases. Catalytic results in the oxidative dehydrogenation of ethane indicate that the selective production of the olefin is strongly related to the development of …
On the influence of the acid-base character of catalysts on the oxidative dehydrogenation of alkanes
Vanadium oxides supported on metal oxide, i.e. Al2O3, MgO and Mg-Al mixed oxide, and V-containing microporous materials (VAPO-5 and MgVAPO-5) have been tested in the oxidative dehydrogenation of C2-C4 alkanes. In all cases, tetrahedral vanadium species (isolated and/or associated) were mainly observed from51V-NMR and diffuse reflectance spectroscopies. The reducibility of V5+-species, determined from the onset-reduction temperature, decreases as follows: VOx/AL > VAPO-5 > MgVAPO-5 =VOx/MG > VOx/MG + AL. The acid character of catalysts, determined from the FTIR spectra of pyridine adsorbed, decreases as: MgVAPO-5 > VOx/AL > VAPO-5 > VOx/MG + AL > VOx/MG. A similar trend between V-reducibilit…
The effect of potassium on the selective oxidation ofn-butane and ethane over Al2O3-supported vanadia catalysts
The catalytic properties of undoped and K-doped (K/V atomic ratio of 0.5) Al2O3-supported vanadia catalysts (∼4.5 wt% of V2O5) for the oxidation ofn-butane and ethane were studied. Isolated tetrahedral V5+ species are mainly observed in both undoped and K-doped samples. The incorporation of potassium decreases both the reducibility of surface vanadium species and the number of surface acid sites. Potassium-free vanadium catalysts show a high selectivity during the oxidative dehydrogenation (ODH) of ethane but a low selectivity during the ODH ofn-butane. However, the presence of potassium on the vanadium catalysts strongly influences their catalytic properties, increasing the selectivity to …
SiO2-supported vanadium magnesium mixed oxides as selective catalysts for the oxydehydrogenation of short chain alkanes
Abstract Unsupported and SiO 2 -supported VMgO mixed oxides catalysts have been prepared, characterized and tested in the oxidation of propane, n -butane and propylene. Mg-vanadates are observed by XRD, IR and Raman spectroscopy in both pure and supported VMgO catalysts, although the effective Mg/V ratio, in the VMgO phases formed, depends on the silica content. Since SiO 2 reacts partially with MgO during the calcination step, forming Mg 2 SiO 4 , the effective Mg/V ratio depends on the silica content. In this sense, pyro -Mg 2 V 2 O 7 is mainly formed on supported catalysts with Mg/V atomic ratios lower than 4, while ortho -Mg 3 V 2 O 8 is observed on supported catalysts with Mg/V atomic …
Reaction products and pathways in the selective oxidation of C-2-C-4 alkanes on MoVTeNb mixed oxide catalysts
[EN] The catalytic properties of MoVTeNbO catalysts during the selective oxidation of short chain alkanes and olefins (C-2-C-4) have been comparatively studied The main reaction products have been ethylene from ethane acrylic acid from propane maim anhydride from n-butane and methacrolein from isobutane FTIR studies of the adsorption of the main reaction products i e olefins and aldehydes over MoVTeNbO catalyst has been carried out Accordingly the reaction pathway is explained on the basis of the characteristics of the alkane fed the stability and reactivity of both the intermediates and the reaction products and the nature of the catalytic sites involved in each reaction (C) 2010 Elsevier …
Support effects on NiO-based catalysts for the oxidative dehydrogenation (ODH) of ethane
[EN] We report on the effect of NiO-support interactions on the chemical nature of Ni species in a series of supported NiO catalysts for the ODH of ethane. SiO2, TiO2-anatase, a high surface area TiO2 and a porous clay hetero-structure (PCH) with TiO2 and SiO2 pillars were used as supports, which led to a selectivity to ethylene in the range 30-90% over supported NiO catalysts. The catalysts were characterized by means of XRD, N-2-Adsorption, H-2-TPR, XPS and in situ (under H-2 reductive atmosphere) and ex situ XAS spectroscopy. The catalytic performance of supported materials is discussed in terms of their reducibility and specific reduction kinetics, but also taking into account the speci…
Oxidative dehydrogenation of propane and n-butane on V-Mg based catalysts
Abstract The catalytic properties of vanadium supported catalysts for the oxidative dehydrogenation of propane and n-butane has been studied. Natural Sepiolite and magnesium oxalate were used as starting support materials. Large differences in the type of crystalline phases were detected on the calcined catalysts depending on the vanadium content and nature of the support. The active and selective sites for the oxidative dehydrogenation of propane and n-butane, are related with isolated V 5+ with atetrahedral coordination. The presence of vanadium species with coordination higher than 4 negatively influence the selectivity to dehydrogenation products.
Selective oxidation of propane and ethane on diluted Mo–V–Nb–Te mixed-oxide catalysts
Abstract Te-free and Te-containing Mo–V–Nb mixed oxide catalysts were diluted with several metal oxides (SiO 2 , γ -Al 2 O 3 , α -Al 2 O 3 , Nb 2 O 5 , or ZrO 2 ), 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 forma…
Oxidative dehydrogenation of ethane on Te-containing MoVNbO catalysts
Abstract Ethylene has selectively been obtained during the oxidative dehydrogenation of ethane on a Mo–V–Te–Nb–O mixed oxide catalyst. The catalyst was prepared hydrothermally and heat-treated at 600 °C for 2 h in a N2-stream. For comparison, undoped and Te-doped Mo–V–Nb–O catalysts and Mo–V–Te–O and Mo–Te–Nb–O mixed oxides have also been prepared. The catalytic performance of the Mo–V–Nb–Te–O mixed oxide catalyst cannot be explained by the incorporation of Te on the surface of a Mo–V–Nb–O mixed oxide but by the presence of an orthorhombic Te2M20O57 (M=Mo, V, Nb) crystalline phase. The role of tellurium in these catalysts is also discussed.
Selective oxidative dehydrogenation of ethane over MoVSbO mixed oxide catalysts
Abstract Mo–V–Sb–O mixed metal oxides were prepared, characterized and tested for the oxidative dehydrogenation of ethane (ODH). These catalysts are active and selective in the oxidative dehydrogenation of ethane to ethylene, although their catalytic performance depends strongly on the calcination temperature. The best catalytic results were obtained on samples heat-treated at 600 °C in N 2 (with selectivities to ethylene higher than 80% at ethane conversions about 65%). Moreover, a loss in the catalyst activity is initially observed on these catalysts as a consequence of modifications in the nature of the crystalline phases. Changes on the oxidation state of antimony ions on the surface of…
Selective oxidation of propane over alkali-doped Mo-V-Sb-O catalysts
[EN] 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 degrees C in N-2. 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 degrees…
Influence of gel composition in the synthesis of MoVTeNb catalysts over their catalytic performance in partial propane and propylene oxidation
[EN] MoVTeNb mixed oxides catalysts have been prepared by a slurry method with different molar compositions (Mo/Te ratio from 2 to 6 and Nb/(V + Nb) ratio from 0 to 0.7) in the synthesis gel leading to different crystalline phases distribution and catalytic behaviour in the partial oxidation of both propane and propylene to acrylic acid. Chemical analysis indicates that the composition of samples before and after the heat-treatment changes, especially the Te-content, since a significant amount of Te is lost during the heat-treatment step when the amount of oxalate (from niobium oxalate) increases in the synthesis gel. Thus, the nature of the crystalline phases and the catalytic performance …
Oxidative dehydrogenation of n-butane on MgO-supported vanadium oxide catalysts
Abstract Vanadium–magnesium oxide (VMgO) catalysts have been prepared, characterized and tested in the ODH of n-butane. The catalysts were prepared by two variations of the wet-impregnation method using aqueous ammonium metavanadate or organically-based methanolic vanadyl acetylacetonate solutions. The catalyst surface area depends on the vanadium content and the preparation method. Catalyst characterization (i.e. XRD, 51V NMR, FTIR, LRS) results indicate the presence of poor crystalline Mg-orthovanadate (Mg3V2O8), while the presence of other Mg-vanadates is not clear. Oxygen isotopic-exchange experiments on VMgO catalysts indicate an R2 process: [ 18 O 2 +2 16 O 2− (s) → ( 18 O 18 O 16 O 1…
Selective oxidative dehydrogenation of ethane on MoVTeNbO mixed metal oxide catalysts
Abstract MoVTeNbO catalysts, prepared by hydrothermal synthesis, are active and highly selective in the ODH of ethane, especially those with a MoVTeNb molar ratio of 1–0.15–0.16–0.17 and heat-treated at 600–650 °C. On the best catalyst, selectivities higher than 80% at ethane conversion levels higher than 80% have been obtained operating at relatively low reaction temperatures (340–400 °C). Thus, yields of ethylene of ca. 75% have been obtained, which exceeds the best yield reported in the literature. Te 2 M 20 O 57 ( M =Mo, V, Nb) and (V,Nb)-substituted θ -Mo 5 O 14 , in addition to small amounts of the Te 0.33 M O 3.33 ( M =Mo, V, Nb) phase, can be proposed in the most selective cataly…
Porous clays heterostructures as supports of iron oxide for environmental catalysis
[EN] Porous Clays Heterostructures (PCH) from natural pillared clays (bentonite with a high proportion of montmorillonite) have been used as supports of iron oxide for two reactions of environmental interest: i) the elimination of toluene (a representative compound of one of the most toxic subsets of volatile organic compounds, aromatics) by total oxidation and ii) the selective oxidation of H2S to elemental sulfur. For both reactions these catalysts have resulted to be remarkably more efficient than similar catalysts prepared using conventional silica as a support. Thus, in the total oxidation of toluene it has been observed that the catalytic activity obtained using siliceous PCH is two o…
Selective oxidative dehydrogenation of ethane over SnO2-promoted NiO catalysts
[EN] Ni-Sn-O mixed oxides catalysts have been investigated for the oxidative dehydrogenation of ethane. The catalysts were prepared through the evaporation of aqueous solutions of nickel nitrate and tin oxalate and finally calcined in air at 500 degrees C for 2 h. These materials have been characterized by several techniques (N-2-adsorption, X-ray diffraction, High-Resolution Electron Microscopy, temperature programmed reduction, X-Ray Photoelectron Spectroscopy, Fourier Transformed Infrared Spectroscopy of adsorbed CO and O-18/O-16 isotope exchange). The addition of just a tiny amount of tin highly increases the selectivity to ethylene (from ca. 40% to 80-90%). Thus, high selectivity to et…
Preparation, characterization and catalytic properties of vanadium oxides supported on calcined Mg/Al-hydrotalcite
Abstract Vanadium oxide supported on calcined hydrotalcite has been investigated for the oxidehydrogenation of n-butane in the 500–550°C temperature interval. Hydrotalcite (Mg/Al atomic ratio of 2.77), consisting of a single phase only, has been employed as a support precursor. The vanadium catalysts (0–50, referred as wt.-% V 2 O 5 ) were prepared by impregnation of calcined hydrotalcite (450°C) with ammonium metavanadate (in an aqueous solution) or vanadyl acetylacetonate (in a methanolic solution), and then calcined at 600°C for 4 h. During the impregnation step, the support is transformed into hydrotalcite if aqueous solutions are used. However, it is not modified if methanolic solution…
The selective oxidative dehydrogenation of ethane over hydrothermally synthesised MoVTeNb catalysts
Mo–V–Te–Nb metal oxide catalysts prepared by hydrothermal synthesis and heat-treated in N2 at high temperatures (600–700 °C) show high activity and selectivity for the oxidative dehydrogenation of ethane to ethene. Yields of ethene of 75% have been obtained at 400 °C on the best catalysts. Dejoz Garcia, Ana Maria, Ana.M.Dejoz@uv.es
V-containing MCM-41 and MCM-48 catalysts for the selective oxidation of propane in gas phase
Well-organised V-containing MCM-41 and -48 (0.3‐1 wt.% of V content) have been synthesised by one-pot synthesis or by grafting using VOSO4 or VOCl3 as V sources, respectively. The samples before and after the calcination step have been characterised by several physicochemical techniques (Ar and N2 adsorption, XRD, diffuse reflectance-UV‐VIS (DR-UV‐VIS) spectroscopy, temperature-programmed reduction). It was found that V species in the as-prepared catalysts were mainly as vanadyl ions (VO 2C ), while highly dispersed V 5C species with tetrahedral coordination were observed in the calcined materials. The catalytic behaviour of the calcined materials for the gas phase oxidation of propane has …
Mo–V–Nb mixed oxides as catalysts in the selective oxidation of ethane
Abstract Mo–V–Nb–O mixed metal oxides, obtained by heat-treatment in N 2 at 425 °C, have been studied as catalysts in the oxidative dehydrogenation of ethane. They present higher catalytic activity, while maintaining the same selectivity to ethylene, than the corresponding metal oxides calcined under air. Both amorphous and crystalline phases are present on active and selective catalysts. The implications of the presence of these phases as well as their physicochemical characteristics on the nature of active and selective sites are discussed.
Mixed oxide Ti Si O prepared by non-hydrolytic Xerogel method as a diluter of nickel oxide for the oxidative dehydrogenation of ethane
Abstract Mixed Ti Si O materials prepared by non-hydrolytic xerogel method have been employed as diluters for nickel oxide and used in the catalytic oxidative dehydrogenation of ethane. These catalysts have been characterized by several physicochemical techniques such as N2 adsorption, XRD, TPR, TEM, HR-TEM, and XPS. Supported nickel oxide catalysts have been reported to be efficient but only if the nature and the amount of support are controlled. In the present article it is shown that highly loaded (80 wt% NiO) nickel catalysts are more efficient when diluted on mixed Ti Si O materials with appropriate Ti/Si ratios than on pure TiO2 and SiO2 diluters. The catalytic results have been expla…
The role of metal oxides as promoters of V2O5/γ-Al2O3 catalysts in the oxidative dehydrogenation of propane
Summary The physicochemical properties of potassium-, bismuth-, phosphorous- and molybdenum-doped (Me/V atomic ratios of 0 to 1) V 2 O 5 /γ-Al 2 O 3 catalysts and their catalytic behavior in the oxidative dehydrogenation of propane have been compared. The incorporation of metal oxides modifies the catalytic behavior of alumina-supported vanadia catalysts by changing both their redox and their acid-base properties. In this way, the addition of potassium leads to the best increase in the selectivity to propylene. This performance can be related to the modification of the acid character of the surface of the catalysts. The possible role of both redox and acid-base properties of catalysts on th…
Mo-containing tetragonal tungsten bronzes. The influence of tellurium on catalytic behaviour in selective oxidation of propene
Abstract Te-free and Te-containing multicomponent Mo-based catalysts presenting tetragonal tungsten bronze (TTB) structure have been prepared, characterized and tested for the selective oxidation of propene. The catalysts were prepared hydrothermally and heat treated at 700 °C. The structural characterization performed by means of XRD, FTIR, SAED and HRTEM confirms the incorporation of tellurium to the TTB structural framework and shows that its presence does not modify in essence the crystalline structure. However, the incorporation of Te strongly modifies the catalytic performance, and the highest yield to acrolein has been achieved on catalysts with Te/Mo atomic ratios in bulk of 0.03. T…
Oxidative dehydrogenation of ethane: A study over the structure and robustness of Ni–W–O catalysts
[EN] The robustness of one selected Ni-W-O catalyst has been studied in the oxidative dehydrogenation of ethane. This catalyst initially deactivates for the first 10 h online decreasing 15% of its catalytic activity compared to its initial stable catalytic activity. However from 10 to 60 h online the catalytic activity keeps almost stable. On the other hand, it has been shown that the Ni-W-O catalyst cannot tolerate an oxygen-free atmosphere (C-2 and He) as nickel oxide is transformed into metallic nickel. Methane and hydrogen as well as abundant coke were formed on the surface of the catalyst in these O-free conditions. However a re-calcination in air leads to the removal of coke, the cata…
Oxidative dehydrogenation of ethane on diluted or promoted nickel oxide catalysts: Influence of the promoter/diluter
Ti- and Nb- containing NiO catalysts have been synthesized by two different preparation methods: i) by precipitation (Me-Ni-O oxides, Me = Nb or Ti), in order to prepare promoted NiO catalysts; and ii) by wet impregnation on TiO or NbO supports, in order to prepare diluted/supported NiO catalysts. The catalysts have been also characterized and tested in the oxidative dehydrogenation of ethane. The catalytic performance of Ti- and Nb-promoted catalysts strongly depends on the composition, although in both cases the optimal one is found at similar Ti or Nb loadings (ca. 90 wt% NiO), showing similar ethylene selectivity in the ODH of ethane (ca. 90% at 10–20% ethane conversion). However, in th…
Tungsten-titanium mixed oxide bronzes: Synthesis, characterization and catalytic behavior in methanol transformation
[EN] Tungsten oxide bronze-based materials show extremely adaptive structural and compositional features that make them suitable for functional properties modulation. Herein we report the preparation of a series of Ti-containing tungsten oxide catalysts presenting a hexagonal tungsten bronze-type structure. The insertion of Ti4+ within the structure (likely in the octahedral framework of the hexagonal tungsten bronze) leads to an increase in the number of strong acid sites, and the disappearance of W5+ surface species found in the undoped tungsten oxide. With the aim of studying the acid-redox properties of the titled catalysts, the catalytic transformation of methanol has been carried out …
The role of molybdenum in Mo-doped V–Mg–O catalysts during the oxidative dehydrogenation of n-butane
Abstract A detailed study on the influence of the addition of molybdenum ions on the catalytic behaviour of a selective vanadium–magnesium mixed oxide catalyst in the oxidation of n-butane has been performed. The catalysts have been prepared by impregnation of a calcined V–Mg–O mixed oxides (23.8 wt% of V2O5) with an aqueous solution of ammonium heptamolybdate, and then calcined, and further characterised by several physico-chemical techniques, i.e. SBET, XRD, FTIR, FT-Raman, XPS, H2-TPR. MgMoO4, in addition to Mg3V2O8 and MgO, have been detected in all the Mo-doped samples. The incorporation of molybdenum modifies not only the number of V5+-species on the catalyst surface and the reducibil…
Nickel oxide supported on porous clay heterostructures as selective catalysts for the oxidative dehydrogenation of ethane
[EN] Porous clay heterostructures (PCH) have shown to be highly efficient supports for nickel oxide in the oxidative dehydrogenation of ethane. Thus NiO supported on silica with a PCH structure shows productivity towards ethylene three times higher than if NiO is supported on a conventional silica. This enhanced productivity is due to the increase in the catalytic activity and especially to the drastic increase in the selectivity to ethylene. Additionally, PCH silica partially modified with titanium in the columns (PCH-Ti) have also been synthesized and used as supports for NiO. An enhanced activity and selectivity to ethylene was found over NiO supported over PCH-Ti compared to the corresp…
Molybdenum–vanadium supported on mesoporous alumina catalysts for the oxidative dehydrogenation of ethane
Abstract Vanadium and/or molybdenum oxides supported on mesoporous alumina have been prepared by a “wet” impregnation method, characterized (by using several physico-chemical techniques TPR, DR-UV–vis, Raman spectroscopies) and tested in the oxidative dehydrogenation (ODH) of ethane. For comparison Mo–V-mixed oxides supported on γ-Al2O3 have also been studied. The characterization results indicate that the main vanadium species in both Mo-free and Mo-containing V-based samples present low aggregation and coordination, whereas molybdenum is present as monomeric or polymeric tetrahedral molybdenum species. Interestingly, no apparent interaction between molybdenum and vanadia takes place. The …
NiO diluted in high surface area TiO2 as efficient catalysts for the oxidative dehydrogenation of ethane
[EN] Catalysts consisting of NiO diluted in high surface area TiO2 can be as efficient in the oxidative dehydrogenation of ethane as the most selective NiO-promoted catalysts reported previously in the literature. By selecting the titania matrix and the NiO loading, yields to ethylene over 40% have been obtained. In the present article, three different titanium oxides (TiO2) have been employed as supports or diluters of nickel oxide and have been tested in the oxidative dehydrogenation of ethane to ethylene. All TiO2 used present anatase as the main crystalline phase and different surface areas of 11,55 and 85 m(2) g(-1). It has been observed that by selecting an appropriate nickel loading …