Effect of pH on the Catalytic Properties of Mo–V–Te–P–O Catalysts for Selective Oxidation of Isobutane

Mo–V–Te–P mixed oxide catalysts, prepared by a dry-up method at various pHs (in the range of about 1.0–9.0), have been tested in the partial oxidation of isobutane. The best catalytic performance was achieved over a catalyst prepared at a pH about 7.0. In this case, high selectivity to methacrolein (37.0%) at an isobutane conversion of 12.7% has been obtained at 380 °C. The surface V⁴⁺/V⁵⁺ ratios of the calcined samples were strongly influenced by the pH in the synthesized solution, which is one of the key factors in the catalytic performance for selective oxidation of isobutane.     

Selective Oxidation and Oxidative Dehydrogenation of Isobutane over Hydrothermally Synthesized Mo–V–O Mixed Oxide Catalysts

A series of Mo–V–O catalysts were prepared by calcining the orthorhombic (M1) Mo–V–O phase containing precursors under different conditions (T = 500 or 600 °C in atmosphere of N₂ or air) and tested for the oxidation of isobutane and isobutene. Characterization results (BET, XRD, XPS, FTIR, and TPR) showed that their structure and properties depend on the composition of the calcined samples and the calcined conditions. Catalytic tests showed that relatively high isobutane conversion and desired product selectivity can be achieved over MoV_0.3-500-N and MoV_0.3-600-A catalysts. It is also found that both orthorhombic M1 phase and (V_0.07M_0.93)₅O₁₄ phase are active and selective for the selective oxidation of isobutane to methacrolein, whereas higher selectivity toward methacrolein (40.4%) can be achieved over the former phase at a moderate isobutane conversion (6.4%). Moreover, (Mo_0.3V_0.7)₂O₅ phase may be propitious to complete oxidation for the selective oxidation of isobutane. On the other hand, the presence of V affects the activity and selectivity, and a low surface V⁴⁺ concentration prefers selective oxidation products. In addition, specific surface areas of the catalysts appear to be little important in determining the catalytic activation.     

Ammoxidation of 3-picoline to nicotinonitrile over vanadium phosphorus oxide-based catalysts

Ammoxidation of 3-picoline to nicotinonitrile was investigated on vanadium phosphorus oxide (VPO), VPO/SiO₂ and additive atom (Cu, Zr, Mn and Co) incorporated VPO catalysts under atmospheric pressure and at 673 K. For the purpose of comparison a conventional V₂O₅–MoO₃/Al₂O₃ catalyst was also studied under identical conditions. These catalysts were characterized by means of X-ray diffraction, electron spin resonance, infrared, ammonia chemisorption and BET surface area methods. The VPO-based catalysts show better performance than the V₂O₅–MoO₃/Al₂O₃ catalyst. Further, the VPO/SiO₂ and VPO catalysts exhibit better conversion and product selectivities than the additive-containing VPO catalysts. Better activity of VPO and VPO/SiO₂ catalysts was related to their high active surface area, higher surface acidity and lower oxidation state of vanadium. The redox couple between (VO)₂P₂O₇ (V⁴⁺) and α_I-VOPO₄ (V⁵⁺) phases appears to be responsible for the ammoxidation activity of VPO catalysts. © 1998 SCI.     

A Study on VPO Specimen Supported on Aluminum-Containing MCM-41 for Partial Oxidation of n-Butane to MA

Dispersed vanadium–phosphorus oxide species supported on Al-MCM-41 with different vanadium loadings have been synthesized for the first time for partial oxidation of butane to MA. It was found that the VPO species was dispersed over the Al-MCM-41 support material, both in the internal channel and on the external surface. With increasing vanadium loading, n-butane conversion increased but MA selectivity decreased considerably under the same reaction conditions. At lower conversions (<30%), rather high MA selectivity (ca. 70%) can be achieved on the low loading sample. Compared with the amorphous structure of large pore SiO₂ support, the unique structure of the MCM-41 and the incorporated Al³⁺ in the framework do have an impact on the reaction behavior of the supported VPO specimen. The chemical nature of the supported VPO species and the interaction between the applied VPO species and the support was found to vary notably with the content of vanadium in the sample and likewise affected the related physico-chemical characteristics and their reaction behaviors.     

Selective oxidation of propylene to acetone by molecular oxygen over Mx/2H5−x[PMo10V2O40]/HMS (M=Cu2+, Co2+, Ni2+)

The transition metal salts (Cu²⁺, Co²⁺ and Ni²⁺) of 10-molybdo-2-vanadophosphoric acid (H₅[PMo₁₀V₂O₄₀]) were supported on hexagonal mesoporous silica (HMS), and the resultant materials were used as catalysts for the selective oxidation of propylene to acetone by molecular oxygen. CuH₃[PMo₁₀V₂O₄₀]/HMS showed a high selectivity for acetone of 84.2% at 17.8% propylene conversion in a tubular fixed-bed reactor system under atmospheric pressure at 423 K. The high yield of acetone over CuH₃[PMo₁₀V₂O₄₀]/HMS at 423 K resulted from the proper acidity and oxidation ability of the heteropoly compound, the nature (acid property, redox property, etc.) of the Cu²⁺ counter-ion, the high surface area of the HMS support and the proper reaction temperature for the propylene oxidation.     

Partial Oxidation of Isobutane Over Hydrothermally Synthesized Mo–V–Te–O Mixed Oxide Catalysts

Mo–V–O and Mo–V–Te–O catalysts were prepared by a hydrothermal synthesis route and tested for the oxidation of isobutane and isobutene. Characterization results (XRD, FT-IR, TPR, BET, and XPS) showed that the structure and property of Mo–V-based catalysts are considerably different depending on the presence of Te element and calcined temperature. Catalytic tests showed that the maximum selectivity of methacrolein (44.2%) can be achieved over a MoV_0.3Te_0.25-600 catalyst for the selective oxidation of isobutane. It is found that TeMo-containing phases are active and selective for the selective oxidation of isobutane to methacrolein.     

Spin–spin exchange in vanadium-containing catalysts studied by in situ-EPR: a sensitive monitor for disorder-related activity

In unsupported V-containing catalysts, V⁴⁺ sites are frequently present in amorphous oxidic clusters and/or crystalline paramagnetic bulk phases in which they are coupled by effective spin–spin exchange interactions. This work presents two EPR procedures for evaluating these interactions and relating their strength to the degree of disorder and catalytic performance, namely (1) evaluating permanent structural disorder by calculating exchange energies and integrals and (2) monitoring transient electronic disorder caused by catalyst–reactant interaction in working catalysts using the ratio of the fourth and the square of the second moment of the EPR signal. Selected application examples comprise VPO catalysts such as (i) (VO)₂P₂O₇, in which a certain degree of structural disorder revealed to be essential for high catalytic performance in the selective oxidation of n-butane to maleic anhydride, (ii) (NH₄)₂(VO)₃(P₂O₇)₂ in which transient perturbation of spin–spin exchange sensitively reflects the strength of reactant adsorption during ammoxidation of toluene and (iii) (NH₄)₂VOP₂O₇ in which an amorphous VO²⁺-containing phase could be identified as active component besides inactive crystalline phases. Based on operando-EPR measurements, reasons for activity differences in MoVTeNb oxide catalysts could be suggested.     

Oxidation of isobutane over Mo–V–Sb mixed oxide catalyst

The catalytic performances of Mo–V–Sb mixed oxide catalysts have been studied in the selective oxidation of isobutane into methacrolein. V–Sb mixed oxide showed the activity for oxidative dehydrogenation of isobutane to isobutene. The selectivity to methacrolein increased by the addition of molybdenum species to the V–Sb mixed oxide catalyst. In a series of Mo–V–Sb oxide catalysts, Mo₁V₁Sb₁₀O_x exhibited the highest selectivity to methacrolein at 440°C. The structure analyses by XRD, laser Raman spectroscopy and XPS showed the coexistence of highly dispersed molybdenum suboxide, VSbO₄ and -Sb₂O₄ phases in the Mo₁V₁Sb₁₀O_x. The high catalytic activity of Mo₁V₁Sb₁₀O_x can be explained by the bifunctional mechanism of highly dispersed molybdenum suboxide and VSbO₄ phases. It is likely that the oxidative dehydrogenation of isobutane proceeds on the VSbO₄ phase followed by the oxidation of isobutene into methacrolein on the molybdenum suboxide phase.     

Nature and Reactivity of the Active Species Formed After NO Adsorption and NO + O2 Coadsorption on an Fe-Containing Zeolite

Reactivity of the NO adspecies on Fe-ZSM-11 was studied by FTIR in situ. The effect of Fe content and the oxidation state of Fe in the samples were correlated with the catalytic activity. The relation between the adsorbed species, the Brønsted sites and catalytic activity in the SCR of NO_x to N₂ was also investigated. Moreover, FTIR allowed us to identify the active sites and the adsorption complexes present in FeMFI. Samples prepared by the sol–gel method with different Fe content displaying vastly different activity and selectivity in the reduction of NO to N₂ with isobutane in excess of O₂. Thus, in contact with pure nitric oxide, NO ions, mononitrosyl groups, nitro groups and nitrate ions have been identified. Feⁿ⁺ active sites are the most probable centers for NO oxidation to NO₂ and its further conversion to adsorbed nitro groups and nitrate ions, steps that are crucial for NO reduction. The concerted action of Feⁿ⁺ and H⁺ sites of the catalysts over the NO conversion to N₂ and isobutane conversion was analyzed.     

Selectivity issues in (amm)oxidation catalysis

Selectivity is currently taking center stage in heterogeneous oxidation catalysis as the cost of feed materials escalates. Particularly important and imperative for commercial processes is selectivity at acceptably high conversions. Dealing with this demanding quest we proposed, some 40 years ago, the concept of site isolation, defining one of the key requirements needed to achieve selectivity in oxidation catalysis. This principle continues to be useful in the conceptual design of new selective oxidation catalysts and has successfully described the selectivity behavior of many commercial (amm)oxidation catalysts, including now the MoVNbTeO system for propane ammoxidation to acrylonitrile (or oxidation to acrylic acid). In its catalytically optimum form, this system is comprised of at least two crystalline phases, orthorhombic Mo_7.8V_1.2NbTe_0.94O_28.9 (M1) and pseudo-hexagonal Mo_4.67V_1.33Te_1.82O_19.82 (M2). The M1 phase is the key paraffin activating and ammoxidation catalyst, its active centers containing all of the key elements V⁵⁺, Te⁴⁺, Mo⁶⁺, properly arranged to catalytically transform propane to acrylonitrile, and four Nb⁵⁺ centers, each surrounded by five molybdenum-oxygen octahedra, isolating the active centers from each other, thereby preventing overoxidation and leading to the observed high selectivity of the desired acrylonitrile product. Symbiosis between the M1 and M2 phases occurs when the two phases are synthesized concurrently in one vessel; or between physical mixtures of the two separately prepared phases provided they are finally divided (≤5 μm), thoroughly mixed and in micro-/nano-scale contact with each other. This phenomenon is particularly pronounced at high propane conversion when the M2 phase begins to serve as a co-catalyst to the M1 paraffin activating phase, converting extraneous, desorbed propylene intermediate, emanating from the M1 phase, effectively to acrylonitrile in a phase cooperation mode. The M2 phase is incapable of propane activation, lacking V⁵⁺ sites, but is a better propylene to acrylonitrile catalyst than the M1 phase since it possesses a higher concentration of Te⁴⁺ sites (i.e., propylene activating sites). Reaction networks for propane (amm)oxidation are proposed for these catalysts.     

Influence of Rare-Earth and Bimetallic Promoters on Various VPO Catalysts for Partial Oxidation of n-Butane

Vanadium phosphorous oxide (VPO) catalyst was prepared using dihydrate method and tested for the potential use in selective oxidation of n-butane to maleic anhydride. The catalysts were doped by La, Ce and combined components Ce + Co and Ce + Bi through impregnation. The effect of promoters on catalyst morphology and the development of acid and redox sites were studied through XRD, BET, SEM, H₂-TPR and TPRn reaction of n-butane/He. Addition of rare-earth element to VPO formulation and drying of catalyst precursor by microwave irradiation increased the fall width at half maximum (FWHM) and reduced the crystallite size of the Vanadyl hydrogen phosphate hemihydrate (VOHPO₄ · 1/2 H₂O, VHP) precursor phase and thus led to the production of final catalysts with larger surface area. The Ce doped VPO catalyst which, assisted by the microwave heating method, exhibited the highest surface area. Moreover, the addition of promoters significantly increased catalyst activity and selectivity as compared to undoped VPO catalyst in the oxidation reaction of n-butane. The H₂-TPR and TPRn reaction profiles showed that the highest amount of active oxygen species, i.e., the V⁴⁺–O^? pair, was removed from the bimetallic (Ce + Bi) promoted catalyst. This pair is responsible for n-butane activation. Furthermore, based on catalytic test results, it was demonstrated that the catalyst promoted with Ce and Bi (VPOD1) was the most active and selective catalyst among the produced catalysts with 52% reaction yield. This suggests that the rare earth metal promoted vanadium phosphate catalyst is a promising method to improve the catalytic properties of VPO for the partial oxidation of n-butane to maleic anhydride.     

Dependence of n-Butane Activation on Active Site of Vanadium Phosphate Catalysts

The nature and the role of oxygen species and vanadium oxidation states on the activation of n-butane for selective oxidation to maleic anhydride were investigated. Bi–Fe doped and undoped vanadium phosphate catalysts were used a model catalyst. XRD revealed that Bi–Fe mixture dopants led to formation of α_II-VOPO₄ phase together with (VO)₂P₂O₇ as a dominant phase when the materials were heated in n-butane/air to form the final catalysts. TPR analysis showed that the reduction behaviour of Bi–Fe doped catalysts was dominated by the reduction peak assigned to the reduction of V⁵⁺ species as compared to the undoped catalyst, which gave the reduction of V⁴⁺ as the major feature. An excess of the oxygen species (O^2?) associated with V⁵⁺ in Bi–Fe doped catalysts improved the maleic anhydride selectivity but significantly lowering the rate of n-butane conversion. The reactive pairing of V⁴⁺-O^? was shown to be the centre for n-butane activation. It is proposed that the availability and appearance of active oxygen species (O^?) on the surface of vanadium phosphate catalyst is the rate determining step of the overall reaction.     

Preparation of Novel Composite VPO/Fumed Silica Catalyst for Partial Oxidation of n-Butane

By applying fumed SiO₂ and the deposition–precipitation method based on organic medium, the composite VPO/fumed SiO₂ catalysts were first prepared and tried for partial oxidation of n-butane to maleic anhydride. In the temperature range of 653–693 K the fumed SiO₂-based catalysts not only showed good activity but also maintained sufficiently high MA selectivity in comparison to some conventional supported VPO catalysts. As an example, the catalyst with 30% VPO content showed butane conversion of 60% and MA selectivity of 58 mol% at 673 K. The turnover rates of low loading samples are found to be higher than that of high loading sample as well as unsupported catalyst. Besides the unique interaction which may exist between VPO component and the fumed SiO₂ material, co-existence of dominant (VO)₂P₂O₇ and minor VOPO₄ in these non-equilibrated catalysts may be favorable for MA formation. Moreover, introducing the additive of polyethylene glycol (PEG) in the preparation medium can obviously enhance the dispersion of VPO component and hence lead to a more selective catalyst.     

碱土金属醇类低共熔溶剂强化钒磷氧催化剂的制备及催化性能研究

钒磷氧(VPO)催化剂是目前实现正丁烷选择性氧化的唯一工业催化剂。利用金属助剂掺杂以及有机助剂强化是提高VPO催化剂性能的有效手段。本工作通过加入氯化镁醇类金属低共熔溶剂,实现了有机-金属助剂同时对VPO催化剂性能的调控。利用扫描电子显微镜(SEM)、BET全自动比表面与孔隙度分析仪(BET)、X射线衍射仪(XRD)和X射线光电子能谱仪(XPS)等表征手段,深入探讨了合成过程中加入不同氢键供体乙二醇(EG)、1-4丁二醇(BDO)和甘油(GL)的低共熔溶剂对VPO催化剂微观形貌、比表面积、物相、表面性质和晶相转变温度的影响,同时利用固定床反应器对VPO催化剂催化正丁烷氧化制备顺酐的性能进行了评价。结果表明,氯化镁乙二醇低共熔溶剂调控制备的VPO催化剂具有分散性良好、比表面积大、活性面(020)的数量多、表面P原子富集和表面V平均价态低等特点,在丁烷氧化选择性制顺酐反应中表现出了良好的催化性能,为VPO催化剂的制备提供了新思路。     

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 C₄-olefins fromn-butane and decreasing the selectivity to ethene from ethane. The role of the acid-base characteristics of catalysts on selectivity to ODH reactions is proposed.On leave from the Department of Industrial Chemistry and Materials, V. le Risorgimento 4, 40136 Bologna, Italy.     

Selective oxidation of isobutane to methacrolein over MoVTe mixed oxide supported on SBA-3 and SiO2

SBA-3 and SiO₂-supported MoVTe mixed oxide catalysts have been prepared by impregnation and/or direct synthesis methods and tested for selective oxidation of isobutane to methacrolein (MAL). It was found that the supported catalysts showed much higher activity than the bulk MoVTe mixed oxide for the reaction. Among the supported catalysts, better isobutane conversion and MAL yield were achieved on the 3% MoV_0.8Te_0.23O_x/SBA-3 catalyst prepared by the impregnation method. The catalysts were characterized with BET, XRD, Raman, H₂-TPR, XPS and FT-IR of pyridine adsorption. The good performance of the SiO₂ and SBA-3 supported MoV_0.8Te_0.23O_x catalysts was attributed to a combination of different properties: (i) formation of well dispersed active phases on large surface areas of SiO₂ and SBA-3 supports, which is beneficial for the isolation of active site and preventing the further oxidation of unstable reaction intermediate as well as product; (ii) improved activity for hydrogen abstraction of C-H bond of isobutane due to the formation of isolated pseudotetrahedral VO₄ species.     

Possible effects of site isolation in antimony oxide-modified vanadia/titania catalysts for selective oxidation of o-xylene

Titania-supported vanadia catalysts were modified by addition of antimony oxide for application in o-xylene selective oxidation to phthalic anhydride. It was shown that active and selective catalysts can be prepared by ball-milling mixtures of powders of TiO₂, V₂O₅and Sb₂O₃followed by calcination. X-ray photoelectron spectroscopy proves the formation of highly dispersed overlayers of vanadium oxide and antimony oxide, in which V⁵⁺is partially reduced to lower oxidation states and Sb³⁺is partially oxidized to Sb⁵⁺. Antimony oxide segregated into the outermost surface layers. It is therefore inferred that the presence of the antimony oxide modifier spatially separates V–O species and leads to site isolation which may be responsible for the positive effect of the modifier for the catalyst's selectivity.     

A vanadium phosphorus oxide catalyst synthesized in rotating packed bed for high-efficiency selective oxidation of n-butane

Oxidation of n-butane to produce maleic anhydride (MA) by the vanadium phosphorus oxide (VPO) catalyst is important for the fine chemical industry. However, the improvement in MA yield exceeding 60% is still a big challenge. In this article, a VPO catalyst with increased MA yield originated from the tailored structure of VPO precursor prepared in a rotating packed bed (RPB) reactor with excellent micro-mixing efficiency. The activated VPO-RPB catalyst displayed the coexistence of X₁-VOPO₄ and α_I-VOPO₄ phases and enhanced reducibility of V⁴⁺ state. Remarkably, the MA yield in n-butane oxidation catalyzed by VPO-RPB reached up to 66%, showing an increment by 14% compared with VPO-STR prepared in a stirring tank reactor (STR). The VPO-RPB showed the repeatable catalytic performance and achieved a promising scale-up production. This work provides the experimental evidence of a dual-phase (X₁-VOPO₄ and α_I-VOPO₄) mechanism for n-butane oxidation, and reveals the structure–activity dependence of VPO catalyst.     

In situ IR,Raman, and UV-Vis DRS spectroscopy of supported vanadium oxide catalysts during methanol oxidation

The application of in situ Raman, IR, and UV-Vis DRS spectroscopies during steady-state methanol oxidation has demonstrated that the molecular structures of surface vanadium oxide species supported on metal oxides are very sensitive to the coordination and H-bonding effects of adsorbed methoxy surface species. Specifically, a decrease in the intensity of spectral bands associated with the fully oxidized surface (V⁵⁺) vanadia active phase occurred in all three studied spectroscopies during methanol oxidation. The terminal V = O (∼1030 cm⁻¹) and bridging V–O–V (∼900–940 cm⁻¹) vibrational bands also shifted toward lower frequency, while the in situ UV-Vis DRS spectra exhibited shifts in the surface V⁵⁺ LMCT band (>25,000 cm⁻¹) to higher edge energies. The magnitude of these distortions correlates with the concentration of adsorbed methoxy intermediates and is most severe at lower temperatures and higher methanol partial pressures, where the surface methoxy concentrations are greatest. Conversely, spectral changes caused by actual reductions in surface vanadia (V⁵⁺) species to reduced phases (V³⁺/V⁴⁺) would have been more severe at higher temperatures. Moreover, the catalyst (vanadia/silica) exhibiting the greatest shift in UV-Vis DRS edge energy did not exhibit any bands from reduced V³⁺/V⁴⁺ phases in the d–d transition region (10,000–30,000 cm⁻¹), even though d–d transitions were detected in vanadia/alumina and vanadia/zirconia catalysts. Therefore, V⁵⁺ spectral signals are generally not representative of the percent vanadia reduction during the methanol oxidation redox cycle, although estimates made from the high temperature, low methoxy surface coverage IR spectra suggest that the catalyst surfaces remain mostly oxidized during steady-state methanol oxidation (15–25% vanadia reduction). Finally, adsorbed surface methoxy intermediate species were easily detected with in situ IR spectroscopy during methanol oxidation in the C–H stretching region (2800–3000 cm⁻¹) for all studied catalysts, the vibrations occurring at different frequencies depending on the specific metal oxide upon which they chemisorb. However, methoxy bands were only found in a few cases using in situ Raman spectroscopy due to the sensitivity of the Raman scattering cross-sections to the specific substrate onto which the surface methoxy species are adsorbed. This revised version was published online in August 2006 with corrections to the Cover Date.     

Methanol selectivity of silica-supported PtFe

Adding Fe to Pt/SiO₂ catalysts improves activity for methanol synthesis from 3H₂/CO at 523 K and 3.19 MPa. Over 90% methanol selectivity can be achieved at low conversion, depending on the metal composition and dispersion.In situ Mössbauer measurements after reduction in hydrogen at 673 K and during steady-state reaction show the presence of PtFe alloy and Fe³⁺ phases only. The amount of PtFe alloy increases as catalysts activate to produce methanol with higher activity and selectivity.