Propane Oxidative Dehydrogenation over Metal Pyrophosphates Catalysts

Metal pyrophosphates (M–P₂O₇, where M is V, Zr, Cr, Mg, Mn, Ni or Ce) have been found to catalyze the oxidative dehydrogenation of propane to propene. The reaction was conducted at 1 atm, 450–550°C and feed flowrate of 75 cm³/min (20 cm³/min propane, 5 cm³/min oxygen and the balance is helium). All catalysts showed increase in degrees of conversion and decrease in olefins selectivity with increase in reaction temperature. At 550°C, MnP₂O₇ exhibited the highest activity (40.7% conversion) and total olefins (C₃H₆ and C₂H₄) yield (29.3%). The other catalysts, indicated by their respective metals, may be ranked (based on olefins yield) as V (16.9%) < Cr (17.5%) < Ce (25.1%) < Zr (26.2%) < Ni (26.8%) < Mg (27.9%). The reactivity of the lattice oxygen was estimated from energy of formation of the corresponding metal oxides. Correlation between the selectivity to propene and the standard energy of formation was attempted. Although there was no clear correlation, the result suggested that the lattice oxygen play a key role in the selectivity-determining step.     

Oxidative Dehydrogenation of Propane on Calcium Hydroxyapatites Partially Substituted with Vanadate

Solid solutions of phosphate and vanadate calcium hydroxyapatites were synthesized and the catalytic activities for the oxidative dehydrogenation of propane to propylene on those catalysts were examined. Although the conversion of propane and the selectivity to propylene were 7.6 and 3.5% on calcium hydroxyapatite (CaHAp), the incorporation of vanadate to CaHAp by V/P=0.05 (atomic ratio) resulted in the enhancement of the conversion and the selectivity to 17.2 and 52.4%, respectively, corresponding to those on Mg₂V₂O₇ under the same reaction conditions (14.0 and 50.9%, respectively).     

Effect of Tetrachloromethane on Redox Behaviors of Copper(II) Oxide in the Oxidative Dehydrogenation of Propane

The oxidative dehydrogenation of propane on CuO has been investigated at 723 K in the presence and absence of tetrachloromethane (TCM). Under oxygen-limiting conditions, the conversion of propane and the selectivity to propylene were enhanced by the introduction of TCM. The catalyst converted to metallic Cu during the oxidation in the absence of TCM while no conversion of CuO was observed in the sample used in the presence of TCM. In contrast, the conversion of propane dramatically decreased upon addition of TCM into the feedstream for the oxidation of propane under the oxygen-excess conditions. The catalyst used under the oxygen-excess conditions was not reduced to metallic Cu, regardless of the addition of TCM. It is suggested that an abstraction of lattice oxygen from the catalyst is strongly influenced by the concentration of oxygen in the feed, resulting in the different effect of TCM on the oxidative dehydrogenation of propane.     

Chromium Oxide Supported on Mesoporous SBA-15 as Propane Dehydrogenation and Oxidative Dehydrogenation Catalysts

The catalytic activity and selectivity of Cr₂O₃ supported on mesoporous SBA-15 for non-oxidative and oxidative dehydrogenation of propane by O₂ and CO₂ have been studied and compared with those of Cr₂O₃/ZrO₂ and Cr₂O₃/-Al₂O₃ catalysts. Cr₂O₃/SBA-15 and Cr₂O₃/ZrO₂/SBA-15 are more selective to propene and more resistant to coking in comparison with Cr₂O₃/ZrO₂ and Cr₂O₃/-Al₂O₃ for non-oxidative dehydrogenation of propane. In oxidative dehydrogenation of propane by O₂ and CO₂, Cr₂O₃/SBA-15 also displays better activity, selectivity and stability than the other two supported catalysts. The propane conversion and propene yield on Cr₂O₃/SBA-15 catalyst for oxidative dehydrogenation of propane by CO₂ at 823 K reach 24.2 and 20.3%, respectively. XPS and TG/DTA have been used to characterize the catalysts before and after reaction. The differences in catalytic behavior of various supported Cr₂O₃ catalysts in the reactions have been discussed on the basis of the characterization results.     

Characterization and Catalytic Behavior of VO x -CeO2 Catalysts for the Oxidative Dehydrogenation of Propane

A series of ceria-supported vanadium catalysts was prepared via impregnation of the support with an ammonium metavanadate solution. The 723 K calcined samples were tested for propane oxydehydrogenation (ODH) activity and selectivity. The sample exhibiting the highest propane conversion was found to be the ceria support material itself, although this showed essentially no selectivity towards propene. An optimum propene yield of 4.2% was obtained at 673 K for the 6 wt% V₂O₅-CeO₂ sample. Conversion decreased with increasing V loading which was attributed to the formation of cerium vanadate (CeVO₄). This phase was found in all samples after calcination, its abundance rising in proportion to the V loading. In the 6 wt% V₂O₅ catalyst hydrated surface VO_x species were present, although they underwent conversion to CeVO₄ at temperatures above 573 K. The low reducibility of these surface vanadates was linked to the oxidation activity. It is inferred that surface polyvanadate species are responsible for the selective ODH of propane with V-O-V and/or V-O-Ce being the active oxygen species.     

Highly Effective Oxidative Dehydrogenation of Propane Over Vanadia Supported on Mesoporous SBA-15 Silica

Vanadia-containing mesoporous SBA-15 catalysts were prepared and characterized for the oxidative dehydrogenation (ODH) of propane. It is demonstrated that the vanadia-supported SBA-15 catalysts exhibit a much higher catalytic activity than those reported in the literature obtained over vanadium-supported mesoporous MCM-41 catalysts in the ODH of propane. The high catalytic performance of the mesoporous SBA-15 catalysts is attributed to the particularly large pore diameters and low surface acidity.     

Effects of calcium cations incorporated into magnesium vanadates on the redox behaviors and the catalytic activities for the oxidative dehydrogenation of propane

The influence of the incorporation of Ca²⁺ into MgV₂O₆, Mg₂V₂O₇ and Mg₃V₂O₈ on the catalytic activities for the oxidative dehydrogenation of propane and the mobility of lattice oxygen in those catalysts has been investigated. On Mg₂V₂O₇ and Mg₃V₂O₈ incorporated with Ca²⁺, the selectivity to propylene evidently increased with increasing the content of Ca²⁺ in those catalysts. A decrease of the conversion of propane was observed on Ca²⁺-added Mg₂V₂O₇ with increasing Ca²⁺-content; while on Ca²⁺-added Mg₃V₂O₈, no dependence on the Ca²⁺-content was observed. The incorporation of Ca²⁺ was rather insensitive to both the selectivity and the conversion on Ca²⁺-added MgV₂O₆. In order to examine the mobility of lattice oxygen in those catalysts, those catalysts were employed for the oxidative dehydrogenation in the absence of oxygen for 2.25 h, followed by the addition of gaseous oxygen into the feedstream. After the addition of gaseous oxygen under the present conditions, oxygen in the effluent was detected at 9, 3.5 and 2 min with Mg₂V₂O₇ incorporated with Ca²⁺ at these Ca/(Mg + Ca) ratios: 0, 0.05 and 0.1. The times were 1.4, 2 and 4 min with Mg₃V₂O₈ incorporated with Ca²⁺ as Mg₂V₂O₇. However, no oxygen was detected with MgV₂O₆ incorporated with Ca²⁺ even 15 min after the addition of the gaseous oxygen. The present results reveal that the mobility of the lattice oxygen in those catalysts is strongly influenced by the amount of Ca²⁺ incorporated, resulting in significant effects on the activities for the oxidative dehydrogenation of propane. ⁵¹V MAS NMR was also employed for the observation of redox behaviors of vanadium species in those catalysts during the reaction.     

Chromium Supported on Mesocellular Silica Foam (MCF) for Oxidative Dehydrogenation of Propane

A series of chromium-containing mesocellular silica foam (MCF) catalysts have been prepared and characterized in the oxidative dehydrogenation (ODH) of propane between 350 and 600 °C. It is demonstrated that the chromium catalysts supported on MCF exhibit much higher catalytic activity in terms of propane conversion and propylene yield than literature results obtained over chromium-supported mesoporous SBA-15 or MCM-41 catalysts during the ODH of propane. Enhanced catalytic performance of the chromium-containing mesoporous MCF catalysts has been attributed to the unique three-dimensional (3D), continuous, ultralarge mesopore structure of the MCF materials, which allow a much faster internal molecular transport during the ODH of propane.     

Modulation of ODH Propane Selectivity by Zeolite Support Desilication: Vanadium Species Anchored to Al-Rich Shell as Crucial Active Sites

The commercially available zeolite HY and its desilicated analogue were subjected to a classical wet impregnation procedure with NH₄VO₃ to produce catalysts differentiated in acidic and redox properties. Various spectroscopic techniques (in situ probe molecules adsorption and time-resolved propane transformation FT-IR studies, XAS, ⁵¹V MAS NMR, and 2D COS UV-vis) were employed to study speciation, local coordination, and reducibility of the vanadium species introduced into the hierarchical faujasite zeolite. The acid-based redox properties of V centres were linked to catalytic activity in the oxidative dehydrogenation of propane. The modification of zeolite via caustic treatment is an effective method of adjusting its basicity—a parameter that plays an important role in the ODH process. The developed mesopore surface ensured the attachment of vanadium species to silanol groups and formation of isolated (SiO)₂(HO)V=O and (SiO)₃V=O sites or polymeric, highly dispersed forms located in the zeolite micropores. The higher basicity of HY_deSi, due to the presence of the Al-rich shell, aided the activation of the C−H bond leading to a higher selectivity to propene. Its polymerisation and coke formation were inhibited by the lower acid strength of the protonic sites in desilicated zeolite. The Al-rich shell was also beneficial for anchoring V species and thus their reducibility. The operando UV-vis experiments revealed higher reactivity of the bridging oxygens V-O-V over the oxo-group V=O. The (SiO)₃V=O species were found to be ineffective in propane oxidation when temperature does not exceed 400 °C.     

Effect of Modifiers on the Reactivity of Cr2O3/Al2O3 and Cr2O3/TiO2 Catalysts for the Oxidative Dehydrogenation of Propane

Chromium oxide supported on alumina and titania supports was modified with oxides of sodium, vanadium and molybdenum. The modified and unmodified chromium oxide catalysts were characterized by several techniques. The presence of surface chromium oxide and surface molybdenum and vanadium oxide species was detected in the unmodified and molybdenum and vanadium oxide modified supported chromium oxide catalysts. The reducibility (T_max and H/Cr ratio) of the surface chromium species was not affected for the vanadium and molybdenum oxide modified catalysts; however, the reducibility changed noticeably for sodium modified supported chromium oxide catalysts. Studies of the reactivity of the ODH of propane revealed the effect of modifiers on the reactivity properties of the surface chromium oxide species. The activity and propene selectivity decreased for sodium modified supported chromium oxide catalysts. However, the activity increased for vanadium oxide modified catalysts and was similar for molybdenum oxide modified catalysts irrespective of the support. The propene selectivity was higher for molybdenum oxide modified chromium oxide catalysts. However, the propene selectivity for vanadium oxide modified catalysts depends on the support since it appears that the inherent selectivity of the surface vanadium oxide species is reflected.     

Solid-state V NMR and its potentiality in investigation of vanadia systems with paramagnetic centres

In this article we will discuss the potentiality of solid-state ⁵¹V NMR technique to characterize heterogeneous catalysts containing paramagnetic cations located on the surface or incorporated in the bulk of heterogeneous catalysts. ⁵¹V NMR data for a number of 3d and rare earth vanadates, where paramagnetic effects are caused by the presence of paramagnetic cations, are considered. We also summarize results available for vanadium bronzes, where some vanadium is in a paramagnetic V⁴⁺ state, and for some vanadium compounds, where closely spaced paramagnetic centers form diamagnetic pairs. The comprehensive ⁵¹V chemical shift scale (database) for paramagnetic solids was compiled.     

Propane Oxidation on MoVTeNbO Mixed Oxide Catalysts: Study of the Phase Composition of Active and Selective Catalysts

Several phases reported as minor or major phases in the active MoVTeNbO catalysts have been prepared and investigated for the oxidation of propane into acrylic acid. Activity and selectivity of pure phases and mixtures of phases obtained either directly from synthesis or by co-grinding have been compared. The results obtained confirmed that the orthorhombic M1 phase is the most active and selective phase and is responsible for the major part of the efficiency of the best catalysts. However, they also clearly demonstrated that a synergism due to a cooperation between phases occurs, similar to that previously proposed between the M1 [(Te₂O)M₂₀O₅₆] and M2 [(TeO)M₃O₉] phases for the ammoxidation of propane. The origin of this phase cooperation is discussed.     

Heterogenization of 12-tungstophosphoric acid on stabilized zeolite Y

Topics in Catalysis - 12-tungstophosphoric acid (PW12) has been supported on dealuminated zeolite Y, containing a secondary pore system with the predominant pore radii of 15 Å. The interaction...     

Formation of Cobalt Phyllosilicate During Solid State Preparation of Co2+/ZSM5 Catalysts from Cobalt Acetate

When CO²⁺/ZSM5 catalysts are prepared by solid state exchange between H-ZSM5 and cobalt acetate, CO²⁺ ions form layered cobalt phyllosilicate at the surface of the zeolite grains, bringing about a reassessment of the chemistry involved in the preparation of catalytic systems by solid state exchange.     

Semiconductive and Redox Properties of Ti and Zr Pyrophosphate Catalysts (TiP2O7 and ZrP2O7). Consequences for the Oxidative Dehydrogenation of n-Butane

The electrical conductivity of titanium and zirconium pyrophosphates used as catalysts in n-butane oxidative dehydrogenation has been measured under oxygen and n-butane at 400 and 500 °C and under subsequent exposures to both gases at the catalytic reaction temperature. The two compounds appeared to be p-type semiconductors under air with positive holes as the main charge carriers but became n-type when contacted with n-butane. If their conductivities are comparable as p-type semiconductors (within one order of magnitude), by contrast, they differ by 3 orders of magnitude when being n-type semiconductors. These results explain the difference in catalytic reaction mechanism encountered on the two solids. The alkane activation was proposed to be related in both cases to the p-type semiconducting properties of the solids, likely through hydrogen abstraction by a surface O^- species, forming a C₄H₉ radical which will similarly undergo a second hydrogen abstraction to form butenes. The changes in activation energy and in selectivity on TiP₂O₇ at higher temperatures (>450 C) are indicative of a change in mechanism, possibly with the transient formation of an alkoxide species.     

丙烷选择氧化制丙烯酸复合金属氧化物催化剂的研究进展

综述了丙烷选择氧化制丙烯酸的复合金属氧化物催化剂(CM0)研究进展，特别是主要金属元素的作用以及催化剂制备过程中金属原子比、混合方法、干燥方式、焙烧气氛和pH值等因素对CMO催化性能的影响，并指出了今后的研究方向。     

Chemical characterization and agronomic effectiveness of phosphorus applied as a polyphosphate-chitosan complex

This work was undertaken to characterize a chitosan-polyphosphate complex (CH-PP) and to evaluate its agronomic effectiveness as a source of phosphorus for ryegrass (Lolium perenne) grown on loamy and clayey soils. High resolution solid state³¹P and¹³C nuclear magnetic resonance were used to characterize this complex and to monitor the structural changes occurring to it during an 8-week incubation period in a loamy soil. A pot experiment was conducted on the two soils after labelling the available P with³²PO₄ ions. This experiment allowed for the determination of the agronomic effectiveness of the chitosan-polyphosphate complex compared to polyphosphate and to monocalcium phosphate. Results showed that chitosan immobilized up to 147 mg P kg^–1 as pyrophosphate and hexametaphosphate. This reaction did not involve major structural changes in the pyrophosphate or hexametaphosphate groups nor in the chitosan. The chitosan-polyphosphate complex was as efficient as the polyphosphate alone to sustain the P nutrition of ryegrass. The relative agronomic effectiveness of these P sources was slightly lower compared to that of monocalcium phosphate. The high P fertilizing value of the chitosan-polyphosphate complex was attributed to its gradual hydrolysis in the soil. The potential interest of chitosan to remove polyphosphates from waste waters while preserving the high P fertilizing value of polyphosphates was addressed.     

Solid-state nuclear magnetic resonance investigation of cation siting in LiNaLSX zeolites

The location of Li⁺ and Na⁺ cations in a series of dehydrated low-silica LiNaX zeolites (LiNaLSX, framework Si/Al ratio=1.0) were characterized by ⁷Li and ²³Na magic-angle spinning (MAS) nuclear magnetic resonance (NMR) spectroscopy. Depending on the Li⁺ content, up to three lines were observed in the ⁷Li MAS NMR spectra attributed to Li⁺ cations on SI′, SII and SIII sites. The ²³Na MAS NMR spectra of the pure sodium form NaLSX and of LiNaLSX samples with low Li⁺ contents contain up to five lines belong to Na⁺ cations located on SI, SI′, SII, and two different SIII′ sites. LiNaLSX zeolites containing more than 40% of Li⁺ show only a single narrow line in the ²³Na MAS NMR spectra attributed to mobile sodium cations. The populations of the different cation sites were determined from the relative line intensities of the MAS NMR spectra. Below about 70% Li⁺ exchange, lithium cations are located only on sites SI′ and SII. Between 70% and 100% Li⁺ content these sites are fully occupied by Li⁺, and the population of site SIII by Li⁺ increases. It was found that the nitrogen-adsorption capacity correlates well with the occupation of Li⁺ at site SIII.     

Evaluating the Catalytic Performances of SAPO-34 Catalysts for the Oxidative Dehydrogenation of Ethane

Acid silicoaluminophosphate SAPO-34 catalysts with a chabasite-related (CHA) structure were tested for the oxidative dehydrogenation of ethane in the temperature range 550-700 °C achieving very interesting catalytic performances (about 70% C₂H₄ selectivity at 45% ethane conversion) which were related to both Lewis and Brønsted acid sites, as found by a NH₃-TPD study.     

Tunability of Propane Conversion over Alumina Supported Pt and Rh Catalysts

Propane conversion over alumina supported Pt and Rh (1 wt% metals loading) was examined under fuel rich conditions (C₃H₈:O₂:He = 1:2.25:9) over the temperature range 450–650 °C. Morphological characteristics of the catalyst materials were varied by calcining at selected temperatures between 500 and 1,200 °C. X-ray diffraction and BET analysis showed the treatment generated catalyts metals with particle sizes in the range of <10 to >500 nm, and support surface areas in the range of 20–240 m²/g. Remarkably, both Rh and Pt yielded product compositions close to equilibrium values (with high H₂ and CO selectivity, complete oxygen conversion and almost complete propane conversion) so long as the metal particle size was sufficiently low, ≲10–15 nm. In cases where the particle size was large, primarily complete oxidation rather than partial oxidation products were observed, along with unreacted C₃H₈, indicative of a direct oxidation pathway in which gas-phase CO and H₂ are not present as intermediate species. It is proposed that the high resistance of Rh to coarsening is largely responsible for the observation of a higher selectivity of this material for syngas products when prepared by procedures similar to those for Pt. Overall, the tunability of the product composition obtained over Rh and Pt via processing steps has direct significance for the incorporation of such catalyts into the anodes of solid oxide fuel cells.