Indium-containing catalysts for oxidative dehydrogenation of organic compounds

For the first time, a method was developed for introducing indium into Mg-Al hydrotalcites—precursors of oxide catalysts for oxidative dehydrogenation of alkanes. Samples of oxide catalysts were synthesized that contained indium oxide and also oxides of magnesium, aluminum, chromium, vanadium, molybdenum, and niobium in various combinations. The catalytic properties of the produced catalysts were studied in the oxidative dehydrogenation of ethane, propane, and isobutane. It was established that the introduction of indium into catalysts increases the selectivity and the yields of desired products. New hydroxo salts with a layered structure of the hydrotalcite type were synthesized: [Al_{1 ? n} In _n Mg _m (OH)_{3 + 2m ? 1}][(NO₃) · nH₂O] and quaternary magnesium indium chromium aluminum hydroxonitrate of the composition [Al_0.5In_0.5Cr_0.5Mg_2.5(OH)_8.5][(NO₃) · nH₂O]; these salts were found to be isostructural. The obtained compounds were studied as catalyst precursors.     

Europium oxide containing catalysts for oxidative dehydrogenation of alkanes

A method is developed to incorporate europium into Mg–Al hydrotalcites, which are precursors for oxide catalysts of oxidative dehydrogenation (ODH) of alkanes; samples of oxide catalysts are prepared, where europium oxide and gallium, magnesium, aluminum, chromium, vanadium, molybdenum, and niobium oxides are contained in various combinations. The catalytic properties of these catalysts in the reactions of ethane, propane, and butane ODH are studied. The incorporation of europium into some of our studied multicomponent catalysts enhances the reaction selectivity and increases yields of desired products.     

Ytterbium-Containing Oxide Catalysts for Oxidative Dehydrogenation of Hydrocarbons

Oxide catalyst samples for the oxidative dehydrogenation (ODH) of alkanes were prepared by heat treatment of precursors, namely, hydrotalcite-related magnesium aluminum double hydroxo salts containing ytterbium, as well as magnesium, aluminum, chromium, vanadium, molybdenum, and niobium in various combinations. Their catalytic activities were studied. Some catalysts were found to have high efficiency in ODH of ethane, propane, and isobutane, increasing the product yield and enhancing the reaction selectivity.     

Praseodymium-containing catalysts for oxidative dehydrogenation of organic compounds

A method is developed for incorporating praseodymium into magnesium–aluminum hydrotalcites, which are precursors for oxide catalysts for oxidative dehydrogenation (ODH) of alkanes. Oxide catalyst samples that contain praseodymium and various combinations of magnesium, aluminum, chromium, vanadium, molybdenum, and niobium are prepared. The catalytic properties of the prepared catalysts in ethane, propane, and butane ODH reactions are studied. Into some of our studied multicomponent catalysts, the incorporation of praseodymium enhances the reaction selectivity and increases yields of desired products.     

Copper-containing catalysts for the oxidative dehydrogenation of organic compounds

A method of doping magnesium aluminum hydrotalcites, which are precursors for oxidative dehydrogenation oxide catalysts of various compositions, with copper(II) was developed, and copper(II)-containing oxide catalyst samples were synthesized. The catalytic properties of these catalysts were studied in the oxidative dehydrogenation of ethane, propane, and hexane. The conversion of ethane into ethylene on the copper-containing catalysts was established to proceed with high selectivities (90?C97%) and at low temperatures (400?C450°C).     

Oxidative dehydrogenation of ethane on VMoTeNbО/Al–Si–O catalysts: Effect of the support on the physicochemical and catalytic properties

Supported oxide catalysts of the overall composition V_0.3Mo₁Te_0.23Nb_0.12/nAl–Si–O (n = 0, 10, 25, 35, 50, and 70 wt %) were tested in oxidative dehydrogenation of ethane and were characterized by chemical analysis, X-ray diffraction analysis, and transmission electron microscopy. The use of the Al–Si–O support in a wide range of its content (from 10 to 50 wt %) favors formation of nanodomains of the active М1 phase ensuring higher, compared to the bulk catalysts, activity in oxidative dehydrogenation of ethane. The formation of secondary phases of aluminum molybdate and vanadium–molybdenum double oxide, observed at the support content increased over 35 wt %, leads to worsening of the catalytic properties.     

Chromium,vanadium, molybdenum,tungsten, magnesium,and aluminum hydrotalcite hydroxo salts and oxide catalysts on their base

A method is developed for the synthesis of chromium-containing catalysts for the oxidative dehydrogenation (ODH) of alkanes, comprising the precipitation, from nitrate solutions, of mixtures of isomorphic hydrotalcite-type magnesium aluminum and magnesium chromium hydroxocarbonates and the incorporation of oxovanadate, oxomolybdate, and oxotungstate ions by means of anion exchange and subsequent heat treatment. A series of oxide catalyst samples with progressively more complex compositions were prepared: Mg-Al, V-Mg-Al, V-Mo-Mg-Al, Cr-V-Mg-Al, Cr-V-Mo-Mg-Al, and Cr-V-Mo-W-Mg-Al. The catalytic properties of these complex oxides in the ODH of ethane and propane are improved with progressively complex compositions. Chromium-containing catalysts have higher selectivities and provide higher conversions compared to state-of-the-art iron- and nickel-containing oxides.     

Oxidative dehydrogenation of propane over chromium and nickel oxide modified V2O5/ZrO2 catalysts

The effect of addition of chromium and nickel oxides on the physicochemical properties and performance of V₂O₅/ZrO₂ catalysts was studied for the oxidative dehydrogenation of propane. Addition of chromium oxide increased, whereas addition of nickel oxide lowered the activity. Selectivity for propene was lower for the doped catalysts. The selectivity was lowered by higher total acidity as well as the higher concentration of stronger acid sites in doped catalysts.     

Aerogel method for preparation of nanocrystalline CoOx·MgO and VOx·MgO catalysts

Cobalt-magnesium and vanadium magnesium oxide catalysts were prepared by aerogel method. The obtained nanocrystalline materials are characterized by uniform distribution of the active component, which is present in a finely dispersed state amorphous to X-rays. The oxides have unique morphology. The size of their nanoparticles does not exceed 10 nm. The aerogel synthesis method was successfully applied for synthesis of two-component CoO_x·MgO and VO_x·MgO catalysts active in CO oxidation and propane oxidative dehydrogenation, respectively.     

负载PtSn金属助剂的镁铝水滑石上的丙烷脱氢反应研究

我们研究了以镁铝水滑石作为载体,利用水滑石层间阴离子的可交换性,负载活性金属铂和锡的丙烷脱氢反应.在镁铝水滑石载体中加入Ga能够影响丙烷脱氢活性,当镓的含量为1%时催化剂丙烷脱氢反应活性最高,反应初始时,丙烷转化率为46.5%,反应2 h后,丙烷转化率仍有37.5%.当以Mg(Ga)(Al)O-1%为载体时,考察了不同H_2/C_3H_8摩尔比对丙烷脱氢活性的影响,结果表明当H_2/C_3H_8摩尔比为0.5∶1时,丙烷脱氢反应具有最佳的反应活性,即当在原料气中加入H_2时,能够使得丙烷脱氢的转化率大幅度提升,且选择性也有所提升.烷烃脱氢是一个吸热反应,同时考察了温度对烷烃脱氢反应性能影响,结果表明温度越高,丙烷脱氢反应具有更高的转化率.对催化剂进行长时间寿命实验考察,发现当反应经过40 h后,丙烷的转化率仍有23.5%,说明Pt Sn-Mg(Ga)(Al)O-1%催化剂具有较好的稳定性.     

Supported MgO–V<Subscript>2</Subscript>O<Subscript>5</Subscript>/Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts for oxidative propane dehydration: Effect of the molar Mg : V ratio on the phase composition and catalytic properties of samples

The physicochemical properties of V₂O₅/Al₂O₃ and MgO–V₂O₅/Al₂O₃ supported catalysts (Mg : V = 1 : 1, 2 : 1, and 3 : 2) obtained by consecutive impregnation of the support with solutions of vanadium and magnesium precursors are studied using a complex of mutually complementary methods (XRD, Raman spectroscopy, UV–Vis spectrometry, and TPR-H₂). The effect of the formation of surface magnesium vanadates of various composition and structure on the catalytic properties of the supported vanadium oxide catalysts in the oxidative dehydrogenation of propane is studied. The introduction of magnesium in the samples and an increase in its content, accompanied by a change in the structure of the surface vanadium oxide phases from polymeric VO₆/VO₅ species to surface metavanadate species, magnesium metavanadate, and further to magnesium divanadate, significantly affects their catalytic properties in the reaction of the oxidative dehydrogenation of propane to propylene.     

Synthesis of vanadium-phosphorus oxide catalysts supported on pyrogenic silica and titanium dioxide

Various methods for the preparation of vanadium-phosphorus oxide (VPO) catalysts supported on aerosils A-300 and A-50 and TiO₂ were studied: a traditional method (in an organic solvent under varying the support addition time, the nature of the reducing agent, and the degree of reduction of vanadium oxide) and barothermal and mechanochemical syntheses. With the use of XRD analysis, it was found that the composition of the resulting VPO phase depends on the time of support addition to the synthesis and the temperature of thermal treatment. Conditions for the formation of a supported phase of VOHPO₄·0.5H₂O, the precursor of the active component (VO)₂P₂O₇, were determined. The presence of vanadium in an oxidation state of +4 was demonstrated using EPR and UV-VIS spectroscopy. The specific surface areas and pore structures of the synthesized catalysts were determined. The catalytic properties of samples in the reactions of n-butane oxidation in an excess of the hydrocarbon and oxidative ethane dehydrogenation were studied. It was found that, as compared with traditional bulk VPO catalysts, the use of the synthesized supported VPO catalysts made it possible to improve the process characteristics of n-butane oxidation and did not change these characteristics in the reaction of oxidative ethane dehydrogenation.     

Ytterbium-Containing Magnesium–Aluminum Hydroxo Salts with a Hydrotalcite-Type Structure

A method is developed for inserting ytterbium into Mg–Al hydroxo salts that have a hydrotalcitetype layered structure, as well as for the chemical analyses of complex hydroxo salts containing ytterbium in various combinations with magnesium, aluminum, chromium, vanadium, molybdenum, and niobium. The formation conditions of these hydroxo salts have been studied by potentiometric titration, their samples have been prepared, and X-ray diffraction patterns recorded. The prepared hydroxo salt samples have been tested as precursors for oxide catalysts of oxidative dehydrogenation (ODH) of alkanes.     

Magnesium iron aluminum hydroxosalts and oxide catalysts for oxidative dehydrogenation of alkanes and alcohols

Methods are developed for the synthesis of precursors for oxide catalysts containing iron hydroxocarbonate and magnesium aluminum hydroxocarbonate with hydrotalcite-type layered structure and decavanadate and paramolybdate ions in anionic interlayers. These precursors are used to synthesize oxide catalysts for oxidative dehydrogenation of alcohols and alkanes with high selectivity and good yields of the desired product in conversion of ethane to ethylene and alcohols to carbonyl compounds.     

Catalytic performance of silica-supported chromium oxide catalysts in ethane dehydrogenation with carbon dioxide

The oxidative dehydrogenation of ethane into ethylene by CO₂ over a series of silica-supported chromium oxide catalysts was investigated. The results showed that the catalysts were effective for the reaction and CO₂ in the feed promoted the catalytic activity. The 5%Cr/SiO₂ catalyst exhibited the excellent performance with 30.7% ethane conversion and 96.5% ethylene selectivity at 700^oC. ESR and UV-DRS were used to probe the active sites and the species with high valent states (Cr⁵⁺ and/or Cr⁶⁺) were found to be important for the reaction.     

Influence of the preparation conditions for catalysts CrO x /SiO2 on their efficiency in propane dehydrogenation in the presence CO2

Several sets of chromium oxide catalysts supported on silica gel were prepared by precipitation. The optimization of the preparation conditions can considerably enhance the activity and stability of the catalysts in propane dehydrogenation in the presence of CO₂. The most stable systems with the chromium content <3 wt.% retain their initial activity after long-duration tests and regenerations. Introducing the active phase on the support in several steps makes it possible to enhance the stability of the samples with a high content of chromium (7 wt.%). It was found that with an increase in the acidity of a solution of chromium nitrate for catalyst preparation (pH from 3 to 1) the rate of their deactivation increases during the work. When the acidity of this solution decreases (pH from 3 to 5), the yield of propylene in propane dehydrogenation increases. As found by UV diffuse reflectance spectroscopy and X-ray diffraction analysis, the CrO _x /SiO₂ catalysts are characterized by the agglomeration of the chromium oxide phase during the work accompanied by a decrease in dispersion and specific activity. The degree of agglomeration increases with an increase in the chromium content.     

Synthesis of complex hydroxo salts of magnesium, nickel, cobalt, aluminum, and bismuth and oxide catalysts on their base

Synthesis methods have been developed for the precursors of oxide catalysts that include the combination of magnesium nickel cobalt aluminum hydroxocarbonate, with a layered hydrotalcite-type structure and decavanadate and paramolybdate ions in the anion layers, and bismuth hydroxocarbonate. On the base of these precursors, multicomponent oxide catalysts have been manufactured for the oxidative dehydrogenation (OD) of light alkanes. Some of these catalysts showed high selectivities and high product yields in the conversion of ethane to ethylene.     

Theoretical study on reactions catalyzed by gallium-substituted zeolites

The dehydrogenation and cracking reactions of light alkanes in gallium-containing zeolites were studied using density functional theory. Gallium isomorphically substituted, generating Brønsted acid sites, was used in the computations. The following reactions were examined: dehydrogenation of methane, ethane, propane, isobutane and cracking of ethane, propane and isobutene, all catalyzed by the framework gallium species. The cracking reaction seems to be favored relative to the dehydrogenation when framework gallium species are used. This behavior is also observed in aluminum-containing zeolites (H-ZSM5). The geometries and energetics of the transition states found for the gallium zeolites were compared with theoretical data for the same transition states in aluminum zeolites. There seems to be no significant difference between framework gallium and framework aluminum species. Therefore the framework gallium should not be the species responsible for the catalytic enhancement observed in gallium-containing zeolites.From the Proceedings of the 28th Congreso de Químicos Teóricos de Expresión Latina (QUITEL 2002)     

Effect of the nature of the active-component precursor on the properties of Pt/MgAlO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> catalysts in propane and <Emphasis Type="Italic">n</Emphasis>-decane dehydrogenation

The Pt/MgAlO _x catalysts, in which a mixed aluminum–magnesium oxide obtained by the heat treatment of corresponding layered double hydroxides was used as a support, were studied. The effects of the nature of active-component precursors ([PtCl₆]^2–, [PtCl₄]^2–, and [Pt₃(CO)₆] ₆ ^2- ), and the Mg/Al ratio in the support on the anchoring of complexes, the disperse state of platinum, and the properties of the obtained catalysts in the reactions of propane and n-decane dehydrogenation were found.     

ZrO2‐Based Alternatives to Conventional Propane Dehydrogenation Catalysts: Active Sites,Design, and Performance

Non‐oxidative dehydrogenation of propane to propene is an established large‐scale process that, however, faces challenges, particularly in catalyst development; these are the toxicity of chromium compounds, high cost of platinum, and catalyst durability. Herein, we describe the design of unconventional catalysts based on bulk materials with a certain defect structure, for example, ZrO₂ promoted with other metal oxides. Comprehensive characterization supports the hypothesis that coordinatively unsaturated Zr cations are the active sites for propane dehydrogenation. Their concentration can be adjusted by varying the kind of ZrO₂ promoter and/or supporting tiny amounts of hydrogenation‐active metal. Accordingly designed Cu(0.05 wt %)/ZrO₂‐La₂O₃ showed industrially relevant activity and durability over ca. 240 h on stream in a series of 60 dehydrogenation and oxidative regeneration cycles between 550 and 625 °C.