晶格氧用于轻烃的选择氧化

In this paper, selective oxidation of n-butane to maleic anhydride (MA) and partial oxidation of methane to synthesis gas with lattice oxygen instead of molecular oxygen are investigated. For the oxidation of butane to MA in the absence of molecular oxygen, the Ce-Fe promoted VPO catalyst has more available lattice oxygen and provides higher conversion and selectivity than that of the unpromoted one. It is supposed that the introduction of Ce-Fe complex oxides improves redox performance of VPO catalyst and increases the activity of lattice oxygen.For partial oxidation of methane to synthesis gas over LaFeO3 and Lao.8Sro.gFeO3 oxides, the reaction with flow switched between 11% O2-Ar and 11% CH4-He at 900℃ was carried out. The results show that methane can be oxidized to CO and H2 with selectivity over 93% by the lattice oxygen of the catalyst in an appropriate reaction condition, while the lost lattice oxygen can be supplemented by air re-oxidation. It is viable for the lattice oxygen of the LaFeO3 and La0.8Sr0.2FeO3 catalyst instead of molecular oxygen to react with methane to synthesis gas in the redox mode.     

Study on oxygen transport and titanium oxidation in coating cracks under parallel gas flow based on LBM modelling

The oxygen transportation from surrounding air to coating cracks is an important factor in the oxidation and ignition of titanium alloy. In this work, the oxygen transport and surface oxidation of titanium in inclined cracks of coating under parallel airflow are studied with the lattice Boltzmann method(LBM).A boundary scheme of LBM about surface reaction is developed. The conversion factors are utilized to build the relationship between the physical scale and the lattice scale. The reliability ...     

CARBON DEPOSITION AND CATALYST DEACTIVATION OF Sb-Fe OXIDE CATALYST IN THE AMMOXIDATION OF PROPYLENE

Carbon deposition and catalyst deactivation of Sb-Fe oxide catalyst in the ammoxidation of propylenewere investigated by means of a fluidized-bed reactor.The reactivity,surface acidity,specific surfacearea,average pore radius,and electron spin resonance spectrum data were obtained from the catalysts ofincreasing carbon deposition.Chemisorption of oxygen and propylene and thermal programmed desorptionof propylene were carried out on the Sb-Fe oxide catalyst as well as a commercial one,Mo-Bi.Isotopicexperiment using acrylonitrile-2-~(14)C as tracer was also accomplished.It was found that carbon deposition due to intermediates and acrylonitrile on selective oxidation sitescould be the primary reason for catalyst deactivation,and that because of the Sb-Fe oxide catalytspossessing a property of easy reduction and difficult reoxidation,the structure of the FeSbO_4 would bedecomposed under the oxygen-lean condition into Sb_2O_3 and Fe_2O_3 which form the deep oxidation catalystcomponent.According to the above investigation a suggestion for improving catalyst properties has been proposed.     

Thermodynamic Properties of Non-Oxide Composite Refractories

For initiative application of non-oxides in refractories, it is essential to study thermodynamic properties of non-oxides. The stability and stable order of non-ox- ides under oxidized atmosphere are analyzed firstly and then a new process, “converse reaction sintering”, is proposed. The results of study on oxidation mechanism of silicon and aluminum nitrides indicate that the gaseous suboxides can be produced observably when the oxygen partial pressure is lower than “conversion oxygen partial pressure”. The suboxides can be deposited near the surface of composite to become a compact layer. This causes the material possessing a performance of “self-impedient oxidation”. Metal Si and Al are the better additives for increasing the density and width of compact layer and increasing the ability of anti-oxidation and anti-corrosion. The study on Si3 N4-Al2O3, Si3N4-MgO, Si3 N4-SiC systems is also enumerated as examples in the paper. The experimental results show that the converse reaction sintering is able to make high performance composites and metal Si and Al not only can promote the sintering but also increase the density and width of compact layer.     

2-甲基-6-乙酰基萘液相催化氧化反应动力学

In this paper,a kinetics model for the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid catalyzed by cobalt-manganese-bromide is proposed.The effects of the reaction temperature,catalyst concentration and ratio of catalyst on the time evolution of the experimental concentration for the constituents including raw material,intermediates and product are investigated.The model parameters are determined in a nonlinear optimization,minimizing the difference between the simulated and experimental time evolution of the product composition obtained in a semi-batch oxidation reactor where the gas and liquid phase were well mixed.The kinetics data demonstrate that the model is suitable to the liquid-phase oxidation of 2-methyl-6-acetyl-naphthalene to 2,6-naphthalene dicarboxylic acid.     

铜基催化剂上甲醇合成的动态反应动力学

Adsorption, surface reaction and process dynamics on the surface of a commercial copper-based cata-lyst for methanol synthesis from CO/CO2/H2 were systematically studied by means of temperature programmed desorption (TPD), temperature programmed surface reaction (TPSR), in-situ Fourier transform-inferred spectroecopy(FTIR) and stimulus-response techniques. As a part of results, an elementary step sequence was suggested and a group of ordinary differential equations (ODEs) for describing transient conversations relevant to all species on the catalyst surface and in the gas phase in a micro-fixed-bed reactor was derived. The values of the parameters referred to dynamic kinetics were estimated by fitting the solution of the ODEs with the transient response data obtained by the stimulus-response technique with a FTIR analyzer as an on-line detector.     

Selective oxidation of cyclopentene with H_2O_2 by using H_3PW_(12)O_(40) and TBAB as a phase transfer catalyst

The selective oxidation of cyclopentene by aqueous H_2O_2 using H_3PW_(12)O_(40) and tetrabutyl ammonium bromide(TBAB) as a phase transfer catalyst has been investigated. The results show that the presence of TBAB significantly improved the oxidation selectivity of cyclopentene. The effects of the reaction conditions on the conversion of cyclopentene were investigated in detail. The optimal reaction conditions are as follows: the H_3PW_(12)O_(40) to TBAB molar ratio, 1:1–1:3; H_3PW_(12)O_(40) to cyclopentene molar ratio,0.54:100–0.64:100; and molar ratio of H_2O_2 to cyclopentene, 1.6:1. The conversion reached to 59.8% in 4h at 35.0 °C, while the selectivity of glutaraldehyde was 38.0% and the selectivity of 1,2-cyclopentanediol was 55.6%. In addition, a route for oxidation of cyclopentene by aqueous H_2O_2 using a heteropoly acid and quaternary ammonium salt as a phase transfer catalyst was proposed.     

新型惰性膜反应器中丁烷氧化脱氢制丁二烯和丁烯

The oxidative dehydrogenation of butane to butadiene and butene was studied using a conventional fixed-bed ractor (FBR), inert membrane reactor (IMR) and mixed inert membrane reactor (MIMR). When IMR and MIMR were employed, a ceramic membrane modified by partially coating with glaze was used to distribute oxygen to a fixed-bed of 24-V-Mg-O catalyst. The oxygen partial pressure in the catalyst bed could be decreased. The effect of feeding modes and operation conditions were investigated. The selectivity of C4 dehydrogenation products (bntene and bntadiene) was found to be higher in IMR than in FBR. The feeding mode with 20% of air mixing with butane in MIMR was found to be more efficient than the feeding mode with all air permeating through ceramic membrane. The MIMR gave the most smooth temperature profile along the bed.     

用于环戊烯氧化合成戊二醛反应的钨基催化剂的表征

Tungsten-containing hexagonal mesoporous silica （W-HMS） supported tungsten oxide catalysts （WOx/W-HMS） was prepared for the selective oxidation of cyclopentene with aqueous hydrogen peroxide to glutaraldehyde. X-ray diffraction （XRD） results indicated that the crystal form of the active phase （tungsten oxide） of the WOx/W-HMS catalysts was dependent on the W loading and calcination temperature. X-ray photoelectron spec- troscopy （XPS） analysis revealed that the dispersed tungsten oxides on the surface of W-HMS support consisted of a mixture of W（V） and W（VI）. It was found that a high content of amorphous W species in （5＋） oxidation state resuited in the high catalytic activity. When the W loading was up to 12% （by mass） or the catalyst precursor was treated at temperature of 623 K, the catalytic activity decreased due to the presence of WO3 crystallites and the oxidation of W（V） to W（VI） on the catalyst surface. Furthermore, NH3-temperature-programmed-desorption （NH3-TPD） analysis showed that the effects of W loading and calcination temperature on the acidity of the catalysts were related to the catalytic activity. A high selectivity of 80.2% for glutaraldehyde with a complete conversion of cyclopentene was obtained over 8%WOx/W-HMS catalyst calcined at 573 K after 14 h of reaction.     

A solvent-free,selective liquid phase hydrogenation of nitroarenes to aniline in slurry bubble mode on porous NiMo bimetallic catalyst

Ni Mo bimetallic catalysts were prepared by a solid reaction method. On the Ni Mo catalyst, the selective liquid phase hydrogenation of nitrobenzene to aniline was achieved in slurry bubble mode. And the high yields(98.9%) were obtained under the conditions of 80 °C, solvent-free and atmospheric pressure. The effect of Mo on the catalytic behavior of Ni based catalyst was investigated. The characterization displayed that the inclusion of Mo could improve the specific surface area and pore volume, and the solid reaction method made metal Mo enrichment on the surface of catalyst. These two aspects should be responsible for excellent catalytic performance of Ni Mo catalyst. In sum, we described a simple and efficient Ni Mo catalyst and provided a facile and green procedure for liquid phase hydrogenation of nitrobenzene to aniline.     

正丁烷选择氧化中吸附氧与晶格氧的作用

引　言丁烷选择氧化制顺酐是以廉价低碳烷烃作为原料的直接选择氧化反应 ,近年来已引起广泛关注并进行了较多的研究[1] .普遍认为 ,这是一个以复合氧化物VPO作为催化剂 ,晶格氧参与催化循环、按氧化还原机理进行的反应[2 ] .为了提高这一反应的选择性 ,杜邦公司按照序贯氧化 还原原理重新组织催化循环的思想 ,率先提出了双反应器循环流化床 (CFB)的专利 ,并进行了晶格氧正丁烷选择氧化制顺酐的技术开发 ,建立了大规模工业示范装置 ,显示了改善性能的潜力[3] .鉴于在空间上和在时间域内使催化循环各步骤分离进行这两类非定态操作在实质上…     

VPO transient lattice oxygen contribution

n-Butane partial oxidation to maleic anhydride is practiced commercially in several reactor types with vanadium phosphorous oxide (VPO) catalyst. DuPont operated a Circulating Fluidized Bed facility in which catalyst was shuttled between a net reducing zone (a transport bed) to a net oxidizing zone (air regenerator). Several advantages have been cited for this technology but the role of oxygen is hotly debated and different models have been proposed to characterize the complicated 14e⁻ exchange. To examine the role of surface lattice oxygen, we carried out transient experiments in which catalyst was subjected to high concentrations of butane followed by an extensive re-oxidation treatment. Carbon accumulates on the surface lattice surface thereby contributing to a reduction in reaction rates and the quantity increases with the butane/oxygen ratio. This carbon reacts in the presence of molecular O₂ during the regeneration step. The surface lattice is capable of storing significant amounts of oxygen and when the catalyst is highly oxidized, both selectivity and activity are higher.     

Transient kinetics of n‐butane partial oxidation at elevated pressure

A transient Mars‐van Krevelen type kinetic model was developed for n‐butane partial oxidation over vanadyl pyrophosphate (VPP) catalyst. The model validity was verified over a relatively wide range of redox feed compositions as well as higher reactor pressure (410 kPa). Oxygen and n‐butane conversion increased with higher pressure while maleic anhydride (MA) selectivity decreased by as much as 20%. However, the overall MA yield was enhanced by up to 30%. High pressure maintains the catalyst in a higher oxidation state (as long as there is sufficient oxygen in the gas phase) and as a consequence, the catalytic activity is improved together with MA yield. High pressure also affects the redox reaction rates and activation energies. © 2012 Canadian Society for Chemical Engineering     

THE ROLE OF LATTICE OXYGEN IN THE DYNAMIC BEHAVIOR OF OXIDE CATALYSTS

The lattice of an oxide catalyst used for oxidation reactions can act as a reservoir for oxygen, storing and releasing it for reactions at the catalyst surface under appropriate conditions. The implication of this oxygen storage property of an oxide catalyst on its dynamic response characteristics has been investigated through an experimental study of 2-butene oxidation over vanadium oxide as a model reaction. Isothermal reaction rate measurements in a differential reactor and nonisothermal studies in a single pellet reactor have been carried out. Following a step increase in the feed butene concentration, isothermal reaction rate overshoot and pellet temperature overshoot were observed. These observations could be modelled in a qualitatively correct way by a very simple model accounting for the participation of lattice oxygen in the catalytic reactions under dynamic conditions. It is demonstrated through model simulations that the ignition characteristics of a catalyst pellet are significantly affected by the participation of the lattice oxygen, when steady state multiplicity is present.     

On the mechanism of the selective oxidation of n-butane, but-1-ene and but-1,3-diene to maleic anhydride over a vanadyl pyrophosphate catalyst

The mechanism of the selective partial oxidation of n-butane, but-1-ene and but-1,3-diene over a vanadyl phosphate catalyst has been investigated by temperature-programmed desorption (TPD) and by anaerobic temperature-programmed oxidation (TPO). TPD showed lattice oxygen to be desorbed in two states at 998 and 1023 K. The anaerobic TPO of n-butane produced butene and butadiene at 1020 K; anaerobic TPO of but-1-ene produced butadiene and furan at 990 K and dehydrofuran at 965 K, while anaerobic TPO of but-1,3-diene produced dehydrofuran at 970 K, furan at 1002 K and maleic anhydride at 1148 K. The total amount of oxygen removed from the lattice in these anaerobic selective partial oxidations was the same as that evolved from the vanadyl phosphate catalyst by TPD. This, and the fact that the selective oxidation reactions occurred at the same temperature at which the oxygen evolves from the lattice, suggests that the lattice oxygen is uniquely selective when it appears at the surface of the catalyst. (Under identical conditions of flow rate, weight of catalyst, heating rate etc., the reaction of n-butane or of but-1,3-diene in air produced only CO₂ and H₂O.) This revised version was published online in July 2006 with corrections to the Cover Date.     

The catalytic oxidation of ammonia: influence of water and sulfur on selectivity to nitrogen over promoted copper oxide/alumina catalysts

The CuO/Al₂O₃ system is active for ammonia oxidation to nitrogen and water. The principal by-products are nitrous oxide and nitric oxide. Nitrous oxide levels increase with the addition of various metal oxides to the basic copper oxide/alumina system. Addition of sulfur dioxide to the reaction stream sharply reduces the level of ammonia conversion, but has a beneficial effect on selectivity to nitrogen. Added water vapour has a lesser effect on activity but is equally beneficial in terms of selectivity to nitrogen. The CuO/Al₂O₃ is also active for the selective catalytic reduction of nitric oxide by ammonia, but this reaction is not effected by sulfur dioxide addition. A mechanism for ammonia oxidation to nitrogen is proposed wherein part of the ammonia fed to the catalyst is converted into nitric oxide. A pool of monoatomic surface nitrogen species of varying oxidation states is established. N₂ or N₂O are formed depending upon the average oxidation state of this pool. An abundance of labile lattice oxygen species on the catalyst surface leads to overoxidation and to N₂O formation. On the other hand, reduced lability of surface lattice oxygen species favours a lower average oxidation state for the monoatomic surface nitrogen pool and leads to N₂ formation.     

Selective oxidation of alcohols using octahedral molecular sieves: influence of synthesis method and property–activity relations

Manganese oxides having a tunnel structure (OMS-2) have been utilized as selective catalysts for alcohol oxidation. In this study manganese oxide catalysts were synthesized in different media and modified by exchanging the tunnel cation by H⁺, using acid treatment or exchanging with NH₄⁺ followed by thermolysis. Various alcohol oxidations were performed using these catalysts to ascertain the influence of synthesis method on their activity. A correlation is made between lattice oxygen instability and activity of the catalysts, which indicates involvement of the lattice oxygen in the mechanism. The exchange of the tunnel cation with the smaller H⁺ ions leads to weakening of the Mn–O bond, as verified by temperature programmed desorption (TPD) results. Only the chemisorbed oxygen on the surface (O⁻) and the lattice oxygen in the layers close to the surface is involved in the oxygen transfer during the reaction.     

Oxydehydrogenation of propane over Mg-V-Sb-oxide catalysts. II. Reaction kinetics and mechanism

Recently we reported that Mg₄V₂Sb₂O_x is selective for propane andn-butane Oxydehydrogenation at low hydrocarbon conversion, and that propane is oxidized in parallel reactions to propylene and CO_x. We report now on the kinetics of propane and propylene oxidations over this catalyst. The partial oxidations of propane and propylene and zero-order in oxygen, whereas deep oxidations of both hydrocarbons are half-order. This difference in reaction order indicates that different forms of reactive oxygen are involved in the partial and deep oxidation reactions. Presumably, nucleophilic lattice oxygen partakes in the partial oxidation, while electrophilic dissociatively adsorbed oxygen is involved in deep oxidation. A single activated surface adsorbed state of the hydrocarbons is thought to be involved in both the partial and deep oxidation reactions. An interpretation of the observed reaction kinetics in context of the Mg₄V₂Sb₂O_x solid state chemistry, and the partial oxidation literature in general, suggests that selective oxydehydrogenation of propane occurs on isolated (Sb-O-V-O-Sb) sites, deep oxidation on multiple vicinal vanadium sites (Sb-O-V-O-V-O-Sb), and partial oxidation of propylene to acrolein on subsurface V-promoted antimony sites (Sb-O-Sb). Therefore, unproved selectivity of desired intermediates (propylene/acrolein) should be achieved by further lowering the vanadium concentration and/or through key solid state positioning of the vanadium in the catalyst lattice. Alternatively, selective doping to electronically decrease the electrophilicity of the waste forming sites and its appended oxygen should also help depress the waste forming reaction channels in favor of the desired partial oxidation channels. Finally it is anticipated that higher useful product yields would be attained with a compositionally optimized Mg-V-Sb-oxide catalyst by opting for a more stable, isolatable intermediate, e.g., acrylonitrile, by reacting propane in the presence of ammonia and oxygen (air) over this catalyst.     

Infrared studies of the reactive adsorption of organic molecules over metal oxides and of the mechanisms of their heterogeneously-catalyzed oxidation

The use of IR spectroscopic techniques to provide information on the mechanisms of catalytic oxidation over metal oxide catalysts is briefly discussed. The data published on studies of the catalytic oxidation of methanol, of linear C₄ hydrocarbons and of methylaromatics over different metal oxide surfaces are reviewed and discussed. Lattice oxygen appears to act as the active oxygen species in both selective and total oxidation. Generalized mechanisms of these complex oxidation reactions are proposed and the catalyst features affecting selectivities in these reactions are discussed. The reaction network is apparently essentially governed by the organic chemistry of the reacting molecule (thus being substantially the same over the different oxide catalysts). However, the catalyst surface governs the rate of the different steps, favoring some paths over others. Thus, selectivity is determined by the catalyst chemical behavior and by the reaction variables (contact time, temperature, gas-phase composition, presence of steam, etc.). IR studies, if performed under conditions where some intermediates are actually detectable and jointly with other techniques, can give valuable information on the catalysis mechanisms. On the other hand, it has been concluded that in situ studies frequently do not give reliable information on reaction mechanisms, because under reaction conditions spectators rather than intermediates are detected.     

Catalytic (amm)oxidation of propane with molecular oxygen over complex metal oxides: Involvement of homogeneous reaction in gas phase

Partial oxidation of propane to acrolein and ammoxidafion to acrylonitrile with molecular oxygen proceed over complex metal oxide catalysts under the restricted conditions of the high partial pressures of both propane and oxygen. The selective formations of acrolein and acrylonitrile also required high reaction temperature around 500°C. Effective catalysts for the selective (amm)oxidation were mostly made up of bismuth oxide and molybdenum oxide and were further modified with another metal oxide. From the studies of the volume effect of pre-catalyst zone on the conversion and the selectivities and of the reactions in the absence of the catalyst, it is suggested that the reactions involve homogeneous reactions in the gas phase where thermally activated propane converts into propene, followed by catalytic oxidation of propene over the metal oxide surface.