Alumina-supported catalysts for propane oxidative dehydrogenation from mixed VXM(6−X)O19 (M=W, Mo) hexametalate precursors

γ-Al₂O₃ supported vanadium oxides were modified by tungsten and molybdenum oxides in order to improve dispersion and selectivity towards olefins in propane oxidative dehydrogenation (ODH). Both vanadium–tungsten and vanadium–molybdenum catalysts were obtained by adsorption of mixed isopolyanions (VW₅O₁₉⁵⁻, V₂W₄O₁₉⁴⁻, VMo₅O₁₉⁵⁻ and V₂Mo₄O₁₉⁴⁻) from aqueous solutions. The isopolyanion solutions were characterized by UV-Vis and ⁵¹V NMR spectroscopy. Vanadium, vanadium–tungsten and vanadium–molybdenum precursors and catalysts were also characterized by UV-Vis (diffuse reflectance) and solid state ⁵¹V NMR spectroscopy. An improved selectivity to propene in the presence of tungsten and molybdenum in VO_x/γ-Al₂O₃ was observed and attributed to dilution of vanadium by tungsten or molybdenum oxides on the γ-Al₂O₃ surface.     

Preparation, Characterisation and Catalytic Behaviour of a New TeVMoO Crystalline Phase

TeM_xMo_1.7O mixed oxides (M = V and/or Nb; x = 0-1.7) have been prepared by calcination of the corresponding salts at 600 °C in an atmosphere of N₂. A new crystalline phase, with a Te/V/Mo atomic ratio of 1/0.2-1.5/1.7, has been isolated and characterised by XRD and IR spectroscopy. This phase is observed in the TeVMo or TeVNbMo mixed oxide but not in the TeNbMo mixed oxide. The new crystalline phase shows an XRD pattern similar to Sb₄Mo₁₀O₃₁ and probably corresponds to the M1 phase recently proposed by Aouine et al. (Chem. Commun. 1180, 2001) to be present in the active and selective MoVTeNbO catalysts. Although these catalysts present a very low activity in the propane oxidation, they are active and selective in the oxidation of propene to acrolein and/or acrylic acid. However, the product distribution depends on the catalyst composition. Acrolein or acrylic acid can be selectively obtained from propene on Nb-free or Nb-containing TeVMo catalysts, respectively. The presence of both V and Nb, in addition to Mo and Te, appears to be important in the formation of acrylic acid from propene.     

Immobilization and activation of vanadium(III) and titanium(III) single‐site catalysts for ethylene polymerization using MgCl2‐based supports

Significant increases in the activity of vanadium(III) amidinate catalysts for ethylene polymerization have been obtained by immobilization on a MgCl₂‐based support prepared by reaction of AlEt₃ with a MgCl₂/ethanol adduct. Catalyst immobilization and activation on this type of support prevents the rapid decay in activity observed under homogeneous polymerization conditions with unsupported catalysts. Stable polymerization activity is also observed with analogous titanium(III) complexes. Polyethylene with narrow molecular weight distribution and spherical particle morphology is obtained without reactor fouling. Copyright © 2005 Society of Chemical Industry     

Sensitometric characteristics of an all‐solid‐state photoelectrochromic pixel for an electrochromic light‐addressable display

Abstract— An all solid‐state photoelectrochromic element (PECE) was developed on the basis of electrochromic layers of WO₃ and polyaniline with a layer of polymer electrolyte placed on a base of polyamidosulfoacid, in which a thin‐film CdS_xSe_1?x photoresistor was used as an electronic key. The dependence of the sensitometric characteristics of the PECE on the applied voltage was studied.     

钼酸盐阻燃抑烟剂研发现状

简要地叙述了钼酸盐类阻燃抑烟剂 ,如八钼酸铵、钼酸锌、钼酸钙、钼酸钴和三氧化钼等阻燃抑烟剂的研发现状     

Gas-phase selective oxidation of toluene on TiO2–sepiolite supported vanadium oxides: Influence of vanadium loading on conversion and product selectivities

Gas-phase selective oxidation of toluene has been carried out on vanadium oxide systems (5–20 wt.% of V₂O₅, equivalent to 0.4–1.7 theoretical monolayers) supported on TiO₂–sepiolite (with titania loading around the theoretical monolayer, 12 wt.%) and on sepiolite. A study has been made on both the influence of vanadia loading and of the support on the catalytic behaviour of the supported vanadium systems. The reducibility by H₂ TPR was also studied as well as the acid and basic/redox sites from the results of conversion of the 2-propanol test reaction of the solids. Benzaldehyde, benzoic acid and several coupling products were the main ones detected, attaining over 50% selectivity towards the benzaldehyde and benzoic acid products at a total conversion around 10%. The activity and selectivity to the selective products exhibited by vanadium systems supported on mixed support were superior to those exhibited by the systems supported on sepiolite and increased notably in both series with the increase in vanadium loading. The best catalytic behaviour exhibited by the vanadium systems supported on mixed support, which also exhibited the highest density of sites capable of being reduced (as well as their reducibility) and of those responsible for propanone formation, could be attributed not only to the different balance of the vanadia species existing in the two supports (monomeric + oligomeric/polymeric), but also to such other factors as the nature of the support and, concretely, its chemical composition.     

Ni-Mo-O催化剂中协同作用对丙烷氧化脱氢的影响

在 Ni-Mo-O体系中 ,加入 Mo O3 能极大地提高丙烷氧化脱氢制丙烯的反应活性。选用固混法、沉淀法、柠檬酸法制备了 Mo O3 过量 1 5 % (摩尔分数 )的α -Ni Mo O4催化剂 ,其中用沉淀法制得催化剂在 5 0 0℃ ,V( C3 H8) /V ( O2 ) /V ( N2 ) =1 0 /1 0 /5 0 ,反应气流量为 70 m L/min的条件下丙烷转化率可达 38.7% ,丙烯选择性达 70 .1 4 %。经 XRD,XPS,TPR表征说明 ,在含有过量 Mo O3 的催化剂中 ,α -Ni Mo O4与 Mo O3 两种晶体之间可产生微小的相互吸引 ;从而发挥协同作用 ,是提高催化剂活性     

SO_3磺化法合成PNTS新工艺的研究

本文采用正交设计及方差分析法,确定了 SO_3磺化法合成 PNTS 新工艺的最佳工艺条件;并从技术及经济方面将新工艺同国内现有的生产老工艺进行了分析对比。     

Reactively sputtered MoO3 films for ammonia sensing

We report the gas-sensing properties of ion-beam sputter deposited MoO₃ thin-films. The change in the DC conductivity was measured in dry N₂ with 10% O₂ in the presence of up to 490 ppm of NH₃, NO, NO₂, C₃H₆, CO and H₂. At ∼440 °C the film was found to be very sensitive to NH₃, with 490 ppm increasing the conductivity by approximately a factor of 70. This was approximately 17 times greater than the response to the other gases. The NH₃ response was strongly affected by the accompanying levels of O₂, NO₂ and H₂O. For example, changing the accompanying O₂ levels from 1% to 20% decreased the NH₃ response by approximately a factor of 20. Similarly, the presence of 100 ppm NO₂ (in 10% O₂) decreased the NH₃ response by approximately a factor of three, and 1% water vapor decreased it by more than a factor of two. The NH₃ response, however, was relatively unaffected by 100 ppm of accompanying NO, C₃H₆, CO or H₂. XPS measurements show that the increased conductivity in the presence of NH₃ was also accompanied by a partial reduction of the surface MoO₃. We observed an increase in the resistance of the films after extended time at elevated temperatures.     

三叶状钒催化剂的研制

介绍了三叶状钒催化剂的研制。工业宏观活性评价和通气测试表明，三叶状催化剂性能优良，其床层压力降介于圆柱状和环状催化剂之间，为圆柱状催化剂的70％左右。在相同的转化条件下，相对于环状催化剂，三叶状催化剂的装填量可减少16．7％。