含氮化合物对NiW体系催化剂芳烃加氢性能的影响

以γ-Al2O3、B改性的γ-Al2O3、F改性的γ-Al2O3、SiO2-Al2O3为载体制备Ni、W含量相同的四种催化剂，通过程序升温还原表征考察活性金属与不同载体的相互作用。利用氮含量不同、四氢萘含量相同的四种原料考察含氮化合物对同种NiW体系催化剂四氢萘加氢的影响以及对活性金属与载体相互作用不同的催化剂四氢萘加氢的影响。结果表明，以γ-Al2O3或SiO2-Al2O3载体制备的催化剂的金属组分与载体相互作用较强，B或F改性的γ-Al2O3能显著削弱活性金属与载体的相互作用；含氮化合物对四氢萘加氢具有强烈的抑制作用，使四氢萘加氢反应的表观活化能增加；在实验研究的四种催化剂中，金属组分与载体相互作用较弱的催化剂受含氮化合物的抑制较强。     

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.     

Niobium-containing catalysts—the state of the art

This review article is devoted to the materials containing niobium, which have been discovered or developed in the past few years and exhibit the potential application in heterogeneous catalysis. Niobium oxides and mixed oxides as well as sulfides, nitrides (oxynitrides), carbides (oxycarbides), and phosphates are considered. Among the catalytic processes in which Nb-containing materials were tested, liquid and gas phase oxidation is described in details, and the role of niobium in the prevention of the catalyst from SO₂ poisoning is mentioned.     

小流域氮流失特征及其影响因素

由非点源流失的氮是造成水体污染的主要因子之一，而土地利用方式往往对氮的流失产生重要影响。本课题在福建省九龙江流域遴选了4个不同土地利用方式的小流域，通过在自然降雨条件下现场采样与室内分析相结合，研究不同土地利用结构的小流域氮的流失特征和影响因素。研究结果表明：总氮、可溶态氮和泥沙结合态氮的浓度通常比径流先达到峰值，然后开始降低；氮的流失以可溶态氮为主(占73%～98.3％)，因此其流失量主要受径流量的影响与雨强关系不大；土地利用方式对氮的流失有明显影响，一般植被覆盖度提高可以降低流失，而农业活动会加剧流失；此外，在高植被覆盖度的天然林地，氮的流失呈现出以泥沙结合态为主。通过本研究可以看出土地利用结构的调整和合理布置是九龙江流域非点源污染控制的重点。     

双室充氮包装机的技术改进

分析了原机型的性能特点和不足之处,介绍了改进方案。     

Sulfated zirconia catalysts: Are Brønsted acid sites the source of the activity?

The thermal decomposition products of pyridinium sulfate differ from those of pyridinium sulfate supported on zirconia which in turn differs from that of pyridine adsorbed on a sulfated zirconia. Unsupported pyridinium sulfate decomposes to produce pyridine and sulfuric acid, and these subsequently react to produce oxides of carbon and sulfur. Zirconia that is sulfated and then exposed to pyridine does not release detectable amount of pyridine during heating in an inert gas; rather the pyridine undergoes oxidation reduction reactions simultaneously to release CO₂ and sulfur compounds. Pyridinium sulfate supported on zirconia decomposes upon heating to release pyridine and sulfuric acid, which reacts with the zirconia. The desorption of pyridine in one case and only CO₂/SO_x in the other case suggests that sulfated zirconia does not contain Brønsted acidity that can form pyridinium sulfate.     

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.     

Rare earth oxides as carbon oxidation catalysts

The behavior of a number of rare earth oxides as catalysts for the oxidation of graphite in air has been investigated by the methods of thermal analysis. Of the oxides studied, only CeO₂ showed significant activity in accelerating the gasification of graphite by oxygen between 500 and 1000°C. Cerium salts, which decompose to a finely dispersed oxide phase at low temperatures, e.g. Ce (III) nitrate and ammonium Ce (IV) nitrate, were found to be very active catalysts. The catalytic effect may be due to a redox process involving the cyclic conversion of the oxide from the Ce (IV) to the Ce (III) oxidation state, or the oxide particles may provide sites for the dissociative chemisorption of oxygen.     

The GENIUS-test-facility—first results on background from Rn daughters

GENIUS-TF (Nucl. Instr. and Meth. A 511 (2003) 341; Nucl. Instr. and Meth. A 481 (2002) 149.) is a test-facility for the GENIUS project (GENIUS-Proposal, 20 November 1997; Z. Phys. A 359 (1997) 351; CERN Courier, November 1997, 16; J. Phys. G 24 (1998) 483; Z. Phys. A 359 (1997) 361; in: H.V. Klapdor-Kleingrothaus, H. Pas. (Eds.), First International Conference on Particle Physics Beyond the Standard Model, Castle Ringberg, Germany, 8–14 June 1997, IOP Bristol (1998) 485 and in Int. J. Mod. Phys. A 13 (1998) 3953; in: H.V. Klapdor-Kleingrothaus, I.V. Krivosheina (Eds.), Proceedings of the Second International Conference on Particle Physics Beyond the Standard Model BEYOND’ 99, Castle Ringberg, Germany 6–12 June 1999, IOP Bristol (2000) 915), a proposed large scale underground observatory for rare events which is based on operation of naked germanium detectors in liquid nitrogen for an extreme background reduction. Operation of naked Ge crystals in liquid nitrogen has been applied routinely already for more than 20 years by the CANBERRA Company for technical functions tests (CANBERRA Company, private communication, 5 March 2004.), but it never had found entrance into basic research. Only in 1997 first tests of application of this method for nuclear spectroscopy have been performed, successfully, in Heidelberg (Klapdor-Kleingrothaus et al., 1997, 1998; J. Hellmig and H.V. Klapdor-Kleingrothaus, 1997).

On May 5, 2003 the first four naked high-purity germanium detectors (total mass 10.52 kg) were installed in liquid nitrogen in the GENIUS Test Facility at the Gran Sasso underground laboratory. Since then the experiment has been running continuously, testing for the first time the novel technique in an underground laboratory and for a long-lasting period.

In this work, we present the first analysis of the GENIUS-TF background after the completion of the external shielding, which took place in December 2003. We focus especially on the background coming from ²²²Rn daughters. This is found to be at present by a factor of 200 higher than expected from simulation. It is still compatible with the scientific goal of GENIUS-TF, namely to search for cold dark matter by the modulation signal, but on the present level would cause serious problems for a full GENIUS—like experiment using liquid nitrogen.