Stability of ruthenium catalysts supported on TiO2 or ZrO2 in catalytic wet air oxidation

The stability of ruthenium catalysts supported on TiO₂ and ZrO₂ were studied in the wet air oxidation of aqueous solution of succinic and p-hydroxybenzoic acids taken as model effluent and on real effluents from the paper-pulp industry. Catalyst recycling experiments were conducted in batch reactor and long-term stability tests were conducted in trickle-bed reactor. In all experiments, ruthenium and support materials were perfectly stable to leaching, sintering and fouling. Ruthenium catalysts experienced a weak deactivation as they were exposed to air, e.g., in recycling experiments however the loss of activity occurred only after the first exposure and was completely reversible upon catalyst reduction. The deactivation was attributed to an over-oxidation of the catalyst surface particularly noticeable in the case of very small Ru-clusters (1 nm).     

Surface and subsurface products of the interaction of O2 with Ag under catalytic conditions

Polycrystalline Ag treated with O₂ at pressures up to 1 bar and at temperatures up to 920 K was examined by TDS. It was found that the peak commonly observed at 595±25 K and assigned to adsorbed atomic oxygen (O_a) is shifted to higher desorption temperatures with rising dosing temperatures. Since saturation of the uptake was not possible either, this peak was identified as dissolved atomic oxygen (O_d). The existence of a maximum for the O₂ uptake after exposure at 820 K was found. Hence, under conditions of formaldehyde synthesis ( 920 K) the ability of the catalyst to dissolve oxygen is near its maximum.     

MCPVT测定1,3-丁二烯氧化动力学

用小型密闭压力容器实验(MCPVT)分别跟踪测定了1,3-丁二烯在氮气和氧气氛围下温度随时间的变化(T-t)和压力随时间的变化(p-t)。利用p-t曲线构建了1,3-丁二烯初期氧化反应动力学。结果表明,在氮气条件下,即使温度达到388.15 K也未检测到1,3-丁二烯发生化学反应。1,3-丁二烯与氧气在343.15～363.15 K范围内发生了氧化反应,反应器内的压力减小。1,3-丁二烯与氧气的初期氧化反应动力学是二级反应。另外,还考察了氧气过量和1,3-丁二烯过量时两种特殊情况下的假一级氧化反应动力学。探讨了过渡态的热力学参数,计算结果表明,1,3-丁二烯的热氧化是一个有序的分子数减少过程。用气相色谱-质谱联用仪和碘量法分析了氧化反应产物,其产物有呋喃和过氧化物。     

玉米淀粉胶粘剂的改性研究

以玉米淀粉为主要原料 ,通过预糊化、氧化、加碱糊化进行化学改性 ,并加入稳定剂可制备固含量高、贮存稳定性好 ,具有一定初粘力和透明性的改性淀粉胶粘剂。本论文主要研究了改性玉米淀粉胶粘剂的主要成分配比及工艺条件对产品性能的影响。结果表明 :淀粉氧化前是否进行预糊化处理、氧化剂的用量、体系pH值、加碱糊化时碱液用量、稳定剂的种类和用量等对改性玉米淀粉胶粘剂性能影响较大。     

Electrochemical investigations of copper behaviour in different cupric complex solutions: Voltammetric study

The electrochemical behaviour of copper has been investigated in different cupric complex solutions by cyclic voltammetry. In pyridinic and picolinic solutions the reduction of cupric complex occurred in two stages leading to Cu(I) and Cu(0), respectively. The electrodeposited copper is oxidized in two steps leading to Cu(I) and Cu(II) as in ammoniacal cupric complex solutions. In glycine, alanine, sulfamic acid and ethylenediamine solutions, the cuprous complex is an intermediate in the cupric complex reduction but it is not detected during the oxidation of the electrodeposited copper in these solutions. In EDTA and triethanolamine solutions, the cuprous complex is not observed. The rate of copper etching was determined in pyridinic and ammoniacal cupric solutions and was shown to be faster in ammoniacal cupric solutions than in the pyridinic solutions.     

Effect of the nature and structure of pillared clays in the catalytic behaviour of supported manganese oxide

In the present work, the complete oxidation of acetone has been studied over a series of supported manganese oxide catalysts on the unpillared and the Al- and Zr-pillared forms of two natural clays, a montmorillonite and a saponite. A significant influence of the clay supports characteristics on the catalytic performance has been found. The following order of improving catalytic performance is established with respect to the pillars composition: Al-pillared clays < unpillared clays < Zr-pillared clays.     

Activation of a Au/TiO2 Catalyst by Loading a Large Amount of Fe–Oxide: Oxidation of CO Enhanced by H2 and H2O

Catalytic activity of a 1 wt% Au/TiO₂ catalyst is markedly improved by loading a large amount of FeO_x, on which the oxidation of CO in excess H₂ is selectively promoted at temperature lower than 60 °C. Oxidation of CO with O₂ on the FeO_x/Au/TiO₂ catalyst is markedly enhanced by H₂, and H₂O moisture also enhances the oxidation of CO but its effect is not so large as the promotion by H₂. We deduced that activation of Au/TiO₂ catalyst by loading FeO_x is not caused by the size effect of Au particles but a new reaction path via hydroxyl carbonyl intermediate is responsible for the superior activity of the FeO_x/Au/TiO₂ catalyst.     

Methanol oxidation on Au/TiO2 catalysts

We have investigated the adsorption and reaction of methanol with Au/TiO₂ catalysts using a pulsed flow reactor, DRIFTS and TPD. The TiO₂ (P25) surface adsorbed a full monolayer of methanol, much of it in a dissociative manner, forming methoxy groups associated with the cationic sites, and hydroxyl groups at the anions. The methoxy is relatively stable until 250 °C, at which point decomposition occurs, producing mainly dimethyl ether by a bimolecular surface reaction. As the concentration of methoxy on the surface diminishes, so the mechanism reverts to a de-oxygenation pathway, producing mainly methane and water (at ~330 °C in TPD), but also with some coincident CO and hydrogen. Au catalysts were prepared by the deposition-precipitation method to give Au loadings between 0.5–3 wt %. The effect of low levels of Au on the reactivity is marked. The pathway which gives methane, which is characteristic of titania, remains, but a new feature of the reaction is the evolution of CO₂ and H₂ at lower temperature (a peak is seen in TPD at 220 °C), and the elimination of the DME-producing state. Clearly this is associated with the presence of Au and appears to be due to the production of a formate species on the surface of the Au component. This formate species is mainly involved in the reaction of methanol with the Au/TiO₂ catalysts which results in a combustion pathway being followed, with complete conversion occurring by ~130 °C.     

过硼酸钠在有机合成中新的应用

介绍了过硼酸钠在有机合成中的一些新的应用。综述了过硼酸钠与芳胺、芳酰胺、有机硼化物、醛等化合物的氧化,取代、酯化反应。     

A molecular level mechanism ofn-butane oxidation to maleic anhydride over vanadyl pyrophosphate

A molecular level mechanism is proposed for the highly selective 14-e^– oxidative transformation ofn-butane to maleic anhydride on the surface of vanadyl pyrophosphate. The mechanism suggests that the dimeric active sites assume at any given time, one of four possible interconvertible states which differ from each other in the number of available oxygen atoms and the formal oxidation states of the individual vanadium atoms. The relative ratios of active sites in each of the four possible states are dictated by the reaction conditions, the redox properties of the reacting gases and the structure of the vanadyl pyrophosphate active surface. A crucial feature of the mechanism is a pseudo-ozonide surface species formed by the interaction of a chemisorbed dioxygen molecule and an adjacent metal-oxo group. This unusual species is responsible for the initial activation of then-butane, which occurs when the chemisorbed dioxygen abstracts an H-atom from the alkane and the adjacent metal-oxo group reacts with the incipient alkyl radical to form an alkoxy group. The proposed mechanism is entirely consistent with literature reports describing the behaviour of (VO)₂P₂O₇ in flow, pulse and TAP reactors.