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.     

焦化生产中含硫容器自燃氧化倾向性分析

分析了炼焦化工生产过程中硫的分布和存在形态、硫铁化合物自燃的影响因素,提出了防止储罐、管道等设备自燃事故的安全控制方法.     

表面引发剂对熔融铝合金直接氧化生长的影响

为了控制熔融铝合金直接氧化法制备Al2O3/Al复合材料的氧化生长,采用ZnO,SiO2和MgO3种表面引发剂,研究它们对Al-Si-Zn合金氧化生长过程及Al2O3/Al复合材料组织形貌的影响.结果表明:与未使用引发剂时相比,使用SiO2,ZnO或MgO表面引发剂制备的粉末都能显著地缩短Al-Si-Zn合金的氧化生长孕育期,提高合金氧化生长速率,改善复合材料的胞状生长方式,提高复合材料的组织均匀度和致密度,为实际生产应用提供了依据.实验发现:ZnO表面引发剂的使用效果最为突出,其最佳添加量为12mg/cm2.     

Synthesis and activation of Pt nanoparticles with controlled size for fuel cell electrocatalysts

Well-dispersed Pt nanoparticles with controlled size and narrow size distribution were prepared by polyalcohol reduction of platinum acetylacetonate, using oleylamine as a capping agent. The particle size was varied from 3.5 nm to 11.5 nm by decreasing the amount of oleylamine added in the synthesis. Size selection of the as-prepared particles by solvent fractionation yielded nearly monodispersed Pt particles. The as-prepared particles were loaded on a carbon support by physical deposition, but showed no electrocatalytic activity due to the oleylamine bound to the particle surface. The particles were activated for electrocatalysis after heating the particles in air at 185 °C for 5 h, conditions that gave no particle-sintering and no oxidation. Cyclic voltammetry showed that the particles after the heat treatment in air were electrocatalytically active for methanol oxidation. The smaller 3.5 nm and 4.0 nm Pt particles had a higher intrinsic activity for methanol oxidation, but a lower tolerance to CO poisoning, compared with 6.0 nm, 9.5 nm and 11.5 nm particles. CO-stripping results suggest that CO is more easily oxidized on larger Pt particles.     

碳/碳复合材料MoSi2/SiC涂层在动态氧化环境下的性能研究

为了考察MoSi₂/SiC防氧化涂层体系在动态氧化环境下的防护能力,对碳/碳复合材料MoSi₂/SiC涂层试样在1100~1500℃下进行了高温燃气高质流冲刷环境下的氧化试验。结果表明,在1100~1500℃的燃气动态环境下,具有稳定的氧化失重速率,氧化失重曲线近似呈直线关系,氧化失重和氧化失重速率均随着氧化温度的升高而降低,表现出该涂层抗高质流冲刷和氧化的能力随温度的升高而提高,在该温度区间内,随着温度的升高,具有更优异的抗氧化和抗高质流冲刷的能力。     

等离子体氧化nc-Si/SiO_2多层膜的蓝光发射

报道了在等离子体增强化学气相沉积 (PECVD)系统中用交替淀积 a-Si对其进行原位等离子体氧化的方法制备了 a-Si∶H/ Si O2 多层膜。随着 a-Si∶H子层的厚度从 3 .8nm减小到 1 .5 nm,a-Si∶H/ Si O2 多层膜的光吸收边和光致发光 (PL )出现了蓝移。在晶化的 a-Si∶ H/ Si O2 多层膜中不仅观察到室温下的红光带 (80 0nm)的发光峰 ,而且还观察到蓝光发射 (4 2 5 nm) ,结合 Raman,TEM和 PL测试 ,对其原因作了简单的分析     

亚硫酸钙氧化为石膏的研究

进行了亚硫酸钙氧化为二水石膏的研究 ,考察了初始 p H值、反应温度、空塔气速、固含量和停留时间对氧化率的影响 ,给出了适宜的反应条件 .在这些条件下 ,氧化率达 96 %以上     

Some aspects of the electrochemistry of the flotation of pyrrhotite

The iron sulfide mineral, pyrrhotite (Fe_(1–x)S), has long been known to be more difficult to recover by flotation from alkaline slurries than many other base metal sulfide minerals. This paper summarizes the results of an electrochemical study of the surface reactions that occur during the flotation of nickeliferous pyrrhotite in the recovery of nickel and the platinum group metals. Mixed potential measurements conducted with natural pyrrhotite electrodes in various stages of an operating flotation plant showed that the mineral potential is positive to the equilibrium potential of the xanthate/dixanthogen couple. Similar results were obtained during batch flotation experiments and in synthetic solutions in the laboratory. Cyclic voltammetric and potentiostatic current/time transient experiments were used to investigate the oxidation of pyrrhotite under various conditions. In addition, the reduction of oxygen, the reaction of copper ions and the oxidation of xanthate ions at the mineral surface were investigated. The formation of dixanthogen on pyrrhotite surfaces is thermodynamically favourable in plant flotation slurries. However the interaction with xanthate at pH values above 7 is inhibited by a surface species formed during the conditioning prior to xanthate addition. In acidic solutions copper ions react readily with pyrrhotite to form a species, possibly CuS that can be oxidized at potentials above 0.4 V. At pH 9 this species does not form and there is no electrochemical reaction between pyrrhotite and copper ions. The beneficial effects of copper ions to flotation performance appear to be related to an enhancement of the oxidation of xanthate.     

钛硅选择性氧化催化剂的研究进展

过渡金属钼、钨、钛、钒等的高价态络合物能有效催化有机过氧化物进行烯烃的环氧化反应。以Ｍｏ（Ⅵ）络合物在有机相中催化过氧化烃来氧化丙烯生产环氧丙烷的方法称之为间接氧化法，是生产环氧丙烷的主要方法之一。７０年代初，荷兰Ｓｈｅｌ研究所发现Ｔｉ（Ⅳ）高分散负...     

Studies on Catalytic Side-Chain Oxidation of Nitroaromatics to Aldehydes with Oxygen

The side-chain oxidation of 2-nitrotoluene in liquid phase in the presence of catalytic amount of manganese sulfate and stoichiometric amount of potassium hydroxide with oxygen was studied. In the most favorable conditions, over 80% of conversion of 2-nitrotoluene and 50% of selectivity to 2-nitrobenzaldehyde was achieved. Effects of the reaction parameters on the conversion of the reactant and the selectivity of the product were examined. These results, together with EPR spectroscopic study, show that a benzyl anion was formed in the early stage of the reaction, which was then converted to the final product via a free radical mechanism.