Reaction pathway of benzonitrile formation during toluene ammoxidation on vanadium phosphate catalysts

The reaction pathway of the ammoxidation of toluene on (VO)₂P₂O₇ used as catalyst and the interaction of potential intermediates with the pyrophosphate were studied by spectroscopic techniques (FTIR, EPR), temperature-programmed chemisorptions/ reactions (TPD, TPRS) and transient studies such as the temporal analysis of products (TAP) technique. NH₃ is chemisorbed on the catalyst surface, forming three different species, i.e., NH ₄ ⁺ ions located on BrØnsted sites, coordinatively bound NH₃ on Lewis sites and NH ₂ ^– groups, presumably P-NH₂. Toluene that is probably adsorbed on Lewis sites reacts in a first step to a benzyl radical. A subsequent partial oxidation by interaction of V^IV=O groups generates a V...O=CH-C₆H₅ surface structure. This benzaldehyde-like surface species reacts with adsorbed NH₃ according to a Langmuir-Hinshelwood mechanism. TAP experiments on ammonium-containing vanadium phosphates revealed that NH ₄ ⁺ ions could act as potential N-insertion species. No formation of benzylamine as well as the generation of V=NH surface groups as possible intermediates or N-insertion sites were observed.     

Time-of-flight studies on catalytic model reactions

Time-of-flight spectroscopy (TOF) and REMPI-TOF (resonance enhanced multi-photon ionization-TOF) were applied to measure the angular and translational energy distribution, as well as the internal state resolved energy distribution of desorption and reaction products on some model systems. Desorption of hydrogen and deuterium from clean and modified Pd(111) surfaces was studied, where the palladium sample was part of a permeation source. Water formation by reaction of oxygen with hydrogen on palladium was investigated by using different types of hydrogen supply: molecular H₂ exposure and atomic H exposure from the gas phase, as well as H exposure by permeating hydrogen. Vanadium oxide nanostructures on Pd(111) were prepared and the influence on D₂ desorption and D₂O production was investigated with the permeation technique. Additionally, deuterium desorption from sulfur and oxygen covered V(111) and V(100) surfaces was studied by TOF and REMPI-TOF spectroscopy. From the TOF spectra information concerning the reaction and desorption dynamics (activation barriers) could be gained.     

Electrochromic display devices of tungstic oxide containing vanadium oxide or cadmium sulphide as a light-sensitive layer

Solid-state electrochromic display devices (ECDs) have been prepared using vacuum deposited tungstic oxide as the primary electrochromic material. Such devices form colour during irradiation from a fluorescent-tube as light source. Initial experiments incorporated (evaporated) CdS films and the proton-conducting poly(ethylene oxide)-phosphoric acid electrolyte (1:1) plasticised with acetonitrile. Successful photoelectrochromic devices were prepared in this way provided the electrolyte was anhydrous, since films of CdS are sensitive to water-attack. Another device to evince photoelectrochromism was one containing layers of WO₃ and V₂O₅. This combination of oxides was the most promising, responding to a 1/20s flash of intense white light. As yet, the colour formed in this way cannot be electro-bleached. These displays may also be used as normal—electrolytically driven—devices in the absence of irradiation.     

退火真空度与氧化钒薄膜物相的相关性

以高纯五氧化二钒(V2O5)粉末(纯度≥99.99%,质量分数)为原料,用真空蒸发工艺制备出氧化钒薄膜,并测试其在真空退火前、后的X射线光电子能谱、X射线衍射谱及电阻-温度关系曲线.结果显示:低真空退火对氧化钒薄膜的还原性比高真空退火的强.但是,在高真空退火下得到的氧化钒薄膜的晶粒尺寸要比在低真空下退火的大.随退火温度升高,高真空下退火制备的薄膜经历了从VO2(B)到V02(B)与V6O13混合,再到V6O13的转变过程,B表示薄膜无热致相变特性.低真空下退火制备的薄膜经历了从VO2(B)到VO2(A)的转变,A表示薄膜有热致相变特性.这些薄膜的电学性质也有很大不同.     

粗四氯化钛除钒工艺现状及发展趋势

概述了使用铜丝、有机物、硫化氢和铝粉4种物质除去粗四氯化钛中的杂质钒方法的优缺点,通过比较指出有机物除钒法和铝粉除钒法是较理想的粗四氯化钛除钒方法。最后,对有机物除钒法目前存在的问题及解决方案进行了分析。     

劣质铁尾矿制备聚硅酸铝混凝剂

研究了以劣质铁尾矿为原料制备高效混凝剂聚硅酸铝(PSA)的方法，确定了合理的生产工艺和操作条件。用该混凝剂处理工业废水，并与传统混凝剂进行了比较，结果表明，PSA混凝剂处理效果好，用药量少。     

粗TiCl4除钒工艺探讨

研究了粗TiCl4除钒的工艺过程，通过试验比较了各种有机物除钒的效果，结果表明矿物油除钒性能优异。1t粗TiCl4加矿物油2～4kg，反应温度135～138℃，反应时间60min，收率大于95％，质量达到企业产品标准要求。     

基于FAHP-IE算法的尾矿库安全性三级评估研究及应用

从系统安全工程学的观点出发,针对尾矿库事故发生的随机性与不确定性特点,结合模糊层次分析法(Fuzzy Analytic Hierarchy Process,FAHP)和信息熵(Information Entropy,IE)建立尾矿库安全性三级综合评价模型。为解决专家评价分析过程中主观不确定性难以量化的问题,利用信息熵方法对FAHP确定的尾矿库安全评价指标权重进行优化,进而建立面向分层指标体系的尾矿库多主体安全评价模型。根据建立的尾矿库安全性综合评价模型,能够计算尾矿库安全综合评价指数,对于具体的尾矿库工程进行评价后分类定级,从而找出尾矿库存在的安全隐患。案例分析表明,FAHP-IE方法计算简便,用于系统安全状态评价不仅具有模糊综合法的特性,而且兼顾了评价主体认知歧异引起的不确定性,信息利用率高、评价结果可靠,可以为现场整改提供量化依据。     

Oxidation of Butane to Maleic Anhydride using Vanadium Phosphate Catalysts: Comparison of Operation in Aerobic and Anaerobic Conditions using a Gas-gas Periodic Flow Reactor

The use of a periodic flow reactor is described for the oxidation of butane to maleic anhydride to compare the catalytic performance of vanadium phosphate catalysts operating under aerobic and anaerobic conditions. It is found that for the catalyst prepared via a standard VPO method, operation in the absence of oxygen leads to a very small enhancement in selectivity when butane concentrations in the range 0.9–2.9% are used. Operation in the absence of oxygen leads to very small differences in conversion such that the overall yield is enhanced and this effect is maximised for reactor feeds containing 1.5% butane. However, the enhancement is negligible when the catalyst is operated at high conversion required for commercial operation, indicating that reactors operating with continuous flow with aerobic conditions are preferred. Similar experiments are conducted for a catalyst prepared by the VPD method and, in contrast, this catalyst gives lower butane conversion and maleic anhydride selectivity when operated in the absence of oxygen.     

乙酰丙酮氧钒的合成与应用

乙酰丙酮氧钒作为助催化剂与烷基过氧化物及其它氧化剂结合可以氧化很多有机官能团,介绍了其在有机合成中的应用,并以五氧化二钒、乙酰丙酮以及双氧水为原料合成目标产物,收率85%。