Electrochemical oxidation of several chlorophenols on diamond electrodes Part I. Reaction mechanism

The electrochemical oxidation of 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol aqueous wastes using boron-doped diamond electrodes was studied. This treatment led to complete mineralization of the wastes regardless of the operating conditions. A simple mechanistic model is consistent with the voltammetric and electrolysis results. According to this model, the electrochemical treatment of chlorophenol aqueous wastes involves the anodic and cathodic release of chlorine followed by the formation of non-chlorinated aromatic intermediates. Subsequent cleavage of the aromatic ring gives rise to non-chlorinated carboxylic acids. Chlorine atoms arising from the hydrodehalogenation of the chlorophenols are converted into more oxidized molecules at the anode. These molecules react with unsaturated C₄ carboxylic acid to finally yield trichloroacetic acid through a haloform reaction. The non-chlorinated organic acids are ultimately oxidized to carbon dioxide and the trichloroacetic acid into carbon dioxide and volatile organo-chlorinated molecules. Both direct and mediated electrochemical oxidation processes are involved in the electrochemical treatment of chlorophenols.     

Complete oxidation of methane at low temperature over Pt and Pd catalysts for the abatement of lean-burn natural gas fuelled vehicles emissions: influence of water and sulphur containing compounds

The catalytic activity of fresh Pd and Pt catalysts supported on γ-alumina in the complete oxidation of CH₄ traces under lean-burn conditions was studied in the presence or the absence of water or H₂S. Steam-aged catalysts were also studied in order to simulate long-term ageing in real lean-burn natural gas fuelled vehicles (NGVs) exhaust conditions. Without water or H₂S added to the feed, Pd catalysts exhibit a superior catalytic activity in methane oxidation compared to Pt ones, whatever the catalysts were fresh or aged. The addition of 10 vol.% water vapour to the feed strongly affects the activity of the fresh Pd catalyst, thus being only slightly more efficient than the fresh Pt one. H₂S has a strong poisoning effect on the catalytic activity of Pd catalysts, while Pt catalysts are more resistant. The fresh H₂S-poisoned Pd/Al₂O₃ catalyst was studied by TPD in O₂/He. Poisoning species decompose above 873 K as SO₂ and O₂ in relative concentrations consistent with the decomposition of surface sulphate species. However, a treatment in O₂/He at temperatures as high as 923 K does not allow the complete regeneration of the catalytic activity of H₂S-poisoned Pd/Al₂O₃. A mechanism involving the poisoning of PdO by sulphate species is proposed. Different diffusion processes by which these sulphate species can migrate back and forth between PdO and the support, depending on the experimental conditions, are suggested.     

Deep oxidation of VOC mixtures with platinum supported on Al2O3/Al monoliths

Pt impregnated metallic monoliths prepared from anodised aluminium foils were tested to study their catalytic activity in complete oxidation of volatile organic compound (VOC) mixtures. The VOCs oxidised were 2-propanol, toluene, methyl ethyl ketone (MEK), acetone and their mixtures. Complete oxidation was obtained in all cases except for the case of 2-propanol, where acetone was found as an oxidation intermediate. Even if the adsorption of the VOC on the Al₂O₃ is governed by its polarity, the reactivity is mainly affected by the competition of the oxygen atoms chemisorbed on the Pt particles.     

钢锭零能少氧化均热轧制的研究

根据计算机的辅助分析,采用新的钢锭传搁、注后强制水冷却、垫铁脱模等工艺后,入炉钢锭的热焓已超过开坯轧制需要,利用普通均热炉代替钢锭保温车,可完全依靠到钢锭自身潜热与显热进行均热。对不同锭型与钢种采用经试验的最佳时间均热后再轧制,收与保温车均热钢锭直接轧制相同的效果。     

Modified Imidazoles: Degradation Inhibitors and Adhesion Promoters for Polyimide Films on Copper Substrates

Polyimide films on copper substrates that are exposed to elevated temperatures and an oxidizing environment will be subject to degradation. In order to halt this degradation without changing the properties of the system, a polymeric agent could be placed between the polyimide and the copper. This paper will investigate three such materials that will not only slow down the degradation of the polyimide and the oxidation of the copper, but will also improve adhesion within the system. Fourier transform infrared reflection-absorption spectroscopy (FTIR-RAS) will be used to investigate the polyimide/polymeric agent/copper system.     

苯酚氧化反应中溶剂选择及催化剂再生方法的研究

考察了水作溶剂对苯酚转化率及产品选择性的影响，并且对催化剂的再生方法进行了改进。研究发现，水及丙酮分别作溶剂时，通过控制反应参数，苯酚转化率可达到相近的水平；水作溶剂时，通过调整反应温度、水量、Ｈ２Ｏ２用量及其加入方式可以得到最大的苯酚转化率及Ｈ２Ｏ２利用率；高温水处理积炭催化剂的方法，可以减少催化剂的焙烧次数，简化原有的再生工艺。     

Surface Chemistry and Catalysis of Rare Earth Oxides I．A Study of the Reactivity of Surface Hydroxyls on CeO_2 and Pr_6O_（11） by FT－IR Spectroscopy

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镧系钙钛矿型氧化物（LaBO3）的催化氧化性能及其净化效果的研究

本文在气相色谱仪联用微反应器装置上,研究了LaBO_3型催化剂中的B位元素对催化氧化活性的影响规律,并进行了程序升温脱附实验。另外,还对LaBO_3型载体催化剂进行了活性筛选,并在柴油机台架上与贵金属Pt/Al_2O_3进行了有害气体净化效果的对比实验。实验结果表明,LaBO_3氧化物中LaMnO_3对CO、CH_4的催化氧化活性最高,且CO、CH_4活性中心并不一致。LaMnO_3/γ-Al_2O_3浸渍微量助化剂后,能使CO在130℃完全氧化,CH_4的氧化温度在300～500℃范围内,LaMnO_3载体催化剂对柴油机有害排放物的净化率很低,浸渍微量助化剂后,净化率提高一倍以上,特别是LaMnO_3/堇青石蜂窝陶瓷,浸渍后的净化效果同贵金属Pt/Al_2O_3接近。     

A FT-IR assessment of iso-C4H8 reactivity with V2O5/TiO2 catalysts

Low-loaded vanadia-titania catalysts have been prepared by impregnation of titania P-25 (Degussa). The catalysts were characterized by X-ray diffraction, specific surface area and porosity assessment by nitrogen adsorption at 77 K. For very low vanadia contents the absence of surface acid Brønsted sites leads to dimerization on surface acid Lewis sites, whereas the presence of surface acid Bransted sites when the vanadia content is increased leads to oxidation to carbonyl and carboxylate species.     

Some kinetic aspects of unsteady-state partial oxidation reactions. Dynamic processes on metal oxide surfaces

It is shown that steady-state kinetic data do not allow the discrimination between the redox and associated mechanisms of the partial oxidation reactions. A discrimination between these mechanisms was performed using transient experiments. The obtained rate expressions are in agreement with experimental kinetic data for catalytic partial oxidation of o-xylene.

An influence of the conjugate oxidation of a catalyst surface on dynamics and kinetics of the heterogeneous catalytic oxidative reactions is considered. Computing simulation of methane oxidative coupling of methane reaction at lowered temperature and elevated pressure has been performed. It showed that the reaction order with respect to oxygen exceeding unity is consistent with the chain branching mechanism of the reaction in the presence of TiSi₂ and TiB₂ and showed the important role of the branching chain cycles in the low-temperature OCM reaction at elevated pressure.