A novel way to treat refractory waste: Sonication followed by wet oxidation (SONIWO)

The effectiveness of the hybrid system sonication followed by wet oxidation (SONIWO) to treat otherwise refractory waste has been demonstrated. In such a hybrid system homogeneous CuSO₄ catalyst was found to be very efficient.     

Reactivity of steam in exhaust gas catalysis III. Steam and oxygen/steam conversions of propane on a Pd/Al2O3 catalyst

A 1% Pd catalyst (38% dispersion) was prepared by impregnating a γ-alumina with palladium acetylacetonate dissolved in acetone. The behaviour of this catalyst in oxidation and steam reforming (SR) of propane was investigated. Temperature-programmed reactions of C₃H₈ with O₂ or with O₂ + H₂O were carried out with different stoichiometric ratios S(S =[O₂]/5[C₃H₈]). The conversion profiles of C₃H₈ for the reaction carried out in substoichiometry of O₂ (S < 1) showed two discrete domains of conversion: oxidation at temperatures below 350°C and SR at temperatures above 350°C. The presence of steam in the inlet gases is not necessary for SR to occur: there is sufficient water produced in the oxidation to form H₂ and carbon oxides by this reaction. Contrary to what was observed with Pt, an apparent deactivation between 310 and 385°C could be observed with Pd in oxidation. This is due to a reduction of PdO_x into Pd⁰, which is much less active than the oxide in propane oxidation. Steam added to the reactants inhibits oxidation while it prevents the reduction of PdO_x into Pd⁰. Compared to Pt and to Rh, Pd has a higher thermal resistance: no deactivation occurred after treatment up to 700°C and limited deactivation after treatment up to 900°C, provided that the catalyst is maintained in an oxygen-rich atmosphere during the cooling.     

The greenhouse effect; Impact upon and the role to be played by construction

The authors highlight several possible ways in which the construction industry could lower present emissions of the greenhouse gas, carbon dioxide. It is an excellent discussion document and is recommended reading.     

Modified atmosphere packaging of a mixed prepared vegetable salad dish

The aim of this study was to design a modified atmosphere package for a mixed vegetable salad consisting of 75 g of cut carrot, 55 g of cut cucumber, 20 g of sliced garlic and 50 g of whole green pepper. Respiration data of all the components were combined with film permeability data to predict package atmospheres and design optimal packages for experimental testing for improved shelf-life of the produce. The optimal package avoided minimum O₂ and maximum CO₂ tolerance limits, and chilling injury temperatures for any component. A pouch form package made of 27 mm low density polyethylene developed a modified atmosphere of 2.0–2.1% O₂ and 5.5–5.7% CO₂, which was beneficial for all components and provided better quality retention than other test packages.     

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.     

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.     

One-step oxidation of cyclohexane to adipic acid

Liquid-phase oxidation of cyclohexane with Co(III) catalyst and gaseous oxygen was found to be influenced by reaction temperature, catalyst concentration and the duration. Maximum adipic acid product selectivity (77%) with about 85% cyclohexane conversion was attained at 100°C using catalyst: cyclohexane molar ratio 0·08. Under these conditions more than 80% cyclohexane was converted in the first hour, although selectivity to adipic acid continued to increase for the next 5 h. Cyclohexyl acetate and cyclohexyl monoadipate were identified as important intermediates. This study supports the mechanism proposed by Schultz, J. G. D. and Opchenko, A., J. Org. Chem., 38 (21) (1973) 3729.     

Al2O3—TiB2陶瓷刀具材料的高温氧化及其对刀具耐磨性能的影响

研究了Ａｌ２Ｏ３－ＴｉＢ２陶瓷刀具材料在１０００℃下的氧化行为，用ＸＲＤ、ＳＥＭ分析了氧化后的相组成及显微结构。结果表明：Ａｌ２Ｏ３－ＴｉＢ２陶瓷材料在１０００℃空气中氧化增重符合抛物线规律；随ＴｉＢ２含量的增加，该材料的抗氧化能力下降。     

Oxidation of methane to formaldehyde over Fe/SiO2 and Sn---W mixed oxides

In an attempt to develop new catalysts for the formation of formaldehyde from methane, the promotion effect of Fe on SiO₂ and that of Sn on WO₃ have been studied. The formation of formaldehyde on silica can be appreciably enhanced by the impregnation of Fe, as far as iron loadings are kept below 0.1 atom.% (Fe/Si × 100). In the case of Sn---W---Ox catalysts, both the addition of Sn to WO₃, and that of W on SnO₂ were effective to the selective formaldehyde formation. Absorption spectra (UV-Vis) and ESR measurements revealed that tetrahedrally coordinated Fe³⁺ in the silica network plays an important role in the formation of formaldehyde. A thin surface layer consisting of W and Sn oxides can account for the selective formaldehyde formation on the Sn---W---Ox catalysts.     

Preparation and characterization of oxygen deficient perovskites,BaBiO3−x

Oxygen nonstoichiometry in the distorted perovskite BaBiO₃ has been studied by thermogravimetric analysis using controlled oxygen pressures. Three distinct regions of nonstoichiometry are observed with composition ranges which narrow as the temperature is lowered. Samples isolated from each region were shown by powder X-ray diffraction to retain the perovskite subcell but show different types of framework distortion. Low temperature reoxidation of the oxygen deficient phases is also described.