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.     

Fabrication of sharp silicon tips employing anisotropic wet etching and reactive ion etching

We developed a process to obtain sharper silicon tips by employing anisotropic etching in a KOH solution followed by SF₆ plasma etch. The tips were further sharpened using the established thermal oxidation technique to decrease the cone angle and, therefore, obtain smaller curvature radii. We have analyzed the impact of such changes in geometry on a figure of merit associated with the field emission characteristics. An increase in the figure of merit by a factor of three was found in relation to the tips before sharpening.     

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.     

Pyrene oxidation as a model reaction for characterizing the mechanism of coke oxidation on Y zeolites

The same effect of temperature on the production of CO, CO₂ and H₂O was found during oxidative treatment of HY zeolites either impregnated with pyrene or coked. Therefore, pyrene oxidation can be used to specify the mechanism of coke oxidation. Three types of reactions can be distinguished: (a) condensation of polyaromatic molecules, (b) oxidation of polyaromatics into aldehydes, ketones, acids and anhydrides and (c) decarbonylation or decarboxylation of oxygenated compounds, all these reactions involving protonic sites.     

Kinetics of phenol oxidation in a trickle bed reactor over active carbon catalyst

The wet air oxidation of phenol over a commercial active carbon catalyst was studied in a trickle bed reactor (TBR) in the temperature and oxygen partial pressure ranges of 120–160 °C and 0.1–0.2 MPa, respectively. The performance of the active carbon was compared in terms of phenol and COD destruction. The weight change of active carbon due to reaction was also measured. Finally, oxic phenol adsorption isotherms were assessed in batch conditions at 25, 125 and 160 °C. In order to use the conversion data obtained from the TBR for a kinetic study, special care was taken to check the kinetic control in the TBR experiments. Several kinetic models including power law or Langmuir–Hinshelwood expressions were considered to describe the catalytic oxidation of phenol over active carbon. The simple power law model with first order dependence on both phenol and oxygen concentration predicted satisfactorily the experimental data not only over the entire range of operating conditions studied, but also outside its validity range. Copyright © 2005 Society of Chemical Industry     

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.     

High-Pressure (up to 140 MPa) Dynamic Viscosity of the Methane and Toluene System: Measurements and Comparative Study of Some Representative Models

The dynamic viscosity of toluene and methane mixtures containing 25.03, 37.19, 49.95, 64.11, and 95.00 mol% methane has been measured using a falling-body viscometer. The measurements (280 data points) have been performed in the temperature range 293.15 to 373.15 K and at pressures up to 140 MPa. The data have been discussed in the framework of recent representative models (hard-sphere scheme, friction theory, and free-volume model) as well as with simple mixing laws and empirical models (particularly the LBC model and the self-referencing model) used in the literature. This comparative study shows that the average absolute deviation of the models is between 4.9 and 26.8%, and the maximum deviation is between 11.6 and 49.5%.     

Anaerobic digestion of alkaline black liquor using an up-flow anaerobic sludge blanket reactor

The anaerobic digestion of alkaline black liquor from a cereal straw pulping mill was studied in batch (serum bottles) and continuous systems (up-flow anaerobic sludge blanket reactor—UASB). The batch digestion studies confirmed that lignin and related compounds (LRC) in the alkaline black liquor were the main inhibitory substances and could not be decomposed by anaerobic bacteria. At organic loading rates of 5–10 kg COD m^?3 day^?1, the UASB reactor achieved 50–60% COD removal efficiencies. Gas production was 2–3 dm³ per dm³ of alkaline black liquor. Two different sludge types were examined in the reactor: granular and cluster-like sludges. Sludge in a cluster, which involved many small granules and flocs, tended to form larger aggregates and possessed good settling ability.     

Catalytic Combustion of Methane over Rare Earth Stannate Pyrochlore

Well-defined Ln₂Sn₂O₇ powders (Ln = La, Sm and Gd) with a phase-pure pyrochlore structure were synthesized by hydrothermal reaction. The catalytic activities of Ln₂Sn₂O₇ powders for methane combustion were measured. Methane oxidation started at 500 °C and increased with oxidation temperature. Catalytic methane combustion is strongly influenced by the presence of oxygen vacancies that form by breaking Sn–O lattice bonds as the temperature increases. Addition of manganese to the rare earth pyrochlores improved methane oxidation activity. Manganese-doped samarium stannate pyrochlore (Sm₂Sn_1.8Mn_0.2O₇) shows highest the catalytic activity. Light-off and complete oxidation temperatures were measured at about 400 and 650 °C, respectively.