Effect of the metal oxide loading on the activity of silica supported MoO3 and V2O5 catalysts in the selective partial oxidation of methane

Precipitated silica catalysts loaded with either MoO₃ (0.2–4.0 wt%) or V₂O₅ (0.2–5.3 wt%) have been studied in the selective partial oxidation of methane to formaldehyde with molecular oxygen at 520 °C. The functionality of the SiO₂ surface towards the formation of HCHO is significantly promoted by V₂O₅, while it is depressed by the MoO₃.     

Effects of oxidation on I2 doping of trans-polyacetylene as studied via e.s.r. and conductivity measurements

Oxidation of trans-polyacetylene lowers the activation energy for conduction from 16 kcal mol^?1 to 11 kcal mol^?1 for oxidation levels of (C₂H₂O_n)_x, n = 0.144, 0.207 and 0.550. Maximum conductivity levels for 0 < x < 0.144 doped with I₂ were almost identical. At long I₂ doping times all samples exhibited some loss of conductivity. E.s.r. experiments indicate that: (1) linewidth is directly proportional to oxygen content, and (2) iodine doping is not diffusion controlled. All data are consistent with a molecular picture of PAC consisting of highly reactive localized spin states that are selectively oxidized, and less reactive delocalized states that affect conductivity more strongly via doping.     

Comments on the characterisation of oxidation catalysts using TPR/TPO

Temperature programmed reduction (TPR) and oxidation (TPO) are used extensively in catalyst characterisation. In this paper, we examine the use of TPR/TPO cycles for the characterisation of a range of molybdates and single oxides. In particular we observe that the first cycle differs from that of subsequent analyses, even when the maximum temperature is limited to that used in the catalytic reaction. The effect is independent of heating rates and cooling atmospheres and has been demonstrated using different bed configurations. This observation has significance when these oxides are used in periodic flow reactors that involve many cyclical reduction/oxidation.     

High catalytic activity of PdOx/MnO2 for CO oxidation and importance of oxidation state of Mn

PdO_x/MnO₂ has been examined as a catalyst for CO oxidation using a conventional flow reactor at reaction temperatures between 50 and 150°C. In the reaction conditions of GHSV (gashourlyspacevelocity) of 1.22 × 10⁵/h and CO concentration of 2000 ppm, PdO_x/MnO₂ showed higher catalytic activity compared with PdO_x/Mn₂O₃, which had been previously reported as an effective catalyst due to the cooperative action of Pd and Mn₂O₃ for this reaction. The reason for higher activity of PdO_x/MnO₂ than PdO_x/Mn₂O₃ has been investigated using TPR (temperatureprogrammed reduction) and XPS studies. TPR showed that PdO_x/MnO₂ could be reduced by CO at much lower temperature than PdO_x/Mn₂O₃. During the experiment of reduction and oxidation, XPS showed that the valence of Mn in the PdO_x/MnO₂ was between 4+ and 3+, which is higher than that of Mn in the PdO_x/Mn₂O₃ catalyst of which the valence has been reported to be between 3+ and 2+. It is known that in this catalyst system the support supplies oxygen onto Pd, where the oxidation occurs with adsorbed CO, and the ability of the support to provide oxygen improves the performance of the catalyst. Therefore, it was concluded that the readiness of MnO₂ to be reduced with maintaining a higher oxidation state showed higher CO oxidation activity than Mn₂O₃ as support for PdO_x.     

Oxidation of pyrite in coal to magnetite

When bituminous coal is heated in an inert atmosphere (He) containing small amounts of oxygen at 393–455 °C, pyrite (FeS₂) in coal is partially converted to magnetite (Fe₃0₄). The maximum amount of Fe₃0₄ formed during the time of heating corresponds to 5–20% of the total pyrite present, depending on the coal sample. The magnetite forms as an outer crust on the pyrite grains. The fact that the magnetic properties of the pyrite grains are substantially increased by the magnetite crust suggests that pyrite can be separated from coal by use of a low magnetic field. In a laboratory test, 75% removal is obtained by means of a 500 Oe magnet on three samples, and 60% on a fourth sample.     

Pore structure of bulk tungsten carbide powder catalysts

Bulk tungsten carbide catalysts are prepared by direct carburization/reduction of tungsten trioxide in methane-hydrogen mixtures. The catalytic properties of such catalysts have been studied by several authors. The porous structure of these catalysts is studied by adsorption of N₂, Kr, CF₄ and neohexane. Adsorption isotherms and hysteresis loops for the catalysts suggest the presence of a microporous structure made of parallel plates distant approximately by 20 Å. These results are compared to those obtained using such catalysts for hydrogen oxidation and where condensation in the porous structure was observed.     

水合肼生产中氧化反应的研究和应用

分析了尿素法生产水合肼的氧化反应历程及影响因素，改进了反应器，并找到了最佳的工艺控制条件：①控制n(尿素)：n(次氯酸钠)=(1．05～1．10)：1，各原料的消耗较低，总经济效益佳；②采用-5℃冷冻盐水移走尿素、次氯酸钠混合段内氯化反应放出的热量，控制物料混合终点温度在15～30℃；③采用列管式加热器，将氯化反应与水解反应在不同的设备中进行，水合肼的收率提高到83％～85％；④采用列管式加热器代替双夹套反应器，提高了加热强度，生产能力大，1套合成反应器可生产1万t／a80％的水合肼。     

Ruthenium tetroxide catalysed oxidation of Illinois No. 6 coal: The formation of volatile monocarboxylic acids

Ruthenium tetroxide selectively oxidizes activated aromatic compounds under mild conditions and has been used for the catalytic oxidation of several different coals. The quantities of the volatile monocarboxylic acids with 2–6 carbon atoms have been determined by an isotope dilution technique. The amount of ethanoic acid ranges from 1 to 3mol/100C and the quantities of propanoic acid, and butanoic acid exceed 0.1 mol/100C. Methylpropanoic, pentanoic, 2-methylbutanoic, 3-methylbutanoicand hexanoic acid are formed in lesser amounts. The outcome of the experiment depends upon whether or not the coal has been extracted prior to oxidation. The results for Illinois No. 6 coal expressed in moles of ethanoic acid produced/l00C illustrate this feature: raw whole coal, 1.9; coal extracted by the method of Hayatsu and co-workers, 1.0. Dehydrogenation with benzoquinone prior to oxidation increases the yield of ethanoic acid to $\text{sol1.5mol}\text{100C.}$ The amounts of ethanoic acid obtained from the other extracted coals are 1.0 for Texas lignite, 1.2 for Rawhide subbituminous, 3.4 for Pittsburgh No. 8, 3.3 for a higher ranking bituminous coal (PSOC 726) and 0.7 for an anthracite (PSOC872). The results obtained in this study are compared with related information concerning the distribution of alkyl groups within coal by other methods.     

Degradation of p-nitrotoluene by 03/H2 02 process and oxidation mechanism

The degradation of p-nitrotoluene by O2/H2O2 process in a bubble contact column was investigated.Effects of the molar ratio of hydrogen peroxide to ozone, pH value and t-butanol on the oxidation process were discussed. It was found that the proper H2 O2/O3 molar ratio for the degradation of p-nitrotoluene was around O. 6, different pH values and the presence of t-butanol highly influenced the removal efficiency of p-nitrotoluene. 5-metbyl-2-nitrophenol, 2-methy1-5-nitrophenol, (4-nitrophenyl) methanol, 5-(hydroxymethyl) -2-nitro phenol, acetic acid, 2-methylpropanc diacid and 2-(hydroxylmethyl) propane diacid were identified as degradation intermediates and products through GC-MS. Radical reaction mechanism and degradation pathway were proposed based on the results of experiments. It is deduced that the benzene ring of p-nitrotoluene can be only destroyed by hydroxyl radicals through a polyhydrexy intermediate pathway. Then unstable polybydroxy intermediates can be oxidized to different acids with low molecular weight rapidly.     

Progress and recent trend in MILD combustion

Moderate or intense low oxygen dilution(MILD)combustion plays a significant role in the mitigation of combustion-generated pollutants and greenhouse gases whilst meeting thermal efficiency needs.However,due to the lack of the fundamental knowledge on this combustion,there is a misconception that MILD combustion should be established by high preheating of the air,which has limited its application.Our research and development on this combustion has been performed for several years. We have found that the requ...