Selective partial oxidation of light paraffins with hydrogen peroxide on thin-layer supported Nafion-H catalysts

Thin-layer carbon supported Nafion-H catalysts were found to be active and highly selective (S>98%) for the partial oxidation of C₁-C₃ alkanes, in a three phase catalytic membrane reactor (3PCMR), under mild conditions and in the presence of H₂O₂. The influences of the catalyst teflon loading and H₂O₂ concentration on the reaction rate have been evaluated. A reaction pathway, based on the electrophilic hydroxylation of the C-H bond of alkanes with protonated hydrogen peroxide (H₃O ₂ ⁺ ), is discussed.     

Yttrium sol–gel coating effects on the cyclic oxidation behaviour of 304 stainless steel

The present results reveal the interest of sol–gel coating technique to improve 304 steel high temperature oxidation resistance. An yttrium sol–gel coating appears to enhance the oxidation resistance during isothermal oxidation test, to decrease widely the oxide weight gain and to reduce the initial transient oxidation stage generally observed in the case of blank steels. Moreover, the experimental results confirm that yttrium sol–gel coating also plays a significant role on the cyclic oxidation behaviour of the 304 steel. In fact, the yttrium addition promotes remarkably the prolongation of the period during which the oxide scale still remains adherent to the substrate.     

Photoelectrocatalytic humic acid degradation kinetics and effect of pH,applied potential and inorganic ions

This study addresses the removal of humic acid (HA) dissolved in an aqueous medium by a photoelectrocatalytic process. UV₂₅₄ removal and the degradation of color (Vis₄₀₀) followed pseudo‐first order kinetics. Rate constants were 1.1 × 10^?1 min^?1, 8.3 × 10^?2 min^?1 and 2.49 × 10^?2 min^?1 (R² > 0.97) for UV₂₅₄ degradation and 1.7 × 10^?1 min^?1, 6.5 × 10^?2 min^?1 and 2.0 × 10^?2 min^?1 for color removal from 5 mg dm^?3, 10 mg dm^?3 and 25 mg dm^?3 HA respectively. Following a 2 h irradiation time, 96% of the color, 98% of the humic acid and 85% of the total organic carbon (TOC) was removed from an initial 25 mg dm^?3 HA solution in the photoanode cell. Photocatalytic removal on the same photoanode was also studied in order to compare the two methods of degradation. Results showed that the photoelectrocatalytic method was much more effective than the photocatalytic method especially at high pH values and with respect to UV₂₅₄ removal. The effect of other important reaction variables, eg pH, external potential and electrolyte concentration, on the photoelectrocatalytic HA degradation was also studied. Copyright © 2003 Society of Chemical Industry     

On the kinetics of the autoxidation of fats: influence of pro‐oxidants,antioxidants and synergists

The influence of minor amounts of pro‐ and anti‐oxidants on the kinetics of the autoxidation of fat has been evaluated. The reaction rates of oxygen with the substrates were found to follow the same basic equation, hitherto established for pure substrates. There is evidence that the surface of the reaction vessel also acts as a reaction catalyst and its effect is proportional to the area of glass in contact with lipids. Oxidation is enhanced by trace metal ions as well as by surface‐active compounds (e.g. hydroperoxides and sterols). Antioxidants such as α‐tocopherol and butylated hydroxyanisole inhibit the oxidation by delaying the start of oxygen consumption (the induction period) while retarders like amino acids only decrease the rate of oxidation. Thus pro‐ and anti‐ oxidants affect either the start or the rate of oxygen consumption. The empirical formula dx/dt = k [O₂] (1‐x/n) f′(t) was found applicable to the different stages of oxidation.     

岩石龟裂系数法在火山岩裂缝储集层预测中的应用

 本文针对辽河东部凹陷油燕沟中生界火山岩的具体特征，采用纵波波速的比值——“龟裂系数”裂缝分析法［1,2,3］，研究了火山岩裂隙发育程度。综合龟裂系数裂缝分析及其他方法发现，该区中生界火山岩有效储集层的测井相特征主要表现为低密度、低中子、高声波时差和高伽马值等特征。此法的关键在于根据不同火山岩的岩性，选用合适的岩石骨架参数，在此基础上利用测井约束地震反演计算火山岩的层速度，进而计算出龟裂系数，然后根据已钻至火山岩井孔的测井相特征编制出火山岩预测厚度图。     

An integrated system of biological and catalytic oxidation for the removal of o-xylene from exhaust

Biofiltration is an efficient technology for treatment of gaseous waste. Its disadvantages, however, include large volume of bioreactor and slow adaptation to fluctuating concentrations in waste gas. Catalytic oxidation offers a high destructive efficiency at relatively low operating temperature and small unit. A bench scale system integrated with a biofilter and a catalytic oxidation unit for the treatment of gases containing o-xylene was investigated in this study. The catalytic oxidation unit was packed with Cu/Al₂O₃ catalyst. The results showed that 90% of o-xylene could be removed in the biofilter at the load below 38.2 g m⁻³ h⁻¹. High o-xylene concentration in inlet gas resulted in an overload of the biofilter. Using the Cu/Al₂O₃ catalytic oxidation unit, the concentration of o-xylene could be reduced evidently. The combination of the chemical and microbial processes not only led to a high and stable efficiency of o-xylene conversion, but also improved capacity resisting the shock loads. The Cu/Al₂O₃ was studied for o-xylene oxidation in temperature range of 90–320 °C. The o-xylene conversion was improved correspondingly with the increasing of oxidation temperature. The reaction mechanism of o-xylene oxidation on Cu/Al₂O₃ was also investigated using diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS).     

Gas-phase selective oxidation of toluene on TiO2–sepiolite supported vanadium oxides: Influence of vanadium loading on conversion and product selectivities

Gas-phase selective oxidation of toluene has been carried out on vanadium oxide systems (5–20 wt.% of V₂O₅, equivalent to 0.4–1.7 theoretical monolayers) supported on TiO₂–sepiolite (with titania loading around the theoretical monolayer, 12 wt.%) and on sepiolite. A study has been made on both the influence of vanadia loading and of the support on the catalytic behaviour of the supported vanadium systems. The reducibility by H₂ TPR was also studied as well as the acid and basic/redox sites from the results of conversion of the 2-propanol test reaction of the solids. Benzaldehyde, benzoic acid and several coupling products were the main ones detected, attaining over 50% selectivity towards the benzaldehyde and benzoic acid products at a total conversion around 10%. The activity and selectivity to the selective products exhibited by vanadium systems supported on mixed support were superior to those exhibited by the systems supported on sepiolite and increased notably in both series with the increase in vanadium loading. The best catalytic behaviour exhibited by the vanadium systems supported on mixed support, which also exhibited the highest density of sites capable of being reduced (as well as their reducibility) and of those responsible for propanone formation, could be attributed not only to the different balance of the vanadia species existing in the two supports (monomeric + oligomeric/polymeric), but also to such other factors as the nature of the support and, concretely, its chemical composition.     

焦化生产中含硫容器自燃氧化倾向性分析

分析了炼焦化工生产过程中硫的分布和存在形态、硫铁化合物自燃的影响因素,提出了防止储罐、管道等设备自燃事故的安全控制方法.     

表面引发剂对熔融铝合金直接氧化生长的影响

为了控制熔融铝合金直接氧化法制备Al2O3/Al复合材料的氧化生长,采用ZnO,SiO2和MgO3种表面引发剂,研究它们对Al-Si-Zn合金氧化生长过程及Al2O3/Al复合材料组织形貌的影响.结果表明:与未使用引发剂时相比,使用SiO2,ZnO或MgO表面引发剂制备的粉末都能显著地缩短Al-Si-Zn合金的氧化生长孕育期,提高合金氧化生长速率,改善复合材料的胞状生长方式,提高复合材料的组织均匀度和致密度,为实际生产应用提供了依据.实验发现:ZnO表面引发剂的使用效果最为突出,其最佳添加量为12mg/cm2.     

Synthesis and activation of Pt nanoparticles with controlled size for fuel cell electrocatalysts

Well-dispersed Pt nanoparticles with controlled size and narrow size distribution were prepared by polyalcohol reduction of platinum acetylacetonate, using oleylamine as a capping agent. The particle size was varied from 3.5 nm to 11.5 nm by decreasing the amount of oleylamine added in the synthesis. Size selection of the as-prepared particles by solvent fractionation yielded nearly monodispersed Pt particles. The as-prepared particles were loaded on a carbon support by physical deposition, but showed no electrocatalytic activity due to the oleylamine bound to the particle surface. The particles were activated for electrocatalysis after heating the particles in air at 185 °C for 5 h, conditions that gave no particle-sintering and no oxidation. Cyclic voltammetry showed that the particles after the heat treatment in air were electrocatalytically active for methanol oxidation. The smaller 3.5 nm and 4.0 nm Pt particles had a higher intrinsic activity for methanol oxidation, but a lower tolerance to CO poisoning, compared with 6.0 nm, 9.5 nm and 11.5 nm particles. CO-stripping results suggest that CO is more easily oxidized on larger Pt particles.