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.     

Mechanical degradation of coating systems in high temperature cyclic oxidation

Cyclic oxidation tests were performed on a large variety of commercially available overlay coatings. The results of cyclic oxidation tests confirmed that the composition of the coating as well as the processing method of the coating can affect the life of the system. Coating life was determined by the time to coating penetration and initiation of substrate attack. As this work was part of a effort to evaluate the relative protectiveness of available coating systems for Industrial Gas Turbine applications at relatively high temperature, an extensive testing programme was undertaken. The different coatings were tested to visual failure. The results presented in this paper concentrate on the surface instability of the coating. Apart from usual oxidation of the coating an additional degradation mechanism was observed. A mechanical effect caused by the instability of the coating as a result of the difference in the thermal coefficient of expansion and mechanical properties between the substrate and coating. This effect, the so-called “rumpling” effect, resulted in a significant reduction in time to penetration and was in some systems the life controlling factor.     

海水介质中高活性镁合金负极的电化学性能

研制了一种新型镁合金负极材料；用电化学方法测定了镁合金负极在人造海水介质中的电化学性能，用浸泡法测定了材料在人造海水介质中的自腐蚀速度，用扫描电子显微镜观察了镁合金腐蚀后的表面形貌，并与AP65合金和纯镁进行了比较。结果表明，新研制的镁合金在人造海水介质中的开路电位增加，自腐蚀速度降低，稳定工作电位提高，电极表面腐蚀均匀，可开发用于高电性能电池的负极材料。     

快速评定砂浆配方对钢筋腐蚀的影响

用电化学方法测定砂浆试件中钢筋的极化电阻，并测定了砂浆的孔隙率，结果发现:砂浆的孔隙率、孔径分布与钢筋极化电阻大小有良好的对应关系。电化学方法能可靠、快速测定砂浆配合比、添加剂对钢筋腐蚀速度的影响。     

Alkali-metal Na Adsorption and Promoted Oxidation on Si(100)2×1 Surface

The alkali-metal Na adsorption on Si(100)2×1 surface and its promoted oxidation and Si oxidegrowth have been investigated by means of thermal desorption,work function,Auger electronspectroscopy and photoemission electron spectroscopy.The experimental data showed that therewas a new state,interface electron state,near the Fermi level after the deposition of Na atoms.It wasfound that the presence of Na always caused an increase of the oxygen initial uptake whereas thepromotion of Si oxide growth was observed only at the coverage of Na greater than 0.5 ML.A newmechanism of Na-promoted Si oxide growth is suggested in this paper.     

Storage Stability of Antioxidant-Washed Myofibrils From Chicken White and Red Muscle

Oxidation and gel-forming ability of chicken white (breast) and red (leg) muscle myofibrillar proteins during storage at 0°C were examined. Breast myofibril gels exhibited greater shear moduli than leg myofibril gels throughout 8 days storage. Shear moduli of both breast and leg gels in the intermediate temperature zone (45–55°C) decreased during storage, but at >55°C, they either increased or remained unchanged. Lipid oxidation was inhibited by washing myofibrils with antioxidants propyl gal-late, ascorbate, and tripolyphosphate. However, these antioxidants did not affect the content of protein carbonyls, and only slightly decreased the amine content during storage. Storage affected the kinetic process of myofibril gelation independently of antioxidant treatments.     

乙烯氧化制环氧乙烷固定床反应器的模拟及稳定性分析

在筛选出合适的乙烯氧化制环氧乙烷动力学方程的基础上,对工业固定床氧化反应器进行一维和二维模型的模拟计算。考察操作工艺参数对反应器稳定性、转化率影响的敏感性以及N_2和CH_4做致稳气时反应温度和转化率的轴向、径向分布。     

聚苯胺电化学性能的改性研究

改善聚苯胺的电化学性能是聚苯胺研究中的一个重点，介绍了对聚苯胺的取代，共聚，复合和掺杂等几种改性方法，及其对聚苯胺电化学性能和其他性能的影响。     

Structural Description of Polyaromatic Nucleus in Residue

The proton nuclear magnetic resonance spectroscopy （1H-NMR）, the synchronous fluorescence spectrometry （SFS） and the ruthenium ions catalyzed oxidation （RICO） method were used to determine the chemical structure of polyaromatic nucleus in Oman residue fractions. The results of 1H-NMR analyses showed that the average numbers of aromatic rings in the aromatics, resins and asphaltenes units were 3.2, 5.6 and 8.2, respectively. SFS was used to investigate the distribution of aromatic rings in residue fractions, the main distribution range of aromatic rings in aromatics, resins and asphaltenes were 3 4 rings, 3--5 rings and more than 5 rings, respectively. The aromatic network in residue fractions was oxidized to produce numerous carboxylic acids. The types and content of benzenepolycarboxylic acids, such as phthalic acid, benzenetricarboxylic acids, benzenetetracarboxylic acids, benzenepentacarboxylic acid and benzenehexacarboxylic acid disclosed the condensed types of aromatic nuclei in the core. The biphenyl fraction （BIPH）, the cata-condensed fraction （CATA）, the peri-condensed fraction （PERI） and the condensed index （BCI） were calculated based on the benzenepolycarboxylic acids formed. The results implied that there was less biphenyl type structures in all residue fractions. The aromatics fraction was almost composed of the cata-condensed type system, and the asphaltenes fraction was wholly composed of the peri-condensed type system, while in the resins fraction co-existed the two types, herein the peri-con- densed type was predominant over the cata-condensed type. Based on the analytical results obtained in the study, the components --aromatics, resins and asphaltenes -- were given the likely structural models.     

The role of carbon deposition on precious metal catalyst activity during dry reforming of biogas

Gold and palladium were supported on a mesoporous TiO₂ for total oxidation of volatile organic compounds (VOCs). Mesoporous high surface area titania support was synthesised using of Ti(OC₂H₅)₂ in the presence of CTMABr surfactant. After removing the surfactant molecules, 0.5 or 1.5 wt% of palladium and 1 wt% of gold were precipitated on the support by, respectively, wet impregnation and deposition–precipitation methods. The activity for toluene and propene total oxidation of the prereduced samples follows the same order: 0.5%Pd-1%Au/TiO₂ > 1.5%Pd/TiO₂ > 0.5%Pd/TiO₂ > 1%Au-0.5%Pd/TiO₂ > 1%Au/TiO₂ > TiO₂. Moreover, a catalytic comparison with samples based on a conventional TiO₂, shows the catalytic advantage of the mesoporous TiO₂ support. The promotional effect of gold added to palladium could be partly explained by small metallic particles (TEM), but meanly by metallic particles made up of Au-rich core with a Pd-rich shell. Moreover, the hydrogen TPR profile of 0.5%Pd-1%Au/TiO₂ shows only the signal attributed to small PdO particles. Gold also implies a protecting effect of the support under reduction atmosphere. Operando diffuse reflectance infrared fourier transform (DRIFT) spectroscopy was carried on and allowed to follow the VOCs oxidation and the formation of coke molecules, but also a metallic electrodonor effect to the adsorbed molecule which increases in the same order as the activity for oxidation reaction. The presence of coke after test was also shown by DTA–TGA by exothermic signals between 300 and 500 °C and by EPR (g = 2.003).