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.     

大功率CO_2激光器非平衡态合成WO_3／Fe_2O_3新型陶瓷催化剂──Ⅱ．WO_3／Fe_2O_3烯烃歧化反应催化剂的催化活性

用大功率ＣＯ２激光器熔制ＷＯ３／Ｆｅ２Ｏ３新型烯烃歧化反应催化剂。考查了催化剂组成、激光功率及熔炼时间与丙烯歧化反应催化活性之间的关系。     

连续重整装置仿真系统的设计开发

为提高操作人员对连续重整装置开停工及事故处理的熟练程度，并对生产进行指导，采用半机理模型结合设计和现场数据介发的连续重整装置仿真系统已在现场成功投用。介绍了该仿真系统的软硬件结构、动态模型及仿真功能。     

哈尔滨炼油厂MTBE装置试生产

介绍了哈尔滨炼油厂ＭＴＢＥ装置的工艺路线、新技术的应用及特点；催化剂的装填及应用情况；总结了生产过程中遇到的一系列问题及解决办法；探索了平稳生产的新徐径，以保证装置安全、平稳、长周期运行；同时对反应器操作温度、催化蒸馏塔操作压力、原料中醇烯比等因素对异丁烯转化率及ＭＴＢＥ产品的影响做了简单的总结。     

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。     

Study of direct and indirect naphtha recycling to a resid FCC unit for maximum propylene production

To satisfy the increasing propylene demand, direct and indirect naphtha recycling schemes around an existing resid fluid catalytic cracking (FCC) unit were investigated. To this aim, light cracked naphtha (LCN), heavy cracked naphtha (HCN) and a PolyNaphtha (PN) oligomerisation product were cracked under a wide range of operating conditions over a commercial Y zeolite based equilibrium catalyst. Experimental data were acquired in three different units: a fixed bed bench scale unit, a fixed fluidised bed unit and an adiabatic circulating fluidised bed pilot plant. It was shown that FCC naphthas require high operating severities to crack, and that even then their conversion remains relatively moderate. Hence, direct recycling to the main riser does not seem a viable pathway to increase propylene product. Feeding FCC naphthas to a second reaction zone operating at high severity allows to increase the propylene yield in a significant manner. Increasing conversion, however, not only leads to higher LPG and propylene yields, but also results in very high dry gas yields. An alternative scheme was proposed, in which the olefinic C₄ and C₅ fractions are converted into a naphtha fraction through oligomerisation in a dedicated unit before being recracked in the secondary riser. As the highly olefinic oligomerised effluent mainly consist of dimerised and trimerised butenes and pentenes, this feed is more easily cracked and high conversions can be achieved. This indirect interconversion of butenes and pentenes into propylene therefore effectively allows to convert these butenes and pentenes into propylene, resulting in a significant increase in propylene yield. Each of the three main naphtha recycle options (directly to the main riser, directly to a secondary riser or indirectly via a light olefin oligomerisation unit) have been analysed and compared to a base case. In the evaluation of each of these schemes, all heat balance effects, both on the riser and the regenerator side, have been accounted for. The proposed process scheme with an indirect recycle via an oligomerisation unit enhances the already inherent flexibility of the FCC unit. The naphtha recycle can be turned on or off, the second reaction zone can be used to crack naphtha or to crack resid feed to maximise throughput, while the effluent of the oligomerisation unit can be recycled to the FCC unit for propylene production or hydrogenated and sent to gasoline and kerosene pool.     

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).