Reaction pathways of ethane oxidative and non-oxidative dehydrogenation on γ-Al2O3 studied by temperature-programmed reaction (TP-reaction)

In this work, the reactions of ethane and ethene in an oxidizing and non-oxidizing atmosphere over γ-alumina were investigated under temperature-programmed conditions, in an attempt to estimate the possible contribution and functionality of the support in the reaction pathway of ethane ODH over MoO₃/Al₂O₃ catalysts. The results indicate that alumina contributes to the primary deep oxidation and dehydrogenation routes of ethane to CO_x and coke respectively, which proceed effectively over the acidic OH groups and the Al³⁺–O²⁻ acidic centers. On the contrary, the formation of ethylene seems to be coupled to the presence of redox sites on the catalytic surface and requires the presence of the molybdena phase. Moreover, the redox sites of the MoO_x species were found to unselectively activate the further overoxidation of the olefin to carbon oxides. Therefore, Al₂O₃ catalyzes the unselective primary oxidation of ethane to carbon oxides, whereas the molybdena phase is involved in the selective oxidative dehydrogenation (ODH) of ethane to ethene and the secondary overoxidation of ethene to CO_x.     

Preparation of Titanium Nitride/Alumina Laminate Composites

A preparation route for TiN/Al₂O₃ laminate composites has been described. A water-based process using Al₂O₃ and TiN slurries with solids contents of 40 and 35 vol%, respectively, was used to make TiN and Al₂O₃ tapes. The removal of the binder was monitored by weight-loss measurements in a thermogravimetry unit. Bodies composed of Al₂O₃ and TiN tapes were densified at temperatures of 1400° and 1500°C using the Spark Plasma Sintering^® (SPS) technique. Densities of >98% of the theoretical densities were approached. Crack-free and almost fully densified TiN/Al₂O₃ compacts were prepared by heating the burned-out green bodies to the final sintering temperature (1500°C) at a rate of 100°C/min, and with a holding time of 5–10 min, under a pressure of 75 MPa. The microstructures of the obtained compacts were studied using scanning electron microscopy. Grain sizes in the sintered Al₂O₃ and TiN compacts were similar to those of the precursor powders. Hardness and indentation fracture toughness were measured at room temperature, and the monolithic compacts as well as the laminate composites exhibited anisotropic mechanical behavior; i.e., the cracks propagated much more easily in a direction parallel to the laminas than perpendicular to them.     

Preparation and Characterization of 17O-Enriched Alumina for Nuclear Fusion Damage Experiments

Alumina enriched in ¹⁷O was successfully fabricated from aluminum isopropoxide and water containing the ¹⁷O isotope. This material was necessary for an experiment to study the radiation damage expected in alumina exposed to a nuclear fusion reactor environment. The enrichment levels of specimens subjected to different preparation schedules were measured using a nuclear reaction analysis technique. Replacement of the ¹⁷O isotope in the ceramic by atmospheric oxygen occurred readily. Therefore, successful fabrication of suitably enriched alumina specimens required that all processing steps be performed under vacuum or inertgas environments. The optimum fabrication procedure produced enriched alumina specimens of >99.5% of theoretical density, ∽10-μm grain size, and a flexural strength of 280 MPa.     

Thermal stability of NO 2 ⋅ and NO⋅ radicals formed in an Al23 catalyst during its preparation from a nitrate precursor

During the preparation of alumina as a catalyst support from aluminium nitrates by precipitation with a NH₄OH base, NO ₂ ^⋅ radicals have been formed in the catalyst after calcination under air in the solid at different temperatures. These radicals remained stable until a calcination temperature of 800°C. When the calcined catalyst was degassed under vacuum above 300 °C, the NO ₂ ^⋅ was reduced to give NO^⋅ and O^- species which were both tightly trapped in the solid. These latter species remained stable until vacuum treatment at 800 °C. This revised version was published online in July 2006 with corrections to the Cover Date.     

Al ionic radius influence on molecular dynamics simulations ofγ-Al2O3

Molecular dynamics (MD) simulations of-Al₂O₃, using a pairwise additive interaction potential of Pauling's type with four different radii for aluminum atoms, were analysed in order to determine the influence of the radius on the modification of coordination numbers of A1 relative to the ideal structure, at two different temperatures of 300 and 1500 K. It is found that the best choice is the radius of penta-coordinated aluminum, reproducing structural and vibrational properties of the compound in excellent agreement with experimentally observed properties.     

Application of the Stepwise-Regression Method in Calculating High-Temperature Ceramic Phases

Phase calculation for nonequilibrium multicomponent systems is attempted using the stepwise-regression method. The experimental data (the amount and composition of glassy phase in a system of Al₂O₃–SiO₂ ceramics as functions of the state of the original materials, the firing temperature, and the composition of the samples) are treated by the proposed method. The equations obtained are accurate in estimating the amount and composition of glassy phases in the system, showing that the stepwise-regression method is effective in phase calculation.     

覆炭载体及镍覆炭催化剂的积炭行为研究

用恒温热重法，以正己烷脱氢反应为指示反应，研究了γ-Al2O3覆炭载体（CCA0，γ-Al2O3，Ni/Al2O3及Ni/CCA催化剂的抗结焦性能；考察了覆炭原料，覆炭量对CCA的抗结焦性能的影响及积炭温度，正己烷浓度和覆炭量对Ni/CCA催化剂的抗结焦性能的影响。结果，CCA，Ni/CCA催化剂的抗结焦性能优于γ-Al2O3，Ni/Al2O3，以环烷烃为覆炭原料得到的CCA的抗结焦性能最好。     

氧化铝上吸附平衡与动力学的分形特性

在实验测定氧化铝吸附氮气的平衡和动力学过程的基础上 ,由平衡数据得到分形维数 ,对动力学结果分别用欧氏几何和分形几何的动力学模型进行处理 ,比较两种方法得到的扩散系数之间的差别。结果表明 :粉状氧化铝的分形维数为 2 .12 ;采用分形动力学模型得到的扩散系数同欧氏几何扩散模型的结果不一样 ,扩散系数不随浓度的变化而改变 ;而欧氏几何扩散模型中的扩散系数随浓度变化发生改变 ,且变化符合Darken关系     

Preparation and reaction mechanistic characterization of sol–gel indium/alumina catalysts developed for NO x reduction by propene in lean conditions

The impregnation and sol–gel preparation methods were investigated to develop high activity catalysts and understand the significance of the indium–aluminium interaction on aluminasupported indium catalysts in NO _x reduction with propene. Active In/alumina catalysts with a very high surface area (270 m²/g) and thermal stability were prepared in controlled conditions by sol–gel processing. When Al isopropoxide and In nitrate in ethyl glycol were used as precursors in aqua media, indium atoms were incorporated evenly distributed as a thermally stable form in the aluminium oxide lattice structure. In wet impregnation it was beneficial to use a certain excess of aqueous In solution (volumes of solution : pores = 2 : 1) to have the highest NO _x reduction activity. The catalyst containing dispersed Al on In oxide (58 wt% In, phaseequilibrium preparation method) showed activity at lower temperatures than any other In–Al oxide catalyst or pure In₂O₃. The adsorption of different reaction intermediates on alumina and stable In₂O₃ sites were detected by FTIR studies. In/alumina catalysts have active sites to oxidize NO to NO₂, partially oxidize HC, form the actual reductant which contains N–H or N–C bonding and react with NO to dinitrogen. The cooperation with indium and aluminium was evident even in the mechanical mixture of sol–gel prepared alumina (301 m²/g) and In₂O₃ powders (27 m²/g), where the probability for molecularscale intimate contact between indium and aluminium sites was very low (particle size 10–250 m). Shortlived gaseous intermediates and surface migration are the possible reasons for the high catalytic activities on the two physically separated active sites both necessary for the reaction sequence.     

Ultrasound as a Tool to Synthesize Nano-Sized Silica–Alumina Catalysts with Controlled Mesoporous Distribution by a Novel Sol–Gel Process

A novel sol–gel process is used to synthesize mesoporous silica–alumina catalysts with controlled pore size distribution without using templates or pore-regulating agents. The nitrogen sorption analysis shows that the synthesized materials have high specific surface area in the range 587–692 m²/g and similar mesoporous distribution within 2–11 nm. Ultrasound is applied to prepare precursor silica–alumina sol with narrow particle diameter distribution. By calculation, it is found that ultrasonic treatment is able to provide 22.94 kJ/mol energy, which is just in accordance with the weak bond's bonding energy. Based on the calculation result, it is proposed that the role of ultrasonic treatment followed by acid peptization is to provide energy to break down the weak bonds. After gelation, the regular and close packing of similar-sized sol particles is capable of formation of controlled-sized interstices which are the precursors of mesopores. Solid-state ²⁷Al MAS NMR and TEM are used to characterize the samples' structure and particle morphology. They show that most of the aluminum is located in the tetrahedral position in the present materials. According to TEM results, it is shown that the synthesized materials have spherical particles with size of about 15 nm.