Study of the alkylation of isobutane with n-butene over WO3/ZrO2 strong solid acid. 1. Effect of the preparation method, WO3 loading, and calcination temperature

A series of strong solid acids composed of WO3/ZrO2 were prepared. Their crystal structure, surface state, and acidity were determined by the methods of X-ray diffraction, thermal gravimetric and differential thermal analysis, temperature-programmed reduction, laser Raman, and acidity measurement. The results revealed that ZrO2 in WO3/ZrO2 existed mainly in the tetragonal phase, the addition of WO3 plays an important role in stabilizing the tetragonal phase of ZrO2, and all of the samples possessed large surface areas. WO3 in WO3/ZrO2 is mainly monolayer dispersed, and a small amount crystallized on the ZrO2 surface and partly reacted with ZrO2 to form the bond of Zr-O-W, acting as the strong solid acid center. The catalytic properties of WO3/ZrO2 strong solid;acids for alkylation of isobutane with butene at different conditions were investigated. They had a better reaction performance than other strong solid acids; a parallel relationship could be drawn between the catalytic activity and the acid amounts as well as the acidic strength of the catalysts.

Studies on the alkylation of isobutane with butene over WO3/ZrO2 strong solid acid (I) - Effect of preparation, load of WO3 and calcination temperature

A series of WO3/ZrO2 strong solid acid prepared under different conditions were studied. Their crystal structures, surface properties and acidities were determined by means of XRD, DTA-TG, H-2- TPR, Laser Raman and acidity measurements. The results revealed that ZrO2 in WO3/ZrO2 existed mainly in tetragonal phase, the addition of WO3 plays an important role to stabilize tetragonal phase of ZrO2 and thus the catalyst had a considerable surface area. WO3 in WO3/ZrO2 was dispersed and crystalized in WO3 crystalite on ZrO2 surface and partly reacted with ZrO2 to form the bond of Zr-O-W, which acts as the strong solid acid site. The catalytic properties of WO3/ZrO2 strong solid acid for alkylation of iso-butane with butene under the different conditions were investigated. They had a better reaction performance than other strong solid acids, a parallel relationship could be drawn between the catalytic activity and the amount of acid sites as well as the acidic strength of the catalysts.

基于窗口精细结构描述的岩体质量评价及力学参数综合优选

This thesis bases on horizontal research project “The research about the fine structure and mechanical parameters of abutment jointed rock mass of high arch dam on Jinping Ⅰ Hydropower Station, Yalong River” and “The research about the fine structure and mechanical parameters of the columnar basalt rock mass on Baihetan Hydropower Station, Jinsha River”. A rounded system about the fine structure description and rock mass classification is established. This research mainly contains six aspects as follow: (1) Methods about fine structure description of the window rock mass; (2) The window rock mass classification about the fine structure; (3) Model test study of intermittent joints; (4) Window rock mass strength theory; (5) Numerical experimentations about window rock mass; (6) The multi-source fusion of mechanical parameters based on Bayes principle. Variation of intact rock strength and joint conditions with the weathering and relaxation degree is studied through the description of window rock mass. And four principal parameters: intact rock point load strength, integration degree of window rock mass, joint conditions, and groundwater condition is selected to assess the window rock mass. Window rock mass is classified into three types using the results of window rock mass fine structure description combined with joints develop model. Scores about intact rock strength, integrality condition, divisional plane condition and groundwater conditions are given based on window rock mass fine structure description. Then quality evaluation about two different types of rock mass: general joint structure and columnar jointing structure are carried out to use this window rock mass classification system. Application results show that the window rock mass classification system is effective and applicable. Aimed at structural features of window structure of “the rock mass damaged by recessive fracture”, model tests and numerical models are designed about intermittent joints. By conducting model tests we get shear strength under different normal stress in integrated samples, through samples and intermittent joints samples. Also, the changing trends of shear strength in various connectivity rates are analyzed. We numerically simulate the entire process of direct shear tests by using PFC2D. In order to tally the stress-strain curve of numerical simulation with experimental tests about both integrated samples and through samples, we adjust mechanical factors between particles. Through adopting the same particle geometric parameter, the numerical sample of intermittent joints in different connective condition is re-built. At the same time, we endow the rock bridges and joints in testing samples with the fixed particle contacting parameters, and conduct a series of direct shear tests. Then the destructive process and mechanical parameters in both micro-prospective and macro-prospective are obtained. By synthesizing the results of numerical and sample tests and analyzing the evolutionary changes of stress and strain on intermittent joints plane, we conclude that the centralization of compressive stress on rock bridges increase the shear strength of it. We discuss the destructive mechanics of intermittent joints rock under direct shear condition, meanwhile, divide the whole shear process into five phases, which are elasticity phase, fracture initiation phase, peak value phase, after-peak phase and residual phase. In development of strength theory, the shear strength mechanisms of joint and rock bridge are analyzed respectively. In order to apply the deducted formulation conveniently in the real projects, a relationship between these formulations and Mohr-Coulomb hypothesis is built up. Some sets of numerical simulation methods, i.e. the distinct element method (UDEC) based on in-situ geology mapping are developed and introduced. The working methods about determining mechanical parameters of intact rock and joints in numerical model are studied. The operation process and analysis results are demonstrated detailed from the research on parameters of rock mass based on numerical test in the Jinping Ⅰ Hydropower Station and Baihetan Hydropower Station. By comparison，the advantages and disadvantages are discussed. Results about numerical simulation study show that we can get the shear strength mechanical parameters by changing the load conditions. The multi-source rock mass mechanical parameters can be fused by the Bayes theory, which are test value, empirical value and theoretical value. Then the value range and its confidence probability of different rock mass grade are induced and these data supports the reliability design.

边坡动力响应分析及应用研究

As a marginal subject, dynamic responses of slopes is not only an important problem of engineering geology (Geotechnical problem), but also of other subjects such as seismology, geophysics, seismic engineering and engineering seismic and so on. Owning to the gulf between different subjects, it is arduous to study dynamic responses of slopes and the study is far from ripeness. Studying on the dynamic responses of slopes is very important in theories as well as practices. Supported by hundreds of bibliographies, this paper systemically details the development process of this subject, introduces main means to analyze this subject, and then gives brief remarks to each means respectively. Engineering geology qualitative analysis is the base of slopes dynamic responses study. Because of complexity of geological conditions, engineering geology qualitative analysis is very important in slopes stability study, especially to rock slopes with complex engineering geology conditions. Based on research fruits of forerunners, this paper summarizes factors influencing slopes dynamic stability into five aspects as geology background, stratums, rock mass structure, and topography as well as hydrogeology condition. Based on rock mass structure controlling theory, engineering geology model of the slope is grouped into two typical classes, one is model with obvious controlling discontinuities, which includes horizontal bedded slope, bedding slope, anti-dip slope, slide as well as slope with base rock and weathered crust; the other is model without obvious controlling discontinuities, which includes homogeneous soil slope, joint rock mass slope. Study on slope failure mechanism under dynamic force, the paper concludes that there are two effects will appear in slope during strong earthquake, one is earthquake inertia force, the other is ultra pore pressure buildup. The two effects lead to failure of the slope. To different types of slope failure, the intensity of two effects acting on the slope is different too. To plastic flow failure, pore pressure buildup is dominant; to falling rock failure and toppling failure, earthquake inertia force is dominant in general. This paper briefly introduces the principle of Lagrangian element method. Through a lot of numerical simulations with FLAC3D, the paper comprehensively studies dynamic responses of slopes, and finds that: if the slope is low, displacement, velocity and acceleration are linear enlarging with elevation increasing in vertical direction; if the slope is high enough, displacement, velocity and acceleration are not linear with elevation any more, on the other hand, they fluctuate with certain rhythm. At the same time, the rhythm appears in the horizontal direction in the certain area near surface of the slope. The distribution form of isoline of displacement, velocity and acceleration in the section of the slope is remarkably affected by the slope angle. In the certain area near the slope surface, isoline of displacement, velocity and acceleration is parallel to the surface of the slope, in the mean time, the strike direction of the extreraum area is parallel to the surface of the slope too. Beyond this area, the isoline direction and the strike direction of the extremum area turn to horizontal with invariable distance. But the rhythm appearing or not has nothing to with the slope angle. The paper defines the high slope effect and the low slope effect of slopes dynamic responses, discusses the threshold height H^t of the dynamic high slope effect, and finds that AW is proportional to square root of the dynamic elastic moduli El P , at the same time, it is proportional to period Tof the dynamic input. Thus, the discriminant of H^t is achieved. The discriminant can tell us that to a slope, if its height is larger than one fifth of the wavelength, its response regular will be the dynamic high slope effect; on the other hand, its response regular will be the dynamic low slope effect. Based on these, the discriminant of different slopes taking on same response under the same dynamic input is put forward in this paper. At the same time, the paper studies distribution law of the rhythm extremum point of displacement, velocity and acceleration, and finds that there exists relationship of N = int among the slope height H, the number of the rhythm extremum VHlhro) point N and ffthre- Furthermore, the paper points out that if N^l, the response of the slope will be dynamic high slope effect; \fNabutment slope of Jinping hydropower station. The forecasting result is almost coincided with numerical simulation result. The Jinping hydropower station, located at the middle stream of Yalongjiang River and the west side of Jinpingdahewan, is the highest double-curvature arch dam planned in building in the world. However, deep fractures are well developed at the left abutment slope, so stability of the slope is a key engineering geological problem. The paper studies the dynamic stability of the slope. In the analysis, considering regional geology and regional seismology of the slope, combining with characteristics of the slope as well as the scale of the project, PGA(peak ground acceleration) of the site is decided (about 197.1cm/s2) by engineering seismology, and then the seismic input used in the slope dynamic analysis is determined. Comprehensive studies are carried out on the slope, especially to its deep fractures, and then the paper concludes that the deep fractures of slope are the result of the combination unloading effect of gravity and tectonic stress. At the same time, the failure model of the slope under dynamic input is attained. Based on these, the stability is comprehensively studied for section IV-IV with numerical simulation method as well as method putting forward in chapter 5. At last, the paper concludes that under dynamic input, the section will slide along fault f9, some deep fractures and fault/5 with certain permanent displacement, and this must be taken into consideration in the engineering.

Fabrication and testing of a doped lanthanum gallate electrolyte thin-film solid oxide fuel cell

A supported lanthanum gallate (LSGM) electrolyte thin-film solid oxide fuel cell with Ni-YSZ cermet anode and strontium-doped lanthanum manganite (LSM)-yttria stabilized zirconia (YSZ) composite cathode was, for the first time, fabricated and tested. The cell was prepared by an unconventional approach, in which an LSGM thin film (about 15 mum thick) was first deposited on a porous substrate such as a porous YSZ disk by a wet process and sintered at a high temperature (above 1400degrees C). NiO was then incorporated into the porous substrate by a carefully controlled impregnation process and fired at a much lower temperature. In this way, the severe reaction between LSGM and NiO at a high temperature, which is required for the full densification of LSGM film, can be avoided. A strontium-doped LaMnO3 (LSM)-YSZ composite cathode was screen printed on the surface of the LSGM film and then fired at 1250degrees C. The electrolyte resistances of the SOFC single cells fabricated by this approach are much lower compared to those of thick LSGM film supported cells. A maximum output power density of over 0.85 W/cm(2) at 800degreesC with H-2 as fuel and air as oxidant for a fabricated cell was achieved. (C) 2002 The Electrochemical Society.

Preparation of titania-based catalysts for formaldehyde photocatalytic oxidation from TiCl4 by the sol-gel method

Titania sols were prepared by acid hydrolysis of a TiCl4 precursor instead of titanium alkoxides. The effect of acid concentration on the particle size and stability of sol was investigated. Stable titania sols with mean particle size of 14 nm could be obtained when the H+/Ti molar ratio was 0.5. The titania sols were modified with Pt, SiO2, ZrO2, WO3 and MoO3 to prepare a series of modified catalysts, which were used for the photocatalytic oxidation of formaldehyde at 37 degreesC. They showed different photocatalytic activities due to the influence of the additives. Comparing with pure TiO2, the addition of silica or zirconia increased the photocatalytic activity, while the addition of Pt and MoO3 decreased the activity, and the addition Of WO3 had little effect on the activity. It is of great significance that the conversion of formaldehyde was increased up to 94% over the SiO2-TiO2 catalyst. The increased activity was partly due to higher surface area and porosity or smaller crystallite size. A comparison of our catalyst compositions with the literature in this field suggested that the difference in activity due to the addition of a second metal oxide maybe caused by the surface chemistry of the catalysts, particularly the acidity. (C) 2001 Elsevier Science B.V. All rights reserved.

Electrochemical performance of mixed ionic-electronic conducting oxides as anodes for solid oxide fuel cell

Mixed ionic-electronic conducting (MIEC) oxides, SrFeCo0.5Ox, SrCo0.8Fe0.2O3-delta and La0.6Sr0.4Fe0.8Co0.2O3-delta have been synthesized and prepared on yttria-stabilized zirconia as anodes for solid oxide fuel cells. Power output measurements show that the anodes composed of such kinds of oxides exhibit modest electrochemical activities to both H-2 and CH4 fuels, giving maximum power densities of around 0.1 W/cm(2) at 950 degrees C. Polarization and AC impedance measurements found that large activation overpotentials and ohmic resistance drops were the main causes for the relative inferior performance to the Ni-YSZ anode. While interlayered with an Ni-YSZ anode, a significant improvement in the electrochemical performance was observed. in particular, for the SrFeCo0.5Ox oxide interlayered Ni-YSZ anode, the maximum power output reaches 0.25 W/cm2 on CH,, exceeding those of both SrFeCo0.5Ox and the Ni-YSZ, as anodes alone. A synergetic effect of SrFeCo0.5Ox and the Ni-YSZ has been observed. Future work is needed to examine the long-term stability of MIEC oxide electrodes under a very reducing environment. (C) 1999 Elsevier Science B.V. All rights reserved.

Structure and impedance of ZrO2 doped with SC2O3 and CeO2

Scandia and ceria doped zirconia samples, with 10 mol% SC2O3 and different content of CeO2, were synthesized and characterized. The XRD results depict that the sintered samples have a cubic phase structure. However, Raman spectra show that besides the main cubic phase, a secondary phase is also present in the sintered samples. The addition of CeO2 can raise the content of the cubic phase, but the minor metastable tetragonal phase (t'-phase) exists even at the CeO2 content as high as 10 mol%. The near-UV Raman spectra indicate that the deformed tetragonal structure predominates at the grain boundary. The addition of CeO2 can reduce the impurity at grain boundary, and no impurity can be found by near-UV Raman spectroscopy at the grain boundary of the samples with high CeO2 content. The impedance measurements show that with the increase of CeO2 content, the impedance of grain boundary decreases and the bulk impedance increases. The low impedance of grain boundary can be attributed to the formation of a clean grain boundary upon CeO2 doping, and the increase of the bulk impedance is due to the blocking effect of the large Ce(IV) ions. (c) 2005 Elsevier B.V All rights reserved.

Energy-dependent in-situ small-angle x-ray scattering study of nano-ceramics

R Winter, D Le Messurier, CM Martin; Cryst Rev 12 (2006) 3 Sponsorship: EPSRC, CCLRC, Pilkington

Avaliação das propriedades mecânicas e microestrutura de um ionómero de vidro experimental reforçado com nano partículas

Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Medicina Dentária

Complicações microbiológicas na interface implante-pilar

Projeto de Pós-Graduação/Dissertação apresentado à Universidade Fernando Pessoa como parte dos requisitos para obtenção do grau de Mestre em Medicina Dentária

Steam reforming of model compounds and fast pyrolysis bio-oil on supported noble metal catalysts

The production of hydrogen by steam reforming of bio-oils obtained from the fast pyrolysis of biomass requires the development of efficient catalysts able to cope with the complex chemical nature of the reactant. The present work focuses on the use of noble metal-based catalysts for the steam reforming of a few model compounds and that of an actual bio-oil. The steam reforming of the model compounds was investigated in the temperature range 650-950 degrees C over Pt, Pd and Rh supported on alumina and a ceria-zirconia sample. The model compounds used were acetic acid, phenol, acetone and ethanol. The nature of the support appeared to play a significant role in the activity of these catalysts. The use of ceria-zirconia, a redox mixed oxide, lead to higher H-2 yields as compared to the case of the alumina-supported catalysts. The supported Rh and Pt catalysts were the most active for the steam reforming of these compounds, while Pd-based catalysts poorly performed. The activity of the promising Pt and Rh catalysts was also investigated for the steam reforming of a bio-oil obtained from beech wood fast pyrolysis. Temperatures close to, or higher than, 800 degrees C were required to achieve significant conversions to COx and H-2 (e.g., H-2 yields around 70%). The ceria-zirconia materials showed a higher activity than the corresponding alumina samples. A Pt/ceria-zirconia sample used for over 9 h showed essentially constant activity, while extensive carbonaceous deposits were observed on the quartz reactor walls from early time on stream. In the present case, no benefit was observed by adding a small amount of O-2 to the steam/bio-oil feed (autothermal reforming, ATR), probably partly due to the already high concentration of oxygen in the bio-oil composition. (c) 2005 Elsevier B.V. All rights reserved.

An investigation of catalysts for the on board synthesis of NH3. A possible route to low temperature NOx reduction for lean-burn engines

Platinum group metal catalysts have been investigated for the formation of NH3 from NO + H-2 at low temperatures in the absence and presence of CO. Although CO inhibits the formation of NH3, substantial amounts are still observed with a Pt catalyst. By combining Pt with a support (ceria-zirconia) that has low temperature NOx storage characteristics it has been shown in transient experiments that NH3 can be formed and stored in situ under rich conditions, and may then be used to reduce NOx under lean burn conditions.

The preparation and properties of coprecipitated Cu-Zr-Y and Cu-Zr-La catalysts used for the steam reforming of methanol

A series of Cu-zirconia catalysts containing various additives (Y2O3, La2O3, Al2O3 and CeO2) have been prepared by coprecipitation and their activities and stabilities under operating conditions have been obtained for the steam reforming of methanol. It has been found that an yttria-promoted catalyst containing 30 mol% Cu and 20 mol% of Y2O3 is not only very active but is also very stable under reaction conditions. The yttria appears to stabilise a high copper surface area and may also have a slight promotional effect on the copper. The results obtained with this material compare very favourably with data for the best catalysts reported in the literature. (C) 2007 Published by Elsevier B.V.