Partial oxidation of ethane to syngas in an oxygen-permeable membrane reactor

A perovskite-type oxide of Ba0.5Sr0.5Co0.8Fe0.2O3-delta (BSCFO) with mixed electronic and oxygen ionic conductivity at high temperatures was used as an oxygen-permeable membrane. A tubular membrane of BSCFO made by extrusion method has been used in the membrane reactor to exclusively transport oxygen for the partial oxidation of ethane (POE) to syngas with catalyst of LiLaNiO/gamma-Al2O3 at temperatures of 800-900 degreesC. After only 30 min POE reaction in the membrane reactor, the oxygen permeation flux reached at 8.2 ml cm(-2) min(-1). After that, the oxygen permeation flux increased slowly and it took 12 h to reach at 11.0 ml cm(-2) min(-1). SEM and EDS analysis showed that Sr and Ba segregations occurred on the used membrane surface exposed to air while Co slightly enriched on the membrane surface exposed to ethane. The oxygen permeation flux increased with increasing of concentration of C2H6, which was attributed to increasing of the driving force resulting from the more reducing conditions produced with an increase of concentration of C2H6 in the feed gas. The tubular membrane reactor was successfully operated for POE reaction at 875 degreesC for more than 100 h without failure, with ethane conversion of similar to 100%, CO selectivity of >91% and oxygen permeation fluxes of 10-11 ml cm(-2) min(-1). (C) 2002 Elsevier Science B.V. All rights reserved.

Performance of a mixed-conducting ceramic membrane reactor with high oxygen permeability for methane conversion

A mixed-conducting perovskite-type Ba0.5Sr0.5Co0.8Fe0.2O3-delta (BSCFO) ceramic membrane reactor with high oxygen permeability was applied for the activation of methane. The membrane reactor has intrinsic catalytic activities for methane conversion to ethane and ethylene. C-2 selectivity up to 40-70% was achieved, albeit that conversion rate were low, typically 0.5-3.5% at 800-900 degreesC with a 50% helium diluted methane inlet stream at a flow rate of 34 ml/min. Large amount of unreacted molecular oxygen was detected in the eluted gas and the oxygen permeation flux improved only slightly compared with that under non-reactive air/He experiments. The partial oxidation of methane to syngas in a BSCFO membrane reactor was also performed by packing LiLaNiO/gamma -Al2O3 with 10% Ni loading as the catalyst. At the initial stage, oxygen permeation flux, methane conversion and CO selectivity were closely related with the state of the catalyst. Less than 21 h was needed for the oxygen permeation flux to reach its steady state. 98.5% CH4 conversion, 93.0% CO selectivity and 10.45 ml/cm(2) min oxygen permeation flux were achieved under steady state at 850 degreesC. Methane conversion and oxygen permeation flux increased with increasing temperature, No fracture of the membrane reactor was observed during syngas production. However, H-2-TPR investigation demonstrated that the BSCFO was unstable under reducing atmosphere, yet the material was found to have excellent phase reversibility. A membrane reactor made from BSCFO was successfully operated for the POM reaction at 875 degreesC for more than 500h without failure, with a stable oxygen permeation flux of about 11.5 ml/cm(2) min. (C) 2001 Elsevier Science B.V. All rights reserved.

Application of heterogeneous catalysts prepared by mechanochemical synthesis

Mechanochemical synthesis has the potential to provide more sustainable preparative routes to catalysts than the current multistep solvent-based routes. In this review, the mechanochemical synthesis of catalysts is discussed, with emphasis placed on catalysts for environmental, energy and chemical synthesis applications. This includes the formation of mixed-metal oxides as well as the process of dispersing metals onto solid supports. In most cases the process involves no solvent. Encouragingly, there are several examples where the process is advantageous compared with the more normal solvent-based methods. This can be because of process cost or simplicity, or, notably, where it provides more active/selective catalysts than those made by conventional wet chemical methods. The need for greater, and more systematic, exploration of this currently unconventional approach to catalyst synthesis is highlighted.

Conduction mechanism in plasma polymerized aniline thin films

Electrical properties of ac plasma polymerized aniline thin films are investigated with a view of determining the dominant conduction mechanism. The current–voltage (I–V) characteristics in symmetric and asymmetric electrode configuration for polyaniline thin films in the thickness range from 1300 to 2000 A ° are investigated. From the studies on asymmetric electrode configuration, it is found that the dominant conduction mechanism in these films is of Schottky type

Na5(Ga4S)(GaS4)3·6H2O: a three-dimensional thiogallate containing a novel octahedral building block

The new thiogallate Na5(Ga4S)(GaS4)3·6H2O has been prepared solvothermally, using 3,5-dimethyl pyridine as a solvent, and characterised by powder and single crystal X-ray diffraction. This material, which exhibits a three-dimensional crystal structure, crystallises in the cubic space group View the MathML sourceF4¯3c (a = 17.557(4) Å). The crystal structure contains octahedral building blocks [Ga4S (GaS4)6]20−, linked into a three-dimensional network with a perovskite-type topology, and sodium hydrate clusters, [Na5(H2O)6]5+, filling the cavities in the [Ga4S(GaS4)6/2]5− framework. UV–Vis diffuse reflectance measurements indicate that this material is a wide band gap semiconductor, with a band gap of ca. 4.4 eV.

Structural and magnetic properties and hyperfine interaction in La(3.5)Ru(4)O(13) compound

Structural, magnetic and hyperfine interaction measurements have been carried out on the novel compound La(3.5)Ru(4)O(13) prepared under two different atmospheres (air and oxygen flow). This compound is formed in the orthorhombic structure (space group Pmmm, # 47). The coexistence of the triple-layered perovskite-type planes (quasi-2D structure) and the rutile-like slabs (1D structure) leads to interesting magnetic and electronic properties in this compound. The magnetic susceptibility of this system shows a peak at T similar to 47 K associated with antiferromagnetic interactions. The Curie-Weiss behaviour of the susceptibility provides an effective magnetic moment consistent with Ru ions in low-spin state. Perturbed angular correlation measurements carried out with (111)Cd probe in the temperature range 10-60 K reveal only quadrupole interactions and indicate the occurrence of structural distortions for T<40K. (C) 2009 Elsevier B.V. All rights reserved.

Structure and optical properties of [Ba(1-x)Y(2x/3)](Zr(0.25)Ti(0.75))O(3) powders

[Ba(1-x)Y(2x/3)](Zr(0.25)Ti(0.75))O(3) powders with different yttrium concentrations (x = 0, 0.025 and 0.05) were prepared by solid state reaction. These powders were analyzed by X-ray diffraction (XRD). Fourier transform Raman scattering (FT-RS), Fourier transform infrared (FT-IR) and X-ray absorption near-edge (XANES) spectroscopies. The optical properties were investigated by means of ultraviolet-visible (UV-vis) absorption spectroscopy and photoluminescence (PL) measurements. Even with the addition of yttrium, the XRD patterns revealed that all powders crystallize in a perovskite-type cubic structure. FT-RS and FT-IR spectra indicated that the presence of [YO(6)] clusters is able to change the interaction forces between the O-Ti-O and O-Zr-O bonds. XANES spectra were used to obtain information on the off-center Ti displacements or distortion effects on the [TiO(6)] clusters. The different optical band gap values estimated from UV-vis spectra suggested the existence of intermediary energy levels (shallow or deep holes) within the band gap. The PL measurements carried out with a 350 nm wavelength at room temperature showed that all powders present typical broad band emissions in the blue region. (C) 2010 Elsevier Masson SAS. All rights reserved.

Highly efficient LaCoO3 nanofibers catalysts for photocatalytic degradation of rhodamine B

Perovskite-type oxide LaCoO₃ nanofibers have been fabricated by electrospinning and subsequent calcination technology. Scanning electron microscopy, transmission electron microscopy, and X-ray diffraction were used to characterize the morphology and structure. Rhodamine B (RhB) was used to evaluate the ultraviolet photocatalytic activity of the as-prepared nanofibers. The effect of calcination temperature and pH of the reaction solution on the decolorization of RhB were investigated. Results showed that the samples calcined at 600°C exhibited the best photocatalytic activity at pH 4. Additionally, the recycling experiments confirmed the attractive stability of the catalysts.

Desenvolvimento de um ressoador retangular de fenda com múltiplas camadas de substrato e com utilização de material PBG para sistema de comunicação sem fio

In the globalized world modern telecommunications have assumed key role within the company, causing a large increase in demand for the wireless technology of communication, which has been happening in recent years have greatly increased the number of applications using this technology. Due to this demand, new materials are developed to enable new control mechanisms and propagation of electromagnetic waves. The research to develop new technologies for wireless communication presents a multidisciplinary study that covers from the new geometries for passive antennas, active up to the development of materials for devices that improve the performance at the frequency range of operation. Recently, planar antennas have attracted interest due to their characteristics and advantages when compared with other types of antennas. In the area of mobile communications the need for antennas of this type has become increasingly used, due to intensive development, which needs to operate in multifrequency antennas and broadband. The microstrip antennas have narrow bandwidth due to the dielectric losses generated by irradiation. Another limitation is the degradation of the radiation pattern due to the generation of surface waves in the substrate. Some techniques have been developed to minimize this limitation of bandwidth, such as the study of type materials PBG - Photonic Band Gap, to form the dielectric material. This work has as main objective the development project of a slot resonator with multiple layers and use the type PBG substrate, which carried out the optimization from the numerical analysis and then designed the device initially proposed for the band electromagnetic spectrum between 3-9 GHz, which basically includes the band S to X. Was used as the dielectric material RT/Duroid 5870 and RT/Duroid 6010.LM where both are laminated ceramic-filled PTFE dielectric constants 2.33 and 10.2, respectively. Through an experimental investigation was conducted an analysis of the simulated versus measured by observing the behavior of the radiation characteristics from the height variation of the dielectric multilayer substrates. We also used the LTT method resonators structures rectangular slot with multiple layers of material photonic PBG in order to obtain the resonance frequency and the entire theory involving the electromagnetic parameters of the structure under consideration. xviii The analysis developed in this work was performed using the method LTT - Transverse Transmission Line, in the field of Fourier transform that uses a component propagating in the y direction (transverse to the real direction of propagation z), thus treating the general equations of the fields electric and magnetic and function. The PBG theory is applied to obtain the relative permittivity of the polarizations for the sep photonic composite substrates material. The results are obtained with the commercial software Ansoft HFSS, used for accurate analysis of the electromagnetic behavior of the planar device under study through the Finite Element Method (FEM). Numerical computational results are presented in graphical form in two and three dimensions, playing in the parameters of return loss, frequency of radiation and radiation diagram, radiation efficiency and surface current for the device under study, and have as substrates, photonic materials and had been simulated in an appropriate computational tool. With respect to the planar device design study are presented in the simulated and measured results that show good agreement with measurements made. These results are mainly in the identification of resonance modes and determining the characteristics of the designed device, such as resonant frequency, return loss and radiation pattern

Ressoador retangular defenda com quatro camadas fotônicas

Recently, planar antennas have attracted interest due to its characteristics as well as the advantages they offer compared to other types of antennas. In the area of mobile communications the need for such antennas has become increasingly intense due to development, which requires antennas that operate in multifrequency and broadband. The microstrip antennas have narrow bandwidth due to losses in the dielectric caused by irradiation. Another limitation is the radiation pattern degradation due to generation of surface waves in the substrate. Some techniques are being developed to minimize this bandwidth limitation, as is the case in the study of type materials PBG - Photonic Band Gap, to compose the dielectric material. The analysis developed in this work were performed with use of the method LTT - Transverse Transmission Line, in the field of Fourier transform that uses a component propagating in the y direction (transerve real direction of propagation z), thus treating the general equations of the fields electric and magnetic fields as a functions of y E and Hy . This work has as main objective the method LTT structures resonator line slot with four layers of material photonic PBG, for obtaining the complex resonant frequency and efficiency of this structure. PBG theory is applied to obtain the relative permittivity for the substrate biases sep compounds photonic material. Numerical-computational results in graph form in two dimensions for all the analysis are presented for the proposed structures that have photonic materials, as substrates

Síntese de Fischer-Tropsch sobre perovskitas LayCu0,4Fe0,6O3

The current natural gas production of 52 Mm3d-1 and the large projects for its expansion has been setting new boundaries for the Brazilian industry of oil and gas. So far, one of the biggest challenges regards to the logistics for gas transportation from offshore fields. Therefore, the transformation of natural gas into gasoline, diesel and/or olefins via Fischer-Tropsch synthesis would be an alternative to this matter. In this work, the production of hydrocarbons by Fischer-Tropsch synthesis in a slurry reactor was investigated and a perovskite-type catalyst (LayCu0,4Fe0,6O3 ± d) was used with y varying from 0 to 1 on a molar basis. In addition, Nb2O5 support was also applied in order to observe the selectivity of the produced hydrocarbons by the Fischer-Tropsch process. It is shown that the hydrogen conversion was influenced by the support as well as the different phases of the samples. The kinetic results for the CO2 production suffered great influence with the introduction of the Nb2O5 support throughout the series of samples studied. The catalysts allowed obtaining welldefined cuts of hydrocarbons in the range of C1-C6 and C17-C28, and these results were clearly influenced by the support and the lanthanum content. The higher olefin/paraffin ratio obtained was 1.8 when using a non-supported perovskite with y equal to 0.8. This would indicate the suitability of using this material for the production of olefins

Morphological and Structural changes of CaxSr1-xTiO3 Powders Obtained by the Microwave-Assisted Hydrothermal Method

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Order-disorder degree of self-assembled clusters: Influence on photoluminescence emission and morphology of BaxSr1-xTiO3 nanocrystals

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Evaluation of the effect of the stoichiometric ratio of Ca/Cu on the electrical and microstructural properties of the CaCu3Ti4O12 polycrystalline system

Fundação de Amparo à Pesquisa do Estado de São Paulo (FAPESP)

Síntese e caracterização estrutural e magnética da ferrita de cálcio

The calcium ferrite (Ca2Fe2O5) has a perovskite-type structure with oxygen deficiency and is used as a chemical catalyst. With the advent of nanoscience and nanotechnology, methods of preparation, physical and chemical characterizations, and the technological applications of nanoparticles have attracted great scientific interest. Calcium nanostructured ferrites were produced via high-energy milling, with subsequent heat treatment. The milling products were characterized by X-ray diffraction, magnetization and Mössbauer spectroscopy. Samples of the type Ca2Fe2O5 were obtained from the CaCO3 and Fe2O3 powder precursors, which were mixed stoichiometrically and milled for 10h and thermally treated at 700ºC, 900ºC and 1100ºC. The Mössbauer spectra of the treated samples were adjusted three subespectros: calcium ferrite (octahedral and tetrahedral sites) and a paramagnetic component, related to very small particles of calcium ferrite, which are in a superparamagnetic state. For samples beats in an atmosphere of methyl alcohol, there is a significant increase in area associated with the paramagnetic component. Hysteresis curves obtained are characteristic of a weak ferromagnetic-like material