Conversão catalítica de clorometano em hidrocarbonetos

Amorphous silica-alumina and modified by incipient impregnation of iron, nickel, zinc and chromium were synthetized in oxide and metal state and evaluated as catalysts for the chloromethane conversion reaction. With known techniques their textural properties were determined and dynamics techniques in programmed temperature were used to find the acid properties of the materials. A thermodynamic model was used to determine the adsorption and desorption capacity of chloromethane. Two types of reactions were studied. Firstly the chloromethane was catalytically converted to hydrocarbons (T = 300 450 oC e m = 300 mg) in a fixed bed reactor with controlled pressure and flow. Secondly the deactivation of the unmodified support was studied (at 300 °C and m=250 g) in a micro-adsorver provided of gravimetric monitoring. The metal content (2,5%) and the chloromethane percent of the reagent mixture (10% chloromethane in nitrogen) were fixed for all the tests. From the results the chloromethane conversion and selectivity of the gaseous products (H2, CH4, C3 and C4) were determined as well as the energy of desorption (75,2 KJ/mol for Ni/Al2O3-SiO2 to 684 KJ/mol for the Zn/Al2O3-SiO2 catalyst) considering the desorption rate as a temperature function. The presence of a metal on the support showed to have an important significance in the chloromethane condensation. The oxide class catalyst presented a better performance toward the production of hydrocarbons. Especial mention to the ZnO/Al2O3-SiO2 that, in a gas phase basis, produced C3 83 % max. and C4 63% max., respectively, in the temperature of 450 oC and 20 hours on stream. Hydrogen was produced exclusively in the FeO/Al2O3-SiO2 catalysts (15 % max., T = 550 oC and 5,6 h on stream) and Ni/SiO2-Al2O3 (75 % max., T = 400 oC and 21,6 h on stream). All the catalysts produced methane (10 à 92 %), except for Ni/Al2O3-SiO2 and CrO/Al2O3-SiO2. In the deactivation study two models were proposed: The parallel model, where the product production competes with coke formation; and the sequential model, where the coke formation competes with the product desorption dessorption step. With the mass balance equations and the mechanism proposed six parameters were determined. Two kinetic parameters: the hydrocarbon formation constant, 8,46 10-4 min-1, the coke formation, 1,46 10-1 min-1; three thermodynamic constants (the global, 0,003, the chloromethane adsorption 0,417 bar-1, the hydrocarbon adsorption 2,266 bar-1), and the activity exponent of the coke formation (1,516). The model was reasonable well fitted and presented a satisfactory behavior in relation with the proposed mechanism

O FRAGMENTO EM TUTAMÉIA E NO LIVRO SOBRE NADA

This study is connected to the research line Poéticas da Modernidade e Pós -Modernidade, of the Programa de Pós-Graduação em Estudos da Linguagem, in the subarea: Comparative Literature - CCHLA/UFRN. Its main goal is to see fragmentation of writing as an aesthetic resource highlighted in the work of Tutaméia by Guimarães Rosa (1908-1967), and in Livro sobre nada by Manoel de Barros (1916). We undertake as a starting point the view that these works are allegorical expressions. We have as a basis the German philosopher Walter Benjamin (1984) conception about baroque allegory, that uses amorphous fragment and constitutes a dialectical expression, in which each person, each thing, each relation, may mean any other one (1984, p. 196). We see the stylistic features as used by Guimarães Rosa and by Manoel de Barros in the construction of poetics capable of breaking the boundaries between artistic genres, literary and discursive, adding oral, musical and plastic elements to writing. We also analyze the development of fragmentary poetics, in which the voice of the narrator/lyrical I, the characters, space, plot and time exhibit the fragment as a factor that contributes to the great ambiguity of the two works and to create a new language, performative and vibrant, rich in alluring images, allegories

Aspectos dinâmicos da água versus álcool e acetona por técnicas de congelamento

Water still represents, on its critical properties and phase transitions, a problem of current scientific interest, as a consequence of the countless open questions and of the inadequacy of the existent theoretical models, mainly related to the different solid and liquid phases that this substance possesses. For example, there are 13 known crystalline forms of water, and also amorphous phases. One of them, the amorphous ice of very high density (VHDA), was just recently observed. Other example is the anomalous behavior in the macroscopic density, which presents a maximum at the temperature of 277 K. In order to experimentally investigate the behavior of one of the liquid-solid phase transitions, the anomaly in its density and also the metastability, we used three different cooling techniques and, as comparison systems, we made use of the solvents: acetone and ethyl alcohol. The first studied cooling system employ a Peltier plate, a device recently developed, which makes use of small cubes made up of semiconductors to change heat among two surfaces; the second system is a commercial refrigerator, similar to the residential ones. Finally, the liquid nitrogen technique, which is used to refrigerate the samples in a container, in two ways: a very fast and other one, almost static. In those three systems, three Beckers of aluminum were used (with a volume of 80 ml, each), containing water, alcohol and acetone. They were closed and maintained at atmospheric pressure. Inside of each Becker were installed three thermocouples, disposed along the vertical axis of the Beckers, one close to the inferior surface, other to the medium level and the last one close the superior surface. A system of data acquisition was built via virtual instrumentation using as a central equipment a Data-Acquisition board. The temperature data were collected by the three thermocouples in the three Beckers, simultaneously, in function of freezing time. We will present the behavior of temperature versus freezing time for the three substances. The results show the characterization of the transitions of the liquid

Deposição de A/N por sputtering não reativo

In this work we deposit via non-reactive magnetron sputtering of radio-frequency nanofilmes of nitreto of aluminum(AlN). The nanofilms aluminum nitride are semiconductors materials with high thermal conductivity, high melting point, piezoelectricity and wide band gap (6, 2 eV) with hexagonal wurtzite crystal structure, belonging to the group of new materials called III-V nitrides in which together with the gallium nitride and indium nitride have attracted much interest because they have physical and chemical properties relevant to new technological applications, mainly in microelectronic and optoelectronic devices. Three groups were deposited with thicknesses nanofilms time dependent on two substrates (glass and silicon) at a temperature of 25 ° C. The nanofilms AlN were characterized using three techniques, X-ray diffraction, Raman spectroscopy and atomic force microscopy (AFM), examined the morphology of these. Through the analysis of X-rays get the thickness of each sample with its corresponding deposition rate. The analysis of X-rays also revealed that nanofilms are not crystalline, showing the amorphous character of the samples. The results obtained by the technique, atomic force microscopy (AFM) agree with those obtained using the technique of X-rays. Characterization by Raman spectroscopy revealed the existence of active modes characteristic of AlN in the samples

Propriedades magnéticas quase-estáticas de filmes ferromagnéticos amorfos de FeCuNbSiB

Today, one of the topics that attracts interest of the scientific community is the understanding of magnetic properties of magnetic systems with reduced dimensions, in particular, ferromagnetic thin films. In this case, the comprehension and control of these properties, as well as the development of routes to obtain them, are crucial issues in many aspects of current and future technologies for storage and transmission of information in the electro-electronic industry. There are several materials that exhibit soft magnetic properties, and we highlight the amorphous alloys and that ones obtained by partial crystallization, so-called nanocrystalline materials. The production of these alloys as magnetic ribbons is very common in scientific and technological area, but there are just a few works related to the production of these alloys as thin films. In this work, we studied the quasi-static magnetic properties of ferromagnetic thin films based on FeCuNbSiB in a wide range of thicknesses, from 20 to 500 nm, produced by sputtering. In particular, after the structural characterization performed via X-ray diffraction, the magnetic properties of the sets of samples were investigated using experimental magnetization curve, obtained using a vibrating sample magnetometer, as well as through theoretical curves obtained by theoretical modeling and numerical computation. The modeling process is based on the Stoner Wohlfarth model applied to three dimensions, and adds some energy terms, using as reference experimental results of magnetization. In this case, from the comparison between theoretical and experimental results and the analysis of the constant anisotropy behavior as a function of film thickness, we aim to obtain further information on the magnetization process of the samples, to identify routes for the production of thin films and develop a theoretical to films to use it, in the future, in the obtainment of the theoretical curves of some magnetic measurements, such as magnetoimpedance and magnetoresistance

Obtenção de biodiesel através da transesterificação do óleo de farelo de arroz utilizando KI/Al2O3

This study proposes to find a biodiesel through transesterification of rice bran oil with KI/Al2O3 checking the influence of two types of alumina (Amorphous and Crystalline) for conversion into methyl esters. The catalyst was synthesized by the wet impregnation method. Adding 30 mL of 35% KI(aq.) in 10 g of alumina, under stirring at 80 °C for 3 hours. The reaction conditions used in this study were optimized, with a molar ratio methanol:oil of 15:1, 8 h of reaction time and reflux temperature. The catalyst amount was varied in the range of 1 to 5 % wt. The solid catalysts materials were analyzed by: x-ray diffraction (XRD), thermogravimetry (TG), N2 adsorption/desorption, scanning electron microscopy (SEM) and basicity, for the identification of its structure and composition, verifying the presence of basic sites. The results showed that Al2O3(A) presents an amorphous structure, high surface area and a better catalytic activity, in relation to the catalyst synthesized with Al2O3(C) support that proved to have a more crystalline structure, having as well, a lesser surface area, enabling difficulties for the incorporation of active sites. The obtained biodiesel with 5% wt. KI/Al2O3(A) presented physicochemical properties within the standards specified by the Resolution No 7/2008 ANP and obtained the best reaction yield with 95.2%, according to quantitative measurement from the TG, which showed 96.2% conversion into methyl esters. It was furthermore found that with the increasing amount of the quantity of the catalyst in the reaction, there was also an increase in the ester content obtained. The specific mass and the kinematic viscosity were reduced with the increase of the amount of quantity of the catalyst, indicating an increase in the conversion of triglycerides

Eficiência do processo de obtenção do biodiesel de girassol usando o catalisador KNO3/Al2O3

It is known that the head office world energetics is leaning in the fossil fuels. However, the world panorama is changing quickly, for linked reasons to three of the humanity's great concerns in that century beginning: environment, global economy and energy. The biodiesel production is based on the transesterificação of vegetable oils or animal fats, using catalysts homogeneous or heterogeneous. The process of heterogeneous transesterificação presents lower conversions in comparison with the homogeneous, however, it doesn't present corrosion problems and it reduces to the occurrence of parallel reactions as saponification. In this sense, this work has for purpose the synthesis of a heterogeneous catalyst, KNO3/Al2O3, that soon afterwards was used in the reaction of transesterificação of the oil of the Helianthus annuus L. (sunflower). The solid materials (it supports and catalyst) they were analyzed by diffraction of ray-X (XRD) and electronic microscope of sweeping (MEV). After the analysis of Al2O3, a structure monophase amorphous tetragonal was verified, with characteristic patterns of that material, what could not be visualized in the difratograma of the catalyst. The biodiesel obtained with 4% wt. of KNO3/Al2O3 it was what obtained a better cinematic viscosity 8,3 mm2/s, comparing with the norms of ANP, and it also presented the best conversion tax in ethyl ésteres, in accordance with the quantitative measure starting from TG, that was of 60%. While the biodiesel with 6% wt. and with 8% wt. of KNO3/Al2O3 it was it that no transesterificou, because it was observed in the analysis termogravimétrica of those two materials, a single thermal event, that it corresponds the decomposition or volatilization of the triglycerides

Estudo de titanatos nanoestruturados obtidos por tratamento hidrotérmico de óxido de titânio em meio alcalino

TiTanate NanoTubes (TTNT) were synthesized by hydrothermal alkali treatment of TiO2 anatase followed by repeated washings with distinct degrees of proton exchange. TTNT samples with different sodium contents were characterized, as synthesized and after heattreatment (200-800ºC), by X-ray diffraction, scanning and transmission electron microscopy, electron diffraction, thermal analysis, nitrogen adsorption and spectroscopic techniques like FTIR and UV-Vis diffuse reflectance. It was demonstrated that TTNTs consist of trititanate structure with general formula NaxH2−xTi3O7·nH2O, retaining interlayer water in its multiwalled structure. The removal of sodium reduces the amount of water and contracts the interlayer space leading, combined with other factors, to increased specific surface area and mesopore volume. TTNTs are mesoporous materials with two main contributions: pores smaller than 10 nm due to the inner volume of nanotubes and larger pores within 5-60 nm attributed to the interparticles space. Chemical composition and crystal structure of TTNTs do not depend on the average crystal size of the precursor TiO2-anatase, but this parameter affects significantly the morphology and textural properties of the nanostructured product. Such dependence has been rationalized using a dissolution-recrystallization mechanism, which takes into account the dissolution rate of the starting anatase and its influence on the relative rates of growth and curving of intermediate nanosheets. The thermal stability of TTNT is defined by the sodium content and in a lower extent by the crystallinity of the starting anatase. It has been demonstrated that after losing interlayer water within the range 100-200ºC, TTNT transforms, at least partially, into an intermediate hexatitanate NaxH2−xTi6O13 still retaining the nanotubular morphology. Further thermal transformation of the nanostructured tri- and hexatitanates occurs at higher or lower temperature and follows different routes depending on the sodium content in the structure. At high sodium load (water washed samples) they sinter and grow towards bigger crystals of Na2Ti3O7 and Na2Ti6O13 in the form of rods and ribbons. In contrast, protonated TTNTs evolve to nanotubes of TiO2(B), which easily convert to anatase nanorods above 400ºC. Besides hydroxyls and Lewis acidity typical of titanium oxides, TTNTs show a small contribution of protonic acidity capable of coordinating with pyridine at 150ºC, which is lost after calcination and conversion into anatase. The isoeletric point of TTNTs was measured within the range 2.5-4.0, indicating behavior of a weak acid. Despite displaying semiconductor characteristics exhibiting typical absorption in the UV-Vis spectrum with estimated bandgap energy slightly higher than that of its TiO2 precursor, TTNTs showed very low performance in the photocatalytic degradation of cationic and anionic dyes. It was concluded that the basic reason resides in its layered titanate structure, which in comparison with the TiO2 form would be more prone to the so undesired electron-hole pair recombination, thus inhibiting the photooxidation reactions. After calcination of the protonated TTNT into anatase nanorods, the photocatalytic activity improved but not to the same level as that exhibited by its precursor anatase

Síntese e Caracterização de Titanatos de Cobalto e Níquel, dopados com Praseodímio, obtidos a partir da decomposição de Nitrilotriacetatos

In recent years, studies about the physicochemical properties of mixed oxides, call attention of the scientific community, properties like as piezoelectricity, photoluminescence, or applications as catalysts, arise in these compounds, when their chemical compositions are modified, in this context some routes are employed in the synthesis of these materials, among which can be cited these methods: ceramic, combustion, co-precipitation, Pechini or polymeric precursor method, hydrothermal, sol-gel; these routes are divided into traditional routes or chemical routes. In this work were synthesized oxides with variable composition, from the thermal decomposition of titanium, cobalt, nickel and praseodymium nitrilotriacetates. The nitrilotriacetates were characterized by IR Spectroscopy (FTIR), Thermogravimetric (TG/ DTG) and Differential Scanning Calorimetry (DSC), while oxides have been characterized by X-ray diffraction (XRD), Spectrofluorimetry and IR Spectroscopy (FTIR). From FTIR data, it was demonstrated that the displacement of the band corresponding to the carboxylate group (νCOOH) at 1712 cm-1, present in nitrilotriacetic acid (H3NTA), for 1680-1545 cm-1, these stretches are characteristics of coordinated nitrilotriacetates, By thermal analysis (TG/DTG /DSC), it was suggested, that in an oxidizing atmosphere (air) oxides are obtained at lower temperatures than in an inert atmosphere N2(g). By results from X-ray Diffraction (XRD), it was determinated that the oxides are crystalline and the predominant phases obtained are summarized titanate phases rutile and ilmenite. By fluorimetry was observed that the intensity of emission bands are directly proportional to the concentration of ions Ni2+, Co2+ and Pr3+, and IR spectroscopy (FTIR) from oxides, demonstrated the disappearance of characteristic bands by nitrilotriacetates, determining the complete decomposition of the nitrilotriacetates in oxides

Obtenção e caracterização físico-química de blendas poliméricas, baseadas em POE e PMMA, dopadas com dióxido de titânio

The study of polymer blends has been an alternative method in the search field of new materials for obtaining materials with improved properties. In this work blends of poly(methyl methacrylate) (PMMA) and poly(ethylene oxide) (PEO) doped with titanium dioxide (TiO2) were studied. The PEO is a polymer semicrystalline structure varying between, 70 and 84% crystallinity, while the PMMA exhibits behavior amorphous in their structure. The use of TiO2 is related to corrosion-resistant of titanium as well as good heat transfer and other characteristics. The study of these polymer blends doped TiO2 gives the properties junction organic (polymer) and inorganic (oxide) which leads to modification of the properties of the resultant material. The blends were doped TiO2 (POE/PMMA/TiO2) in different proportions of the PMMA with the PEO and TiO2 fixed. The ratios were: 90/10/0,1; 85/15/0, 1; 80/20/0,1, 75/25/0,1 and 70/30/0,1. The resulting material was obtained in powder form and being characterized by Fourier Transformed Infrared (FTIR) Spectroscopy, Scanning Electron Microscopy (SEM), X-Ray Diffraction (XRD), Thermogravimetric Analysis (TGA) and Electrochemical Impedance Spectroscopy (EIS). The infrared spectra (IR) for the blends in different ratios showed a band at 1744 cm-1, characteristic of the C=O stretching, which increases in intensity with increasing PMMA composition, while in the spectrum of pure PEO this band is absent. This may suggest that the interaction is occurring between the polymers. In the micrographs of the blends also observed change in their surfaces with variation of the composition of PMMA, contributing to the change of the electrical properties of the material. The EIS data showed that the material exhibited conductivity of the order of 10-6 S.cm-1. The blend in the ratio B2(85/15/0, 1) showed better conductivity, σ = 1.56 x 10-6 S.cm-1. It was observed that the diffusion coefficient for the blends, B5(70/30/0, 1) was the largest, 1.07 x 10-6 m2.s-1. The XRD data showing that, with the variation in the composition of the PMMA blend crystallinity of the material is decreased reaching a minimum B3(80/20/0,1), and then increases again. Thermal analysis suggests that blends made from the material obtained can be applied at room temperature

Confecção e caracterização físico-química de filmes compósitos autossustentáveis NaAlg-TiO2-WO3

A new self-sustainable film was prepared through the sol-gel modified method, previously employed in our research group; sodium alginate was used as the polymer matrix, along with plasticizer glycerol, doped with titanium dioxide (TiO2) and tungsten trioxide (WO3). By varying WO3 concentration (0,8, 1,6, 2,4 and 3,2 μmol) and keeping TiO2 concentration constant (059 mmol), it was possible to study the contribution of these oxides on the obtained films morphological and electrical properties. Self-sustainable films have analyzed by Fourier Transform Infrared Spectroscopy (FTIR), X-Ray Diffraction (XDR), Scanning Electron Microscope (SEM), Energy Dispersive X-ray Spectroscopy (EDS) and Electrochemical Impedance Spectroscopy (EIS). By the IR specters, it was possible identify the TiO2, and posteriorly WO3, addition has provided dislocation of alginate characteristics bands to smaller vibrations frequencies indicating an electrostatic interaction between the oxides and the polymer matrix. Diffractograms show predominance of the amorphous phase in the films. SEM, along with EDX, analysis revealed self-sustainable films showed surface with no cracks and relative dispersion of the oxides throughout the polymer matrix. From Impedance analysis, it was observe increasing WO3 concentration to 2,4 μmol provided a reduction of films resistive properties and consequent improvement of conductive properties

Obtenção e caracterização do sistema compósito alginato de sódio-dióxido de titânio em formas de pó e de membrana

The alginates are copolymers of 1→4-linked β-D-mannuronic acid (M) and α-Lguluronic acid (G) residues that are arranjed in a block structure along a linear chain. Titanium dioxide, TiO2, is a ceramic material and can exist in three distinct crystallography forms: anatase, brookite and rutile. composites of organic and inorganic materials have better properties than the components alone. Thus, this study aims to synthesize, characterize and analyze the composite NaAlg-TiO2 in the form of powder and film. The synthesis of composite powders was performed using the sol-gel process and obtain the composite film was performed using the slow evaporation process, then the composites were analyzed by infrared spectroscopy, fluorescence x ray, thermal analysis, attenuated total reflection (ATR), x ray diffraction and impedance spectroscopy. The X ray diffraction patterns of composite powders show that with increasing calcination temperature, there were no complete transition of rutile-anatase crystalline phase, since at all temperatures studied (300, 500, 700, 900 and 1100ºC) were observed peaks of anatase phase. Thermal analysis shows that at 400°C caused the decomposition of sodium alginate in sodium carbonate and above 600°C, we observe an exothermic peak related to the decomposition of sodium carbonate and in the presence of titanium dioxide becomes sodium titanate. The XRD results confirm the formation of sodium carbonate at 700ºC and the formation sodium titanate in the temperature range 900-1100ºC. The sodium titanate influenced the electrical properties of the material, because with increasing temperature there was a decrease in conductivity, probably due to the creation of Ti vacancies, since the sodium can induce the reduction of surface Ti4+ ions into Ti3+ species. The infrared spectra of the composites in the form of powder and film showed a small shift in the bands compared to the spectrum of pure alginate, indicating that these shifts, even small ones, have evidence of miscibility between the polymer and ceramic material

Utilização de rejeitos de Caulins na Síntese de Zeólita A

Three studies were performed using tailings kaolin for the synthesis of zeolite A. The first synthesis of zeolite A was performed using a kaolin waste generated from the beneficiation of kaolin for paper production process was studied. The kaolin waste was thermally activated at a temperature range of 550-800°C. For comparison was performed a synthesis pattern of Zeolite A(procedure IZA). The prepared materials were characterized by 27Al MAS NMR, X-ray diffraction and scanning electron microscopy with microprobe rays. The pre-tramento proved to be the most appropriate and suitable temperatures are between 600 and 700°C. Observed the formation of zeolite A in all materials, reaching 52% crystallinity, and the presence of phase sodalite and amorphous material. The second study was the use of a highly reactive metakaolin originating from the Jari region in the synthesis of zeolite A by a new method of hydrothermal synthesis. The zeolite is obtained pure and highly crystalline employing the Jari kaolin calcined at 600 ° C for 2h when the transformation to metakaolin occurs. Get to zeolite phase A at 4pm. The best crystallization time was of 24 h afforded a crystallinity of 67.9%. The third study was the evaluation of the NaOH / metakaolin and crystallization time on the synthesis of zeolite NaA from a sample of kaolin waste, named Kaolin Coverage. The experiments were performed using statistical design (axial points) and rejoinder the center point. The samples were characterized by X-ray diffraction (XRD), scanning microscopic analysis and chemical analysis using an EPMA microprobe. The results showed that a relationship exists between the amount of NaOH added and the crystallization time. The experiment performed using the lowest ratio NaOH / metakaolin (0.5) and shorter (4 h) produced an amorphous material. The increase ratio of NaOH / metakaolin and crystallization time leads to formation of a more crystalline NaA phase, but the presence of phase with sodalite as impurities