Estudo das propriedades termofísicas com variação da expansibilidade de compósito desenvolvido com matriz PUR-NOP e carga funcional de argilomineral

In this study were conducted experimental procedures for determination of variation of the expandability of rigid polyurethane foam (PUR) from a natural oil polyol (NOP), specifically the Castor oil plant, Ricinus communis, pure and additions of the vermiculite in phase dispersed in different percentage within a range from 0% to 20%, mass replacement. From the information acquired, were defined the parameters for production of bodies of test, plates obtained through controlled expansion, with the final volume fixed. Initially, the plates were subjected to thermal performance tests and evaluated the temperature profiles, to later be extracted samples duly prepared in accordance with the conditions required for each test. Was proceeded then the measurement of the coefficient of thermal conductivity, volumetric capacity heat and thermal diffusivity. The findings values were compared with the results obtained in the tests of thermal performance, contributing to validation of the same. Ultimately, it was investigated the influence that changes in physical-chemical structure of the material had exerted on the variation of thermophysical quantities through gas pycnometry, scanning electron microscopy (SEM) combined with energy dispersive X-ray fluorescence spectroscopy (EDXRF), infrared spectroscopy using Fourier transform (FTIR), thermogravimetric analysis (TGA) and differential thermal analysis (DTA). Based on the results obtained was possible to demonstrate that all load percentage analyzed promoted an increase in the potential expansion (PE) of the resin. In production of the plates, the composites with density near at the free expansion presented high contraction during the cure, being the of higher density adopted as definitive standard. In the thermal performance tests, the heating and cooling curves of the different composites had presented symmetry and values very close for lines of the temperature. The results obtained for the thermophysical properties of composites, showed little difference in respect of pure foam. The percentage of open pores and irregularities in the morphology of the composites were proportionate to the increment of vermiculite. In the interaction between the matrix and dispersed phase, there were no chemical transformations in the region of interface and new compounds were not generated. The composites of PUR-NOP and vermiculite presented thermal insulating properties near the foam pure and percentage significantly less plastic in its composition, to the formulation with 10% of load

Estudo do aproveitamento de resíduo de gesso como carga para compósito com matriz de resina expansiva de mamona

In the execution of civil engineering works, either by wasting during the coating of wall or demolition of gypsum walls, the generation of the gypsum waste involves serious environmental concerns. These concerns are increased by the high demand of this raw material in the sector and by the difficulties of proper disposal byproduct generated. In the search for alternatives to minimize this problem, many research works are being conducted, giving emphasis in using gypsum waste as fillers in composites materials in order to improve the acoustic, thermal and mechanical performances. Through empirical testing, it was observed that the crystallization water contained in the residue (CaSO4.2H2O) could act like primary agent in the expanding of the polyurethane foam. Considering that polyurethane produced from vegetable oils are biodegradable synthetic polymers and that are admittedly to represent an alternative to petrochemical synthetic polyurethane, this research consist an analysis of the thermal behavior of a composite whose matrix obtained from a resin derived from the expansive castor oil seed, with loads of 4%, 8%, 12% and 16% of gypsum waste replacing to the polyol prepolymer blend. Contributors to this analysis: a characterization of the raw material through analysis of spectroscopy by Fourier transform infrared (FTIR), chemical analysis by X-Ray Fluorescence (XRF) and mineralogical analysis by X Ray Diffraction (XRD), complemented by thermo gravimetric analysis (TGA). In order to evaluate the thermo physical properties and thermal behavior of the composites manufactured in die closed with expansion contained, were also carried tests to determine the percentage of open pore volume using a gas pycnometer, scanning electronic microscopy (SEM), in addition to testing of flammability and the resistance to contact with hot surfaces. Through the analysis of the results, it appears that it is possible to produce a new material, which few changes in their thermo physical properties and thermal performance, promotes significant changes and attractive to the environment

Obtenção de compósitos cerâmicos reforçados com carbetos refratários a partir de precursores poliméricos

In this work, were produced ceramic matrix composites based in SiCxOy e Al2O3 reinforced with NbC, by hydrosilylation reaction between D4Vi and poly(methylhydrosiloxane) mixtured with Al2O3 as inert filler, Nb and Al as reactive filler. After the mixture and compactation at 80ºC (warm pressing), the samples were pyrolised at 1200 and 1400ºC and infiltred with ICZ and LZSA respectively, and thermically, physical and structurally characterized by X-ray diffraction, density and porosity, flexural mechanical strength and fracture surface by scanning electron microscopy. The yield ceramic obtained after pyrolysis for studied composition at 1200ºC was 95%. The obtained phases had been identified as being Al3Nb, NbSi2 and NbC. The composite material presented apparent porosity varying of 15 up to 32% and mechanical flexural strenght of 32 up to 37,5MPa. After the fracture surface analysis, were observed a phases homogeneous dispersion, with some domains of amorphous and crystalline aspect. The samples that were submitted the infiltration cycle presented a layer next the surface with reduced pores number in relation to the total volume

Obtenção e caracterização de um compósito de poliuretano de mamona e pó de vidro para aplicações em insolantes térmicos

Thermal insulation is used to protect the heated or cooled surfaces by the low thermal conductivity materials. The rigid ricin polyurethane foams (PURM) are used for thermal insulation and depend on the type and concentration of blowing agent. Obtaining PURM occurs by the use of polyol, silicone, catalyst and blowing agent are pre -mixed, reacting with the isocyanate. The glass is reusable, returnable and recyclable heat insulating material, whose time of heat dissipation determines the degree of relaxation of its structure; and viscosity determines the conditions for fusion, operating temperatures, annealing, etc. The production of PURM composites with waste glass powder (PV) represents economical and renewable actions of manufacturing of thermal insulating materials. Based on these aspects, the study aimed to produce and characterize the PURM composites with PV, whose the mass percentages were 5, 10, 20, 30, 40 and 50 wt%. PURM was obtained commercially, while the PV was recycled from the tailings of the stoning process of a glassmaking; when the refining process was applied to obtain micrometer particles. The PURM + PV composites were studied taking into account the standard sample of pure PURM and the influence of the percentage of PV in this PURM matrix. The results of the chemical, physical and morphological characterization were discussed taking into account the difference in the microstructural morphology of the PURM+PV composites and the pure PURM, as well the results of the physicochemical, mechanical e thermophysical tests by values obtained of density, hardness, compressive strength, specific heat, thermal conductivity and diffusivity. In general, the structure of pure PURM showed large, elongated and regular pores, while PURM+PV composites showed irregular, small and rounded pores with shapeless cells. This may have contributed to reducing their mechanical strength, especially for PURM - PV50. The hardness and density were found to have a proportional relationship with the PV content on PURM matrix. The specific heat, thermal diffusivity and thermal conductivity showed proportional relationship to each other. So, this has been realized that the increasing the PV content on PURM matrix resulted in the rise of diffusivity and thermal conductivity and the decrease of the specific heat. However, the values obtained by the PURM composites were similar the values of pure PURM, mainly the PURM-PV5 and PURM-PV10. Therefore, these composites can be applied like thermal insulator; furthermore, their use could reduce the production costs and to preserve the environment

Nano emulsões aplicadas a recuperação avançada de petróleo

A exploração de petróleo está a cada dia em circunstâncias mais adversas, no que diz respeito à profundidade dos poços como também, em relação à fluidez do óleo. Os reservatórios de descobertas recentes não possuem energia própria para produzir ou os métodos convencionais não são eficientes para fazer com que esses reservatórios tenham uma vida útil elevada, devido a alterações das propriedades físico-químicas, como por exemplo a viscosidade, que torna o deslocamento do óleo pelos poros do reservatório até a superfície cada vez mais complexo. O presente trabalho tem como objetivo estudar a preparação, caracterização e a utilização de nanoemulsões obtidas a partir de sistemas microemulsionados, com e sem a presença de polímero. Esses sistemas foram aplicados como método químico de recuperação de petróleo, com o intuito de obter maior eficiência de volume de óleo deslocado. O interesse por esse tipo de sistema existe devido a sua baixa tensão superficial, o pequeno tamanho de gotícula e, principalmente, pelo baixo percentual de matéria ativa presente em sua composição. Os ensaios realizados para caracterizar esses sistemas foram: aspecto físico, medidas de tamanho de gotícula, índice de polidispersão, tensão superficial, pH e condutividade. Ensaios de reologia e de adsorção dos sistemas foram realizados com o objetivo de avaliar sua influencia na recuperação de petróleo. Os ensaios de recuperação foram realizados em um equipamento que simula as condições de um reservatório de petróleo, utilizando plugs de rocha arenito Botucatu. Esses plugs foram saturados com salmoura (KCl 2%) e com petróleo proveniente da Bacia Potiguar do campo de Ubarana. Após essas etapas foi realizada a recuperação convencional utilizando a salmoura e, por último, foi injetada, a nanoemulsão, como método de recuperação avançada. Os sistemas obtidos variaram de 0% à 0,4% de polímero. Os ensaios de tamanhos de partícula obtiveram como resultado uma variação de 9,22 a 14,8 nm, caracterizando que as nanoemulsões estão dentro da faixa de tamanho inerente a esse tipo de sistema. Para ensaios de tensão superficial os valores foram na faixa de 33,6 a 39,7 dynas/cm, valores semelhantes à microemulsões e bem abaixo da tensão superficial da água. Os resultados obtidos para os valores de pH e condutividade se mantiveram estáveis ao longo do tempo de armazenamento, essa avaliação indica estabilidade das nanoemulsões estudadas. O teste de recuperação avançada utilizando nanoemulsão com baixo percentual de matéria ativa obteve como resultado de eficiência de deslocamento 39,4%. Porém esse valor foi crescente, de acordo com o aumento do percentual de polímero na nanomeulsão. Os resultados de eficiência de deslocamento de petróleo estão diretamente relacionados com o aumento da viscosidade das nanoemulsões. A nanoemulsão V (0,4% polímero) é o sistema mais viscoso dentre os analisados, e obteve o maior percentual de óleo deslocado (76,7%), resultando na maior eficiência de deslocamento total (90%). Esse estudo mostrou o potencial de sistemas nanoemulsionados, com e sem polímeros, na recuperação avançada de petróleo. Eles apresentam algumas vantagens com relação a outros métodos de recuperação avançada, como: o baixo percentual de matéria ativa, baixo índice de adsorção do polímero, dissolvido em nanoemulsão, na rocha e alta eficiência de recuperação

Estudo de sistemas microemulsionados utilizando água do mar na recuperação avançada de petróleo

Petroleum exists in the nature in certain underground formations where it is adsorbed into the rocks pores. For the conventional recovery methods usually only 30% of the oil is extracted and this can be credited, basically, to three aspects: high viscosity of the oil, geology of the formation and high interfacial tensions between the reservoir s fluids. The enhanced recovery methods use the injection of a fluid or fluids mixture in a reservoir to act in points where the conventional process didn't reach the recovery rates. Microemulsion flooding, considered an enhanced method, has the purpose to desorb the oil from the rock formation and to attain an efficient displacement of the oil emulsion. With this in mind, this work was accomplished with two main objectives: the study of the parameters effect that influence a microemulsified system (surfactant and cosurfactant types, C/S rate and salinity) and the evaluation of displacement efficiency with the microemulsions that showed stability in the rich aqueous area. For the analyzed parameters it was chose the microemulsions composition used in the recovery stage: 25% water, 5% kerosene, 46.7% of butanol as cosurfactant and 23.3% of BC or SCO cosurfactant. The core plugs of Assu and Botucatu sandstones were appraised in porosity and permeability tests and then submitted to the steps of saturation with seawater and oil, conventional recovery with water and enhanced recovery with the selected microemulsions. The Botucatu sandstone presented better recovery parameters, and the microemulsion composed with BS surfactant had larger recovery efficiency (26.88%)

Síntese e caracterização de aluminofosfato impregnado com molibdênio/zinco visando a dessulfurização por adsorção

Discussions about pollution caused by vehicles emission are old and have been developed along the years. The search for cleaner technologies and frequent weather alterations have been inducing industries and government organizations to impose limits much more rigorous to the contaminant content in fuels, which have an direct impact in atmospheric emissions. Nowadays, the quality of fuels, in relation to the sulfur content, is carried out through the process of hydrodesulfurization. Adsorption processes also represent an interesting alternative route to the removal of sulfur content. Both processes are simpler and operate to atmospheric temperatures and pressures. This work studies the synthesis and characterization of aluminophosphate impregnate with zinc, molybdenum or both, and its application in the sulfur removal from the gasoline through the adsorption process, using a pattern gasoline containing isooctane and thiophene. The adsorbents were characterized by x-ray diffraction, differential thermal analysis (DTG), x-ray fluorescence and scanning electron microscopy (SEM). The specific area, volume and pore diameter were determined by BET (Brunauer- Emmet-Teller) and the t-plot method. The sulfur was quantified by elementary analysis using ANTEK 9000 NS. The adsorption process was evaluated as function of the temperature variation and initial sulfur content through the adsorption isotherm and its thermodynamic parameters. The parameters of entropy (ΔS), enthalpy variation (ΔH) and free Gibbs energy (ΔG) were calculated through the graph ln(Kd) versus 1/T. Langmuir, Freundlich and Langmuir-Freundlich models were adjusted to the experimental data, and the last one had presented better results. The thermodynamic tests were accomplished in different temperatures, such as 30, 40 and 50ºC, where it was concluded the adsorption process is spontaneous and exothermic. The kinetic of adsorption was studied by 24 h and it showed that the capability adsorption to the adsorbents studied respect the following order: MoZnPO > MoPO > ZnPO > AlPO. The maximum adsorption capacity was 4.91 mg/g for MoZnPO with an adsorption efficiency of 49%.

Desenvolvimento de componentes nanométricos para aplicação em células a combustível à base de sólidos estruturados e filmes finos

The present work aims the preparation of filmes of strontium-doped lanthanum manganite (perovskita) yttria-stabilized zirconia (LSM-SDC) films deposited on substrate of YSZ by means of spin coating technique having as principal objective their application to solid oxide fuel cells of intermediate temperature. La0,8Sr0,2MnO3 and Ce0,8Sm0,2O1,9 were obtained by modified Pechini method by use of gelatin which act as polymerization agent. The powders obtained were characterized by Xray fluorescence, X ray diffraction, electronic scanning microscopy and the superficial area by BET method. The results obtained by X-ray fluorescence showed that the route adopted for obtention of powders was effective in the obtention of the compositions with close values to the stoichiometrics. Ethyl cellulose was used as pore-forming agent and mixed with the LSM-SDC powders in weight proportions of 1:24, 2:23 and 1:9. The films were sintered at 1150 °C for 4 h and characterized by X-ray diffraction and scanning electron microscopy technique (SEM) and atomic force. The phases quantification of the precursory powders and of the obtained films was carried through Rietveld method. According with the analysis of SEM, as the content of ethyl cellulose was increased, the pore distribution in films become more uniform and the pore size reduced. The methodology used for the obtention of the films was very efficient, considering a material was obtained with characteristics that were proper to the application as electrolyte/cathode system to solid oxide fuel cells

Síntese, caracterização e aplicação do MCM-41 e A1-MCM-41 na pirólise do resíduo atmosférico de petróleo

In present work, mesoporous materials of the M41S family were synthesized, which were discovered in the early 90s by researchers from Mobil Oil Corporation, thus allowing new perspectives in the field of catalysis. One of the most important members of this family is the MCM-41, which has a hexagonal array of mesopores with pore diameters ranging from 2 to 10 nm and a high surface area, enabling it to become very promising for the use as a catalyst in the refining of oil in the catalytic cracking process, since the mesopores facilitate the access of large hydrocarbon molecules, thereby increasing the production of light products, that are in high demand in the market. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more beneficial for application in the petrochemical industry. The mesoporous materials MCM-41 and Al-MCM-41 (ratio Si / Al = 50) were synthesized through the hydrothermal method, starting with silica gel, NaOH and distilled water. CTMABr was used as template, for structural guiding. In Al-MCM-41 the same reactants were used, with the adding of pseudoboehmite (as a source of aluminum) in the synthesis gel. The syntheses were carried out over a period of four days with a daily adjustment of pH. The optimum conditions of calcination for the removal of the organic template (CTMABr) were discovered through TG / DTG and also through analysis by XRD, FTIR and Nitrogen Adsorption. It was found that both the method of hydrothermal synthesis and calcination conditions of the studies based on TG were promising for the production of mesoporous materials with a high degree of hexagonal array. The acidic properties of the materials were determined by desorption of n-butylamine via thermogravimetry. One proved that the addition of aluminum in the structure of MCM-41 promoted an increase in the acidity of the catalyst. To check the catalytic activity of these materials, a sample of Atmospheric Residue (RAT) that is derived from atmospheric distillation of oil from the Pole of Guamaré- RN was used. This sample was previously characterized by various techniques such as Thermogravimetry, FTIR and XRF, where through thermal analysis of a comparative study between the thermal degradation of the RAT, the RAT pyrolysis + MCM-41 and RAT + Al- MCM-41. It was found that the Al-MCM-41 was most satisfactory in the promotion of a catalytic effect on the pyrolysis of the RAT, as the cracking of heavy products in the waste occurred at temperatures lower than those observed for the pyrolysis with MCM-41, and thereby also decreasing the energy of activation for the process and increasing the rates of conversion of residue into lighter products

Síntese e caracterização da peneira molecular MCM-41 contendo terras raras na dessulfurização, utilizando tiofeno como molécula sonda

Mesoporous molecular sieves of MCM-41 type are considered as promising support for metal in the refining processes of petroleum-based materials as catalysts and adsorbents for environmental protection. In this work, mesoporous molecular sieves MCM-41 were modified with different rare earth ions (La, Eu e Yb) for the obtaining nanostrutured materials with catalytic properties. The catalysts were synthesized by the hydrothermal method at 100oC for 120 h, presenting, all the samples, in the gel of synthesis molar ratio Si/Ln = 50. The obtained materials after calcination at 500oC for 2 h were characterized by XRD, surface area BET, TG/DTG, FTIR, and hydrothermal stability at 700ºC. The XRD analysis of the catalysts indicated that the materials containing rare earth presented characteristic hexagonal structure of the mesoporous materials of the type MCM-41. The TG curves showed that the decomposition of the structural template occurs in the materials at temperatures lower than 500oC. The samples presented variations as the specific superficial area, average diameter of pores and thickness of the silica wall, as a function of the nature of the rare earth impregnated in the mesoporous material. Hydrotermal stability was evaluated through the exposition of the materials to water vapour at 700°C. The thiophene adsorptions reach a maximum at 80% of conversion and incorporation of the rare earths showed influence in the process. Adsorption capacity followed the sequence: Yb-MCM-41 < La-MCM-41 < Eu-MCM-41 < MCM-41

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

Membranas de quitosana micro e macroporosas : preparo, caracterização e estudos de permeabilidade

Two methodologies were proposed to obtain micro and macroporous chitosan membranes, using two different porogenic agents. The methodologies proved to be effective in control the porosity as well as the pore size. Thus, microporous membranes were obtained through the physical blend of chitosan and polyethylene oxide (PEO) on an 80:20 (m/m) ratio, respectively, followed by the partial PEO solubilization in water at 80 ◦C. Macroporous chitosan membranes with asymmetric morphology were obtained using SiO2 as the porogenic agent. In this case, chiotsan-silica ratios used were 1:1, 1:3 and 1:5 (m/m). Membranes characterization were carried out by SEM (scanning electronic microscopy), X-ray diffraction, Fourier Transform Infrared Spectroscopy (FTIR), Thermal analysis (TG, DTG , DSC and DMTA). Permeability studies were performed using two model drugs: sodium sulfamerazine and sulfametoxipyridazine. By transmission FTIR it was possible to confirm the complete removal of SiO2. The SEM images confirmed the porous formation for both micro and macroporous membranes and also determined their respective sizes. By thermal analysis it was possible to show differences related with water sorption capacity as well as thermal stability for both membranes. DTG and DSC allowed evidencing the PEO presence on microporous membranes. The absorbance x time curves obtained on permeability tests for micro and macroporous membranes showed a linear behavior for both drugs in all range of concentration used. It was also observed, through P versus C curves, an increase in permeability of macroporous membranes according to the increase in porosity and also a decrease on P with increase in drug concentration. The influences of the drug molecular structure, as well as test temperatures were also evaluated

Obtenção de diesel verde por craqueamento termocatalítico de óleo de buriti (Mauritia flexuosa L.) sobre materiais nanoestruturados do tipo LaSBA-15

In order to obtain a biofuel similar to mineral diesel, lanthanum-incorporated SBA- 15 nanostructured materials, LaSBA-15(pH), with different Si/La molar ratios (75, 50, 25), were synthesized in a two-steps hydrothermal procedure, with pH-adjusting of the synthesis gel at 6, and were used like catalytic solids in the buriti oil thermal catalytic cracking. These solids were characterized by X-ray fluorescence (XRF), powder X-ray diffraction (XRD), thermogravimetric analysis (TG/DTG), infrared spectroscopy (FTIR), nitrogen porosimetry and ethanol dehydration, aiming to active sites identify. Taken together, the analyses indicated that the synthesis method has employed to obtain materials highly ordered mesostructures with large average pore sizes and high surface area, besides suggested that the lanthanum was incorporated in the SBA-15 both into the framework as well as within the mesopores. Catalytic dehydration of ethanol over the LaSBA-15(pH) products has shown that they have weak Lewis acid and basic functionalities, indicative of the presence of lanthanum oxide in these samples, especially on the La75SBA-15(pH) sample, which has presented the highest selectivity to ethylene. The buriti oil thermal and thermal catalytic cracking, realized from the room temperature to 450 ºC in a simple distillation system, has allowed obtaining two liquid fractions, each consisting of two phases, one aqueous and another organic, organic liquid (OL). The OL obtained from first fractions has shown high acid index, even in the thermal catalytic process. One the other hand, OL coming from second ones, called green diesel (GD), have presented low acid index, particularly that one obtained from the thermal catalytic process realized over LaSBA-15(pH) samples. The acid sites presence in these samples, associated to their large average pore sizes and high surface areas, have allowed them, especially the La75SBA-15(pH), to present deoxygenating activity in the buriti oil thermal catalytic cracking, providing an oxygenates content reduction, particularly carboxylic acids, in the GD. Furthermore, the GD comes from the second liquid fraction obtained in the buriti oil thermal catalytic cracking over this latest solid sample has shown hydrocarbons composition and physic-chemical properties similar to that mineral diesel, beyond sulfur content low

Carregadores de oxigênio a base de níquel suportado em materiais mesooros para aplicação na recirculação química com reforma (RQR)

Oxygen carriers are metal oxides which have the ability to oxidize and reduce easily by various cycles. Due to this property these materials are widely usedin Chemical-Looping Reforming processes to produce H2 and syngas. In this work supports based on MCM-41 and La-SiO2 were synthesized by hydrothermal method. After the synthesis step they were calcined at 550°C for 2 hours and characterized by TG, XRD, surface area using the BET method and FTIR spectroscopy. The deposition of active phase, in this case Nickel, took place in the proportions of 5, 10 and 20% by weight of metallic nickel, for use as oxygen carriers.The XRD showed that increasing in the content of Ni supported on MCM-41 resulted in a decrease in spatial structure and lattice parameter of the material. The adsorption and desorption curves of the MCM-41 samples exhibited variations with the increase of Ni deposited. Surface area, average pore diameter and wall density of silica showed significant changes , due to the increase of the active phase on the mesoporous material. By other hand, in the samples with La-SiO2 composition was not observed peaks characteristic of hexagonal structure, in the XRD diffractogram. The adsorption/desorption isotherms of nitrogen observed are type IV, characteristic of mesoporous materials. The catalytic test indicates that the supports have no influence in the process, but the nickel concentration is very important, because the results for minor concentration of nickel are not good. The ratio H2/O2 was close to 2, for all 15 cycles involving the test storage capacity of O2, indicating that the materials are effective for oxygen transport

Estudo do desempenho de catalisadores tipo Ni/CexM1-xO2 (M = Zr ou Mn) na reação de oxidação parcial do metano

One of the main applications of methane is in the production of syngas, a mixture of hydrogen and carbon monoxide. Procedures used in this process are steam reforming, CO2 reforming, partial oxidation and autothermal reforming. The present study evaluated and compared the behavior of nickel catalysts supported on mixed oxides of cerium and manganese in the partial oxidation of methane with that of nickel catalysts supported on mixed oxides of cerium and zirconium. Mixed oxides of cerium and zirconium or cerium and manganese were synthesized using two different preparation methods, the polymeric precursor based on Pechini method and combustion reaction using a microwave. This was followed by impregnation with nickel content of 15 %. Samples were calcined at 300, 800 and 900 °C and characterized by specific surface area (SSA), X-ray fluorescence (XRF), X-ray diffraction (XRD), scanning electron microscopy (SEM), temperature programmed reduction (TPR) and the reaction of partial oxidation of methane. The specific areas of samples decrease with the rise in calcination temperature and after nickel impregnation. Metal-cerium solid solution was formed and the presence of other manganese species outside the solid solution structure was confirmed in the compound with the highest amounts of manganese oxides showed. With regard to scanning electron microscopy, supports based on cerium and zirconium prepared by Pechini method exhibited agglomerated particles without uniform geometry or visible pores on the surface. However, compounds containing manganese presented empty spaces in its structure. Through synthesis by combustion reaction, morphology acquired independently of the proposed composition demonstrated greater porosity in relation to Pechini synthesis. Although catalysts were prepared using different synthesis methods, the insertion of nickel showed very similar reduction profiles (TPR). In relation to nickel catalysts supported on mixed oxide of cerium and zirconium, there is an initial reduction of NiO species that present certain interaction with the support. This is followed by the reduction of Ce4+ in Ce3+ surface, with subsequent bulk reduction. For catalysts containing manganese, a reduction of nickel oxide species occurs, followed by two stages of reduction for species Mn2O3 in Mn3O4 and Mn3O4 in MnO, with subsequent reduction of bulk. With respect to partial oxidation reactions, the nickel catalyst supported on mixed oxide of cerium and zirconium, prepared using the Pechini method, exhibited CH4 conversion of approximately 80 %, with conversion of 81 % when prepared by combustion. This behavior continued for 10 hours of reaction. Manganese content was also found to directly influence catalytic activity of materials; the greater the manganese oxide content, the faster deactivation and destabilization occurred in the catalyst. In both synthesis methods, the nickel catalyst supported on mixed oxide of cerium and zirconium maintained an H2/CO ratio very close to 2 during the 10 hours of partial oxidation reaction. Samples containing manganese displayed smaller H2/CO ratios and lower performance in partial oxidation.