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

Análise dos Processos de Flotação e Oxidação Avançada para o Tratamento de Efluente Modelo da Indústria do Petróleo

The generation of wastes in most industrial process is inevitable. In the petroleum industry, one of the greatest problems for the environment is the huge amount of produced water generated in the oil fields. This wastewater is a complex mixture and present great amounts. These effluents can be hazardous to the environmental without adequate treatment. This research is focused in the analysis of the efficiencies of the flotation and photo-oxidation processes to remove and decompose the organic compounds present in the produced water. A series of surfactants derivated from the laurilic alcohol was utilized in the flotation to promote the separation. The experiments have been performed with a synthetic wastewater, carefully prepared with xylene. The experimental data obtained using flotation presented a first order kinetic, identified by the quality of the linear data fitting. The best conditions were found at 0.029 g.L-1 for the surfactant EO 7, 0.05 g.L-1 for EO 8, 0.07 g.L-1 for EO 9, 0.045 g.L-1 for EO 10 and 0.08 g.L-1 for EO 23 with the following estimated kinetic constants: 0.1765, 0.1325, 0.1210, 0.1531 and 0.1699 min-1, respectively. For the series studied, the most suitablesurfactant was the EO 7 due to the lower reagent consumption, higher separation rate constant and higher removal efficiency of xylene in the aqueous phase (98%). Similarly to the flotation, the photo-Fenton process shows to be efficient for degradation of xylene and promoting the mineralization of the organic charge around 90% and 100% in 90 min

Estudo termoanalítico de medicamentos de referência, genérico e similar

This study aimed to apply, thermogravimetriy /derivative Thermogravimetriy (TG/DTG), differential scanning calorimetry (DSC), Differential Thermal Analysis (DTA), to conduct a comparative study on drug reference, generic and whose active principles are similar captopril hydrochlorothiazide, ampicillin, paracetamol, aspirin and mebendazole sold in local pharmacies. Samples of the active ingredients and dosage forms were also characterized by absorption infrared spectroscopy (IR), X-ray diffraction (XRD) and microscopy scanning electron (SEM). The TG / DTG curves showed a general similarity in the thermal behavior of the samples, but also showed the influence of excipients on the thermal stability. The DSC curve of the generic base hydrochlorothiazide showed no peak on the fusion of the drug due to interference of lactose as a diluent, which causes interaction with the active principle causing their degradation before the merger. The DSC curves of the drugs consisting of paracetamol showed reproducibility at the melting point of the active and the other thermal events. The DSC result of binary mixtures involving captopril / magnesium stearate and mebendazole/magnesium stearate showed possible interactions or incompatibilities evidenced by the displacement of the melting point of both drugs. The other mixtures showed no change. The infrared spectra presented were very similar, indicating the presence of functional groups characteristic of the constituents of the samples. The X-ray diffraction showed peaks indicative of crystalline structure of the active ingredients as well as some of the ingredients in the formulation of the drug and the micrographs indicate a general heterogeneity in the size distribution of particles in the samples

Uso do pó da palha de carnaúba em compósitos de quitosana

In this work a biodegradable composite using the carnauba straw s powder as reinforcement on chitosan matrix polymeric were manufactured. Firstly, were carried out the chemistry characterization of the carnauba straw s powder before and after treatments with NaOH and hexane. Goering and Van Soest method (1970), flotation test, moisture absorption, FTIR, TG/DTG, DSC and SEM have also being carried out. Composites were developed with variations in granulometry and in powder concentrations. They were characterized by TG/DTG, SEM and mechanicals properties. The results of chemical composition showed that the carnauba straw s powder is composed of 41% of cellulose; 28,9% of hemicellulose and 14% of lignin.The flotation test have indicated that the chemical treatment with NaOH decreased the powder s hidrophilicity.The thermal analysis showed increased of thermal stability of material after treatments. The results of FTIR and SEM revealed the removal of soluble materials from the powder (hemicelluloses and lignin), the material became rougher and clean. The composites obtained showed that the mechanicals properties of the composites were decreased in respect at chitosan films, and the composites with the powder at 150 Mesh showed less variation in the modulus values. The speed test of 10 mm/min showed the better reproducibility of the results and is in agreement to the standard ASTM D638. The SEM analysis of fracture showed the low adhesion between the fiber/matrix. The increase of volume of powder in the composite caused a decrease in values of stress and strain for the samples with untreated powder and treated with hexane. The composite with 50% of the powder s treated in NaOH didn t have significant variation in the values of stress and strain as compared with the composites with 10% of the powder, showing that the increase in the volume of fiber didn t affect the stress and strain of the composite. Thereby, it is concluded that the manufacture of polymeric composites of chitosan using carnauba straw s powder can be done, without need for pre-treatment of reinforcement, become the couple of carnauba straw s powder-chitosan a good alternative for biodegradable composites

Avaliação da remoção de hidrocarbonetos aromáticos (BTEX) em águas utilizando materiais nanoestruturados do tipo Ti-MCM-41

Volatile Organic Compounds are pollutants coming mainly from activities that use fossil fuels. Within this class are the BTEX (benzene, toluene, ethylbenzene and xylenes) compounds that are considered hazardous. Among the various existing techniques for degradation of pollutants, there is advanced oxidation using H2O2 generating hidoxil radical ( OH). In this work, the mesoporous material of MCM-41 was synthesized by hydrothermal method and then was used as support, the impregnation of titanium by the method of synthesis with excess solvent to obtain the catalyst Ti-MCM-41. The catalyst was used in the reaction catalyzed removal of BTEX in water using H2O2 as oxidant. The materials were characterized by: XRD, TG/DTG, FTIR, nitrogen adsorption-desorption and FRX-EDX, in order to verify the method of impregnation of the mesoporous titanium support was effective. Catalytic tests were carried out in reactors of 20 mL containing BTEX (100.0 μg/L), H2O2 (2.0 M) and Ti-MCM-41 (2.0 g/L) in acid medium. The reaction occurred for 5 h at 60 °C and analysis were performed by gas chromatography with photoionization detector and static headspace sampler. The characterizations have proven the effectiveness of the synthesis method used and the incorporation of titanium lt in the support. The catalytic tests showed satisfactory results with conversion of more than 95 % for the studied compounds, where the catalyst 48% Ti-MCM-41 showed a higher removal efficiency of the compounds under study

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

Conciliação entre modelos de mecanismos avançados de oxidação eletroquímica

Many pollutants dumped in waterways, such as dyes and pesticides, have become so ubiquitous that they represent a serious threat to human health. The electrochemical oxidation is presented as an alternative clean, efficient and economic degradation of wastewater containing organic compounds and a number of advantages of this technique is to just not make use of chemical reagents, since only electrical energy is consumed during the removal of pollutants organic. However, despite being a promising alternative, still needs some tweaking in order to obtain better efficiency in the elimination of persistent pollutants. Thus, this study sought a relationship between a recently discovered phenomenon that reflects the participation of dissolved oxygen in solution in the electrochemical oxidation process, as an anomaly, present a kinetic model that shows instantaneous current efficiency (ICE) above 100% limited by theory, manifested for some experiments with phenolic compounds with H2SO4 or HClO4 as supporting electrolyte with electrodes under anodic oxidation on boron doped diamond (BDD). Therefore it was necessary to reproduce the data ICE exposes the fault model, and thus the 2-naphthol was used as phenolic compound to be oxidised at concentrations of 9, 12 and 15 mmol L-1, and H2SO4 and HClO4 to 1 mol L-1 as a supporting electrolyte under a current density of 30 mA cm-2 in an electrochemical reactor for continuous flow disk configuration, and equipped with anodes DDB at room temperature (25 oC). Experiments were performed using N2 like as purge gas for eliminate oxygen dissolved in solution so that its influence in the system was studied. After exposure of the anomaly of the ICE model and investigation of its relationship with dissolved O2, the data could be treated, making it possible for confirmation. But not only that, the data obtained from eletranálise and spectroscopic analysis suggest the involvement of other strongly oxidizing species (O3 (ozone) and O radicals and O2 -), since the dissolved O2 can be consumed during the formation of new strong oxidizing species, not considered until now, something that needs to be investigated by more accurate methods that we may know a little more of this system. Currently the performance of the electrocatalytic process is established by a complex interaction between different parameters that can be optimized, so it is necessary to the implementation of theoretical models, which are the conceptual lens with which researchers see

Craqueamento térmico e termocatalítico do óleo de girassol (Hellianthus annus L.) sobre materiais micro e mesoporosos

Microporous materials zeolite type Beta and mesoporous type MCM-41 and AlMCM-41 were synthesized hydrothermally and characterized by methods of X-ray diffraction, Fourier transform infrared, scanning electron microscopy, surface acidity, nitrogen adsorption, thermal analysis TG / DTG. Also we performed a kinetic study of sunflower oil on micro and mesoporous catalysts. The microporous material zeolite beta showed a lower crystallinity due to the existence of smaller crystals and a larger number of structural defects. As for the mesoporous materials MCM-41 and AlMCM-41 samples showed formation of hexagonal one-dimensional structure. The study of kinetic behavior of sunflower oil with zeolite beta catalysts, AlMCM-41 and MCM-41 showed a lower activation energy in front of the energy of pure sunflower oil, mainly zeolite beta. In the thermal cracking and thermocatalytic of sunflower oil were obtained two liquid fractions containing an aqueous phase and another organic - organic liquid fraction (FLO). The FLO first collected in both the thermal cracking as the thermocatalytic, showed very high level of acidity, performed characterizations of physicochemical properties of the second fraction in accordance with the specifications of the ANP. The second FLO thermocatalytic collected in cracking of sunflower oil presented results in the range of diesel oil, introducing himself as a promising alternative for use as biofuel liquid similar to diesel, either instead or mixed with it

Contribuição de fungos micorrízicos arbusculares autóctones no crescimento de Guazuma ulmifolia em solo de cerrado degradado

Ensaios foram conduzidos, em casa de vegetação, com solos de pastagem degradada reflorestada e cerrado preservado (controle) visando avaliar a contribuição de fungos micorrízicos arbusculares (FMA) autóctones no crescimento de mutambo (Guazuma ulmifolia Lamb.). As mudas foram transplantadas para sacos de plástico (2 kg) com substratos esterilizados na proporção 4:1 (solo:areia), e o tratamento inoculado recebeu 300 esporos de FMA por saco. A inoculação não proporcionou aumento significativo na produção da matéria seca da parte aérea, matéria fresca das raízes e altura da planta, sugerindo que a G. ulmifolia não é responsiva à micorrização.

Persistência de palhada e liberação de nutrientes do nabo forrageiro no plantio direto

A palhada das plantas de cobertura, mantida sobre o solo no plantio direto, representa uma reserva de nutrientes para cultivos subseqüentes. O objetivo deste trabalho foi avaliar a decomposição e a liberação de macronutrientes de resíduos de nabo forrageiro. O experimento foi realizado no campo, durante o ano de 1998, no Município de Marechal Cândido Rondon, PR. O nabo forrageiro foi dessecado e manejado com rolo-faca 30 dias após a emergência. Avaliaram-se a persistência de palhada e a liberação de nutrientes dos resíduos aos 0, 13, 35 e 53 dias após o manejo. O delineamento experimental foi de blocos casualizados, com quatro repetições. O nabo forrageiro produziu, até o estádio de pré-florescimento, elevada quantidade de massa seca da parte aérea em cultivo de inverno (2.938 kg ha-1), acumulando 57,2, 15,3, 85,7, 37,4, 12,5 e 14,0 kg ha-1, respectivamente, de N, P, K, Ca, Mg e S. O manejo do nabo forrageiro no estádio de pré-florescimento apresenta rápida degradação da palhada, acarretando liberação de quantidades significativas de macronutrientes. Os nutrientes disponibilizados em maior quantidade e velocidade para a cultura subseqüente, são o K e o N. A maior velocidade de liberação de macronutrientes pelo nabo forrageiro ocorre no período compreendido entre 10 e 20 dias após o manejo da fitomassa.

Avaliação dos atributos físicos do solo em consórcio de forrageiras e milho em sucessão com soja em região de cerrados

O uso intensivo de áreas do Cerrado para produção agropecuária aliado ao manejo inadequado tem causado degradação dos solos. Nesse sentido há necessidade da incorporação de sistemas sustentáveis como plantio direto e a integração lavoura-pecuária. Este trabalho objetivou identificar o efeito da sucessão de milho+forrageiras e soja nos atributos físicos do solo. Para tanto foi realizado, em área experimental da Unesp, campus de Ilha Solteira, um ensaio composto do consórcio de milho com quatro forrageiras (Brachiaria brizantha,B. ruziziensis, Panicum maximum cv. Tanzânia e P. maximum cv. Áries) semeadas em três modalidades (na linha de semeadura do milho misturada ao adubo, a lanço simultânea à semeadura do milho e a lanço no estádio V4 do milho) e o milho sem consorciação (testemunha). A soja de verão foi implantada sobre os restos culturais dos tratamentos anteriores. Foram realizadas coletas para determinar a macro e microporosidade, porosidade total e densidade do solo em duas épocas de amostragem, após as colheitas do milho e da soja. Pelos resultados, pôde-se concluir que, em regiões de cerrados, a sucessão de culturas utilizada promoveu a melhoria da macroporosidade, porosidade total e densidade do solo, independentemente da utilização de forrageiras em consórcio com milho.

Uso de lodo de esgoto na reestruturação de solo degradado

O uso do solo nem sempre dá lugar a um novo sistema ecológico sustentável, seja de lavouras, seja de pastagens. Com isso, solos utilizados intensamente e de forma inadequada são levados à degradação. Nesse sentido, este trabalho teve como objetivo estudar a influência do lodo de esgoto na recuperação de propriedades físicas de um Latossolo Vermelho degradado, cultivado há 2,5 anos com eucalipto (Eucalyptus citriodora Hook) e braquiária (Brachiaria decumbens) no município de Selvíria, MS. O delineamento experimental utilizado foi em blocos casualizados com seis tratamentos e quatro repetições. Os tratamentos foram: 1-vegetação de Cerrado; 2-solo exposto sem tratamento para recuperação; 3-solo cultivado com eucalipto e braquiária sem uso do lodo de esgoto e adubação mineral; 4-solo cultivado com eucalipto e braquiária com adubação mineral; 5-solo cultivado com eucalipto e braquiária com uso de 30 Mg ha-1 de lodo de esgoto; e 6-solo cultivado com eucalipto e braquiária com uso de 60 Mg ha-1 de lodo de esgoto. Nas camadas do solo de 0,00-0,05; 0,05-0,10; 0,10-0,20; e 0,20-0,30 m, foram estudadas as propriedades físicas do solo: macroporosidade, microporosidade; porosidade; e densidade do solo. Na braquiária foram avaliadas as matérias verde e seca e, no eucalipto, a altura média de planta e o DAP (diâmetro à altura do peito). Concluiu-se que o solo estudado está sendo recuperado por meio dos tratamentos estabelecidos. Dentre eles, destacam-se os tratamentos com a utilização do lodo, que influenciaram as propriedades físicas do solo, proporcionaram mais rendimentos de matérias verde e seca da braquiária e promoveram maior crescimento das plantas de eucalipto. O crescimento vegetal, a densidade do solo, a porosidade total e a macroporosidade foram os melhores indicadores da recuperação do solo.

Rotação de culturas e propriedades físicas e químicas em Latossolo Vermelho de Cerrado sob preparo convencional e semeadura direta em adoção

O manejo inadequado do solo tem promovido a degradação de suas propriedades físicas, químicas e biológicas. O objetivo deste trabalho foi avaliar, após três anos da instalação de sistemas de manejo do solo, os efeitos da rotação com adubo verde, soja ou milho (verão) e feijão de inverno, sendo utilizadas as seguintes espécies na adubação verde: mucuna-preta, milheto, crotalária e guandu, nas propriedades físicas e químicas de um Latossolo Vermelho distroférrico e na produtividade das culturas. Outro tratamento foi adicionado como alternativa à adubação verde, o pousio. Os sistemas de manejo do solo foram: semeadura direta não consolidada e preparo convencional. O estudo foi realizado em Selvíria-MS, no ano agrícola de 1999/2000. O delineamento experimental foi em blocos casualizados com parcelas subdivididas e quatro repetições. O sistema de semeadura direta, após três anos de instalada a rotação, degradou mais as propriedades físicas do solo na camada superficial. Por outro lado, neste sistema e camada de solo, houve acréscimo no teor de matéria orgânica e no pH, bem como na produtividade do milho, superior à do sistema de preparo convencional. O feijão em rotação à cultura do milho, na semeadura convencional, e em rotação à soja, na semeadura direta, foi a melhor opção quanto à produtividade.

Estabilidade de agregados de um latossolo vermelho degradado em recuperação com adubos verdes, calcário e gesso

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

Effects of soil management systems on soil microbial activity, bulk density and chemical properties

Este trabalho teve por objetivo estudar os efeitos de diferentes sistemas de uso e manejo na densidade do solo nas suas propriedades químicas e na atividade microbiana em um Latossolo Vermelho distrófico (Oxisol). As amostras de solo foram retiradas de parcelas dos seguintes tratamentos: cerrado denso preservado, pastagem de Brachiaria decumbens degradada (20 anos), plantio direto com rotação de culturas (8 anos) e sistema convencional com rotação de culturas anuais (10 anos). O delineamento experimental utilizado foi o inteiramente casualizado, com dez repetições. O uso contínuo de plantio direto resultou em mais alta taxa de C-biomassa microbiana e menor perda relativa de carbono pela respiração basal, podendo determinar, desta forma, maior acúmulo de C no solo a longo prazo. Proporcionou, ainda, melhoria na densidade aparente e nas propriedades químicas do solo. Assim, o sistema plantio direto, com manejo de culturas, mostrou ser uma alternativa para a conservação e manutenção das condições físicas e do potencial produtivo de solos de cerrado.