Determinação de carbono orgânico por oxidação pelo dicromato de potássio e titulação do excesso do oxidante por iodometria

Aula Prática 7

Obtenção de óxidos a base de níquel e cobalto para reação de oxidação parcial do metano

Nickel-based catalysts supported on alumina have been widely used in various reactions to obtain synthesis gas or hydrogen. Usually, higher conversion levels are obtained by these catalysts, however, the deactivation by coke formation and sintering of metal particles are still problems to be solved. Several approaches have been employed in order to minimize these problems, among which stands out in recent years the use of additives such as oxides of alkali metals and rare earths. Similarly, the use of methodologies for the synthesis faster, easier, applicable on an industrial scale and to allow control of the microstructural characteristics of these catalysts, can together provide the solution to this problem. In this work, oxides with spinel type structure AB2O4, where A represents divalent cation and B represents trivalent cations are an important class of ceramic materials investigated worldwide in different fields of applications. The nickel cobaltite (NiCo2O4) was oxides of spinel type which has attracted considerable interest due to its applicability in several areas, such as chemical sensors, flat panel displays, optical limiters, electrode materials, pigments, electrocatalysis, electronic ceramics, among others. The catalyst precursor NiCo2O4 was prepared by a new chemical synthesis route using gelatine as directing agent. The polymer resin obtained was calcined at 350°C. The samples were calcined at different temperatures (550, 750 and 950°C) and characterized by X ray diffraction, measurements of specific surface area, temperature programmed reduction and scanning electron microscopy. The materials heat treated at 550 and 750°C were tested in the partial oxidation of methane. The set of techniques revealed, for solid preparations, the presence of the phase of spinel-type structure with the NiCo2O4 NixCo1-xO solid solution. This solid solution was identified by Rietveld refinement at all temperatures of heat treatment. The catalyst precursors calcined at 550 and 750°C showed conversion levels around 25 and 75%, respectively. The reason H2/CO was around 2 to the precursor treated at 750°C, proposed reason for the reaction of partial oxidation of methane, one can conclude that this material can be shown to produce synthesis gas suitable for use in the synthesis Fischer-Tropsch process

Síntese e caracterização de óxidos de cério e cobalto obtidos por gel-combustão e Pechini aplicados às reações de oxidação de n-hexano

Oxide type spinel AB2O4 presents structure adjusted for application in the automobile industry. The spinel of cobalt has many practical applications had its excellent physical and chemical properties such as catalyst in hydrocarbon oxidation reaction. The CeO2 has been used in many of these processes because it assigns to a material with excellent thermal resistance and mechanics, high capacity of oxygen stockage (OSC) among others properties. This work deals with the synthesis, characterization and catalytic application of spinel of cobalt and CeO2 with fluorita structure, obtained for method of Pechini and method of Gel-Combustion. The process of Pechini, the puff was obtained at 300 ºC for 2 h in air. In the process of Gel-Combustion the approximately at 350 ºC material was prepared and burnt for Pyrolysis, both had been calcined at 500 ºC, 700 ºC, 900 ºC and 1050 ºC for 2 h in air. The materials of the calcinations had been characterized by TG/DTA, electronic microscopy of sweepings (MEV), spectroscopy of absorption in the infra-red ray (FTIR) and diffraction of X-rays (DRX). The obtained material reaches the phase oxide at 450 oC for Pechini method and 500 °C for combustion method. The samples were submitted catalytic reaction of n-hexane on superficies of materials. The reactor function in molar ration of 0, 85 mol.h-1.g-1 and temperature of system was 450 °C. The sample obtained for Pechini and support in alumine of superficial area of 178,63 m2.g-1 calcined at 700 ºC, give results of catalytic conversions of 39 % and the sample obtained for method of gel-combustion and support in alumina of 150 mesh calcined at 500 ºC result 13 % of conversion. Both method were selective specie C1

Síntese de catalisadores do tipo LaNixFe1-xO3 como precursores catalíticos para reação oxidação parcial do metano

Nickel-bases catalysts have been used in several reform reactions, such as in the partial oxidation of methane to obtain H2 or syngas (H2 + CO). High levels of conversion are usually obtained using this family of catalysts, however, their deactivation resulting from carbon deposition still remains a challenge. Different approaches have been tested aiming at minimizing this difficulty, including the production of perovskites and related structures using modern synthesis methods capable of producing low cost materials with controlled microstructural characteristics at industrial scale. To establish grounds for comparison, in the present study LaNixFe1-xO3 (x=0, 0.3 or 0.7) perovskites were prepared following the Pechini method and by microwave assisted self-combustion. All samples were sub sequently calcined at 900 °C to obtain the target phase. The resulting ceramic powders were characterized by thermogravimetric analysis, infrared spectroscopy, X ray diffraction, specific area and temperature programmed reduction tests. Calcined samples were also used in the partial oxidation reaction of methane to evaluate the level of conversion, selectivity and carbon deposition. The results showed that the calcined samples were crystalline and the target phase was formed regardless of the synthesis method. According to results obtained by Rietveld refinement, we observed the formation of 70.0% of LaNi0.3Fe0.7O3 and 30.0% of La2O3 for samples LN3F7-900- P, LN3F7-900-M and 41,6% of LaNi0.7Fe0.3O3, 30.7% of La2NiO4 and 27.7% of La2O3 for samples LN7F3-900-P and LN7F3-900-M.Temperature-programmed profiles of the LaNiO3 sample revealed the presence of a peak around 510 °C, whereas the LaFeO3 sample depicted a peak above 1000°C. The highest l evel of methane conversion was obtained for LaNiO3 synthesized by the Pechini method. Overall, catalysts prepared by the Pechini method depicted better conversion levels compared to those produced by microwave assisted self-combustion

Membrana de alumina anódica: comportamento da microestrutura e estudo das propriedades ópticas após tratamento térmico

Thin commercial aluminum electrolytic and passed through reactions was obtained with anodic alumina membranes nanopores. These materials have applications in areas recognized electronic, biomedical, chemical and biological weapons, especially in obtaining nanostructures using these membranes as a substrate or template for processing nanowires, nanodots and nanofibers for applications noble. Previous studies showed that the membranes that have undergone heat treatment temperature to 1300° C underwent changes in morphology, crystal structure and optical properties. This aim, this thesis, a study of the heat treatment of porous anodic alumina membranes, in order to obtain and to characterize the behavior changes structures during the crystallization process of the membranes, at temperatures ranging between 300 and 1700° C. It was therefore necessary to mount a system formed by a tubular furnace resistive alumina tube and controlled environment, applying flux with special blend of Ag-87% and 13% N2, in which argon had the role of carrying out the oxygen nitrogen system and induce the closing of the pores during the densification of the membrane. The duration of heat treatment ranged from 60 to 15 minutes, at temperatures from 300 to 1700° C respectively. With the heat treatment occurred: a drastic reduction of porosity, grain growth and increased translucency of the membrane. For the characterization of the membranes were analyzed properties: Physical - thermogravimetric, X-ray diffraction, BET surface area; morphological - SEM, EDS through compositional and, optical absorbance, and transmittance in the UV-VIS, and FTIR. The results using the SEM showed that crystallization has occurred, densification and significant changes in membrane structure, as well as obtaining microtube, the BET analysis showed a decrease in specific surface area of the membranes has to 44.381 m2.g-1 to less than 1.8 m2.g-1 and in the analysis of transmittance and absorbance was found a value of 16.5% in the range of 800 nm, characteristic of the near infrared and FTIR have confirmed the molecular groups of the material. Thus, one can say that the membranes were mixed characteristics and properties which qualify for use in gas filtration system, as well as applications in the range of optical wavelength of the infra-red, and as a substrate of nanomaterials. This requires the continuation and deepening of additional study

Caracterização de superfícies de titânio modificado por oxidação à plasma

Recent years have seen a significant growth in surface modifications in titanium implants, resulting in shorter healing times in regions with low bone density. Among the different techniques, subtraction by chemical agents to increase oxidation has been applied for surface treatment of dental implants. However, this technique is generally unable to remove undesirable oxides, formed spontaneously during machining of titanium parts, raising costs due to additional decontamination stages. In order to solve this problem, the present study used plasma as an energy source to both remove these oxides and oxidize the titanium surface. In this respect, Ti disks were treated by hollow cathode discharge, using a variable DC power supply and vacuum system. Samples were previously submitted to a cleaning process using an atmosphere of Ar, H2 and a mixture of both, for 20 and 60 min. The most efficient cleaning condition was used for oxidation in a mixture of argon (60%) and oxygen (40%) until reaching a pressure of 2.2 mbar for 60 min at 500°C. Surfaces were characterized by scanning electron microscopy (SEM), X-ray diffraction (XRD), atomic force microscopy (AFM), adhesion and cell proliferation. SEM showed less cell spreading and a larger number of projections orfilopodia in the treated samples compared to the control sample. AFM revealed surface defects in the treated samples, with varied geometry between peaks and valleys. Biological assays showed no significant difference in cell adhesion between treated surfaces and the control. With respect to cell proliferation, the treated surface exhibited improved performance when compared to the control sample. We concluded that the process was efficient in removing primary oxides as well as in oxidizing titanium surfaces

Efeito da estimulação transcraniana por corrente contínua anódica sobre o controle do movimento em para-halterofilistas

Introduction: The sport practiced by people with disabilities has been growing in recent years. Consequently, advances in assessment and training methods have emerged. However, the paralympic sport keeps in tow these advances, with few specific studies that consider disability as intervening factor. The transcranial direct current stimulation (tDCS) is a technique that has proven to be capable of modulating brain function. Studies show beneficial effects of tDCS on muscle strength, power and fatigue during exercise. Objective: Investigate de the effect of tDCS on movement control in para-powerlifters. Methods: Eight subjects underwent two sessions of motion capture, which previously applied the anodic tDCS or sham sessions in the cerebellum. Three movements were performed with increasing load between 90-95% of 1MR. The movements were recorded by an 10 infrared cameras system which reconstructed the 3D trajectory of markers placed on the bar. Results: There have been changes between the anodic and sham conditions over bar level (initial, final, maximum during the eccentric and concentric phase) and in the difference between the final and initial bar level. Moreover, there was difference in bar level (final and during the eccentric phase) comparing athletes amputees and les autres. Conclusion: The findings of this study suggest that tDCS applied prior to the exercise over the cerebellum in para-powerlifters acts differently according to disability

Estudo da oxidação superficial de ligas odontológicas de Ni-Cr em plasma pulsado para uso em restaurações metalocerâmicas

Metal ceramic restorations matches aesthetic and strength, and in your making occurs an interface oxide layer, wetting resulting and atomic and ionic interactions resulting between metal, oxide and porcelain. However, frequent clinical fails occurs in this restoration type, because lost homogeneous deposition oxide layer and lost interface bond. Thus, in this study, thought depositate homogeneous oxide films above Ni-Cr samples surfaces polite previously, at plasma oxide environment. Six samples was oxided at 300 and 400ºC at one hour, and two samples was oxided in a comum chamber at 900ºC, and then were characterized: optical microscopic, electronic microscopic, micro hardness, and X ray difratometry. Colors stripes were observed at six samples plasma oxided and a grey surface those comum oxided, thus like: hardness increase, and several oxides from basic metals (Ni-Cr)

Estudo da oxidação do metabissulfito de sódio contido no efluente da carcinicultura

The shrimp farming is a process of creation of shrimp that has been growing rapidly in the country, occupying a meaningful space in the Brazilian exporting. In 2003, this activity presented a volume of 60 millions of tons and 220 millions of dollars, being the main generator of employment and income of the primary sector of the northeast economy. However, it is a new activity with c.a. five years in the Rio Grande do Norte State and therefore needs investment in the technological area. Among the wastewaters of this activity, the sulphite solution is being usually applied in the process of fishing, i.e. retrieval of the shrimps from the farming. The aim of this work is to present the oxidation experimental results of the sulphite that may be and to determine what it s the most efficient method, trough laboratory experiments. The measurements were carried out in a mixing reactor inserting air and with hydrogen peroxide addition with and without UV light. The solutions were prepared synthetically with concentrations found in the wastewater of fishing and also collected in locu. The oxidation process using air was monitorated by iodometric analysis for the sulphite and the oxidation using hydrogen peroxide was evaluated with turbidimetric analysis for sulphate, by spectrophotometer. The sulphite was totally oxidized in both processes. The experimental results permit to conclude that the oxidation by hydrogen peroxide is more efficient and allowed to determine the optimum operational conditions in terms of concentration and time of treatment

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 suitable surfactant was the EO 7 due to the lower reagent onsumption, 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

Síntese e caracterização do carbeto de molibdênio nanoestruturado para fins catalíticos na reação de oxidação parcial do metano

The nanostructures materials are characterized to have particle size smaller than 100 nm and could reach 1 nm. Due to the extremely reduced dimensions of the grains, the properties of these materials are significantly modified relatively when compared with the conventional materials. In the present work was accomplished a study and characterization of the molybdenum carbide, seeking obtain it with particles size in the nanometers order and evaluate its potential as catalyst in the reaction of partial methane oxidation. The method used for obtaining the molybdenum carbide was starting from the precursor ammonium heptamolybdate of that was developed in split into two oven, in reactor of fixed bed, with at a heating rate of 5ºC/min, in a flow of methane and hydrogen whose flow was of 15L/h with 5% of methane for all of the samples. The studied temperatures were 350, 500, 600, 650, 660, 675 and 700ºC and were conducted for 0, 60, 120 and 180 minutes, and the percent amount and the crystallite size of the intermediate phases were determined by the Rietveld refinement method. The carbide obtained at 660ºC for 3 hours of reaction showed the best results, 24 nm. Certain the best synthesis condition, a passivating study was accomplished, in these conditions, to verify the stability of the carbide when exposed to the air. The molybdenum carbide was characterized by SEM, TEM, elemental analysis, ICP-AES, TG in atmosphere of hydrogen and TPR. Through the elemental analysis and ICP-AES the presence carbon load was verified. TG in atmosphere of hydrogen proved that is necessary the passivating of the molybdenum carbide, because occur oxidation in room temperature. The catalytic test was accomplished in the plant of Fischer-Tropsch of CTGAS, that is composed of a reactor of fixed bed. Already the catalytic test showed that the carbide presents activity for partial oxidation, but the operational conditions should be adjusted to improve the conversion

Oxidação úmida de fenóis com catalisadores de ferro suportado em argilominerais em reator de leito de lama (slurry)

The wet oxidation of organic compounds with CO2 and H2O has been demonstrated to be an efficient technique for effluent treatment. This work focuses on the synthesis, characterization and catalytic performance of Fe-MnO2/CeO2, K-MnO2/CeO2/ palygorskite and Fe/ palygorskite toward the wet oxidative degradation of phenol. The experiments were conducted in a sludge bed reactor with controlled temperature, pressure and stirring speed and sampling of the liquid phase. Experiments were performed on the following operating conditions: temperature 130 ° C, pressure 20.4 atm, catalyst mass concentration of 5 g / L initial concentration of phenol and 0.5 g / L. The catalytic tests were performed in a slurry agitated reactor provided with temperature, pressure and agitation control and reactor liquid sampling. The influences of iron loaded on the support (0.3; 7 and 10%, m/m) and the initial pH of the reactant medium (3.1; 6.8; 8.7) were studied. The iron dispersion on the palygorskite, the phase purity and the elemental composition of the catalyst were evaluated by X-Ray Difraction (XRD), Scanning Electron Microscopy (SEM) and X-Ray Flourescence (XRF). The use of palygorskite as support to increase the surface area was confirmed by the B.E.T. surface results. The phenol degradation curves showed that the Fe3+ over palygorskite when compared with the other materials tested has the best performance toward the (Total Organic carbonic) TOC conversion. The decrease in alkalinity of the reaction medium also favors the conversion of TOC. The maximum conversion obtained from the TOC with the catalyst 3% Fe / palygorskite was around 95% for a reaction time of 60 minutes, while reducing the formation of acids, especially acetic acid. With products obtained from wet oxidation of phenol, hydroquinone, p-benzoquinone, catechol and oxalic acid, identified and quantified by High Performance Liquid Chromatography was possible to propose a reaction mechanism of the process where the phenol is transformed into the homogeneous and heterogeneous phase in the other by applying a kinetic model, Langmuir-Hinshelwood type, with evaluation of kinetic constants of different reactions involved.

Hidróxido de níquel suportado em carbono: um catalisador de baixo custo para a eletro-oxidação de alcoóis em meio alcalino

Conselho Nacional de Desenvolvimento Científico e Tecnológico (CNPq)

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