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

Reforma a vapor catalítica do metano: Otimização da produção e seletividade em hidrogênio por absorção in situ do CO2 produzido

Topics of research related to energy and environment have significantly grown in recent years, with the need of its own energy as hydrogen. More particularly, numerous researches have been focused on hydrogen as energy vector. The main portion of hydrogen is presently obtained by reforming of methane or light hydrocarbons (steam, oxy, dry or auto reforming). During the methane steam reforming process the formation of CO2 undesirable (the main contributor to the greenhouse effect) is observed. Thus, an oxide material (sorbent) can be used to capture the CO2 generated during the process and simultaneously shifting the equilibrium of water gas shift towards thermodynamically more favorable production of pure hydrogen. The aim of this study is to develop a material with dual function (catalyst/sorbent) in the reaction of steam reforming of methane. CaO is well known as CO2 sorbent due to its high efficiency in reactions of carbonation and easy regeneration through calcination. However the kinetic of carbonation decreases quickly with time and carbonation/calcination cycles. A calcium aluminate (Ca12Al14O33) should be used to avoid sintering and increase the stability of CaO sorbents for several cycles. Nickel, the industrial catalyst choice for steam reforming has been added to the support from different manners. These bi-functional materials (sorbent/catalyst) in different molar ratios CaO.Ca12Al14O33 (48:52, 65:35, 75:25, 90:10) were prepared by different synthesis methodologies, among them, especially the method of microwave assisted self-combustion. Synthesis, structure and catalytic performances of Ni- CaO.Ca12Al14O33 synthesized by the novel method (microwave assisted selfcombustion) proposed in this work has not being reported yet in literature. The results indicate that CO2 capture time depends both on the CaO excess and on operating conditions (eg., temperature and H2O/CH4 ratio). To be efficient for CO2 sorption, temperature of steam reforming needs to be lower than 700 °C. An optimized percentage corresponding to 75% of CaO and a ratio H2O/CH4 = 1 provides the most promising results since a smaller amount of water avoids competition between water and CO2 to form carbonate and hydroxide. If this competition is most effective (H2O/CH4 = 3) and would have a smaller amount of CaO available for absorption possibly due to the formation of Ca(OH)2. Therefore, the capture time was higher (16h) for the ratio H2O/CH4 = 1 than H2O/CH4 = 3 (7h) using as catalyst one prepared by impregnating the support obtained by microwave assisted self-combustion. Therefore, it was demonstrated that, with these catalysts, the CO2 sorption on CaO modifies the balance of the water gas-shift reaction. Consequently, steam reforming of CH4 is optimized, producing pure H2, complete conversion of methane and negligible concentration of CO2 and CO during the time of capture even at low temperature (650 °C). This validates the concept of the sorption of CO2 together with methane steam reforming

Síntese e caracterização de cerâmicas nanométricas para produção de gás de síntese

In this work, ceramic powders belonging to the system Nd2-xSrxNiO4 (x = 0, 0.4, 0.8, 1.2 and 1.6) were synthesized for their use as catalysts to syngas production partial. It was used a synthesis route, relatively new, which makes use of gelatin as organic precursor. The powders were analyzed at several temperatures in order to obtain the perovskite phase and characterized by several techniques such as thermal analysis, X-rays diffraction, Rietveld refinement method, specific surface area, scanning electron microscopy, energy dispersive spectroscopy of X-rays and temperature programmed reduction. The results obtained using these techniques confirmed the feasibility of the synthesis method employed to obtain nanosized particles. The powders were tested in differential catalytic conditions for dry reforming of methane (DRM) and partial oxidation of methane (POM), then, some systems were chosen for catalytic integrals test for (POM) indicating that the system Nd2-xSrxNiO4 for x = 0, 0.4 and 1.2 calcined at 900 °C exhibit catalytic activity on the investigated experimental conditions in this work without showing signs of deactivation

Preparação e caracterização de catalisadores à base de titânio suportado em MCM-41 para produção de compostos oxigenados através da pirólise catalítica do capim elefante

In recent years, the area of advanced materials has been considerably, especially when it comes to materials for industrial use, such as is the case with structured porosity of catalysts suitable for catalytic processes. The use of catalysts combined with the fast pyrolysis process is an alternative to the oxygenate production of high added value, because, in addition to increasing the yield and quality of products, allows you to manipulate the selectivity to a product of interest, and therefore allows greater control over the characteristics of the final product. Based on these arguments, in this work were prepared titanium catalysts supported on MCM-41 for use in catalytic pyrolysis of biomass, called elephant grass. The reactions of pyrolysis of biomass were performed in a micro pyrolyzer, Py-5200, coupled to GC / MS, the company CDS Corporation, headquartered in the United States. The catalysts Ti-MCM-41 in different molar ratios were characterized by XRD, TG / DTG, FT-IR, SEM, XRF, UV-visible adsorption of nitrogen and the distribution of particle diameter and specific surface area measurement by the BET method. From the catalytic tests it was observed that the catalysts synthesized showed good results for the pyrolysis reaction.The main products were obtained a higher yield of aldehydes, ketones and furan. It was observed that the best reactivity is a direct function of the ratio Si/Ti, nature and concentration of the active species on mesoporous supports. Among the catalysts Ti-MCM-41 (molar ratio Si / Ti = 25 and 50), the ratio Si / Ti = 25 (400 ° C and 600 ° C) favored the cracking of oxygenates such as acids , aldehydes, ketones, furans and esters. Already the sample ratio Si / Ti = 50 had the highest yield of aromatic oxygenates

Síntese e caracterização de catalisadores de LaNiO3 não suportados e suportados em Al2O3 e ZrO2 para a reforma a vapor do metano

Ionic oxides with ABO3 structure, where A represents a rare earth element or an alkaline metal and B is a transition metal from group VIII of the periodic table are potential catalysts for oxidation and good candidates for steam reforming reaction. Different methods have been considered for the synthesis of the oxide materials with perovskite structure to produce a high homogeneous material with low amount of impurities and low calcination temperatures. In the current work, oxides with the LaNiO3 formula had been synthesized using the method of the polymeric precursors. The thermal treatment of the materials took place at 300 ºC for 2h. The material supported in alumina and/or zirconia was calcined at 800 ºC temperature for 4h. The samples had been characterized by the following techniques: thermogravimetry; infrared spectroscopy; X-ray diffraction; specific surface area; distribution of particle size; scanning electron microscopy and thermo-programmed reduction. The steam reforming reaction was carried out in a pilot plant using reducing atmosphere in the reactor with a mixture of 10% H2-Argon, a mass about 5g of catalyst, flowing at 50 mL.min-1. The temperature range used was 50 - 1000 oC with a heating rate of 10 oC.min-1. A thermal conductivity detector was used to analyze the gas after the water trapping, in order to permit to quantify the consumption of hydrogen for the lanthanum nickelates (LaNiO3). The results showed that lanthanum nickelate were more efficient when supported in alumina than when supported in zirconia. It was observed that the methane conversion was approximately 100% and the selectivity to hydrogen was about 70%. In all cases were verified low selectivity to CO and CO2

Pirólise térmica e catalítica de resíduos de vácuo gerados no refino de petróleo

In this study, was used a very promising technique called of pyrolysis, which can be used for obtaining products with higher added value. From oils and residues, since the contribution of heavier oils and residues has intensified to the world refining industry, due to the growing demand for fuel, for example, liquid hydrocarbons in the range of gasoline and diesel. The catalytic pyrolysis of vacuum residues was performed with the use of a mesoporous material belonging the M41S family, which was discovered in the early 90s by researchers Mobil Oil Corporation, 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 arrangement of mesopores with pore diameters between 2 and 10 nm and a high specific surface area, making it very promising for use as a catalyst in petroleum refining for catalytic cracking, and their mesopores facilitate the access of large hydrocarbon molecules. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more positive for application in the petrochemical industry. The mesoporous material of the type Al-MCM41 (ratio Si / Al = 50) was synthesized by hydrothermal method starting from the silica gel, NaOH and distilled water added to the gel pseudobohemita synthesis. Driver was used as structural CTMABr. Removal of organic driver (CTMABr) was observed by TG / DTG and FTIR, but this material was characterized by XRD, which was observed the formation of the main peaks characteristic of mesoporous materials. The analysis of adsorption / desorption of nitrogen this material textural parameters were determined. The vacuum residues (VR's) that are products of the bottom of the vacuum distillation tower used in this study are different from oil fields (regions of Ceará and Rio de Janeiro). Previously characterized by various techniques such as FTIR, viscosity, density, SARA, elemental analysis and thermogravimetry, which was performed by thermal and catalytic degradation of vacuum residues. The effect of AlMCM-41 was satisfactory, since promoted a decrease in certain ranges of temperature required in the process of conversion of hydrocarbons, but also promoted a decrease in energy required in the process. Thus enabling lower costs related to energy expenditure from degradation during processing of the waste

Reforma a seco de metano com catalisadores Ni/MCM-41 sintetizados a partir de fontes alternativas de sílica

The production of synthesis gas has received renewed attention due to demand for renewable energies to reduce the emissions of gases responsible for enhanced greenhouse effect. This work was carried out in order to synthesize, characterize and evaluate the implementation of nickel catalysts on MCM-41 in dry reforming reactions of methane. The mesoporous molecular sieves were synthesized using as silica sources the tetraethyl orthosilicate (TEOS) and residual glass powder (PV). The sieves were impregnated with 10% nickel to obtain the metallic catalysts (Ni/MCM-41). These materials were calcined and characterized by Thermogravimetric Analysis (TG), Infrared spectroscopy (FTIR), X-ray Diffraction (XRD), Temperature-Programmed Reduction (TPR) and N2 Adsorption/Desorption isotherms (BET/BJH). The catalytic properties of the samples were evaluated in methane dry reforming with CO2 in order to produce synthesis gas to be used in the petrochemical industry. The materials characterized showed hexagonal structure characteristic of mesoporous material MCM-41 type, being maintained after impregnation with nickel. The samples presented variations in the specific surface area, average volume and diameter of pores based on the type of interaction between the nickel and the mesoporous support. The result of the the catalytic tests showed conversions about 91% CO2, 86% CH4, yelds about 85% CO and 81% H2 to Ni/MCM-41_TEOS_C, and conversions about 87% CO2, 82% CH4, yelds about 70% CO and 59% H2 to Ni/MCM-41_PV_C. The similar performance confirms that the TEOS can be replaced by a less noble materials

Pirólise rápida catalítica do capim elefante utilizando materiais mesoporosos e óxidos metálicos para deoxigenação em bio-óleo

The fast pyrolysis of lignocellulosic biomass is a thermochemical conversion process for production energy which have been very atratactive due to energetic use of its products: gas (CO, CO2, H2, CH4, etc.), liquid (bio-oil) and charcoal. The bio-oil is the main product of fast pyrolysis, and its final composition and characteristics is intrinsically related to quality of biomass (ash disposal, moisture, content of cellulose, hemicellulose and lignin) and efficiency removal of oxygen compounds that cause undesirable features such as increased viscosity, instability, corrosiveness and low calorific value. The oxygenates are originated in the conventional process of biomass pyrolysis, where the use of solid catalysts allows minimization of these products by improving the bio-oil quality. The present study aims to evaluate the products of catalytic pyrolysis of elephant grass (Pennisetum purpureum Schum) using solid catalysts as tungsten oxides, supported or not in mesoporous materials like MCM-41, derived silica from rice husk ash, aimed to reduce oxygenates produced in pyrolysis. The biomasss treatment by washing with heated water (CEL) or washing with acid solution (CELix) and application of tungsten catalysts on vapors from the pyrolysis process was designed to improve the pyrolysis products quality. Conventional and catalytic pyrolysis of biomass was performed in a micro-pyrolyzer, Py-5200, coupled to GC/MS. The synthesized catalysts were characterized by X ray diffraction, infrared spectroscopy, X ray fluorescence, temperature programmed reduction and thermogravimetric analysis. Kinetic studies applying the Flynn and Wall model were performed in order to evaluate the apparent activation energy of holoceluloce thermal decomposition on samples elephant grass (CE, CEL and CELix). The results show the effectiveness of the treatment process, reducing the ash content, and were also observed decrease in the apparent activation energy of these samples. The catalytic pyrolysis process converted most of the oxygenate componds in aromatics such as benzene, toluene, ethylbenzene, etc

A encruzilhada da vida política em assentamentos de reforma agrária no Rio Grande do Norte

The rural settlements represent a mark in the expensive historical process of fight by the land in Brazil. At first offer basic terms of survival, through the access the land and of the fundamental supports for exploration. At the same time, have stimulated organization forms politicizes of the families who manage to work with the new challenges of the everyday. The moment that follows the land conquest, and therefore, the settlements construction while life and work project, it is crossed for objective and subjective demands, with highlight for options of agricultural production and strategies of collective action. Originally formed as representation instance legitimates of the families - front to the government and social actors - the settlers associations are private spaces for political sociability, that guided by principles participative, can lead the settlers the new conquests through indeed democratic experiences. The goal of this work is to comprehend the participation forms in the scope of these associations and the way as that translates in life best terms for the group, from the settlements experiences located in the Territories of the Citizenship Mato Grande and Açu-Mossoró, in Rio Grande do Norte's State. The theoretical conceptions that guide this analysis are concentrate on discussions about democracy and participation (Patermam, Putnam, Bodernave) and in the reflections about the rural world (Medeiros, Martins, Woodman e Woodman and Bergamansco). About methodological, different point of view strategies were developed: The direct observation, the application in locate of questionnaires to the families settlers and interviews semi-structured with the internal leaderships. With that could verify that the participation forms in the associations operate in two heartfelt: Of a side, they promote assimilation opportunities of democratic abilities accompanied of notions of social rights and redefinition of political standards; Of another, it offers indeed the possibility of the settlers lead, with relative autonomy, the political organization and her changes in direction to a way of life that wish to have in the settling

"Reforma urbana já"; "arroz, feijão, saúde e habitação" :A luta por moradia na grande João Pessoa

Our object of study in this work concerns to the movement of fight for the housing in the Great João Pessoa, Paraíba, Brazil, and looks for to investigate the conditions and context of the occupations of building, public or private, for devoid populations that do not have where to live. Front to the absence of politics effective directed to the habitation or the cities, in a picture of unemployment and impoverishment of the population, the result of the habitation point of view, is the absolute lack of popular housings, the degradation of the cities and the growth of the number of homeless and also of its occupations. The urban occupations today represent a reply of these devoid populations that from an involvement with parties or Not Governmental Organizations, and social movements leave for the class action known by the occupation of abandoning public or private buildings. These occupations, even so initially if assume as pressure instrument or of visibility for attainment of housings, for the delay in obtaining the attention of the public agencies and a solution for the problem, becomes definitive or is drawn out per many years. E this if gives although the deficiencies, of the accumulation or families neither in an adequate, always precarious space nor in sanitary installations, that the necessary privacy does not allow. The study it consisted of an empirical research, through the participant comment and open and half-open interviews, and counted on the audiovisual register of two occupations, one in the downtown of João Pessoa City (old building of the INSS, in the Ponto dos Cem Réis) and other (Community of the Cajueiro), next to the Beach "Praia do Jacaré", in the city of Cabedelo.The choice of the Visual Anthropology as research instrument is on to a concern in better translating other ways of life, therefore the accomplishment of the video in allows them to know with more precision the reality where the citizens of the research live. We also use as methodological resource in the research the deepened interview, in intention to better understand the description of the way of life of the studied families and the movements of fight for the housing, particularly the MDM - Movement of Right for the Housing, and the MNLM- Nacional Movement of Fight for the Housing

Reforma administrativa e gestão de políticas sociais em Mossoró: a falácia dos atores institucionais e sociais

The thesis entitled The administrative reform and social political management in Mossoró: the institutional and social staff's falacy. Comprehends a moment of apprehensiveness and analysis in the reestrcturing process of the city, whose process will show the formation of strategies and deployment of its relation with the social political affectiveness. It represents a single moment in the approach of such a kind of experience in the city. The analysis starts from the third mandate of the Mayor Rosalba Ciarlini Rosado, during the quadriennium 2001/2004, for being the time in which the public management got materialized, such as in the operational way of the social politics. For that, we delimitate this study in two distinct moments: the first one refers to the reform elaboration from the creation of the additional law nº 001/2000 GP/PMM: the second one refers to a practical reform from the social and institutional staff's speech. Within that scenary it was seen that the approaching, though partially, the State Reform and, consequently, the master plan of the state apparatus, which were made of theoretical matrices of such a project locally. However, that is a complex experience, that required the use of field and documental research for the proposed investigation and at the same time, prove the guiding hypothesis of it, what means a grouping of areas like: education, healthy, and social development in only one department City Citizenship Department that is able to materialize a new intitutional arrangement, according to the management principles in the public administration at the govern local level, configuring a reform and not just an institutional adequacy. In that context, it got necessary to apprehending the institutional and social actors' falacy as a way to prove or not the presented hypothesis. Among the first staff, we have the mayor's direct leaders and advisors' perception that express the politcal administrative aspects of the reform and, in the second, the perception of the political view of what has changed concerning the management of the social politics

Desenvolvimento e políticas públicas: uma avaliação do PRONAF nos assentamentos de reforma agrária do Rio Grande do Norte

The research DEVELOPMENT AND PUBLIC POLICY: AN EVALUATION OF PRONAF IN THE SETTLEMENTS AGRARIAN REFORM OF RIO GRANDE DO NORTE aimed to evaluate the effectiveness of the National Program for Strengthening Family enhancerelement od development in rural settlements od Rio Grande do Norte. The methodological approach consisted of the completion of desk research and literature on development issues, policies, and rural credit and field research through semi- structured interviews with managers and technicians who work with the program and conducting focus with farmers settles who accessed the PRONAF the period from 2000 to 2006. The survey results confirm the central hypothesis of this work, that acces to PRONAF A is not causing efetivations relevant in the lives of farm workers settlers in Rio Grande do Norte. In the setllements where efetivations these occur, they are short of what the program intends to carry out and rely on a set of conditionalities that are beyond the operational frameworks of the same. Such questions point to the need to revise the program in order to estabilish adjustments that in practice the approach of the proposed objectives. For this purpose it is necessary to invest in factor that contribute to the program has a positive effect not only to increase income, but to contribute to the autonomy of the resettled farmers, expanding its capabilities and increased the power of choise with respect to life who wish to take

Desenvolvimento como acesso às políticas públicas: a reforma do estado e a concretização dos direitos prestacionais

The state s evolution, after its liberal and the social stages, arrives at the post-social state, also regarded as regulatory state, which, in order to accomplish the state s aims, employs indirect interventions in the economy. The new model of administration adapts principles and concepts form the private sector such as the quest for efficience and tangible results, also striving for the decentralization of state s power to improve effectiveness before the new paradigm of handling of affairs of public interest. Present state derives its legitimacy from the efficiency principle, the legitimacy of the public administration cannot be limited to an analysis of legality, but the fulfillment of the ends envisaged by the public authority on its policies. These public policies have the objective of satisfying fundamental rights of the citizens. The access to public policies set by states as a way of enjoyment of the aforementioned rights constitute a legal and demandable path of development. The creation of public policies and the access to them must abide to the efficiency principle. This access must be taken unther the principles of legal and material equality, inasmuch as the liberty and real liberty. The access must also be observed as a matter of limited resources to grant, in reality, the access and enjoyment of these rights. The demandable nature of the access to public policies binds the public authority into broadening the range of these policies to every one who needs them. Thus, in this spectrum, the role of the Regulatory State, as the legal instruments for access of public policies as a legal path to development, is analyzed in the present work

Vida, experiência, conhecimento : a reforma do sujeito cognoscente em Tsunessaburo Makiguchi

Utilizing a great part of the works by Japanese educator Tsunesaburo Makiguchi and the register of fragments of his life, this thesis affirms that knowledge emerges from peoples` experience as they go about their daily lives. Facts, events, genetic inheritance, cultural patrimony, family history, the place where one was born and lived, and psychological predispositions nurture and form a vision of the world and of life in general. In Makiguchi s case, this multi-causal constellation led him to conceive the system of the value-creating pedagogy of good, gain and beauty; discussing the importance of cognition and evaluation in the experience of the human being. His life is exemplary in demonstrating that these aspects are inter-connected and, in a recursive movement between knowledge and self-knowledge, they can generate creative systems for understanding the world and introducing, essentially, the author into the epistemological problematic of complexity. The Makiguchian system and Edgar Morin s complexity approach suggest a pragmatic, paradigmatic reform of education and a thought reformation in the direction of the complex pedagogy, and that it creates a web that connects master-disciple, subject-object, human-world, local-global and singular-universal

O ideário modernizador do governo graccho cardoso (1922-26) e a reforma da instrução pública de 1924 em Sergipe

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