Síntese e caracterização de NiO-CGO para anodo e eletrólitos sólidos e base de Céria para SOFC

The direct use of natural gas makes the Solid Oxide Fuel Cell (SOFC) potentially more competitive with the current energy conversions technologies. The Intermediate Temperature SOFC (IT-SOFC) offer several advantages over the High Temperature SOFC (HT-SOFC), which includes better thermal compatibility among components, fast start with lower energy consumption, manufacture and operation cost reduction. The CeO2 based materials are alternatives to the Yttria Stabilized Zirconia (YSZ) to application in SOFC, as they have higher ionic conductivity and less ohmic losses comparing to YSZ, and they can operate at lower temperatures (500-800°C). Ceria has been doped with a variety of cations, although, the Gd3+ has the ionic radius closest to the ideal one to form solid solution. These electrolytes based in ceria require special electrodes with a higher performance and chemical and termomechanical compatibility. In this work compounds of gadolinia-doped ceria, Ce1-xGdxO2-δ (x = 0,1; 0,2 and 0,3), used as electrolytes, were synthesized by polymeric precursors method, Pechini, as well as the composite material NiO - Ce0,9Gd0,1O1,95, used as anode, also attained by oxide mixture method, mixturing the powders of the both phases calcinated already. The materials were characterized by X ray diffraction, dilatometry and scanning electronic microscopy. The refinement of the diffraction data indicated that all the Ce1-xGdxO2-δ powders were crystallized in a unique cubic phase with fluorite structure, and the composite synthesized by Pechini method produced smaller crystallite size in comparison with the same material attained by oxide mixture method. All the produced powders had nanometric characteristics. The composite produced by Pechini method has microstructural characteristics that can increase the triple phase boundaries (TPB) in the anode, improving the cell efficiency, as well as reducing the mass transport mechanism effect that provokes anode degradation

Sinterização de Ce1-XEuXO2-(X/2) para aplicação como eletrólito sólido em células a combustível de temperaturas intermediárias

Given the environmental concern over global warming that occurs mainly by emission of CO2 from the combustion of petroleum, coal and natural gas research focused on alternative and clean energy generation has been intensified. Among these, the highlight the solid oxide fuel cell intermediate temperature (IT-SOFC). For application as electrolyte of the devices doped based CeO2 with rare earth ions (TR+ 3) have been quite promising because they have good ionic conductivity and operate at relatively low temperatures (500-800 ° C). In this work, studied the Ce1-xEuxO2-δ (x = 0,1, 0,2 and 0,3), solid solutions synthesized by the polymeric precursor method to be used as solid electrolyte. It was also studied the processing steps of these powders (milling, compaction and two step sintering) in order to obtain dense sintered pellets with reduced grain size and homogeneous microstructure. For this, the powders were characterized by thermal analysis, X-ray diffraction, particle size distribution and scanning electrons microscopy, since the sintered samples were characterized by dilatometry, scanning electrons microscopy, density and grain size measurements. By x-ray diffraction, it was verified the formation of the solid solution for all compositions. Crystallites in the nanometric scale were found for both sintering routes but the two step sintering presented significant reduction in the average grain size

Avaliação do efeito de particulados sólidos na eficiência de um inibidor de corrosão recomendado para meios salinos com CO2

The main problem on the exploration activity on petroleum industry is the formation water resulted on the fields producing. The aggravating of this problem is correlated with the advancing technologies used on the petroleum extractions and on its secondary approach objecting the reobtainment of this oil. Among the main contaminants of the water formation are corrosives gases such as: O2, CO2 and H2S, some solids in suspension and dissolved salts. Concerning to those gases the CO2 is the one that produce significant damage for carbon steel on corrosion process of the petroleum and gas industries. Corrosion inhibitors for carbon steel in formation water is one of the most used agents in control of those damages. In this context, the poor investigations of carbon steel corrosion proceeding from solids in suspension is an opened field for studies. On this work the inhibitor effect of the commercial CORRTREAT 703 was evaluated on some specific solids in suspension at saline medium containing 10.000 ppm of de-aerated chloride using CO2 until non oxygen atmosphere been present. For that, quartz, calcium carbonate, magnetite and iron sulphide were subjected to this investigation as the selected solids. The effect of this inhibitor on corrosion process correlated with those specific solids, was measured using electrochemical (resistance of linear polarization and galvanic pair) and gravimetrical techniques. During all the experimental work important parameters were monitored such as: pH, dissolved oxygen, temperature, instantaneous corrosion rate and galvanic current. According to the obtained results it was proved that the suspension solids calcium carbonate and iron sulphide decrease the corrosion process in higher pH medium. Meanwhile the quartz and magnetite been hardness increase corrosion by broking of the passive layer for erosion. In the other hand, the tested inhibitor in concentration of 50 ppm, showed to be effective (91%) in this corrosion process

Estudo de Matérias-Primas do Rio Grande do Norte para Uso em Revestimento Poroso: Influência do teor de dolomita e temperatura de calcinação nas propriedades físico-mecânicas

The state of Rio Grande do Norte presents a great potentiality for the production of ceramic tiles because of having natural raw material in quantity and quality making its economical exploration possible, beyond the great energetic differential of the state, the natural gás. This works aims to study the influence of the dolomite and granulometry concentration and calcinations temperature in the obtaining of formulations for porous coverings which have to be coherent to the project,s specifications. The experiments have involved the physical-chemical and mineralogical characterizations of raw materials and mechanical tests in the dry and burnt proof bodies preceding a mixture experiment planning with the use of the response surface methodology, in order to get the best raw materials combinations to produce a ceramic mass with specific properties. The twelve ceramic masses studied in this work were prepared by the via dry process, characterized, shaped by uniaxial pressing and sinterized in the temperatures of 940ºC, 1000ºC, 1060ºC, 1120ºC and 1180ºC, using a fast burning cycle. The crystalline phases formed during the sintering in the temperatures in study have revealed the presence of anorthite and diopside beyond quartz with a remaining phase. These phases were the main responsible ones by the physical- mechanical properties of the sinterized proof bodies. The proof bodies after the sintering stage have presented water absorption higher than 10% and a good dimensional stability in all studied temperatures. However, the flexural breaking strength results in the temperatures of 940ºC, 1000ºC and 1060ºC, under the temperature zone of the vitrification of ceramic whiteware do not reach the flexural breaking strength specific for the porous wall tile (15 MPa), but in the temperature of 1120ºC next to the vitrification temperature zone, some whiteware ceramic (formulations) has reached the specified value for the porous wall tile. The results of this work have showed that the studied raw materials have great importance for used in the production of porous wall tiles (BIII)

Análise das emissões gasosas de um veículo flex funcionando com diferentes combustíveis

Efforts in research and development of new technologies to reduce emission levels of pollutant gases in the atmosphere has intensified in the last decades. In this context, it can be highlighted the modern systems of electronic engine management, new automotive catalysts and the use of renewable fuels which contributes to reduce the environmental impact. The purpose of this study was a comparative analysis of gas emissions from a automotive vehicle, operating with different fuels: natural gas, AEHC or gasoline. To execute the experimental tests, a flex vehicle was installed on a chassis dynamometer equipped with a gas analyzer and other complementary accessories according to the standard guidelines of emission and security procedures. Tests were performed according to NBR 6601 and NBR 7024, which define the urban and road driving cycle, respectively. Besides the analysis of exhaust gases in the discharge tube, before and after the catalyst, using the suction probe of the gas analyzer to simulate the vehicle in urban and road traffic, were performed tests of fuel characterization. Final results were conclusive in indicating leaded gasoline as the fuel which most contributed with pollutant emissions in atmosphere and the usual gasoline being the fuel which less contributed with pollutant emissions in atmosphere

Avaliação da corrosão em dutos por técnica gravimétrica e de resistência elétrica

With the increasing of demand for natural gas and the consequent growth of the pipeline networks, besides the importance of transport and transfer of oil products by pipeline, and when it comes to product quality and integrity of the pipeline there is an important role regarding to the monitoring internal corrosion of the pipe. This study aims to assess corrosion in three pipeline that operate with different products, using gravimetric techniques and electrical resistance. Chemical analysis of residues originated in the pipeline helps to identify the mechanism corrosive process. The internal monitoring of the corrosion in the pipelines was carried out between 2009 and 2010 using coupon weight loss and electrical resistance probe. Physico-chemical techniques of diffraction and fluorescence X-rays were used to characterize the products of corrosion of the pipelines. The corrosion rate by weight loss was analyzed for every pipeline, only those ones that has revealed corrosive attack were analyzed located corrosion rate. The corrosion potential was classified as low to pipeline gas and ranged from low to severe for oil pipelines and the pipeline derivatives. Corrosion products were identified as iron carbonate, iron oxide and iron sulfide

Os conflitos de competência normativa do estado regulador brasileiro no setor administrado pela ANP

The dissertation has by objective describe the administrative activity of regulation exercised by independent regulatory agencies, observing that this activity was already done before this structures creation, however, after a really deep administrative reform that had as objective built a Public Administration with more efficiency, it passed to be done with some own peculiarities of these new structures of regulation. The work gave especial attention to what concern the conflicts of normative competency that really often happen between ANP (Agência Nacional do Petróleo, Gás Natural e Biocombustíveis) and the legislatives organs of the Republic Federative of Brazil, because energetic area has unbelievable mater to any country, and the fact of some juridical norm be against the law and be accepted is very dangerous, it affronts the constitutional principle of the legality e may put in risk the democratic Estate of law, them, regulatory dogmatic must be scientifically knows, and developed, thought and especially there are so many doctrinaires divergences about regulation constitutionality. As a theorist point, the investigation got the Logical nocontradiction principle, according Hans Kelsen and Lourival Vilanova thought, doing a philosophical reflection about the system of positive law, in which there are many antinomies, or conflicts of norms, what include the conflicts of the administrative acts expedited by ANP and the legislation of the brazilian regulatory Estate. For a better understanding and exemplify some perplexities treated by the doctrinaire angle, this work did a lucubration about a possibility of a normative conflict between a ANP resolution and the municipal legislation in a specific case, also, brought several jurisprudences for the brazilians courts of justice, that confirm the empiric existence of normative conflicts among ANP s administrative norms and federal legislation. Finally, concludes observing that the regulation is not a legislative competency delegation to regulatory agencies, is just a new exercise of the administrative function, it is a technical specialization of the public administration, that using this know-how can acting with more efficiency, however the normative power of regulatory agencies must respect the empire of law, so in this terms, the dissertation suggests the ponderation of the constitutionals principles of efficiency and legality how form to harmonizing the democratic legitimate inherent to legal norm supremacy, with the perspective of an efficient economic and institutional development

A revenda de combustível e os limites constitucionais para a sua regulação: uma análise aplicada aos aspectos concorrênciais e ao controle de preços

The gas retail represents the end of a section of the oil and natural gas derivative chain, for it is at this stage where the commercialization of those merchandises takes place towards the costumers. This process involves an enormous amount of economic agents, which reflects on an activity of great influence on the citizen's everyday. By the time of the gas retail price liberalization, in 2002, there were great expectations towards that measure, for the insertion of that segment in a competitive market was likely to create a decrease in prices. As there was not a drastic drop off in cost, the question was no longer the price itself, but, predominantly, the conduct taken by the economic agents that operate the market. Not in vain, the segment introduces a greater number of different procedures combined with the organs that compose the Brazilian System of Competition Protection. What is understood, however, is that many of these complaints are made in a lightly way, without a proper analysis of the market and its practices, that being why, in this paper, evidences the causes of these complaints and explained what, in fact, occurs in this market. Also, the organs that protect the free initiative in the sector use different methods to assess anticompetitive practices, which are counterproductive on the combat of anticompetitive practice, that being why the present paper analyzes the used methods on a critic perspective, choosing one which is believed to be the most adequate. The present work also tries to present the gas retail prices on a constitutional, free competition, free initiative and consumers defense perspective, analyzing the competition s aspects on the gas market; the shaping of the gas prices; the market boundaries; the anti-competitive practices under the gas market; and analyze the possibility, according to the defined economic standards in the constitutional text of existing a greater control or gas price indexing and/or regulation which limits the distributors and resellers profit on gas. Still, in consequence of this analysis, a study on Natal s market behavior will be developed in its competitive feature. That being said, moreover being a theoretical-descriptive study, data and statistics gathered is used, which will lead, willing to grasp an experiential study on a few aspects of the Potiguar gas retail market

Caminhos e descaminhos dos municípios produtores de petróleo: o papel dos royalties no desempenho das finanças públicas municipais no estado do Rio Grande do Norte

It analyzes the magnitude, the nature and the direction of public revenues and the public expenses in oil and natural gas producing municipalities in the state of Rio Grande do Norte in the post-constituent period, and, more precisely, from the approval of Law 9.478/97, called Oil Law . It argues the fiscal federalism normative theory, the typology and the role of the intergovernamental transferences in the performance of the public finances of the local governments. Shows that the economy of Rio Grande do Norte went through deep social-economic changes in the last few decades, among which includes the discovery of the oil and the natural gas and its importance for the growth of the industrial and services sectors. It points out that the increase of the production and the international price of the oil contributed for the growth in revenues of royalties and the special participation in the beneficiary cities, what did not mean an automatic increase in the resources destined to the investment and in the quality on the provision of the goods and services come back toward the local development. On the contrary, the main conclusion of the work is that the trajectory of the oil producing municipalities is marked by paths and embezzlements in the performance of the public finances and in the provision of public goods and services. Paths, that lead to the improvement of the performance of the public finances and the quality of the public goods and services. Embezzlements, that lead to the inefficiency in the provision of goods and services and the capture of the public resources. That is, the fiscal decentralization is a necessary condition, however not enough to improve the amount and the quality of the public goods and services given by these municipalities. For that it is necessary to advance in the fiscal federalism normative theories, in search of optimum model of federalism in local governments where still predominated by patrimonialism, clientelism, fiscal illusion and the capture of the public resources in benefit of the private interests

Modelagem de decisão na seleção de equipamento: um estudo usando o processo analítico hierárquico na contratação de sondas de perfuração de poços de petróleo

The main goal of this dissertation is to develop a Multi Criteria Decision Aid Model to be used in Oils and Gas perforation rigs contracts choices. The developed model should permit the utilization of multiples criterions, covering problems that exist with models that mainly use the price of the contracts as its decision criterion. The AHP has been chosen because its large utilization, not only academic, but in many other areas, its simplicity of use and flexibility, and also fill all the requirements necessary to complete the task. The development of the model was conducted by interviews and surveys with one specialist in this specific area, who also acts as the main actor on the decision process. The final model consists in six criterions: Costs, mobility, automation, technical support, how fast the service could be concluded and availability to start the operations. Three rigs were chosen as possible solutions for the problem. The results reached by the utilizations of the model suggests that the utilization of AHP as a decision support system in this kind of situation is possible, allowing a simplifications of the problem, and also it s a useful tool to improve every one involved on the process s knowledge about the problem subject, and its possible solutions

Um Estudo de Politicas e Práticas do uso do GNV no transporte público urbano do Brasil

The use of Natural Gas Vehicle has had a fast increase lately. However, in order to have a continuous success this Program needs to develop converting devices of Otto-cycle engines, gasoline or alcohol, to the use of NGV (Natural Gas Vehicle) that presents low cost, maintaining the same original development of the vehicle and low level of emissions, considering the PROCONVE rules. Due to the need to diversify the matrix in order to avoid energetic dependence and due to strict pollution control, it has increased in the Brazilian market the number of vehicles converted to the use of NGV. The recent regulation of the PROCONVE, determining that the converted engines with kits should be submitted to emission testing, comes to reinforce the necessity of the proposed development. Therefore, if we can obtain kits with the characteristics already described, we can reach a major trust in the market and obtain an increase acceptance of the vehicle conversion for NGV. The use of natural gas as vehicle fuel presents several advantages in relation to liquid fuels. It is a vehicle fuel with fewer indexes of emissions when compared to diesel; their combustion gases are less harmful, with a major level of safety than liquid fuels and the market price is quite competitive. The preoccupation that emerges, and the motivation of this project, is to know which are the main justifications for such technology, well accepted in other countries, with a low index or emission, with a high level of safety, where its maintenance becomes low, reminding that for this it is necessary that this technology has to be used properly, and once available in the market will not motivate interest in the urban transportation companies in Brazil, in research centers in general. Therefore this project exists to show the society in a general way the current vision of the main governmental factors, of the national research centers and of the private companies concerning the use of natural gas vehicles in urban transport vehicles, in order to give a major reliability to the population as well as to motivate national market competitiveness with a low cost and reliable product and to enrich the national technology

Técnicas de inteligência artificial para a geração dinâmica de set points para uma coluna de destilação

Artificial Intelligence techniques are applied to improve performance of a simulated oil distillation system. The chosen system was a debutanizer column. At this process, the feed, which comes to the column, is segmented by heating. The lightest components become steams, by forming the LPG (Liquefied Petroleum Gas). The others components, C5+, continue liquid. In the composition of the LPG, ideally, we have only propane and butanes, but, in practice, there are contaminants, for example, pentanes. The objective of this work is to control pentane amount in LPG, by means of intelligent set points (SP s) determination for PID controllers that are present in original instrumentation (regulatory control) of the column. A fuzzy system will be responsible for adjusting the SP's, driven by the comparison between the molar fraction of the pentane present in the output of the plant (LPG) and the desired amount. However, the molar fraction of pentane is difficult to measure on-line, due to constraints such as: long intervals of measurement, high reliability and low cost. Therefore, an inference system was used, based on a multilayer neural network, to infer the pentane molar fraction through secondary variables of the column. Finally, the results shown that the proposed control system were able to control the value of pentane molar fraction under different operational situations

Desenvolvimento de um software de comunicação sem fio aplicado à instrumentação de unidade de elevação de petróleo tipo Plunger Lift

This dissertation aims to develop a software applied to a communication system for a wireless sensor network (WSN) for tracking analog and digital variables and control valve of the gas flow in artificial oil s elevation units, Plunger Lift type. The reason for this implementation is due to the fact that, in the studied plant configuration, the sensors communicate with the PLC (Programmable and Logic Controller) by the cables and pipelines, making any changes in that system, such as changing the layout of it, as well as inconveniences that arise from the nature of the site, such as the vicinity s animals presence that tend to destroy the cables for interconnection of sensors to the PLC. For software development, was used communication polling method via SMAC protocol (Simple Medium Access ControlIEEE 802.15.4 standard) in the CodeWarrior environment to which generated a firmware, loaded into the WSN s transceivers, present in the kit MC13193-EVK, (all items described above are owners of Freescale Semiconductors Inc.). The network monitoring and parameterization used in its application, was developed in LabVIEW software from National Instruments. The results were obtained through the observation of the network s behavior of sensors proposal, focusing on aspects such as: indoor and outdoor quantity of packages received and lost, general aspects of reliability in data transmission, coexistence with other types of wireless networks and power consumption under different operating conditions. The results were considered satisfactory, which showed the software efficiency in this communication system

Estudo e especificação de um sistema de instrumentação para unidades de elevação de petróleo utilizando tecnologia sem fio

Wireless sensor networks are reality nowadays. The growing necessity of connectivity between existing industrial plant equipments pushes the research and development of several technologies. The IEEE 802.15.4 LR-WPAN comes as a low-cost and powersaving viable solution, which are important concerns while making decisions on remote sensoring projects. This study intends to propose a wireless communication system which makes possible the monitoring of analogic and/or digital variables (i. e., the pressure studied) involved on the artificial methods for oil and gas lifting. The main issues are: To develop a software based on SMAC Standard in order to create a wireless network to monitoring analogic and/or digital variables; To evaluate the communication link based on the number of lost packets tested in different environments (indoor and outdoor) and To propose an instrumentation system consisting of wireless devices

Análise estatística das emissões de CO e HC produzidas por gases da exaustão veicular oriundos de gasolina, GNV e mistura álcool/gasolina

The vehicles are the main mobile sources of carbon monoxide (CO) and unburned hydrocarbons (HC) released into the atmosphere. In the last years the increment of the fleet of vehicles in the municipal district of Natal-RN it is contributing to the increase of the emissions of those pollutants. The study consisted of a statistical analysis of the emissions of CO and HC of a composed sample for 384 vehicles with mechanization Gasoline/CNG or Alcohol/Gasoline/CNG of the municipal district of Natal-RN. The tests were accomplished in vehicles submitted to Vehicular Safety's Inspection, in the facilities of INSPETRANS, Organism of Vehicular Inspection. An partial gases analyzer allowed to measure, for each vehicle, the levels of CO and HC in two conditions of rotation of the motor (900 and 2500 rpm). The statistical analysis accomplished through the STATISTICA software revealed a sensitive reduction in the efficiency of the converters catalytic after 6 years of use with emission average it is of 0,78% of CO and 156 (ppm) of HC, Which represents approximately 4 (four) times the amount of CO and the double of HC in comparison with the newest vehicles. The result of a Student s t-test, suggests strongly that the average of the emissions of HC (152 ppm), at 900 rpm, is 40% larger than at 2500 rpm, for the motor without load. This result reveals that the efficiency of the catalytic conversion is limited kinetically in low engine speeds. The Study also ends that when comparing the emissions of CO and HC considering the influence of the fuels, it was verified that although the emissions of CO starting from CNG are 62% smaller than arising from the gasoline, there are not significant differences among the emissions of HC originating from of CNG and of the gasoline. In synthesis, the results place the current criteria of vehicular inspection, for exhaust gases, in doubt, leading the creation of emission limits of pollutant more rigorous, because the efficiency of the converters catalytic is sensibly reduced starting from 6 years of use. It is also raised the possibility of modifications in the test conditions adopted by the current norms, specifically in the speed engine, have seen that in the condition without load the largest emission indexes were registered in slow march. That fact that allows to suggest the dismissal of the tests in high speed engine, reducing the time of inspection in half and generating economy of fuel