Modelagem e simulação da solubilidade de sais em sistemas aquosos com Monoetilenoglicol

Primary processing of natural gas platforms as Mexilhão Field (PMXL-1 ) in the Santos Basin, where monoethylene glycol (MEG) has been used to inhibit the formation of hydrates, present operational problems caused by salt scale in the recovery unit of MEG. Bibliographic search and data analysis of salt solubility in mixed solvents, namely water and MEG, indicate that experimental reports are available to a relatively restricted number of ionic species present in the produced water, such as NaCl and KCl. The aim of this study was to develop a method for calculating of salt solubilities in mixed solvent mixtures, in explantion, NaCl or KCl in aqueous mixtures of MEG. The method of calculating extend the Pitzer model, with the approach Lorimer, for aqueous systems containing a salt and another solvent (MEG). Python language in the Integrated Development Environment (IDE) Eclipse was used in the creation of the computational applications. The results indicate the feasibility of the proposed calculation method for a systematic series of salt (NaCl or KCl) solubility data in aqueous mixtures of MEG at various temperatures. Moreover, the application of the developed tool in Python has proven to be suitable for parameter estimation and simulation purposes

Estudo de adsorvente obtido de terras diatomáceas para remoção de metais pesados em águas produzidas: processamento, caracterização e dinâmica em leito fixo

The acceleration of industrial growth in recent decades on all continents aroused the interest of the companies to counter the impacts produced on the environment, spurred primarily by major disasters in the petroleum industry. In this context, the water produced is responsible for the largest volume of effluent from the production and extraction of oil and natural gas. This effluent has in its composition some critical components such as inorganic salts, heavy metals (Fe, Cu, Zn, Pb, Cd, ), presence of oil and chemicals added in the various production processes. In response to impact, have been triggered by research alternative adsorbent materials for water treatment and water produced, in order to removing oils and acids and heavy metals. Many surveys of diatomaceous earth (diatomite) in Brazil involve studies on the physico-chemical, mineral deposits, extraction, processing and applications. The official estimated Jazi are around 2.5 million tonnes, the main located in the states of Bahia (44%) and Rio Grande do Norte (37,4%). Moreover, these two states appear as large offshore producers, earning a prominent role in research of adsorbents such as diatomite for treatment of water produced. Its main applications are as an agent of filtration, adsorption of oils and greases, industrial load and thermal insulator. The objective of this work was the processing and characterization of diatomite diatomaceous earth obtained from the municipality of Macaíba-RN (known locally as tabatinga) as a low cost regenerative adsorbent for removal of heavy metals in the application of water produced treatment. In this work we adopted a methodology for batch processing, practiced by small businesses located in producing regions of Brazil. The characterization was made by X-ray diffraction (XRD), scanning electron microscopy (SEM) and specific surface area (BET). Research conducted showed that the improvement process used was effective for small volume production of diatomite concentrated. The diatomite obtained was treated by calcination at temperature of 900 oC for 2 hours, with and without fluxing Na2CO3 (4%), according to optimal results in the literature. Column adsorption experiments were conducted to percolation of the in nature, calcined and calcined fluxing diatomites. Effluent was used as a saline solution containing ions of Cu, Zn, Na, Ca and Mg simulating the composition of produced waters in the state of Rio Grande do Norte, Brazil. The breakthrough curves for simultaneous removal of copper ions and zinc as a result, 84.3% for calcined diatomite and diatomite with 97.3 % for fluxing. The calcined fluxing diatomite was more efficient permeability through the bed and removal of copper and zinc ions. The fresh diatomite had trouble with the permeability through the bed under the conditions tested, compared with the other obtained diatomite. The results are presented as promising for application in the petroleum industry

Estudo de adsorvente obtido de terras diatomáceas para remoção de metais pesados em águas produzidas: processamento, caracterização e dinâmica em leito fixo

The acceleration of industrial growth in recent decades on all continents aroused the interest of the companies to counter the impacts produced on the environment, spurred primarily by major disasters in the petroleum industry. In this context, the water produced is responsible for the largest volume of effluent from the production and extraction of oil and natural gas. This effluent has in its composition some critical components such as inorganic salts, heavy metals (Fe, Cu, Zn, Pb, Cd, ), presence of oil and chemicals added in the various production processes. In response to impact, have been triggered by research alternative adsorbent materials for water treatment and water produced, in order to removing oils and acids and heavy metals. Many surveys of diatomaceous earth (diatomite) in Brazil involve studies on the physico-chemical, mineral deposits, extraction, processing and applications. The official estimated Jazi are around 2.5 million tonnes, the main located in the states of Bahia (44%) and Rio Grande do Norte (37,4%). Moreover, these two states appear as large offshore producers, earning a prominent role in research of adsorbents such as diatomite for treatment of water produced. Its main applications are as an agent of filtration, adsorption of oils and greases, industrial load and thermal insulator. The objective of this work was the processing and characterization of diatomite diatomaceous earth obtained from the municipality of Macaíba-RN (known locally as tabatinga) as a low cost regenerative adsorbent for removal of heavy metals in the application of water produced treatment. In this work we adopted a methodology for batch processing, practiced by small businesses located in producing regions of Brazil. The characterization was made by X-ray diffraction (XRD), scanning electron microscopy (SEM) and specific surface area (BET). Research conducted showed that the improvement process used was effective for small volume production of diatomite concentrated. The diatomite obtained was treated by calcination at temperature of 900 oC for 2 hours, with and without fluxing Na2CO3 (4%), according to optimal results in the literature. Column adsorption experiments were conducted to percolation of the in nature, calcined and calcined fluxing diatomites. Effluent was used as a saline solution containing ions of Cu, Zn, Na, Ca and Mg simulating the composition of produced waters in the state of Rio Grande do Norte, Brazil. The breakthrough curves for simultaneous removal of copper ions and zinc as a result, 84.3% for calcined diatomite and diatomite with 97.3 % for fluxing. The calcined fluxing diatomite was more efficient permeability through the bed and removal of copper and zinc ions. The fresh diatomite had trouble with the permeability through the bed under the conditions tested, compared with the other obtained diatomite. The results are presented as promising for application in the petroleum industry

Potencial de redução de emissões de GEE do bioetanol: contributo da análise de ciclo de vida da beterraba sacarina e do cardo como fontes de biomassa nacionais

Dissertação apresentada na Faculdade de Ciências e Tecnologia da Universidade Nova de Lisboa para obtenção do grau de Mestre em Engenharia do Ambiente, perfil de Gestão e Sistemas Ambientais

Possibilidade e rentabilidade da utilização do gás de xisto em Portugal

Mestrado em Engenharia Mecânica- Energia

Indicadores de desempenho ambiental do sector eléctrico em Portugal

O sector da energia, e em particular, da energia eléctrica representa um papel na sociedade que dificilmente se equipara a qualquer outro. O crescimento populacional e o aumento da procura energética em prol da evolução tecnológica levaram à expansão dos sistemas de fornecimento de energia eléctrica, com graves consequências ambientais. A presente dissertação tem como principal objectivo a análise do desempenho ambiental do Sector Eléctrico em Portugal. Neste trabalho foram comparadas as seis principais tecnologias (carvão, gás natural, gasóleo, hídrica, eólica e fotovoltaica) que constituem o mix de produção nacional segundo uma abordagem de análise de ciclo de vida e foram avaliados os impactes ambientais segundo os seis indicadores do método Ecoblok (extracção de água (WA), extracção de recursos (RE), uso do solo (LU), emissão de gases com efeito de estufa (GHG), poluição do ar (PA) e poluição da água e solo (PWL)). Os resultados obtidos foram divididos segundo a produção de uma unidade funcional (kWh, MWh ou GWh) e segundo uma perspectiva nacional. Em termos globais e como era esperado, a tecnologia térmica-carvão revelou os maiores impactes na maioria dos indicadores, nomeadamente nos indicadores RE, WA, GHG e PWL. No indicador WA, o consumo de água da componente térmica deve-se ao arrefecimento dos grupos de geradores da central, enquanto que na componente hídrica é referente à evaporação que foi considerada como consumo. Dada a área que ocupam, os aproveitamentos hidroeléctricos registaram impactes muito significativos ao nível do indicador LU, nomeadamente a barragem do Alqueva. Surpreendentemente, na emissão de poluentes para o ar, foi concluído que a energia eólica, devido às emissões nos processos de produção e processamento metalúrgico dos vários materiais, regista os valores mais elevados. Os resultados obtidos revelam a utilidade e importância de uma abordagem de ciclo de vida na análise a sistemas energéticos.

Proposta e avaliação termodinâmica de soluções para o aproveitamento da exergia na regaseificação de GNL

Uma vez que o gás natural liquefeito (GNL) é transportado a uma temperatura criogénica de -162 °C e como os gasodutos recebem o gás natural (GN) à temperatura ambiente, existe neste sistema exergia que pode ser usada na produção de energia elétrica. A presente dissertação consiste na proposta, avaliação e comparação termodinâmica de diferentes ciclos para produção de energia elétrica, através do aproveitamento da exergia do GNL, aquando da sua transformação em GN, para introdução nos gasodutos. Neste trabalho, considerou-se como caso de estudo o terminal de GNL de Sines, em Portugal, que atualmente não tem implementada nenhuma solução para o aproveitamento da exergia disponível. Considerando os critérios de projeto, definidos de acordo com as características do terminal de Sines e, usando água do mar como fonte de calor, simularam-se e compararam-se os seguintes tipos de ciclos: o ciclo existente no terminal (CE), sem produção de energia; o ciclo de expansão direta do GN (CED); os ciclos tipo Rankine (CTR); os ciclos tipo Rankine com expansão direta (CTR+ED); e os ciclos tipo Rankine com apoio de energia solar (CTRS). Consideraram-se sete fluidos de trabalho (FT) diferentes: propano, etano, etileno, dióxido de carbono, R134a, R143a e propileno. As potências líquidas máximas obtidas para cada ciclo demonstram que: com o CE gastam-se cerca de 1182 kW para fazer o processamento de GNL; com o CED é possível gastar apenas 349 kW; com os CTR é possível obter uma potência líquida positiva ao processar o GNL, produzindo até 2120 kW (usando propileno como FT); com os CTR+ED é possível produzir 2174 kW (também usando propileno com FT); e com os CTRS é possível produzir até 3440 kW (valor médio anual) (usando etano como FT). Fez-se a otimização multi-objetivo dos ciclos tendo-se considerado alguns aspetos económicos. Além da maximização da potência líquida, para os CED, CTR e CTR+ED minimizou-se a área de transferência de calor total dos permutadores de calor e para os CTRS minimizou-se a área de coletores solares instalada.

Utilização de reserva de óleo e gás em modelos de avaliação por múltiplos para empresas petrolíferas

O aumento global dos investimentos gerou a necessidade de uma melhor determinação do valor justo das empresas, para tanto, no presente, existem diversas metodologias de avaliação. A metodologia do Fluxo de Caixa Descontado (FCD) e a Avaliação Relativa, também conhecida como múltiplos, são as mais utilizadas. Ao mesmo tempo, o setor de petróleo e gás natural transformou-se em um dos principais segmentos econômicos, principalmente para países em desenvolvimento. Para as empresas desse setor, as reservas de petróleo são cruciais, pois são indicativos de previsão de produção e a garantia de geração de fluxo de caixa no futuro. Dentro desta perspectiva, este trabalho procura quantificar qual a influência do volume das reservas provadas de empresas petrolíferas integradas com ações listadas na bolsa de valores de Nova York (NYSE) no valor de mercado do patrimônio líquido destas empresas. Ou seja, vamos procurar identificar qual a influência do volume das reservas provadas na avaliação relativa por múltiplos, que são indicadores de valor de mercado. O resultado obtido sugere que a acumulação de reservas como estratégia de valorização de uma empresa de petróleo, sem reflexo na lucratividade ou no valor patrimonial, será penalizada pelo mercado.

REPETRO - Regime Aduaneiro Especial de Importação e Exportação de Bens Destinados à Pesquisa e Lavra de Petróleo e Gás: análise dos entraves e propostas de soluções

REPETRO, the special tax regime for importing and exporting goods for the exploration and drilling of oil and gas, aims at bringing foreign assets to Brazil enjoying a suspension or even an exemption of taxes, so that Brazilian industry may profit from about 8 billion American dollars in investments. The creation of normative devices as well as the management of the REPETRO model are under the exclusive responsibility of the Brazilian Internal Revenue Services. REPETRO was created in 1999 and is composed of the following customs treatments: importation of goods with suspension of taxes by use of the drawback special regime, suspension mode for national exporting industry; exportation with fictitious exit for the national industry; temporary admission of goods or assets used in oil exploration and production, attending to the needs of both the national and foreign market. Considering the inability of the Brazilian government in restructuring its foreign trade model so that a strong investment in technology could provide for the sector¿s needs, we must ask how we can change REPETRO to help the various companies in the oil business? The issue is very important for one of our main economic activities, though not enough studied. The energy sector has a strategic importance for the development and the economic independence of any country. The winds of globalization lead Brazil to open its economy in the last decade and the national policy for exploration and drilling (E&D) was altered. The government created a new agency dedicated to market control and energy policies, the National Agency for Oil and Biofuels (ANP). With the opening of the market, Petróleo Brasileiro S.A. - Petrobras, the Brazilian giant, lost the monopoly of the oil business. The P-50 Platform, with a capacity for 180,000 barrels per day, was imported based on REPETRO. When it began operating on April 21st, 2006, Brazil achieved self-sufficiency in oil production. The present work intends to estimate the main variables affecting the importation and exportation of goods and assets for E&D, showing how REPETRO works. We also intend to look at the results yielded by the REPETRO model for the development of the production of oil and gas in Brazil, as well as show proposals for its modernization. It has been established that even though since its implementation the REPETRO model has brought fiscal advantages through the reduction of tax costs relating to foreign commerce operations and the incentive of investments in the E&D area with the increase in the national oil production there remain the following limitations: lack of preparation and of knowledge of the model; lack of adjustement of the model to the reality of actitity of E&D of oil and gas; taxes over the pre-operational stage or investment in oil production stage; non-allowance of full access by the national industry to the supply of goods and products relating to the industrialization of goods allowed by REPETRO; other fiscal and administrative difficulties. We conclude that the REPETRO model is important for the development of the area of E&D of oil and gas, but not completely effective. It is necessary to change it or create a new model based on a new perspective of the customs treatment of the activities of exploration and production, minimizing administrative procedures relating to the operations of exportation and importation.

Da revolução do gás não convencional nos EUA tendo como substrato uma interferência governamental persistente no estímulo a atividade econômica e no fomento as inovações tecnológicas afetas ao setor

O presente estudo versa sobre os fatores tecnológicos e ambientais que vêm resultando no crescimento da produção de gás natural não convencional nos EUA. Os objetos de analise principais serão as políticas públicas, assim como a dinâmica entre os atores sociais e o ambiente propício que fora criado para que houvesse o adensamento do fomento e do estímulo às inovações tecnológicas sucedidas no setor.

A compra do botijão de gás na cidade de Petrópolis (RJ): uma tradição de família

O mercado de gás liquefeito de petróleo brasileiro passou por profundas mudanças após a desregulamentação governamental iniciada a partir da segunda metade da década de 1990. Neste período, a intervenção estatal foi substituída por um modelo de livre concorrência que impulsionou a expansão das quatro principais empresas do setor para uma atuação nacional. Estes movimentos criaram um novo cenário competitivo no mercado. Após uma década destas mudanças, e apesar da forte competição entre as quatro grandes companhias que detém 86 % do mercado, a liderança do segmento residencial em cada estado brasileiro continua sendo exercida pela mesma marca do passado (ou sua sucessora). Este fato indica a necessidade das companhias adotarem uma nova abordagem de marketing para alterar de maneira significativa a percepção do consumidor em relação à sua preferência de marca. Logo, o conhecimento dos fatores críticos na escolha de botijões de gás para uso residencial é fundamental para esta mudança. Este estudo propõe uma nova abordagem das estratégias de mercado na indústria do GLP no Brasil, baseada numa perspectiva antropológica, que tenha como pilar o estudo do consumo doméstico deste produto como um processo de natureza cultural e simbólica, contradizendo a visão utilitarista que o estrutura como um simples reflexo de uma razão prática, fundamentada em critérios econômicos. Para atingir este objetivo, o pesquisador realizou uma análise do comportamento do consumidor de botijões de gás para uso doméstico apoiado nos principais estudos sobre o consumo na base da pirâmide, abordando os aspectos culturais brasileiros que possuem influência relevante nesta decisão de compra. Este estudo também contemplou os principais conceitos sobre a formação de hábitos de compra bem como a teoria sobre a lógica dominante em serviços. Os dados primários foram obtidos no município de Petrópolis/RJ, através de metodologia qualitativa, utilizando as entrevistas em profundidade como técnica de coleta de dados. Como resultado deste trabalho, foi proposto pelo autor um modelo teórico para explicar o fenômeno de compra do botijão de gás para uso doméstico no Brasil. Este modelo explica que a formação do hábito de compra do botijão de gás tem início na transmissão familiar da preferência por determinada marca para os membros mais novos da família, através do convívio e observação da rotina de escolha. Em seguida a nova consumidora experimenta o produto habitual da família e confirma as promessas de serviço embutidas na preferência familiar. Após esta fase, a consumidora consolida a preferência e coloca a recompra do botijão de gás no modo automático, disparando o loop do hábito de consumo deste produto. Segundo esta proposta, apenas uma dissonância cognitiva gerada pelo não cumprimento da promessa de serviço prestado é capaz de interromper o loop do hábito de compra da marca preferida pela família.

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

Estudo de massa cerâmica triaxial visando à otimização do ciclo de queima da indústria de cerâmica estrutural

Over recent years the structural ceramics industry in Brazil has found a very favorable market for growth. However, difficulties related to productivity and product quality are partially inhibiting this possible growth. An alternative for trying to solve these problems and, thus, provide the pottery industry the feasibility of full development, is the substitution of firewood used in the burning process by natural gas. In order to contribute to this process of technological innovation, this paper studies the effect of co-use of ceramic phyllite and kaolin waste on the properties of a clay matrix, verifying the possible benefits that these raw materials can give to the final product, as well as the possibility of such materials to reduce the heat load necessary to obtain products with equal or superior quality. The study was divided into two steps: characterization of materials and study of formulations. Two clays, a phyllite and a residue of kaolin were characterized by the following techniques: laser granulometry, plasticity index by Atterberg limits, X-ray fluorescence, X-ray diffraction, mineralogical composition by Rietveld, thermogravimetric and differential thermal analysis. To study the formulations, specifically for evaluation of technological properties of the parts, was performed an experimental model that combined planning involving a mixture of three components (standard mass x phyllite x kaolin waste) and a 23 factorial design with central point associated with thermal processing parameters. The experiment was performed with restricted strip-plot randomization. In total, 13 compositional points were investigated within the following constraints: phyllite ≤ 20% by weight, kaolin waste ≤ 40% by weight, and standard mass ≥ 60% by weight. The thermal parameters were used at the following levels: 750 and 950 °C to the firing temperature, 5 and 15 °C/min at the heating rate, 15 and 45min to the baseline. The results showed that the introduction of phyllite and/or kaolin waste in ceramic body produced a number of benefits in properties of the final product, such as: decreased absorption of water, apparent porosity and linear retraction at burn; besides the increase in apparent specific mass and mechanical properties of parts. The best results were obtained in the compositional points where the sum of the levels of kaolin waste and phyllite was maximal (40% by weight), as well as conditions which were used in firing temperatures of 950 °C. Regarding the prospect of savings in heat energy required to form the desired microstructure, the phyllite and the residue of kaolin, for having small particle sizes and constitutions mineralogical phases with the presence of fluxes, contributed to the optimization of the firing cycle.

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