Otimização e análise mecânica de pastas geopoliméricas para uso em poços sujeitos à injeção cíclica de vapor

Oil wells subjected to cyclic steam injection present important challenges for the development of well cementing systems, mainly due to tensile stresses caused by thermal gradients during its useful life. Cement sheath failures in wells using conventional high compressive strength systems lead to the use of cement systems that are more flexible and/or ductile, with emphasis on Portland cement systems with latex addition. Recent research efforts have presented geopolymeric systems as alternatives. These cementing systems are based on alkaline activation of amorphous aluminosilicates such as metakaolin or fly ash and display advantageous properties such as high compressive strength, fast setting and thermal stability. Basic geopolymeric formulations can be found in the literature, which meet basic oil industry specifications such as rheology, compressive strength and thickening time. In this work, new geopolymeric formulations were developed, based on metakaolin, potassium silicate, potassium hydroxide, silica fume and mineral fiber, using the state of the art in chemical composition, mixture modeling and additivation to optimize the most relevant properties for oil well cementing. Starting from molar ratios considered ideal in the literature (SiO2/Al2O3 = 3.8 e K2O/Al2O3 = 1.0), a study of dry mixtures was performed,based on the compressive packing model, resulting in an optimal volume of 6% for the added solid material. This material (silica fume and mineral fiber) works both as an additional silica source (in the case of silica fume) and as mechanical reinforcement, especially in the case of mineral fiber, which incremented the tensile strength. The first triaxial mechanical study of this class of materials was performed. For comparison, a mechanical study of conventional latex-based cementing systems was also carried out. Regardless of differences in the failure mode (brittle for geopolymers, ductile for latex-based systems), the superior uniaxial compressive strength (37 MPa for the geopolymeric slurry P5 versus 18 MPa for the conventional slurry P2), similar triaxial behavior (friction angle 21° for P5 and P2) and lower stifness (in the elastic region 5.1 GPa for P5 versus 6.8 GPa for P2) of the geopolymeric systems allowed them to withstand a similar amount of mechanical energy (155 kJ/m3 for P5 versus 208 kJ/m3 for P2), noting that geopolymers work in the elastic regime, without the microcracking present in the case of latex-based systems. Therefore, the geopolymers studied on this work must be designed for application in the elastic region to avoid brittle failure. Finally, the tensile strength of geopolymers is originally poor (1.3 MPa for the geopolymeric slurry P3) due to its brittle structure. However, after additivation with mineral fiber, the tensile strength became equivalent to that of latex-based systems (2.3 MPa for P5 and 2.1 MPa for P2). The technical viability of conventional and proposed formulations was evaluated for the whole well life, including stresses due to cyclic steam injection. This analysis was performed using finite element-based simulation software. It was verified that conventional slurries are viable up to 204ºF (400ºC) and geopolymeric slurries are viable above 500ºF (260ºC)

Adição do resíduo de biomassa da cana-de-açúcar em pastas para cimentação de poços petrolíferos produtores de óleos pesados

The Potiguar basin has large fields of viscous oil where the used method for recovering is based on vapor injection; this operation is carried out by injecting vapor in the oilwell directly, without the protection of a revetment through thermal insulation, what causes its dilation and, consequently, cracks in the cement placed on the annular, and lost of hydraulic insulation; this crack is occasioned by the phenomenon of retrogression of the compressive resistance due to the conversion of the hydrated calcium silicate in phases calcium-rich, caused by the high temperatures in the wells, subjected to thermal recuperation. This work has evaluated the application of composite pastes with addition of residue of biomass of ground sugar-cane bagasse as anti-retrogression mineral admixture for cementation of oil-wells subjected to thermal recuperation. The addition of the mineral residue was carried out considering a relative amount of 10, 20, 30, 40 and 59% in relation to cement mass, trying to improve the microstructure of the paste, still being developed a reference paste only with cement and a paste with addition of 40% of silica flour - renowned material in the oil industry as anti-retrogression additive. Pozzolanic activity of the ash was evaluated through XRD, TG/DTG, as the resistance to compression, and it was also determined the physical and mechanical behavior of the pastes when submitted to cure at low temperatures (22 and 38º C); besides it was evaluated the behavior of the pastes when submitted to two cycles of cure at high temperature (280ºC) and pressure (7 MPa). It was verified that the ash of the sugar-cane biomass presents pozzolanic reaction and has great efficiency in decrease the permeability of the paste by filler effect, as well as that addition of ash in a relative amount of 10, 20 e 30% increases cured compressive resistance at low temperatures. It was also showed that the ash in a relative amount of 40% and 59% has very significant efficiency as anti-retrogression additive, since it prevents the decrease of compressive resistance and forms hydrated calcium silicate type xenotlita and tobermorita which have more resistance and stability in high temperatures

Formulação de pastas cimentícias com adição de suspensões de quitosana para cimentação de poços de petróleo

Primary cementing is one of the main operations in well drilling responsible for the mechanical stability and zonal isolation during the production of oil. However, the cement sheath is constantly under mechanical stresses and temperature variations caused by the recovery of heavy oil. In order to minimize fracture and wear of the cement sheath, new admixtures are developed to improve the properties of Portland cement slurries and avoid environmental contamination caused by leaking gas and oil. Polymers with the ability to form polymeric films are candidates to improve the properties of hardened cement slurries, especially their fracture energy. The present study aimed at evaluating the effect of the addition of a chitosan suspension on cement slurries in order to improve the properties of the cement and increase its performance on heavy oil recovery. Chitosan was dissolved in acetic ac id (0.25 M and 2 M) and added to the formulation of the slurries in different concentrations. SEM analyses confirmed the formation of polymeric films in the cementitious matrix. Strength tests showed higher fracture energy compared to slurries without the addition of chitosan. The formation of the polymeric films also reduced the permeability of the slurry. Therefore, chitosan suspensions can be potentially used as cementing admixtures for heavy oil well applications

Perceção da evasão e fraude fiscal em Portugal: um estudo sociológico

A presente dissertação versa sobre a análise da perceção da evasão e fraude fiscais em Portugal. A literatura internacional sublinha a existência de diversos fatores ou determinantes que influenciam a decisão do contribuinte cumprir ou não cumprir com as suas obrigações fiscais. Entre eles salientamos os fatores demográficos, económicos, culturais, sociológicos, psicológicos e técnicos (Torgler, 2006; Tsakumis, 2007; McGee, 2009). A nossa investigação pretende dar uma pequena contribuição para o estudo da relação entre os fatores sociológicos e os diversos comportamentos dos contribuintes em relação ao cumprimento ou não cumprimento fiscal. Para atingir estes objectivos, recorremos, para o efeito, a uma amostra heterogénea da população de contribuintes individuais portugueses, no sentido de aferir acerca do comportamento dos contribuintes em relação à atitude de cumprir ou não cumprir com o sistema tributário, bem como em relação aos fatores que influenciam essas mesmas atitudes. Da nossa análise podemos, em síntese, concluir que a evasão e fraude fiscais se encontram associadas a fatores como o género, a idade, o nível de escolaridade ou a profissão e actividade exercida, os quais refletem a realidade social do país. Verificou-se, ainda, que cerca um terço dos contribuintes inquiridos admitiu que a evasão fiscal é justificável em determinadas circunstâncias. Os principais argumentos justificativos da evasão fiscal estão associados à injustiça do sistema fiscal, à elevada carga tributária, ao desperdício ou má utilização do dinheiro dos impostos e à corrupção entre a classe política. Ao invés, um dos argumentos menos forte encontra-se relacionado com o facto de os contribuintes poderem vir a ser descobertos pelas autoridades fiscais, verificando-se, então, que este não é um elemento dissuasor da prática da evasão e fraude fiscais em Portugal.

Utilização de nanosílica como aditivo estendedor para pastas cimentantes de baixa densidade destinadas à cimentação de poços petrolíferos

Cementing operations are conducted at different times of the well s life and they have high importance, because the functions are fundamental to keep good properties during a long life of the well, such as, maintain the mechanical stability of the well, to promote the isolation hydraulic and support the tubing. In some situations, the rocky zones have low fractures pressures and require the use of lightweight slurries to prevent the hydrostatic pressure in the formation is greater than the pressure of fracture. There are three ways to reduce the density of cement slurries: exterders water additives, microspheres and foamed slurries. The most used extender water additive is sodium bentonite, which is a clay with a good capacity of water absorption and expansion of its volume, the main disadvantage of this additive is the reduction of the strength. Currently, the use of nanoscale particles has received special attention, mainly because they get new functionalities. Following this trend, this paper aims to use a colloidal solution of nano-silica as an exterders water additives for use in oil wells. Slurries were designed with fixed 13lb/gal density and concentration of nano silica 0.1 gpc; 0.4 gpc; 0.7 and 1gpc, the influence of nano-silica was studied at these levels in isolation and combined varying concentrations of CaCl2,. Tests including rheology, stability, strength, thickening time, porosity and permeability. Besides the API tests, microstructural characterizations were performed after 28 days of the slurries, X-ray diffraction (XRD) and scanning electron microscopy (SEM)

Transição de fase topológica e transporte eletrônica em grafenos e nanofitas zigzag grafeno tensionados

Tese (doutorado)—Universidade de Brasília, Instituto de Física, 2015.

Avaliação da adição de Nanosílica e silicato de sódio em pastas de cimento para poços de petróleo com baixo gradiente de fratura

The oil wells cementing is a critical step during the phase of well drilling, because problems during the operation of slurry pumping and an incomplete filling of the annular space between the metal casing and the formation can cause the slurry loss. Therefore, the slurry adopted in primary cementing an oil well must be properly dosed so that these problems are avoided during its pumping. When you drill a well in a weak rock formation requires even more careful, because should be a limit of hydrostatic pressure exerted during cementation, that does not occur rock collapse. With the objective of performing the cementing of a well whose formation is weak or unconsolidated are employed lighter slurries. Thus, this study used slurries with sodium silicate and nano silica in concentrations of 0,1; 0,4; 0,7 e 1,0 gpc, in which the slurries with nano silica showed the rheological parameters higher concentrations of up to 0.7 gpc and for concentration of 1.0 the slurry with sodium silicate obtained the highest values, remaining above the limits for application in fields, mainly wells with low fracture gradient, because a significant increase in viscosity may result in an increase in pressure pumping in operations of secondary cementations. Furthermore, there was no decrease in strength with increasing concentration of additive. Then, it is possible use of these additives to formulate Lighter slurry

Desenvolvimento de um sistema misto de pasta à base de geopolímero e cimento portland para correção de perda de circulação

The materials engineering includes processes and products involving several areas of engineering, allowing them to prepare materials that fulfill the needs of various new products. In this case, this work aims to study a system composed of cement paste and geopolymers, which can contribute to solving an engineering problem that directly involves the exploitation of oil wells subject to loss of circulation. To correct it, has been already proposed the use of granular materials, fibers, reducing the drilling fluid or cement paste density and even surface and downhole mixed systems. In this work, we proposed the development of a slurry mixed system, the first was a cement-based slurry and the second a geopolymer-based slurry. The cement-based slurry was formulated with low density and extenders, 12.0 ppg (1.438 g/cm ³), showing great thixotropic characteristics. It was added nano silica at concentrations of 0.5, 1.0 and 1.5 gps (66.88, 133.76 and 200.64 L/m3) and CaCl2 at concentrations of 0.5, 1, 0 and 1.5%. The second system is a geopolymer-based paste formulated from molar ratios of 3.5 (nSiO2/nAl2O3), 0.27 (nK2O/nSiO2), 1.07 (nK2O/nAl2O3) and 13.99 (nH2O/nK2O). Finally, we performed a mixture of these two systems, for their application for correction of circulation lost. To characterize the raw materials, XRD, XRF, FTIR analysis and titration were performed. The both systems were characterized in tests based on API RP10B. Compressive strength tests were conducted after curing for 24 hours, 7 and 28 days at 58 °C on the cement-based system and the geopolymer-based system. From the mixtures have been performed mixability tests and micro structural characterizations (XRD, SEM and TG). The results showed that the nano silica, when combined with CaCl2 modified the rheological properties of the cement slurry and from the concentration of 1.5 gpc (200.64 L / m³) it was possible to obtain stable systems. The system mixture caused a change in the microstructure of the material by favoring the rate of geopolymer formation to hinder the C3S phase hydration, thus, the production of CSH phases and Portlandite were harmed. Through the mixability tests it can be concluded that the system, due to reduced setting time of the mixture, can be applied to plug lost circulation zones when mixed downhole

Influência da adição do NaCl e KCl em sistemas de pastas contendo sílica para poços de petróleo em zonas evaporíticas e carbonáticas

One of the major challenges faced nowadays by oil companies is the exploration of pre-salt basins. Thick salt layers were formed in remote ages as a consequence of the evaporation of sea water containing high concentrations of NaCl and KCl. Deep reservoirs can be found below salt formations that prevent the outflow of oil, thus improving the success in oil prospection. The slurries used in the cement operations of salt layers must be adequate to the properties of those specific formations. At the same time, their resulting properties are highly affected by the contamination of salt in the fresh state. It is t herefore important to address the effects of the presence of salt in the cement slurries in order to assure that the well sheath is able to fulfill its main role to provide zonal isolation and mechanical stability. In this scenario, the objective of the present thesis work was to evaluate the effect of the presence of NaCl and KCl premixed with cement and 40% silica flour on the behavior of cement slurries. Their effect in the presence of CO2 was also investigated. The rheological behavior of slurries containing NaCl and KCl was evaluated along with their mechanical strength. Thermal and microstructural tests were also carried out. The results revealed that the presence of NaCl and KCl affected the pozzolanic activity of silica flour, reducing the strength of the hardened slurries containing salt. Friedel´s salt was formed as a result of the bonding between free Cl- and tricalcium aluminate. The presence of CO2 also contributed to the degradation of the slurries as a result of a process of carbonation/bicarbonataion

Comportamento reológico de materiais cimentícios para poços de petróleo contendo naftaleno condensado ou policarboxilato

Pastas a base de cimento Portland são utilizadas na cimentação de poços de petróleo. Elas consistem de uma mistura de partículas sólidas de cimento dispersas em água e aditivos. Atualmente, diversos materiais alternativos são utilizados como aditivos, objetivando a modificação e a melhoria das propriedades das pastas de cimento, especialmente no aumento da fluidez. Novos aditivos plastificantes são capazes de suportar as diversas condições de poços, promovendo propriedades no estado fluido compatíveis às condições exigidas para cimentação.Dispersantes são os componentes da pasta que garantem fluidez, além de proporcionar controle na água perdida por filtração na formação porosa, garantindo o sucesso da operação de bombeio. Em deter minados campos, além do efeito da profundidade, as condições geológicas das formações promovemvariações do gradiente de pressão e temperatura ao longo da profundidade vertical do poço. Recentemente, diversos aditivos químicos da indústria da construção civil tem sido estudados em condições de cimentação de poços de petróleo. Vários produtos testados tem apresentado desempenho superior aos produtos normalmente empregados pela indústria de petróleo com boa relação custo/benefício em função do volume de mercado da construção civil. Resultados promissores na seleção de aditivos com função dispersante da construção civil para operações de cimentação de poços de petróleo onshore foram obtidos para temperaturas até 80°C. O potencial de uso desses aditivos permite estabelecer novas soluções para problemas encontrados na cimentação de poços de petróleo HPHT, poços sujeitos à injeção de vapor, poços depletados e poços produtores de gás. Na construção civil, os superplastificantes permitem reduzir o fator água/cimento das argamassas proporcionando melhoria de propriedades como resistência mecânica e fluidez. Assim, o objetivo deste trabalho foi o estudo e a caracterização reológica de pastas constituídas de cimento Portland, água e aditivos do tipo plastificante, com função dispersante a base de naftaleno condensado e policarboxilato, na faixa de temperaturas de 58°C e 70ºC. As condições utilizadas para a avaliação dos aditivos alternativos foram baseadas em uma cimentação primária para um poço hipotético de 2200 m de profundidade e gradientes geotérmicos de 1,7°F/100 pés e 2,1°F/100 pés. Os resultados demonstraram a grande eficiência e o poder dispersivo do policarboxilato para as temperaturas estudadas. O aditivo promoveu alta fluidez, sem efeitos de sedimentação da pasta. O dispersante à base de naftaleno reduziutant o a viscosidade plástica como o limite de escoamento acimada concentração a partir de 0,13%. O modelo de Bingham descreveu bem o comportamento reológico das pastas com policarboxilato para todas as concentrações

Caracterização do manejo de agroecossistemas cafeeiros convencional, organo-mineral, orgânico e agroflorestal em Minas Gerais.

O presente trabalho teve o intuito de caracterizar agroecossistemas cafeeiros sob manejos convencional, organo-mineral, orgânico e agroflorestal conduzidos nos municípios de Machado e Poço-Fundo, localizados no sul de Minas Gerais. A pesquisa foi realizada com base no Diagnóstico Rural Participativo (DRP). Verificou-se que o agroecossistema convencional é extremamente dependente de fontes externas de insumos, principalmente agroquímicos. O sistema orgânico também utiliza insumos de fora da propriedade como o farelo de mamona, estercos de animais e produtos orgânicos industrializados e atingiu a maior média de produtividade entre os sistemas (45 sacas ha-1). O agroecossistema organo- mineral utiliza adubação química com diversificação através de culturas intercalares. A agrofloresta apresenta a menor produtividade média (14 sacas ha-1) entre os sistemas e seu manejo caracteriza-se pela roçada da vegetação espontânea, utilização da palha de café própria e a arborização da lavoura.

Fotodegradação de pesticidas: caso do fenarimol

Tese dout. em Química, Unidade de Ciências Exactas e Humanas, Univ. do Algarve, 1997

Poli-líquidos iônicos e complexos solúveis de Eu3+ e Tb3+ : bioimageamento celular seletivo

Dissertação (mestrado)—Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015.

Compósitos Portland-biopolímeros para cimentação de poços de petróleo

The oil production in mature areas can be improved by advanced recovery techniques. In special, steam injection reduces the viscosity of heavy oils, thus improving its flow to surrounding wells. On the other hand, the usually high temperatures and pressures involved in the process may lead to cement cracking, negatively affecting both the mechanical stability and zonal isolation provided by the cement sheath of the well. The addition of plastic materials to the cement is an alternative to prevent this scenario. Composite slurries consisting of Portland cement and a natural biopolymer were studied. Samples containing different contents of biopolymer dispersed in a Portland cement matrix were prepared and evaluated by mechanical and rheological tests in order to assess their behavior according to API (American Petroleum Institute) guidelines. FEM was also applied to map the stress distribution encountered by the cement at bottom bole. The slurries were prepared according to a factorial experiment plan by varying three parameters, i.e., cement age, contents of biopolymer and water-to-cement ratio. The results revealed that the addition of the biopolymer reduced the volume of free water and the setting time of the slurry. In addition, tensile strength, compressive strength and toughness improved by 30% comparing hardened composites to plain Portland slurries. FEM results suggested that the stresses developed at bottomhole may be 10 to 100 times higher than the strength of the cement as evaluated in the lab by unconfined mechanical testing. An alternative approach is proposed to adapt the testing methodology used to evaluate the mechanical behavior of oilwell cement slurries by simulating the confined conditions encountered at bottornhole

Avaliação do comportamento reológico de pastas de cimento para poços de petróleo com adição de plastificantes

The isolation of adjacent zones encountered during oilwell drilling is carried out by Portland-based cement slurries. The slurries are pumped into the annular positions between the well and the casing. Their rheological behavior is a very important component for the cementing process. Nowadays, several alternative materials are used in oilwell cementing, with goal the modification and the improvement of their properties, mainly the increase of the fluidity. And this can be reached by using plasticizers additives able to account for different oilwell conditions, yielding compatible cement slurries and allowing enough time for the complete cementing operation. If the rheological properties of the slurry are properly characterized, the load loss and flow regime can be correctly predicted. However, this experimental characterization is difficult. Rheological models capable of describing the cement slurry behavior must be capable of predicting the slurry cement deformation within reasonable accuracy. The aim of this study was to characterize rheologically the slurries prepared with a especial class of Portland cement, water and plasticizers based on lignosulfonate, melamine and polycarboxylate at temperatures varying from 27°C to 72°C. The tests were carried out according to the practical recommendations of the API RP 10B guidelines. The results revealed a great efficiency and the dispersive power of the polycarboxylate, for all temperatures tested. This additive promoted high fluidity of the slurries, with no sedimentation. High lignosulfonate and melamine concentrations did not reduce the rheological parameters (plastic viscosity and yield stress) of the slurries. It was verified that these additives were not compatible with the type of cement used. The evaluated rheological models were capable of describing the behavior of the slurries only within concentration and temperature ranges specific for each type of additive