Inhibition of photosynthesis by high temperature in oak (Quercus pubescens L.) leaves grown under natural conditions closely correlates with a reversible heat-dependent reduction of the activation state of ribulose-1,5-bisphosphate carboxylase/oxygenase

Inhibition of the net photosynthetic CO2 assimilation rate (Pn) by high temperature was examined in oak (Quercus pubescens L.) leaves grown under natural conditions. Combined measurements of gas exchange and chlorophyll (Chl) a fluorescence were employed to differentiate between inhibition originating from heat effects on components of the thylakoid membranes and that resulting from effects on photosynthetic carbon metabolism. Regardless of whether temperature was increased rapidly or gradually, Pn decreased with increasing leaf temperature and was more than 90% reduced at 45 °C as compared to 25 °C. Inhibition of Pn by heat stress did not result from reduced stomatal conductance (gs), as heat-induced reduction of gs was accompanied by an increase of the intercellular CO2 concentration (Ci). Chl a fluorescence measurements revealed that between 25 and 45 °C heat-dependent alterations of thylakoid-associated processes contributed only marginally, if at all, to the inhibition of Pn by heat stress, with photosystem II being remarkably well protected against thermal inactivation. The activation state of ribulose-1,5-bisphosphate carboxylase/oxygenase (Rubisco) decreased from about 90% at 25 °C to less than 30% at 45 °C. Heat stress did not affect Rubisco per se, since full activity could be restored by incubation with CO2 and Mg2+. Western-blot analysis of leaf extracts disclosed the presence of two Rubisco activase polypeptides, but heat stress did not alter the profile of the activase bands. Inhibition of Pn at high leaf temperature could be markedly reduced by artificially increasing Ci. A high Ci also stimulated photosynthetic electron transport and resulted in reduced non-photochemical fluorescence quenching. Recovery experiments showed that heat-dependent inhibition of Pn was largely, if not fully, reversible. The present results demonstrate that in Q. pubescens leaves the thylakoid membranes in general and photosynthetic electron transport in particular were well protected against heat-induced perturbations and that inhibition of Pn by high temperature closely correlated with a reversible heat-dependent reduction of the Rubisco activation state.

The cellular and molecular responses to a novel nucleotide analogue, GS-9219

GS-9219 is a cell-permeable double-prodrug of the acyclic nucleotide analogue 9-(2-phosphonylmethoxyethyl)guanine (PMEG). The conversion of GS-9219 to its active metabolite, PMEG diphosphate (PMEGpp), involves several intracellular enzymatic reactions which reduces the concentration of nephrotoxic PMEG in plasma. PMEGpp competes with the natural substrate, dGTP, for incorporation by DNA polymerases. The lack of a 3'-hydroxyl moiety makes PMEGpp a de facto DNA chain-terminator. The incorporation of PMEGpp into DNA during DNA replication causes DNA chain-termination and stalled replication forks. Thus, the primary mechanism of action of GS-9219 in replicating cells is via DNA synthesis inhibition. GS-9219 has substantial antiproliferative activity against activated lymphocytes and tumor cell lines of hematological malignancies. Tumor cell proliferation was significantly reduced as measured by PET/CT scans in dogs with advanced-stage, spontaneously occurring non-Hodgkin's lymphoma (NHL).^ The hypothesis of this dissertation is that the incorporation of PMEGpp into DNA during repair re-synthesis would result in the inhibition of DNA repair and accumulation of DNA damage in chronic lymphocytic leukemia (CLL) cells and activate signaling pathways to cell death.^ To test this hypothesis, CLL cells were treated with DNA-damaging agents to stimulate nucleotide excision repair (NER) pathways, enabling the incorporation of PMEGpp into DNA. When NER was activated by UV, PMEGpp was incorporated into DNA in CLL cells. Following PMEGpp incorporation, DNA repair was inhibited and led to the accumulation of DNA strand breaks. The combination of GS-9219 and DNA-damaging agents resulted in more cell death than the sum of the single agents alone. The presence of DNA strand breaks activated the phosphatidylinositol 3-kinase-like protein kinase (PIKK) family members ataxia-telangiectasia mutated (ATM) and DNA-dependent protein kinase (DNA-PK). The activated ATM initiated signaling to the downstream target, p53, which was subsequently phosphorylated and accumulated to exert its apoptotic functions. P53-targeted pro-apoptotic genes, Puma and Bax, were upregulated and activated when DNA repair was inhibited, likely contributing to cell death. ^

Atenuación natural monitorizada (ANM)

La atenuación natural monitorizada se presenta como una tecnología que trabaja in situ, con los componentes naturales del suelo y napas, para lograr una disminución del impacto negativo que produce en ellos la presencia de sustancias contaminantes. Con ANM se busca proteger ante todo la seguridad y salud tanto humana como medioambiental y que el proceso se lleve adelante en periodos de tiempo razonables. Este trabajo tiene como objeto presentar a la ANM como una opción de manejo óptima para casos de suelos y aguas subterráneas contaminadas con hidrocarburos de la industria del petróleo en la Provincia de Mendoza, dentro de la Cuenca Cuyana. Se comenzó el estudio con la recopilación de datos históricos y presentes de la zona afectada a fin de establecer la base de partida para llevar adelante la aplicación de las tres líneas de evidencia presentadas por la Guía Técnica de Atenuación Natural Monitorizada propuesta por la Agencia de Protección Ambiental de los Estados Unidos. Éstas incluyen, en primer lugar, estudios químicos de la contaminación que demuestren que su extensión se encuentra disminuyendo, en segundo lugar los estudios de la hidrogeología y geoquímica del área contaminada y en tercer lugar el estudio de las posibles comunidades de microorganismos con capacidad de utilizar los contaminantes como fuente de energía y así disminuir su concentración y por ende su impacto negativo. Durante el estudio se realizaron análisis sobre suelo y napa. En el suelo, los resultados obtenidos demostraron la presencia de microorganismos responsables de llevar adelante el proceso de atenuación natural monitorizada, así como sus subproductos o los productos que estos organismos utilizan como aceptores de electrones, que se presentan como evidencia de su efectividad y viabilidad. En la napa se estudió la disminución de la pluma de contaminación a lo largo de un periodo de tiempo de alrededor de 6 años obteniendo resultados positivos que dieron lugar a la propuesta de llevar adelante un plan de monitoreo y seguimiento posterior. En base a los resultados a los que se arribó con este estudio y teniendo en cuenta las bondades de la atenuación natural monitorizada como tecnología de remediación desde el punto de vista ambiental y social, se expone como conclusión que es una buena opción como tecnología para el manejo óptimo de Recursos Naturales Renovables suelo y agua subterránea contaminados con hidrocarburos del petróleo.

Dimensionamiento del proceso de licuación de una planta de gas natural Offshore

Este proyecto consiste en el dimensionamiento del proceso de licuación de una planta offshore para la producción de gas natural licuado, usando únicamente N2 como refrigerante, evitando de este modo riesgos potenciales que podrían surgir con el uso de refrigerantes mixtos compuestos de hidrocarburos. El proceso ha sido diseñado para acomodar 35,23 kg/s (aproximadamente un millón de toneladas por año) de gas natural seco, sin separación de gases licuados de petróleo (GLP) y ajustarlo dentro de los parámetros requeridos en las especificaciones del proceso. Para proceder al dimensionamiento del proceso de licuación de gas natural de la planta se ha empleado el programa Aspen Plus. Los sistemas floating production, storage and offloading para licuar el gas natural (LNG-FPSO), es una nueva unidad conceptual y un modo realista y efectivo para la explotación, recuperación, almacenamiento, transporte y agotamiento de los campos marginales de gas y las fuentes de gas asociadas offshore. En el proyecto se detalla el proceso, equipos necesarios y costes estimados, potencia aproximada requerida y un breve análisis económico. ABSTRACT This project consist of the dimensioning of a liquefaction process in an offshore plant to produce liquefied natural, using only N2 as refrigerant in the cooling cycles to avoid potential hazards of mixed hydrocarbon refrigerants. The process was designed to accommodate 35.23 kg/s (roughly 1 MTPA) of raw natural gas feed without separation of LPG, and fits within all parameters required in the process specifications. The plant has been designed with the computer tool Aspen Plus. The floating production, storage and offloading system for liquefied natural gas (LNGFPSO), is a new conceptual unit and an effective and realistic way for exploitation, recovery, storage, transportation and end-use applications of marginal gas fields and offshore associated-gas resources. The following report details the process, equipment needs and estimated costs, approximated power requirements, and a brief economic analysis.

Modelo del sistema de gestión de la calidad y el desempeño organizacional en la producción de petróleo

El proceso de cambio de una sociedad industrial a una sociedad del conocimiento, que experimenta el mundo globalizado en el siglo XXI, induce a las empresas y organizaciones a desarrollar ventajas competitivas y sostenibles basadas en sus activos intangibles, entre los cuales destacan los sistemas de gestión en general y los sistemas de gestión de la calidad (SGC) en particular. Las organizaciones dedicadas a la producción de petróleo están influenciadas por dicha tendencia. El petróleo es un recurso natural con reservas limitadas, cuya producción y consumo ha crecido progresivamente, aportando la mayor cuota (35 %) del total de la energía que se consume en el mundo contemporáneo, aporte que se mantendrá hasta el año 2035, según las previsiones más conservadoras. Por tanto, se hace necesario desarrollar modelos de producción innovadores, que contribuyan a la mejora del factor de recobro de los yacimientos y de la vida útil de los mismos, al tiempo que satisfagan los requerimientos de producción y consumo diarios de los exigentes mercados globales. El objeto de esta investigación es el desarrollo de un modelo de gestión de la calidad y su efecto en el desempeño organizacional, a través del efecto mediador de los constructos satisfacción del cliente interno y gestión del conocimiento en la producción de petróleo. Esta investigación de carácter explicativo, no experimental, transeccional y ex-postfacto, se realizó en la región petrolífera del lago de Maracaibo, al occidente de Venezuela, la cual tiene más de 70 años en producción y cuenta con yacimientos maduros. La población objeto de estudio fue de 369 trabajadores petroleros, quienes participaron en las mesas técnicas de la calidad, durante los meses de mayo y julio del año 2012, los cuales en su mayoría están en proceso de formación como analistas, asesores y auditores de los SGC. La técnica de muestreo aplicada fue de tipo aleatorio simple, con una muestra de 252 individuos. A la misma se le aplicó un cuestionario diseñado ad hoc, el cual fue validado por las técnicas de juicio de expertos y prueba piloto. El procedimiento de investigación se realizó a través de una secuencia, que incluyó la elaboración de un modelo teórico, basado en la revisión del estado del arte; un modelo factorial, sobre la base del análisis factorial de los datos de la encuesta; un modelo de regresión lineal, elaborado a través del método de regresión lineal simple y múltiple; un modelo de análisis de sendero, realizado con el software Amos 20 SPSS y finalmente, un modelo informático, realizado con el simulador Vensim PLE v.6.2. Los resultados obtenidos indican que el modelo teórico se transformó en un modelo empírico, en el cual, la variable independiente fue el SGC, la variable mediadora fue la integración de las dimensiones eliminación de la no conformidad, satisfacción del cliente interno y aprendizaje organizacional (ENCSCIAO) y la variable respuesta la integración de las dimensiones desempeño organizacional y aprendizaje organizacional (DOOA). Se verificó el efecto mediador del ENSCIAO sobre la relación SGC-DOOA con una bondad del ajuste, del 42,65%. En el modelo de regresión múltiple se encontró que las variables determinantes son eliminación de la no conformidad (ENC), conocimiento adquirido (CA) y conocimiento espontáneo (CE), lo cual fue corroborado con el modelo de análisis de sendero. El modelo informático se desarrolló empleando datos aproximados de una unidad de producción tipo, generándose cuatro escenarios; siendo el más favorable, aquel en el cual se aplicaba el SGC y variables relacionadas, reduciendo la desviación de la producción, incrementando el factor de recobro y ampliando la vida útil del yacimiento. Se concluye que la aplicación del SGC y constructos relacionados favorece el desempeño y la producción de las unidades de explotación de yacimientos petrolíferos maduros. Los principales aportes de la tesis son la obtención de un modelo de gestión de la producción de petróleo en yacimientos maduros, basado en los SGC. Asimismo, el desarrollo de un concepto de gestión de la calidad asociado a la reducción de la desviación de la producción petrolífera anual, al incremento del factor de recobro y al aumento de la vida útil del yacimiento. Las futuras líneas de investigación están orientadas a la aplicación del modelo en contextos reales y específicos, para medir su impacto y realizar los ajustes pertinentes. ABSTRACT The process of change from an industrial society to a knowledge-based society, which undergoes the globalized world in the twenty-first century, induces companies and organizations to develop a sustainable and competitive advantages based on its intangible assets, among which are noteworthy the management systems in general and particularly the quality management systems (QMS). Organizations engaged in oil production are influenced by said trend. Oil is a natural resource with limited reserves, where production and consumption has grown progressively, providing the largest share (35%) of the total energy consumed in the contemporary world, a contribution that will remain until the year 2035 according to the more conservative trust estimations. Therefore, it becomes necessary to develop innovative production models which contribute with the improvement of reservoirs´ recovery factor and the lifetime thereof, while meeting the production requirements and daily consumption of demanding global markets. The aim of this research is to develop a model of quality management and its effect on organizational performance through the mediator effect of the constructs, internal customer satisfaction and knowledge management in oil production. This research of explanatory nature, not experimental, transactional and expos-facto was carried out in the oil-region of Maracaibo Lake located to the west of Venezuela, which has more than 70 years in continuous production and has mature reservoirs. The population under study was 369 oil workers who participated in the technical quality workshops, during the months of May and July of 2012, the majority of which were in the process of training as analysts, consultants and auditors of the QMS. The sampling technique applied was simple random type. To a sample of 252 individuals of the population it was applied an ad hoc designed questionnaire, which was validated by the techniques of expert judgment and pilot test. The research procedure was performed through a sequence, which included the elaboration of a theoretical model, based on the review of the state of the art; a factorial model with based on factorial analysis of the survey data; a linear regression model, developed through the method of simple and multiple linear regression; a structural equation model, made with software °Amos 20 SPSS° and finally, a computer model, performed with the simulator Vensim PLE v.6.2. The results indicate that the theoretical model was transformed into an empirical model, in which the independent variable was the QMS, the mediator variable was the integration of the dimensions: elimination of non-conformity, internal customer satisfaction and organizational learning (ENCSCIAO) and the response variable the integration of the dimensions, organizational performance and learning organizational (DOOA). ENSCIAO´s mediator effect on the relation QMS-DOOA was verified with a goodness of fit of 42,65%. In the multiple regression model was found to be the determining variables are elimination of nonconformity (ENC), knowledge acquired (CA) and spontaneous knowledge (EC), which was verified with the structural equation model. The computer model was developed based on approximate data of an oil production unit type, creating four (04) scenarios; being the most favorable, that one which it was applied the QMS and related variables, reducing the production deviation, increasing the recovery factor and extending the lifetime of the reservoir. It is concluded that QMS implementation powered with the related constructs, favors performance and production of mature oilfield of exploitation reservoirs units. The main contributions of this thesis are obtaining a management model for oil production in mature oilfields, based on QMS. In addition, development of a concept of quality associated to reduce the annual oil production deviation, increase the recovery factor and increase oilfield lifetime. Future lines of research are oriented to the implementation of this model in real and specific contexts to measure its impact and make the necessary adjustments that might take place.

Estación de servicio de gas natural licuado y comprimido para vehículos

Se propone la construcción de una planta satélite de gas natural anexa a una estación de servicio de carburante. El interés del proyecto se centra en el ahorro económico que supone el uso de este combustible para el transporte por carretera (hasta 50 %). Además el gas natural es, en relación al petróleo, más limpio y la relación reservas/producción es mayor. En España la infraestructura de esta tecnología es una de las mayores y mejor consolidadas de Europa. Se ha elegido la E.S. localizada en el km 26 de la autopista A1 con sentido Burgos (San Sebastián de los Reyes, Madrid). Esta autopista es una de las principales vías de conexión entre España y el resto de Europa, resultando interesante pensando en el sector trasportista. La planta dispondrá de un tanque criogénico de 60 m3 para almacenar gas natural licuado (GNL) a una temperatura de -163 ºC. Parte de éste será comprimido a 290 bar y después conducido a un vaporizador ambiental de alta presión que lo gasificará. Finalmente el gas resultante se odorizará obteniendo gas natural comprimido (GNC) que quedará preparado para su almacenaje en vasijas. El tanque criogénico (GNL) y las botellas (GNC) se conectarán a sus respectivos surtidores para el suministro de combustible. La planta incluirá un surtidor de GNC y otro de GNL para vehículos pesados. Se realizará el montaje e instalación de los equipos y líneas necesarios para el almacenaje, manipulación y suministro de gas natural vehicular.

Estudo das forças capilar, viscosa e gravitacional através de grupos adimensionais na simulação da drenagem gravitacional assistida por gás (GAGD)

The distribution and mobilization of fluid in a porous medium depend on the capillary, gravity, and viscous forces. In oil field, the processes of enhanced oil recovery involve change and importance of these forces to increase the oil recovery factor. In the case of gas assisted gravity drainage (GAGD) process is important to understand the physical mechanisms to mobilize oil through the interaction of these forces. For this reason, several authors have developed physical models in laboratory and core floods of GAGD to study the performance of these forces through dimensionless groups. These models showed conclusive results. However, numerical simulation models have not been used for this type of study. Therefore, the objective of this work is to study the performance of capillary, viscous and gravity forces on GAGD process and its influence on the oil recovery factor through a 2D numerical simulation model. To analyze the interplay of these forces, dimensionless groups reported in the literature have been used such as Capillary Number (Nc), Bond number (Nb) and Gravity Number (Ng). This was done to determine the effectiveness of each force related to the other one. A comparison of the results obtained from the numerical simulation was also carried out with the results reported in the literature. The results showed that before breakthrough time, the lower is the injection flow rate, oil recovery is increased by capillary force, and after breakthrough time, the higher is the injection flow rate, oil recovery is increased by gravity force. A good relationship was found between the results obtained in this research with those published in the literature. The simulation results indicated that before the gas breakthrough, higher oil recoveries were obtained at lower Nc and Nb and, after the gas breakthrough, higher oil recoveries were obtained at lower Ng. The numerical models are consistent with the reported results in the literature

Obtenção de Mo2C com adição de Co por reação gás-sólido em reator de leito fixo

Sulfur compounds emissions have been, on the late years, subject to more severe environmental laws due to its impact on the environment (causing the acid rain phenomena) and on human health. It has also been object of much attention from the refiners worldwide due to its relationship with equipment’s life, which is decreased by corrosion, and also with products’ quality, as the later may have its color, smell and stability altered by the presence of such compounds. Sulfur removal can be carried out by hydrotreating (HDT) which is a catalytic process. Catalysts for HDS are traditionally based on Co(Ni)-Mo(W)/Al2O3. However, in face of the increased contaminants’ content on crude oil, and stricter legislation on emissions, the development of new, more active and efficient catalysts is pressing. Carbides of refractory material have been identified as potential materials for this use. The addition of a second metal to carbides may enhance catalytic activities by increasing the density of active sites. In the present thesis Mo2C with Co addition was produced in a fixed bed reactor via gas-solid reaction of CH4 (5%) and H2(95%) with a precursor made of a mix of ammonium heptamolybdate [(NH4)6[Mo7O24].4H2O] and cobalt nitrate[Co(NO3)2.6H2O] at stoichiometric amounts. Precursors’ where analyzed by XRF, XRD, SEM and TG/DTA. Carboreduction reactions were carried out at 700 and 750°C with two cobalt compositions (2,5 and 5%). Reaction’s products were characterized by XRF, XRD, SEM, TOC, BET and laser granulometry. It was possible to obtain Mo2C with 2,5 and 5% cobalt addition as a single phase at 750°C with nanoscale crystallite sizes. At 700°C, however, both MoO2 and Mo2C phases were found by XRD. No Co containing phases were found by XRD. XRF, however, confirmed the intended Co content added. SEM images confirmed XRD data. The increase on Co content promoted a more severe agglomeration of the produced powder. The same effect was noted when the reaction temperature was increased. The powder synthesized at 750°C with 2,5% Co addition TOC analysis indicated the complete conversion from oxide material to carbide, with a 8,9% free carbon production. The powder produced at this temperature with 5% Co addition was only partially converted (86%)

Aplicação de nanoemulsão ácida em acidificação de poços de petróleo

A constante busca da indústria de petróleo pelo aumento de produção à um baixo custo operacional faz necessário o desenvolvimento de tecnologias que una as duas necessidades. A Acidificação de matriz é um método de estimulação frequentemente empregado para aumentar produção de um poço de petróleo com um custo menor se comparado a um fraturamento. O objetivo deste trabalho é estudar a obtenção de nanoemulsões ácidas para aplicação em acidificação de matriz. As nanoemulsões são capazes de retardar reações, por diminuir a difusão do ácido no meio, possibilitando a acidificação em reservatórios com baixa permeabilidade. Os reagentes utilizados para formar os sistemas nanoemulsionados foram UNT L90/OMS e RNX 110 como tensoativos, Sec-butanol como cotensoativo, Xileno e Querosene como fase óleo e Solução de HCl como fase aquosa. As nanoemulsões foram obtidas a partir da diluição de microemulsões com água ou solução de HCl. Foi realizado estudo das tensões superficiais, estudo das cinéticas de reação, avaliação da injeção em rocha carbonática e remoção de borra asfáltica. As nanoemulsões apresentaram tensão superficial menor que suas microemulsões de origem. As nanoemulsões tiveram êxito em retardar a reação entre CaCO3 e HCl, onde o sistema mais eficiente é composto por UNT L90/OMS, Secbutanol, Querosene e solução de HCl. As nanoemulsões foram eficientes em formar wormholes em plugs de carbonato calcitico com baixa permeabilidade natural. As wormholes proporcionaram incremento de permeabilidade alcançando valores de até 390 mD. O sistema ácido apresentou bom resultado de remoção de borra asfáltica, mostrando o potencial das nanoemulsões em remover esse tipo de dano. Conclui-se que os sistemas nanoemulsionados têm grande potencial de aplicação em acidificação de matriz.

Estudo da injeção de água e gás em um reservatório com características do pré-sal brasileiro

The pre-salt province is composed by large amounts of light oil and with good quality, a reality that puts Brazil in a strategic position facing the great demand for energy worldwide. In this province are the largest discoveries in the world in the last ten years; areas as Libra, Franco and Lula field, everyone containing volumes greater than 8 billion recoverable oil barrels. To develop and optimize the production of these fields, a study was done for choosing the improved oil recovery methods. The main motivations were the presence of carbon dioxide (CO2) as a contaminant and the strategic decision of do not discard it, combined with high GOR (gas-oil ratio) of the reservoir fluid. The method should take advantage of the unique abundant resources: seawater and produced gas. This way, the process of matching these resources in the water alterning gas injection (WAG) became a good option. In this master’s dissertation, it was developed a reservoir model with average characteristics of the Brazilian pre-salt, where was applied the improved oil recovery method of water alternating gas. The production of this reservoir was analyzed by parameters as: the first fluid injected in the injection process, position of the injection wells completion, injection water and gas rate and cycle time. The results showed a good performance of the method, with up to 26% of gains in the recovery factor regarding the primary recovery, since the application of water injection and gas, individually, was not able to overcome 10 % of gain. The most influential parameter found in the results was the cycle time, with higher recovery factor values obtained with the use of shorter times.

Análisis de las simulaciones del proceso de deshidratación del gas natural con Aspen Hysys y Aspen Plus

El gas natural ha tomado un rol estratégico importante en el suministro de energía a nivel mundial como consecuencia de la creciente demanda global de energía. El agua es probablemente el componente indeseable más común en el gas natural no tratado ya que su presencia puede ocasionar la formación de hidratos y problemas de corrosión. Debido a las potenciales consecuencias costosas, el gas debe ser sometido a procesos de acondicionamiento a fin de alcanzar las especificaciones requeridas para su venta, transporte hacia los centros de distribución y consumo final. En los últimos años, la simulación de procesos está jugando un papel muy importante en la industria del gas y petróleo como una herramienta adecuada y oportuna para el diseño, caracterización, optimización y monitoreo del funcionamiento de procesos industriales. En el presente trabajo se describe el desarrollo de dos simulaciones estacionarias del proceso de deshidratación de gas natural por absorción con trietilenglicol (TEG), empleando los simuladores comerciales de procesos Aspen HYSYS V8.3 y Aspen PLUS V8.2. La composición del gas natural, la configuración del proceso y las condiciones de operación empleadas en los cálculos y la simulación son típicas de los yacimientos y plantas de acondicionamiento de la provincia de Salta (Argentina).

Influência da vermiculita expandida na resistência à compressão e reologia de pastas cimentantes de poços de petróleo

Several problems related to the loss of hydraulic seal in oilwells, causing gas migration and/or contamination of the production zone by water, have been reported. The loss of the hydraulic seal is a consequence of cracks which can be occasioned either by the invasion of gas during the wait on cement or by the expansion of the casing causing the fracture of the cement sheath. In case of the pressure of the formation is higher than the pressure in the annulus, gas can migrate into the slurry and form microannulus, which are channels where gas migrates after the cement is set. Cracks can be also occasioned by the fracture of the cement sheath when it does not withstand the thermal and dynamic loads. In reservoirs where the oil is heavy, steam water injection operation is required in order to get the oil flowing. This operation increases the temperature of the casing, and then it expands and causes the fracture of the cement sheath in the annulus. When the failures on the cement are detected, remedial cementing is required, which raise costs caused by the interventions. Once the use of cement in the construction civil sector is older than its use in the petroleum sector, it is common to bring technologies and solutions from the civil construction and apply them on the petroleum area. In this context, vermiculite, a mineral-clay widely encountered in Brazil, has been used, on its exfoliated form, in the civil construction, especially on the manufacture of lights and fireproof concretes with excellent thermal and acoustical properties. It has already been reported in scientific journals, studies of the addition of exfoliated vermiculite in Portland cements revealing good properties related to oilwell cementing operations. Thus, this study aimed to study the rheological behavior, thickening time, stability and compressive strength of the slurries made of Portland cement and exfoliated vermiculite in 5 different compositions, at room temperature and heated. The results showed that the compressive strength decreased with the addition of exfoliated vermiculite, however the values are still allowed for oiwell cementing operations. The thickening time of the slurry with no exfoliated vermiculite was 120 min and the thickening time of the slurry with 12 % of exfoliated vermiculite was 98 min. The stability and the rheological behavior of the slurries revealed that the exfoliated vermiculite absorbed water and therefore increased the viscosity of the slurries, even though increasing the factor cement-water. The stability experiment carried out at 133 ºF showed that, there was neither sedimentation nor reduction of the volume of the cement for the slurry with 12 % of exfoliated vermiculite. Thus, the addition of exfoliated vermiculite accelerates the set time of the cement and gives it a small shrinkage during the wait on cement, which are important to prevent gas migration

Avaliação da influência do nacl em pastas de cimento portland para cimentação de poços de petróleo em zonas evaporíticas

One of the major current challenges for oilwell companies is the extraction of oil from evaporitic zones, also known as pre-salt basins. Deep reservoirs are found under thick salt layers formed from the evaporation of sea water. Salt layers seal the flow of oil from underneath rock formations, which store hydrocarbons and increase the probability of success in oil and gas exploration. Oilwells are cemented using Portland-based slurries to promote mechanical stability and zonal isolation. For pre-salt oilwells, NaCl must be added to saturate the cement slurries, however, the presence of salt in the composition of slurries affects their overall behavior. Therefore, the objective of the present study was to evaluate the effect of the addition of 5 to 25% NaCl on selected properties of Portland-based slurries. A series of tests were carried out to assess the rheological behavior, thickening time, free water and ultrassonic compressive strength. In addition, the slurries were also characterized by thermal analysis, X ray diffraction and scanning electron microscopy. The results showed that the addition of NaCl affected the thickening time of the slurries. NaCl contents up to 10% shortened the thickening time of the slurries. On the other hand, concentrations in excess of 20% not only extended the thickening time, but also reduced the strength of hardened slurries. The addition of NaCl resulted in the formation of a different crystalline phase called Friedel´s salt, where free chlorine is bonded to tricalcium aluminate

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

Efeito da incorporação de diatomita na estabilidade e permeabilidade de compósitos cimentíceos espumados aplicados a poços de petróleo

Lightweight oilwell cement slurries have been recently studied as a mean to improve zonal isolation and sheath-porous formation adherence. Foamed slurries consisting of Portland cement and air-entraining admixtures have become an interesting option for this application. The loss in hydrostatic pressure as a consequence of cement hydration results in the expansion of the air bubbles entrapped in the cement matrix, thus improving the sheath-porous formation contact. Consequently, slurries are able to better retain their water to complete the hydration process. The main objective of the present study was to evaluate the effect of the addition of an air-entraining admixture on the density, stability and permeability of composite slurries containing Portland cement and diatomite as light mineral load. Successful formulations are potential cementing materials for low fracture gradient oilwells. The experimental procedures used for slurry preparation and characterization were based on the American Petroleum Institute and ABNT guidelines Slurries containing a pre-established concentration of the air-entraining admixture and different contents of diatomite were prepared aiming at final densities of 13 to 15 lb/gal. The results revealed that the reduction of 15 to 25% of the density of the slurries did not significantly affect their strength. The addition of both diatomite and the air-entraining admixture increased the viscosity of the slurry providing better air-bubble retention in the volume of the slurry. Stable slurries depicted bottom to top density variation of less than 1.0 lb/gal and length reduction of the stability sample of 5.86 mm. Finally, permeability coefficient values between 0.617 and 0.406 mD were obtained. Therefore, lightweight oilwell cement slurries depicting a satisfactory set of physicochemical and mechanical properties can be formulated using a combination of diatomite and air-entraining admixtures for low fracture gradient oilwells