Incorporação de resíduo cerâmico para prevenção da retrogressão da resistência de cimentos de poços de petróleo submetidos à injeção de vapor

Steam injection is the most used thermal recovery method of oil nowadays because of the high degree of development of the technique that allows high recovery factors. However, injection of superheated steam into the reservoir affects the entire structure of the well, including the cemented layer that presents a retrogression of compressive strength and increases the permeability due to formation of more crystalline and denser phases at temperatures above 110 °C. These changes result in failures in the cement that favor the entrance of formation fluids into the annulus space resulting in unsafe operations and restrictions in the economic life of the well. But the strength retrogression can be prevented by partial replacement of cement by silica-based materials that reduce the CaO/SiO2 ratio of cement slurries changing the trajectory of the reactions, converting those deleterious phases in phases with satisfactory mechanical strength and permeability. The aim of this study was to evaluate the behavior of a ceramic waste material rich in silica in partial and total substitution of a mineral additive used to fight the strength retrogression of cement slurries subjected to high temperatures. The evaluation was made by compression, X-ray diffraction (XRD) and thermogravimetry (TG/DTG). The samples were submitted to a cycle of low temperature (38 °C) for 28 days and a cycle of low temperature followed by exposure to 280 ºC and 1000 psi by 3 days. The results showed that slurries with additions of up to 30% of the waste material are not enough to prevent the strength retrogression, while slurries with additions of the waste material combined with silica flour in various proportions produced hydrated products of low Ca/Si ratios that maintained the compressive strength at satisfactory levels

Síntese de catalisadores nanoporosos na ausência total e parcial de direcionadores orgânicos para pirólise catalítica de óleos pesados e intermediários

The processing of heavy oil produced in Brazil is an emergency action and a strategic plan to obtain self-sufficiency and economic surpluses. Seen in these terms, it is indispensable to invest in research to obtain new catalysts for obtaining light fraction of hydrocarbons from heavy fractions of petroleum. This dissertation for the degree of Doctor of Philosophy reports the materials preparation that combine the high catalytic activity of zeolites with the greater accessibility of the mesoporosity, more particularly the HZSM-5/MCM-41 hybrid, done by synthesis processes with less environmental impact than conventional ones. Innovative methodologies were developed for the synthesis of micro-mesoporous hybrid material by dual templating mechanism and from crystalline zeolitic aluminosilicate in the absence of organic template. The synthesis of hybrid with pore bimodal distribution took place from one-single organic directing agent aimed to eliminate the use of organic templates, acids of any kind or organic solvents like templating agent of crystalline zeolitic aluminosilicate together with temperature-programmed microwave-assisted, making the experimental procedures of preparation most practical and easy, with good reproducibility and low cost. The study about crystalline zeolitic aluminosilicate in the absence of organic template, especially MFI type, is based on use of H2O and Na+ cation playing a structural directing role in place of an organic template. Advanced characterization techniques such as X-Ray Diffraction (XRD), Fourier Transform Infrared Spectroscopy (FTIR), Scanning Electron Microscopy (SEM), Highresolution Transmission Electron Microscopy (HRTEM), Adsorption of N2 and CO2, kinetic studies by Thermogravimetric Analysis (TGA) and Pyrolysis coupled to Gas Chromatography/Mass Spectrometry (Pyrolysis-GC/MS) were employed in order to evaluate the synthesized materials. Achieve the proposed objectives, has made available a set of new methodologies for the synthesis of zeolite and hybrid micro-mesoporous material, these suitable for catalytic pyrolysis of heavy oils aimed at producing light fraction

Caracterização geológico-geofísica do meio aqüífero fissural : uma contribuição aos modelos de fluxo e armazenamento de água subterrânea

Northeastern Brazil is mainly formed by crystalline terrains (around 60% in area). Moreover, this region presents a semi-arid climate so that it is periodically subject to drought seasons. Furthermore, ground water quality extracted fromwells usually presents poor quality because of their high salinity contents. Nevertheless, ground water is still a very important source of water for human and animal consumption in this region. Well sitting in hard rocks terrains in Northeastern Brazil offers a mean success index of aboul 60%, given that a successful siting is defined by a well producing at least 0.5 m³/h. This low index reveals lack of knowledga about the true conditions of storage and percolation of ground water in crystalline rocks. Two models for structures storing and producing ground water in crystalline rocks in Northeastem Brazil have been proposed in the literature. The first model,tradnionally used for well sitting since the sixties are controlled by faults or fractures zones. This model is commonly referred, in Brazilian hydrogeological literature, as the "creek-crack" model (riacho-fenda in Portuguese). Sites appearing to present dense drainage network are preferred for water well siting - particularly at points where the drainages cross-cul each other. Field follow up work is usually based only on geological criteria. The second model is the "eluvio-alluvial through" (calha eluvio-aluvionar in Portuguese); it is also described in the literature but it is not yet incorporated in well sitting practice. This model is based on the hypothesis that reclilinear drainages can also be controlled by the folietion of the rock. Eventually, depending upon the degree of weathering, a through-shaped structure filled with sediments (alluvium and regolith) can be developed which can store and water can be produced from. Using severalfield case studies, this Thesis presents a thorough analysis ofthe two above cited models and proposes a new model. The analysis is based on an integrated methodological approach using geophysics and structural geology. Both land (Resitiviy and Ground Penetrating Radar- GPR) and aerogeophysical (magnetics and frequency domain eletromagnetics) surveys were used. Slructural analysis emphasized neolectonic aspects; in general, itwas found that fractures in the E-W direction are relatively open, as compared to fracturas inthe N-S direction, probably because E-W fractures were opened by the neotectonic stress regime in Northeastern Brazil, which is controlled by E-W compression and N-S extension. The riacho-fenda model is valid where drainages are controlled by fractures. The degree of fracturing and associated weathering dictale the hydrogeological potential of the structure. Field work in structural analogues reveals that subvertical fractures show consistent directions both in outcrop and aerophotograph scales. Geophysical surveys reveal subvertical conductive anomalies associated to the fracture network controlling the drainage; one of the borders of the conductive anomaly usually coincide wih the drainage. An aspect of particular importance to the validation of fracture control are the possible presence of relalively deep conductive anomalies wihoul continuation or propagalion to the surface. The conductive nature of lhe anomaly is due to the presence of wealhered rock and sedirnenls (alluvium and/or regolilh) storing ground waler which occur associated to the fracture network. Magnetic surveys are not very sensisnive to these structures.lf soil or covering sedirnents are resislive (> 100 Ohm.m), GPR can ba used to image precisely lhe fracture network. A major limialion of riacho-fenda model, revealed by GPR images, is associated to the fact thal subhorizontal fractures do play a very important role in connecting the fracture network, besides connect shallow recharge zones to relalively deep subvertical frecture zones. Iffractures play just a secondary control on the drainage, however, r/acho-fenda model may have a very limiled validny; in these cases, large portions oflhe drainage do nol coincide wilh frectures and mosl oflhewells localed in lhe drainage surrounding would resull dry. Usually, a secondary conlrol on lhe drainage by Ihefraclure networkcan be revealed only wilh detailed geophysical survey. The calha elClv1o-aluvlonarmodel is valid where drainages are conlrolled by folialion. The degree 01 wealhering 01 lhe lolialion planes dictales lhe hydrogeological polenlial 01 lhe slruclure. Outcrop analysis reveals Ihal lolialion and drainage direclions are parallel and Ihal no Iraclures, orfraclures wilh diflerent directions 01 lhe drainage direclion occur. Geophysical surveys reveal conduclive anomalies in a slab lorm associaled 10 lhe Ihrough 01 lhe wealhered rock and sedimenls (alluvium and/or regolith). Magnelic surveys can ofler a very good conlrol on lolialion direclion. An importanl aspect 10 validale lolialion conlrol are lhe presence 01 conductive anomalies showing shallow and deep portions area which are linked. Illhere is an exlensive soil cover, r/acho-fenda and calha eIClv1o-aluv/onar conlrols can be easily misinlerpreled in lhe absence 01 geophysical conlrol. Certainly, Ihis lacl could explain at leasl a part of lhe failure index in well sitting. The model wealhering sack (bolsllo de Intempertsmo in Portuguese) is proposed to explain cases where a very inlensive wealhering occur over lhe crystalline rock so Ihal a secondary inlerslilial porosity is crealed. The waler is Ihen stored in lhe porous of lhe regolilh in a similar mannerlo sedimentary rocks. A possible example ofthis model was delecled by using land geophysical survey where a relalivelyvery deep isolaled conduclive anomaly, in a slab form, was delected. Iflhis structure does store ground waler, certainly Ihere must be a link 01 lhe deep slructure wilh lhe surface in orderlo provide walerfeeding. This model mighl explain anomalous waler yields as greal as 50 m³/h Ihalsomelimescan occur in crystalline rocks in Northeaslern Brazil