Submitted by Sandra Pereira (srpereira@ufrrj.br) on 2016-08-31T18:29:21Z No. of bitstreams: 1 2011 - Ludmila Fonseca da Silva.pdf: 418709 bytes, checksum: 3fdbea46dfe13f8e8414fea7b84fbd88 (MD5) / Made available in DSpace on 2016-08-31T18:29:21Z (GMT). No. of bitstreams: 1 2011 - Ludmila Fonseca da Silva.pdf: 418709 bytes, checksum: 3fdbea46dfe13f8e8414fea7b84fbd88 (MD5) Previous issue date: 2011-02-25 / Conselho Nacional de Desenvolvimento Cient?fico e Tecnol?gico - CNPq / Two experiments were installed. The first experiment was conducted to evaluate the physiological quality of sunflower seeds after hydration by the methods of humid atmosphere and soak substrate combined to 10 and 20?C to increase the water content of seeds for 15, 20 and 25%. For this, the initial physiological quality and after the moistening of the seeds was determined by germination tests and vigor. The second experiment was conducted to evaluate the precocity of the primary root emission of sunflower seeds as a vigor test. For this, four seed lots were tested for germination and vigor, among them, the primary root emission aiming percentage of emission and precocity index. From the results it was concluded that the method of soak substrate at 10?C to increase the water content at 15 and 20% was positive for moistening the seeds of high quality, although it has seen little reduction in seedling vigor. The test root emission after 48 hours was effective in classifying different levels of vigor lots of sunflower seeds / Foram instalados dois experimentos. O primeiro foi realizado com o objetivo de avaliar a qualidade fisiol?gica das sementes de girassol ap?s a hidrata??o pelos m?todos da atmosfera ?mida e substrato ?mido combinados a 10 e 20?C para elevar o teor de ?gua das sementes para 15, 20 e 25%. Para isto, a qualidade fisiol?gica inicial e ap?s o umedecimento das sementes foi determinada pelos testes de germina??o e de vigor. O segundo experimento foi realizado com o objetivo de avaliar a precocidade da emiss?o de raiz prim?ria de sementes de girassol como teste de vigor. Para isto, quatro lotes de sementes foram submetidos a testes de germina??o e vigor, entre eles, o de emiss?o de raiz prim?ria, visando a porcentagem de emiss?o e o ?ndice de precocidade. Pelos resultados foi poss?vel concluir que o m?todo do substrato ?mido a 10?C visando aumentar o teor de ?gua a 15 e 20% foi favor?vel para o umedecimento das sementes de elevada qualidade, embora tenha sido observado pequena redu??o do vigor das pl?ntulas. O teste de emiss?o de raiz prim?ria ap?s 48 horas foi eficiente na classifica??o de distintos n?veis de vigor dos lotes de sementes de girassol.

L'auteur présente une étude comportementale des milieux granulaires humides. Une première phase de caractérisation de tels milieux, couplant des aspects mécaniques et texturaux, aura pour ambition d'établir les bases d'une représentation schématique de l'état hydrique et textural d'un milieu granulaire. Cette représentation sera investie dans l'analyse du processus d'agglomération et permettra, grâce à une étude couplant des aspects hydro-texturaux et morpho-granulométriques, d'analyser les modifications subies par des milieux granulaires soumis à une opération de mouillage et de malaxage. Ces modifications seront analysées aux deux échelles du mélange : à l'échelle des agglomérats, il sera montré que la phase d'agglomération peut être envisagée comme un processus de type fractal ; à l'échelle globale du milieu, une phénoménologie de texturation en trois étapes sera mise en évidence. La dernière phase de ce travail consistera en une étude plus particulière des effets de contraintes vibratoires ou axiales sur le phénomène de texturation préalablement mis en évidence sur le milieu vrac. Il s'agira d'étudier dans quelle mesure ce type de contraintes (tassement, compactage), postérieure à l'élaboration du milieu, est susceptible de modifier l'allure du phénomène de texturation et de déterminer les facteurs susceptibles d'influer sur la succession des différentes phases de ce phénomène. L'étude des cinétiques de relaxation sous contraintes vibratoires permettra également de proposer un nouveau modèle de relaxation établi selon une approche mécanique.

The transport of components and phases plays a fundamental role in the success of an EOR process. Because many reservoirs have harsh conditions of salinity, temperature and rock heterogeneity, which limit process options, a robust system with flexibility is required. Systematic experimental study of formulations capable to transport surfactant as foam at 94°C, formulated in sea water, is presented. It includes methodology to conduct core floods in sand packs using foaming surfactants and to develop “surfactant blend ratio- salinity ratio maps” using equilibrium phase behavior to determine favorable conditions for oil recovery in such floods. Mathematical model able to reproduce the foam strength behavior observed in sand packs with the formulations studied is presented. Visualization of oil recovery mechanism from matrix is realized using a model system of micro-channels surrounded by glass beads to mimic matrix and fractures respectively. The observations illustrate how components may distribute within the matrix, thereby releasing oil into the fractures. The use of chemicals to minimize adsorption is required when surfactant adsorption is important. The presence of anhydrite may limit the use of sodium carbonate to reduce adsorption of carbonates. A methodology is presented to estimate the amount, if any, of anhydrite present in the reservoir. The method is based on brine software analysis of produced water compositions and inductively coupled plasma (ICP) analysis of core samples. X-ray powder diffraction (XRD) was used to verify the mineralogy of the rock. X-ray photoelectron spectroscopy (XPS) was used to obtain surface composition for comparison with bulk composition of the rock. Adsorption of surfactants was measured using dynamic and static adsorption experiments. Determining the flow properties of the rock samples via tracer analysis permitted the simulation of the dynamic adsorption process using a mathematical model that considers the distribution of adsorbed materials in the three different regions of pore space. Using this method allows one to predict adsorption in a reservoir via simulation.

Water-flooding in water-wet fractured reservoirs can recover significant amounts of oil through capillary driven imbibition. Unfortunately, many of the fractured reservoirs are mixed-wet/oil-wet and water-flooding leads to poor recovery as the capillary forces hinder imbibition. Surfactant injection and immiscible gas injection are two possible processes to improve recovery from fractured oil-wet reservoirs. In both these EOR methods, the gravity is the main driving force for oil recovery. Surfactant has been recommended and shown a great potential to improve oil recovery from oil-wet cores in the laboratory. To scale the results to field applications, the physics controlling the imbibition of surfactant solution and the scaling rules needs to be understood. The standard experiments for testing imbibition of surfactant solution involves an imbibition cell, where the core is placed in the surfactant solution and the recovery is measured versus time. Although these experiments prove the effectiveness of surfactants, little insight into the physics of the problem is achieved. This dissertation provides new core scale and pore scale information on imbibition of anionic surfactant solution into oil-wet porous media. In core scale, surfactant flooding into oil-wet fractured cores is performed and the imbibition of the surfactant solution into the core is monitored using X-ray computerized tomography(CT). The surfactant solution used is a mixture of several different surfactants and a co-solvent tailored to produce ultra-low interfacial tension (IFT) for the specific oil used in the study. From the CT images during surfactant flooding, the average penetration depth and the water saturation versus height and time is calculated. Cores of various sizes are used to better understand the effect of block dimension on imbibition behavior. The experimental results show that the brine injection into fractured oil-wet core only recovers oil present in the fracture; When the surfactant solution is injected, the CT images show the imbibition of surfactant solution into the matrix and increase in oil recovery. The surfactant solution imbibes as a front. The imbibition takes place both from the bottom and the sides of the core. The highest imbibition is observed close to the bottom of the core. The imbibition from the side decreases with height and lowest imbibition is observed close to the top of the core. Experiments with cores of different sizes show that increase in either the length or the diameter of the core causes decrease in the fractional recovery rate (%OOIP). Numerical simulation is also used to determine the physics that controls the imbibition profiles. %The numerical simulations show that the relative permeability curves strongly affect the imbibition profiles and should be well understood to accurately model the process. Both experimental and numerical simulation results imply that the gravity is the main driving force for the imbibition process. The traditional scaling group for gravity dominated imbibition only includes the length of the core to upscale the recovery for cores of different sizes. However based on the measurements and simulation results from this study, a new scaling group is proposed that includes both the diameter and the length of the core. It is shown that the new scaling group scales the recovery curves from this study better than the traditional scaling group. In field scale, the new scaling group predicts that the recovery from fractured oil-wet reservoirs by surfactant injection scales by both the vertical and horizontal fracture spacing. In addition to core scale experiments, capillary tube experiments are also performed. In these experiments, the displacement of oil by anionic surfactant solutions in oil-wet horizontal capillary tubes is studied. The position of the oil-aqueous phase interface is recorded with time. Several experimental parameters including the capillary tube radius and surfactant solution viscosity are varied to study their effect on the interface speed. Two different models are used to predict the oil-aqueous phase interface position with time. In the first model, it is assumed that the IFT is constant and ultra-low throughout the experiments. The second model involves change of wettability and IFT by adsorption of surfactant molecules to the oil-water interface and the solid surface. Comparing the predictions to the experimental results, it is observed that the second model provides a better match, especially for smaller capillary tubes. The model is then used to predict the imbibition rate for very small capillary tubes, which have equivalent permeability close to oil reservoirs. The results show that the oil displacement rate is limited by the rate of diffusion of surfactant molecules to the interface. In addition to surfactant flooding, immiscible gas injection can also improve recovery from fractured oil-wet reservoirs. In this process, the injected gas drains the oil in the matrix by gravity forces. Gravity drainage of oil with gas is an efficient recovery method in strongly water-wet reservoirs and yields very low residual oil saturations. However, many of the oil-producing fractured reservoirs are not strongly water-wet. Thus, predicting the profiles and ultimate recovery for mixed and oil-wet media is essential to design and optimization of improved recovery methods based on three-phase gravity drainage. In this dissertation, we provide the results from two- and three-phase gravity drainage experiments in sand-packed columns with varying wettability. The results show that the residual oil saturation from three-phase gravity drainage increases with increase in the fraction of oil-wet sand. A simple method is proposed for predicting the three-phase equilibrium saturation profiles as a function of wettability. In each case, the three-phase results were compared to the predictions from two-phase results of the same wettability. It is found that the gas/oil and oil/water transition levels can be predicted from pressure continuity arguments and the two-phase data. The predictions of three-phase saturations work well for the water-wet media, but become progressively worse with increasing oil-wet fraction. / text

L'imbibition d’eau pour les matériaux granulaires induit des changements dans la morphologie des ponts capillaires qui passent d'une forme isolée (entre deux grains voisins), à une forme fusionnée (entre plusieurs grains voisins). Ces changements de morphologie des ponts liquides influencent le comportement mécanique de ces matériaux, et peuvent être à l’origine d’instabilités telles que l’effondrement capillaire. La thèse présente une approche expérimentale multi-échelle au laboratoire de l'effondrement capillaire de matériaux granulaires lors d'une imbibition d'eau. L’approche concerne les trois échelles: macroscopique d'un Volume Élémentaire Représentatif, mésoscopique de quelques grains et locale de trois ou quatre grains. À l'échelle macroscopique, des essais d’imbibition, dans une cellule triaxiale, ont permis l'identification et l'analyse du phénomène d'effondrement capillaire en mettant l'accent sur l'évolution des déformations dans le temps. Les essais sont réalisés sur deux types de matériaux granulaires, le premier est un matériau constitué de billes de verre et le deuxième est un sable concassé. Une fraction argileuse est parfois incorporée au matériau. Plusieurs paramètres ont été étudiés en vue de comprendre leurs contributions dans le déclenchement du phénomène d'effondrement comme : la granularité, la teneur en eau initiale, la compacité initiale et le pourcentage des particules argileuses. Aux échelles mésoscopique et locale, on propose une étude expérimentale de caractérisation du comportement mécanique des matériaux granulaires dans le régime pendulaire et funiculaire. On s’intéresse en particulier à l’effet de l’imbibition et de la coalescence sur la force capillaire entre les grains solides à l’échelle considérée. Les essais d'imbibition sont réalisés par ajout d’incréments de volume d’eau aux ponts capillaires. Les résultats relatifs au comportement et à l’effondrement à l’échelle macroscopique lors de l'imbibition d'eau sont discutés en s’aidant des résultats obtenus aux échelles inférieures. / Wetting in granular materials induces changes in the morphology of capillary bridges which pass from an isolated form (between two neighboring grains) to a merged form (between several neighboring grains). These changes in the morphology of the liquid bridges impact the mechanical behavior of these materials, and can lead to instabilities such as capillary collapse. The thesis presents a multi-scale experimental approach in the laboratory of the capillary collapse of granular materials during wetting. The approach concerns the three scales: macroscopic of a Representative Elementary Volume, mesoscopic of several grains and local of three or four grains. At the macroscopic scale, the wetting tests, carried out in a triaxial cell, allowed the identification and the analysis of capillary collapse phenomenon, focusing on the evolution of deformations over time. The tests are carried out on two granular materials, the first is a material made of glass beads and the second is a crushed sand. A clay fraction is sometimes incorporated into the material. Several parameters have been studied in order to understand their contributions to the triggering of the collapse phenomenon, such as: grain size, initial water content, initial compactness and percentage of clay particles. At the mesoscopic and local scales, an experimental study is proposed to characterize the mechanical behavior of a granular materials, in the pendular and funicular regimes. In particular, this study focus on the effect of the wetting and the coalescence of bridges, on the capillary force between grains at the considered scale. Wetting tests were performed by adding water volume increments to the capillary bridges. The results on behavior and collapse at the macroscopic scale during wetting are discussed using the results obtained on the lower scales.

La silice de précipitation, poreuse à l'échelle de 10 nm, a de nombreuses applications industrielles dans lesquelles elle est mélangée avec des fondus de polymère, composés de molécules de dimension nanométrique. La surface de la silice est de haute énergie, si bien qu'elle tend à être recouverte par la plupart des liquides. Par conséquent, lorsqu'une goutte de liquide est déposée sur la surface de la silice, un film " précurseur " s'étale au-devant de celle-ci, avec une épaisseur de l'ordre du nm. A l'aide d'observations macroscopiques et par imagerie ellipsométrique, nous avons mis en évidence que le polybutadiène et le polystyrène sont en conditions de mouillage pseudo-partiel avec la silice : une goutte macroscopique coexiste à l'équilibre avec le film précurseur en raison de la présence de forces à longue portée attractive à l'échelle du film. Le film précurseur est en fait formé de molécules quasi-isolées qui diffusent avec un coefficient de diffusion égal au coefficient d'auto diffusion mesuré en volume. Ceci nous donne des indications précieuses sur les interactions polymère/silice. Par ailleurs nous observons dans certains cas la croissance d'une instabilité, prenant la forme d'un film " secondaire " d'épaisseur supérieure à celle du film précurseur. Le polydiméthylsiloxane est quant à lui en conditions de mouillage total sur la silice, et seul un film existe à l'équilibre, les forces à longues portées étant répulsives. L'imbibition de la silice poreuse peut également se relier à ces observations. Finalement, nous déduisons que le film précurseur pour des faibles masses de polymères a peu d'impact sur la dynamique d'imbibition de pastilles de silice poreuse. / Precipitated silica, which is porous at the 10 nm scale, has various industrial uses where it is mixed with polymer melts, with characteristic molecular sizes in the nanometer range. Having a high surface energy, silica tends to be covered by most liquids. As a consequence, when a liquid droplet is deposited on silica surfaces, a thin “precursor” film spreads in front of the droplet, with a thickness of a few nanometers. By combining macroscopic observations and ellipsometry imaging, we found that polybutadiene and polystyrene melts on silica are in pseudo-partial wetting conditions, for which a droplet coexists with a precursor film at equilibrium, due to attractive long range forces at the film length scale. The precursor film is composed of quasi-isolated molecules diffusing in two dimensions with a diffusion coefficient equal to the bulk self-diffusion coefficient. This provides valuable information on the polymer/silica interactions. Furthermore, we occasionally observe the growth of an instability, as a “secondary” film which is thicker than the precursor film. In contrast, polydimethylsiloxane melts are in total wetting conditions on silica: at equilibrium, a polymer film covers the silica surface and no droplets coexist with the film, due to repulsive long range forces. Our observations of the imbibition of porous silica by polymer melts were related to these results. Eventually, for low molar mass polymers, we find that the precursor film has no significant impacts on porous silica pellets imbibition.

This study provides independent analysis of Residual Oil Zones (ROZs) in the Permian Basin from a regional perspective, focusing on the formation mechanism and present ROZ locations. Results demonstrate widespread potential for ROZs, defined here as thick volumes of reservoir rock containing near-residual saturations of predominantly immobile oil formed by natural imbibition and displacement of oil by dynamic buoyant or hydrodynamic forces. Previous work suggests hydrodynamic forces generated by regional tectonic uplift drove widespread oil remobilization and ROZ creation. To test the hypothesis, uplift and tilting are quantified and the resulting peak regional potentiometric gradient used as a physical constraint to compute and compare predicted ROZ thicknesses from hydrodynamics for several ROZ-bearing San Andres fields with known ROZ thicknesses. Late-Albian Edwards Group geologic contacts, which are interpreted to have been deposited near sea level prior to uplift, are used as a regional datum. Approximate elevations determined for the present datum show ~1800 m of differential uplift since Edwards deposition, with an average regional slope of ~0.128˚. This post-Edwards tilting increased the pre-existing regional structural gradient of the San Andres Formation to ~0.289˚. Using the calculated post-Edwards gradient results in to prediction of ROZ thicknesses from hydrodynamics that is consistent with measured ROZ thicknesses at several fields. When compared with countervailing buoyancy forces, hydrodynamics is calculated to be the more dominant driving force of oil movement for reservoirs with structural dips less than 1.5˚, which is the common dip for San Andres Formation platform deposits where ROZs have been identified. To predict the location of ROZs, ROZ-related oil field properties were identified and analyzed for over 2,800 Permian Basin reservoirs. A strong basin-wide correlation between API and crude sulfur content is consistent with the expected outcome of oil degradation driven by oil-water interaction, and supports the use of API and sulfur content as proxies for ROZ potential in the Permian Basin. Spatial analysis of sulfur data shows that the highest probability for ROZ existence exists in Leonardian through Guadalupian-age reservoirs, distributed primarily in shelf and platform areas of Permian structures. Combined, these results support the widespread potential for ROZs across the Permian Basin generated primarily by regional scale tilting and resultant hydrodynamic forces. / text

Les particules colloïdales transportées dans la zone non saturée du sol facilitent le transport des contaminants vers les eaux souterraines. Dans cette thèse, l'intérêt est porté sur la mobilisation in-situ et le transport des particules naturellement présentes dans des colonnes de sol non remaniées, et ceci sous des conditions non saturées d'écoulement. L'étude soulève la problématique de la disponibilité et de la possibilité de régénération ou d'épuisement du stock (« pool ») de particules mobilisables. L'objectif de la thèse est d'étudier l'évolution temporelle du stock de particules que ce soit pendant l'événement pluvieux ou pendant la durée d'interruption de pluie (la pause) qui sépare deux événements pluvieux successifs.<br><br>En s'appuyant sur les données expérimentales, un modèle de mobilisation et de transport préférentiel des particules dans des lysimètres (70 cm hauteur, 25 cm diamètre) a été élaboré. Le modèle utilise l'approche des ondes cinématiques dispersives pour décrire le transfert de l'eau, et l'équation convection dispersion avec un terme source/puit pour décrire la mobilisation et le transfert des particules. L'idée de base du modèle est de prendre en compte la possibilité d'une évolution temporelle du stock de particules mobilisables pendant l'événement pluvieux. Ceci est fait à travers une cinétique de détachement (source) de premier ordre ayant un coefficient de détachement variable avec le temps. Quant au terme puit, il est décrit par une cinétique d'attachement de premier ordre ayant un coefficient d'attachement constant avec le temps. Le modèle reproduit avec satisfaction les tendances des particulogrammes pour différentes conditions physico-chimiques expérimentales.<br><br>L'évolution temporelle du pool de particules mobilisables pendant la pause qui sépare deux événements pluvieux est étudiée expérimentalement. Ceci est fait en observant l'impact de la durée de pause sur la mobilisation ultérieure de particules. Pour cela, une large gamme de durées de pauses (allant d'une heure à un mois et demi) est essayée sur deux sols différents et avec deux forces ioniques et deux intensités de pluie différentes. Les pauses sont imposées dans un ordre croissant, régulier ou irrégulier. Les résultats montrent que la mobilisation de particules durant la pause dépend de sa durée. Le comportement de mobilisation observé est assez particulier : la masse de particules mobilisées par événement pluvieux augmente, passe par un maximum puis diminue pour des pauses croissantes. Les forces capillaires semblent être le mécanisme responsable de la mobilisation de particules durant la pause.<br><br>L'application du modèle de transport de particules sur tous les particulogrammes résultant de l'étude de l'effet de pause sur la mobilisation ont permis de lier le paramètre décrivant le détachement par accélération du flux d'eau à une condition expérimentale : la durée de pause.

La condensation à l'équilibre dans les milieux poreux met en jeu l'adsorption et la condensation capillaire. La distribution des dimensions de pores détermine le rôle de chaque phénomène. Le spectre poreux du mortier est étudié par trois méthodes comparées: injection de mercure, sorption d'azote,condensation d'eau. Les transferts de masse isothermes résultent de la combinaison de la diffusion moléculaire et effusive de la vapeur et de l'écoulement visqueux du liquide, L'équilibre local peut-être satisfait ou non. Sur la base d'expériences d'imbibition à quatre températures, avec mesure gammamétrique de la teneur en eau, on analyse la nature des transferts dans le mortier. Le schéma de la superposition d'un flux diffusif de vapeur et d'un flux visqueux de liquide aboutit à certaines contradictions. Le coefficient de transfert expérimental peut être expliqué, aux faibles teneurs en eau, par la diffusion de vapeur dans les macropores interconnectés, et aux fortes teneurs en eau par l'écoulement visqueux du liquide dans des chemins composés de pores de toutes dimensions. Aux teneurs en eau moyennes, on propose un schéma où la phase gazeuse contient des ilots liquides intervenant par un mécanisme de condensation-évaporation avec équilibre local. Des expériences d'humidification du mortier au contact d'air humide ventilé font apparaître un transfert considérablement plus lent qu'en imbibition. La diffusion de vapeur vers le matériau ne suffit pas à expliquer le phénomène. On conclut que les îlots liquides, sièges ici uniquement de condensation, n'interviennent pas dans le transfert, assuré par la seule diffusion gazeuse. On propose en outre un schéma de transfert hors-équilibre comportant une loi gouvernant la vitesse de condensation.

Surfactants both change the wettability and lower the interfacial tension by various degrees depending on the type of surfactant and how it interacts with the specific oil. Ultra low IFT means almost zero capillary pressure, which in turn indicates little oil should be produced from capillary imbibition when the surfactant reduces the IFT in naturally fractured oil reservoirs that are mixed-wet or oil-wet. What is the transport mechanism for the surfactant to get far into the matrix and how does it scale? Molecular diffusion and capillary pressure are much too slow to explain the experimental data. Recent dynamic laboratory data suggest that the process is faster when a pressure gradient is applied compared to static tests. A mechanistic chemical compositional simulator was used to study the effect of pressure gradient on chemical oil recovery from naturally fractured oil reservoirs for several different chemical processes (polymer, surfactant, surfactant-polymer, alkali-surfactant-polymer flooding). The fractures were simulated explicitly by using small gridblocks with fracture properties. Both homogeneous and heterogeneous matrix blocks were simulated. Microemulsion phase behavior and related chemistry and physics were modeled in a manner similar to single porosity reservoirs. The simulations indicate that even very small pressure gradients (transverse to the flow in the fractures) are highly significant in terms of the chemical transport into the matrix and that increasing the injected fluid viscosity greatly improves the oil recovery. Field scale simulations show that the transverse pressure gradients promote transport of the surfactant into the matrix at a feasible rate even when there is a high contrast between the permeability of the fractures and the matrix. These simulations indicate that injecting a chemical solution that is viscous (because of polymer or foam or microemulsion) and lowers the IFT as well as alters the wettability from mixed-wet to water-wet, produces more oil and produces it faster than static chemical processes. These findings have significant implications for enhanced oil recovery from naturally fractured oil reservoirs and how these processes should be optimized and scaled up from the laboratory to the field. / text