Mesoestruturas porosas a partir de materiais naturais

The MCM-41 mesoporous synthesis was done using rice hulls ash and chrysotile as natural alternative silica sources. For the using of these sources, chemical and thermic treatments were done in both materials. After chemical and thermic treatments, these materials were employed on the MCM-41 mesoctructures synthesis. The natural materials treated and employed in the synthesis were characterized by several techniques such as X-ray diffraction, N2 adsorption and desorption, scanning electronic microscopy and thermogravimetric analysis. MCM-41 standart samples synthetized with aerosil 200 commercial sílica were used to evaluation. The formed material from rice hulls ash showed values from BET specific area about 468 m².g-1, N2 adsorption and desorption isotherms and loss mass similar to reference materials. The silica from chrysotile calcined and leached was employed to mesoporous materials synthesis. The BET specific area showed values about 700 m².g-1, N2 adsorption and desorption isotherms type IV and loss mass similar to mesoporous materials. The formed material from calcined and leached chrysotile, without calcination, applied to phenol remotion carried high performance liquid chromatography and evaluated with organophilic clays with different treatments. By the characterization techniques were proved that mesoporous materials with lesser order that reference samples. The material formed from rice hulls ash without the calcination step achieved better adsorption results than organophilic clays

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)

Síntese de zeólita A a partir de diatomita como fonte de aluminossilicato

The synthesis of zeolites from natural sources of silicon and aluminum are promising alternative routes to obtain porous or zeolite MCM family. Such materials are typically used in catalytic processes and / or adsorption is to obtain new products or for separation and purification processes thereof. Environmental legislation is becoming stricter and requires the use of materials more efficient, aiming to achieve pollution prevention, by gas or liquid contaminants in the environment. In order to obtain a material with environmentally friendly features, this study aimed at the synthesis of zeolite A, from an amorphous sediment, diatomite, which is found in abundance in the northeast region of Brazil, may be substituted for conventional products the production of zeolite, involving higher costs. The methodology for obtaining the "Zeolite A" using as a source of silica and alumina diatomite is simple, since this is a source of silicon, not requiring therefore a structural driver, but also by heat treatment, only drying conventional to remove water. The "zeolite A" was obtained from diatomite, but as an intermediate step we obtained the sodalite. The characterization was made by the following techniques: EDX, XRD, FT-IR, SEM and determining a specific area by the BET method and the BJH method for checking the diameter of pores. By characterization of the obtained material was first demonstrated the achievement of sodalite and after modification of the same, there was obtained zeolite A

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

Estudos comparativos do ciclo de regeneração de diferentes tipos de silicoaluminofosfatos

Different types of heterogeneous catalysts of the silicoaluminophosphate type, (SAPO-5, SAPO-11, SAPO-31, SAPO-34 and SAPO-41), molecular sieves with a: AFI, AEL, ATO, CHA and AFO structure, respectively, were synthesized through the hydrothermal method. Using sources such as hydrated alumina (pseudobohemita), phosphoric acid, silica gel, water, as well as, different types of organic structural templates, such as: cetyltrimethylammonium bromide (CTMABr), di-isopropylamine (DIPA), di-n- propylamine (DNPA) and tetraethylammonium hydroxide (TEOS), for the respective samples. During the preparation of the silicoaluminophosphates, the crystallization process of the samples occurred at a temperature of approximately 200 ° C, ranging through periods of 18-72 h, when it was possible to obtain pure phases for the SAPOs. The materials were furthermore washed with deionized water, dried and calcined to remove the molecules of the templates. Subsequently the samples were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), absorption spectroscopy in the infrared region (FT-IR), specific surface area and thermal analysis via TG/DTG. The acidic properties were determined using adsorption of n-butylamine followed by programmed termodessorption. These methods revealed that the SAPO samples showed a typically weak to moderate acidity. However, a small amount of strong acid sites was also detected. The deactivation of the catalysts was conducted by artificially coking the samples, followed by n-hexane cracking reactions in a fixed bed with a continuous flow micro-reactor coupled on line to a gas chromatograph. The main products obtained were: ethane, propane, isobutene, n-butane, n-pentane and isopentane. The Vyazovkin (model-free) kinetics method was used to determine the catalysts regeneration and removal of the coke

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

Pirólise térmica e catalítica de resíduos de vácuo gerados no refino de petróleo

In this study, was used a very promising technique called of pyrolysis, which can be used for obtaining products with higher added value. From oils and residues, since the contribution of heavier oils and residues has intensified to the world refining industry, due to the growing demand for fuel, for example, liquid hydrocarbons in the range of gasoline and diesel. The catalytic pyrolysis of vacuum residues was performed with the use of a mesoporous material belonging the M41S family, which was discovered in the early 90s by researchers Mobil Oil Corporation, allowing new perspectives in the field of catalysis. One of the most important members of this family is the MCM-41, which has a hexagonal arrangement of mesopores with pore diameters between 2 and 10 nm and a high specific surface area, making it very promising for use as a catalyst in petroleum refining for catalytic cracking, and their mesopores facilitate the access of large hydrocarbon molecules. The addition of aluminum in the structure of MCM-41 increases the acidity of the material, making it more positive for application in the petrochemical industry. The mesoporous material of the type Al-MCM41 (ratio Si / Al = 50) was synthesized by hydrothermal method starting from the silica gel, NaOH and distilled water added to the gel pseudobohemita synthesis. Driver was used as structural CTMABr. Removal of organic driver (CTMABr) was observed by TG / DTG and FTIR, but this material was characterized by XRD, which was observed the formation of the main peaks characteristic of mesoporous materials. The analysis of adsorption / desorption of nitrogen this material textural parameters were determined. The vacuum residues (VR's) that are products of the bottom of the vacuum distillation tower used in this study are different from oil fields (regions of Ceará and Rio de Janeiro). Previously characterized by various techniques such as FTIR, viscosity, density, SARA, elemental analysis and thermogravimetry, which was performed by thermal and catalytic degradation of vacuum residues. The effect of AlMCM-41 was satisfactory, since promoted a decrease in certain ranges of temperature required in the process of conversion of hydrocarbons, but also promoted a decrease in energy required in the process. Thus enabling lower costs related to energy expenditure from degradation during processing of the waste

Hidrocarbonetos alifáticos em sedimentos de fundo do estuário do Rio Potengi, grande Natal (RN): implicações ambientais

The Potengi river estuary is located in the region of Natal (RN, Brazil), comprising a population of approximately 1,000,000 inhabitants. Besides the dominant urban presence, the estuary has fragments of mangrove forest. The objective of this study is to determine the aliphatic hydrocarbons found in the bottom sediments of this estuary, identifying their levels, distribution and their possible origins through the diagnostic rates, indexes and results comparisons with the local anthropic and natural characteristics. The samples were obtained according to a plan that allowed sampling of the estuary up to 12 km upstream from it as mounth. 36 stations were selected, grouped into 12 cross sections through the course of the river and spaced on average by 1 km. Each section consisted of three stations: the right margin, the deepest point and the left margin. The hydrocarbon n-alkanes from C10 to C36, the isoprenoids pristane and phytane, the unresolved complex mixture (UCM) and the total resolved hydrocarbons were analyzed by gas chromatography. N-alkanes, pristane, phytane and UCM were detected only at some stations. In the other, the concentration was below the detection limit defined by the analytical method (0.1 mg / kg), preventing them from being analyzed to determine the origin of the material found. By using different parameters, the results show that the estuary receives both the input of petrogenic hydrocarbons, but also of biogenic hydrocarbons, featuring a mixture of sources and relatively impacted portions. Based on the characteristics and activities found in the region, it is possible to affirm that petrogenic sources related to oil products enter the estuary via urban runoff or boats traffic, boat washing and fueling. Turning to the biogenic source, the predominant origin was terrestrial, characterized by vascular plants, indicating contribution of mangrove vegetation. It was evident the presence of, at specific points in the estuary, hydrocarbon pollution, and, therefore is recommended the adoption of actions aimed at interrupting or, at least, mitigating the sources potentially capable of damp petrogenic hydrocarbons in the estuary studied.

Efeito da adição de microfibras de lã de vidro na tenacidade à ruptura de pastas de cimento para poços de petróleo

Although there are a wide variety of additives that act in fresh state, to adjust the properties of cement, there is also a search by additions that improve the tenacity of the cement in the hardened state. This, in turn, can often be increased by inserting fibers, which act on the deflection of microcracks. This study aimed to use a microfiber glass wool (silica-based) as an additive reinforcing the cement matrix, improving the rupture tenacity, in order to prevent the propagation of microcracks in the cement sheath commonly found in oil wells submitted to high temperatures. The fibers were added at different concentrations, 2 to 5% (BWOC) and varied average sizes, grinding for 90 s, 180 s, 300 s, 600 s. The cement slurries were made with a density of 1,90 g/ cm3 (15,6 lb/gal), using Portland cement CPP- Special Class as the hydraulic binder and 40% silica flour. The characterization of the fiber was made by scanning electron microscopy (SEM), particle size by sieving, X-ray fluorescence (XRF), X-ray diffraction (XRD) and thermogravimetry (TG / DTG). Were performed technological tests set by the API (American Petroleum Institute) by rheology, stability, free water, compressive strength, as well as testing rupture energy, elastic modulus and permeability. The characterization results showed good thermal stability of the microfiber glass wool for application in oil wells submitted to steam injection and, also, that from the particle size data, it was possible to suggest that microfibers milled up to 300 s, are ideal to act as reinforcement to the cement slurries. The rheological parameters, there was committal of plastic viscosity when larger lengths were inserted of microfiber (F90). The values obtained by free water and stability were presented according to API. The mechanical properties, the incorporation of microfiber to the cement slurries gave better rupture tenacity, as compared to reference cement slurries. The values of compressive strength, elastic modulus and permeability have been maintained with respect to the reference cement slurries. Thus, cement slurries reinforced with microfiber glass wool can ensure good application for cementing oil wells submitted to steam injection, which requires control of microcracks, due to the thermal gradients

Evolução diagenética e caracterização dos reservatórios da seção devoniana na Bacia do Rio do Peixe-Nordeste do Brasil

The Rio do Peixe Basin represents a main basin of northeastern Brazil and pioneering work positioned the rocks of this basin in the Early Cretaceous. However, a recent study, based on integrated pollen analysis from three wells, found an unprecedented siliciclastic sedimentary section, in the region, of early Devonian age. Therefore, the present study aims a detailed petrographic and petrological analysis of this devonian section, in the Rio do Peixe Basin and proposes a diagenetic evolution, to understand the characteristics of the porous system, identify the main reservoir petrofacies with the main factors impacting on the quality of these rocks as reservoirs and a quick study on the provenance of this section. The petrographic study was based on samples obtained from subsurface and surface. The diagenetic evolution of petrofacies and its identification were based only on subsurface samples and the study of provenance was based on surface samples. The thin sections were prepared from sandstones, pelites and sandstones intercalated with pelites. The original detrital composition for this section is arcosean and the main diagenetic processes that affected these rocks occur in various depths and different conditions, which resulted in extensive diagenetic variety. The following processes were identified: early fracture and healing of grains; albitization of K-feldspar and plagioclase; siderite; precipitation of silica and feldspar; mechanical infiltration of clay and its transformation to illite/esmectite and illite; autigenesis of analcime; dissolution; autigenesis of chlorite; dolomite/ferrous dolomite/anquerite; apatite; calcite; pyrite; titanium minerals and iron oxide-hidroxide. The occurrence of a recently discovered volcanism, in the Rio do Peixe Basin, may have influenced the diagenetic evolution of this section. Three diagenetic stages affected the Devonian section: eo, meso and telodiagenesis. This section is compositionally quite feldspathic, indicating provenance from continental blocks, between transitional continental and uplift of the basement. From this study, we observed a wide heterogeneity in the role of the studied sandstones as reservoirs. Seven petrofacies were identified, taking into account the main diagenetic constituent responsible for the reduction of porosity. It is possible that the loss of original porosity was influenced by intense diagenesis in these rocks, where the main constituent for the loss of porosity are clays minerals, oxides and carbonate cement (calcite and dolomite)

Efeito da adição de cargas minerais leves na resistência mecânica de grautes para cimentação de poços offshore

The preparation of cement slurries for offshore well cementing involves mixing all solid components to be added to the mixing water on the platform. The aim of this work was to study the formulation of pre-prepared dry mixtures, or grouts, for offshore oilwell cementing. The addition of mineral fillers in the strength of lightweight grouts applied for depths down to 400 m under water depths of 500 m was investigated. Lightweight materials and fine aggregates were selected. For the choice of starting materials, a study of the pozzolanic activity of low-cost fillers such as porcelain tile residue, microsilica and diatomaceous earth was carried out by X-ray diffraction and mechanical strength tests. Hardened grouts containing porcelain tile residue and microsilica depicted high strength at early ages. Based on such preliminary investigation, a study of the mechanical strength of grouts with density 1.74 g/cm3 (14.5 lb/gal) cured initially at 27 °C was performed using cement, microsilica, porcelain tile residue and an anti-foaming agent. The results showed that the mixture containing 7% of porcelain tile residue and 7% of microsilica was the one with the highest compressive strength after curing for 24 hours. This composition was chosen to be studied and adapted for offshore conditions based on testes performed at 4 °C. The grout containing cement, 7% of porcelain tile residue, 7% of active silica and admixtures (CaCl2), anti-foaming and dispersant resulted satisfactory rheology and mechanical strength after curing for 24 hours of curing

Pirólise rápida catalítica do capim elefante utilizando materiais mesoporosos e óxidos metálicos para deoxigenação em bio-óleo

The fast pyrolysis of lignocellulosic biomass is a thermochemical conversion process for production energy which have been very atratactive due to energetic use of its products: gas (CO, CO2, H2, CH4, etc.), liquid (bio-oil) and charcoal. The bio-oil is the main product of fast pyrolysis, and its final composition and characteristics is intrinsically related to quality of biomass (ash disposal, moisture, content of cellulose, hemicellulose and lignin) and efficiency removal of oxygen compounds that cause undesirable features such as increased viscosity, instability, corrosiveness and low calorific value. The oxygenates are originated in the conventional process of biomass pyrolysis, where the use of solid catalysts allows minimization of these products by improving the bio-oil quality. The present study aims to evaluate the products of catalytic pyrolysis of elephant grass (Pennisetum purpureum Schum) using solid catalysts as tungsten oxides, supported or not in mesoporous materials like MCM-41, derived silica from rice husk ash, aimed to reduce oxygenates produced in pyrolysis. The biomasss treatment by washing with heated water (CEL) or washing with acid solution (CELix) and application of tungsten catalysts on vapors from the pyrolysis process was designed to improve the pyrolysis products quality. Conventional and catalytic pyrolysis of biomass was performed in a micro-pyrolyzer, Py-5200, coupled to GC/MS. The synthesized catalysts were characterized by X ray diffraction, infrared spectroscopy, X ray fluorescence, temperature programmed reduction and thermogravimetric analysis. Kinetic studies applying the Flynn and Wall model were performed in order to evaluate the apparent activation energy of holoceluloce thermal decomposition on samples elephant grass (CE, CEL and CELix). The results show the effectiveness of the treatment process, reducing the ash content, and were also observed decrease in the apparent activation energy of these samples. The catalytic pyrolysis process converted most of the oxygenate componds in aromatics such as benzene, toluene, ethylbenzene, etc