Estudo do aproveitamento do rejeito da mineração de esmeraldas na produção de refratários conformados isolantes

Emerald mining is an important area of the economy in Brazil, country which is in second place among the exporting nations of this gem. Due to the process of extraction, a great amount of reject is generated. Since there is no appropriate destination, the reject is abandoned around the mining industries, contributing to environment degradation. Nowadays, some of the most relevant things to an industry in general are: energy conservation, cost reduction, quality and productivity enhancement. The production of isolating, transformed refractory materials achieves the sustainability dimension when protection of the environment is incorporated to such process. This work investigates the use of emerald mining rejects in the ceramic body of refractory materials, aiming at obtaining a product whose characteristics are compatible with commercial products and, at the same time, allow the use of such rejects to solve the environmental issue caused by its disposal in nature. X-ray fluorescence analysis show that the emerald reject obtained after the flotation to extract molybdenum and mica has 70% of silica and alumina (SiO2+Al2O3) and 21% of a basic oxides and alkaline metals and earthy alkaline mixture (Na2O, K2O, CaO e MgO). Because of the significant amount of silica and alumina present in the reject, four refractory ceramic bodies were prepared. Samples with a rectangular shape and dimensions 100x50x10 mm were pressed in a steel mold at 27,5 MPa and sintered at 1200ºC for 40 min. under environment atmosphere in a resistive oven. The sintered samples were characterized in relation to the chemical composition (FRX), mineralogical composition (DRX), microstructure (MEV) and physical and mechanical properties. The results indicate that the mixture with 45% of reject, 45% of alumina and 10% of kaolin presents a refractory quality of 1420ºC, dimensional linear variation below 2.00%, apparent specific mass of 1,56 g/cm3 and porosity of 46,68%, which demonstrates the potential use of the reject as raw material for the industry of isolating transformed refractory materials

Aplicação de microemulsões na solubilização de frações pesadas de petróleo

This work presents studies related to the use of microemulsions in the solubilization of heavy crude oil fractions responsible by the formation of deposits. The first stage of the work was addressed to the construction of phases diagrams, with the intention of determining the area within which the microemulsion is formed. The following systems were studied: UNITOL L 90 n-Butanol - Water - Kerosene (system 1); UNITOL L 90 - n-Butanol - Water - Xylene (system 2); UNITOL L 90 n-Butanol - Water - Kerosene/Xylene 10% (system 3); UNITOL L 90 - Sec-Butanol - Water - Xylene (system 4). In parallel experiments of physical adsorption were carried out by the static method, with the intention of simulating natural conditions of reservoirs. Crude oil of the Fazenda Belém field (Rio Grande do Norte), was used as solute, xylene as solvent and the Assu sandstone (Rio Grande do Norte, Brazil) and Botucatu sandstone (Paraná, Brazil) as rock reservoirs. The curves of adsorption presented the S format type, in agreement with the classification proposed by Giles, Smith and Huitson (1974). The solubilization process was accomplished in the batch method, by varying the time of agitation, the microemulsions and the solid/solution ratio. The experiments showed that the microemulsions presented high efficiency in the solubilization of the crude oil adsorbed on the sandstones. System 2 presented an efficiency of 99% for the Assu sandstone and 97% for the Botucatu sandstone

Avaliação da molhabilidade de soluções de tensoativos em aço inoxidável

With the increasing industrialization of the planet caused by globalization, it has become increasingly common to search for highly resistant and durable materials for many diverse branches of activities. Thus, production and demand for materials that meet these requirements have constantly increased with time. In view of this, stainless steel is presented as one of the materials which are suitable applications, due to many features that are interesting for several segments of the industry. Concerns of oil companies over heavy oil reservoirs have grown steadily for the last decades. Rheological properties of these oils impair their transport in conventional flow systems. This problem has created the need to develop technologies to improve flow and transport, reducing operation costs so as to enable oil production in the reservoir. Therefore, surfactant-based chemical systems are proposed to optimize transport conditions, effected by reduction of interfacial tensions, thereby enhancing the flow of oil in ducts and reducing load losses by friction. In order to examine such interactions, a study on the wettability of metallic surfaces has been undertaken, represented by measuring of contact angle of surfactant solutions onto flat plates of 304 stainless steel. Aqueous solutions of KCl, surfactants and mixtures of surfactants, with linear and aromatic hydrocarbon chain and ethoxylation degrees ranging between 20 to 100, have been tested. The wettability was assessed by means of a DSA 100 krüss goniometer. The influence of roughness on the wettability was also investigated by machining and polished the stainless steel plates with sandpapers of references ranging between 100 of 1200. The results showed that sanding and polishing plates result in decrease of wettability. As for the solutions, they have provided better wettability of the stainless steel than the KCl solutions tested. It was also been concluded that surfactant mixtures is an option to be considered, since they promote interactions that generate satisfactory contact angles for a good wettability on the stainless steel plate. Another conclusion refers to the influence of the ethoxylation degree of the nonionic surfactant molecules on wettability. It has been observed that contact angles decrease with decreasing ethoxylation degrees. This leads us to conclude that molecules with higher ethoxylation degree, being more hydrophobic, decrease the interaction of water with the ducts, thereby reducing friction and improving the flow

Reciclagem de material asfáltico fresado utilizando solventes e microemulsões

With the increase of asphalt milling services was also a significant increase in recycling services pavements. The techniques used today are basically physical processes in which the milled material is incorporated into new asphalt mixtures or executed on site, with the addition of virgin asphalt and rejuvenating agent. In this paper seeks to analyze the efficiency of extraction of CAP (Petroleum Asphalt Cement) mixtures from asphalt milling, using commercial solvents and microemulsions. The solvents were evaluated for their ability to solubilize asphalt using an extractor reflux-type apparatus. Pseudoternary diagrams were developed for the preparation of microemulsion O/W surfactant using a low-cost coconut oil saponified (OCS). Microemulsions were used to extract the CAP of asphalt through physicochemical process cold. Analysis was performed concentration of CAP in solution by spectroscopy. The data provided in the analysis of concentration by the absorbance of the solution as the basis for calculating the percentage of extraction and the mass flow of the CAP in the solution. The results showed that microemulsions prepared with low concentration of kerosene and butanol/OCS binary has high extraction power of CAP and its efficiency was higher than pure kerosene, reaching 95% rate of extraction

Determinação experimental e modelagem termodinâmica do ponto de turbidez de sistemas aquosos com tensoativos nonilfenolpolietoxilados

The nonionic surfactants are composed of substances whose molecules in solution, does not ionize. The solubility of these surfactants in water due to the presence of functional groups that have strong affinity for water. When these surfactants are heated is the formation of two liquid phases, evidenced by the phenomenon of turbidity. This study was aimed to determine the experimental temperature and turbidity nonilfenolpoliethoxyled subsequently perform a thermodynamic modeling, considering the models of Flory-Huggins and the empirical solid-liquid equilibrium (SLE). The method used for determining the turbidity point was the visual method (Inoue et al., 2008). The experimental methodology consisted of preparing synthetic solutions of 0,25%, 0,5%, 1%, 2%, 3%, 4%, 5%, 6%, 7%, 8%, 9%, 10%, 12,5%, 15%, 17% and 20% by weight of surfactant. The nonionic surfactants used according to their degree of ethoxylation (9.5, 10, 11, 12 and 13). During the experiments the solutions were homogenized and the bath temperature was gradually increased while the turbidity of the solution temperature was checked visually Inoue et al. (2003). These temperature data of turbidity were used to feed the models evaluated and obtain thermodynamic parameters for systems of surfactants nonilfenolpoliethoxyled. Then the models can be used in phase separation processes, facilitating the extraction of organic solvents, therefore serve as quantitative and qualitative parameters. It was observed that the solidliquid equilibrium model (ESL) was best represented the experimental data.

Aplicação de ultrassons no deslocamento de petróleo em meio poroso

The objective of this study was to evaluate the displacement of petroleum/diesel solutions, at different concentrations, observing the effect of ultrasonic vibrations in fluids present in porous media to obtain an increase in oil production. The bubbles produced by ultrasound implode asymmetrically in the rock, generating liquid jets with high speed, displacing the oil present in porous media. The oil/diesel solutions were prepared with concentrations ranging from 20 g/L to 720 g/L in oil in relation to diesel and its viscosities were obtained in a Brookfield Rheometer RS2000, with temperature ranging from 25 to 55 °C. After, calculations were performed to obtain the activation energy data for oil/diesel solutions. For oil recovery experiments, cylindrical samples of porous rock (core samples), with resin around the perimeter and its two circular bases free to allow the passage of fluids, were first saturated with 2% KCl solution and after with oil solutions. The results of oil extraction were satisfactory for all studied solutions, being obtained up to 68% partial displacement with saline solution injection. The ultrasound system was used after saline injection, increasing oil displacement, with oil extractions ranging from 63% to 79%. During the experiments, it was observed the warming of core samples, helping to reduce the viscosity of more concentrated systems, and consequently enhancing the percentage of advanced recovery for all studied solutions

Remediação de solos contaminados com óleo diesel utilizando um sistema de lavagem com microemulsão

The underground reservoirs of fuel retailing system represent an environmental threat, because once in bad conservation, these tanks allow fuel leakage and infiltration. For soil contaminated with fuel, such as diesel oil, the present study introduces the microemulsion systems used by the method of washing. In tests carried out in column with a sample of sandy soil artificially contaminated and previously characterized as to its void level to porosity, to permeability which is an important parameter concerning the study of the method of washing. While microemulsions were characterized for their viscosity and wettability, a variation of active matter was also done departing from the original formulation. The hydraulic diffusivity of the microemulsion was studied so as the injection of such fluid in a soil with sandy characteristics. The results of the extractions revealed the excellent performance of these systems which get to remove around 95% of diesel fuel. This proves the efficiency of the microemulsion in the process of removal of diesel fuel from the soil with the advantage of being a system easily obtainable and less aggressive to the environment when compared to organic solvents.

Desenvolvimento de sistemas de pastas leves para aplicação em cimentação de poços petrolíferos com baixo gradiente de fratura

All around the world, naturally occurring hydrocarbon deposits, consisting of oil and gas contained within rocks called reservoir rocks , generally sandstone or carbonate exists. These deposits are in varying conditions of pressure and depth from a few hundred to several thousand meters. In general, shallow reservoirs have greater tendency to fracture, since they have low fracture gradient, ie fractures are formed even with relatively low hydrostatic columns of fluid. These low fracture gradient areas are particularly common in onshore areas, like the Rio Grande do Norte basin. During a well drilling, one of the most favorable phases for the occurrence of fractures is during cementing, since the cement slurry used can have greater densities than the maximum allowed by the rock structure. Furthermore, in areas which are already naturally fractured, the use of regular cement slurries causes fluid loss into the formation, which may give rise to failures cementations and formation damages. Commercially, there are alternatives to the development of lightweight cement slurries, but these fail either because of their enormous cost, or because the cement properties were not good enough for most general applications, being restricted to each transaction for which the cement paste was made, or both reasons. In this work a statistical design was made to determine the influence of three variables, defined as the calcium chloride concentration, vermiculite concentration and nanosilica concentration in the various properties of the cement. The use of vermiculite, a low density ore present in large amounts in northeastern Brazil, as extensor for cementing slurries, enabled the production of stable cements, with high water/cement ratio, excellent rheological properties and low densities, which were set at 12.5 lb / gal, despite the fact that lower densities could be achieved. It is also seen that the calcium chloride is very useful as gelling and thickening agent, and their use in combination with nanosilica has a great effect on gel strength of the cement. Hydrothermal Stability studies showed that the pastes were stable in these conditions, and mechanical resistance tests showed values of the order of up to 10 MPa

Estudo dos parâmetros de extração de fenol de efluentes aquosos por um tensoativo não iônico

Environmental sustainability has become one of the topics of greatest interest in industry, mainly due to effluent generation. Phenols are found in many industries effluents, these industries might be refineries, coal processing, pharmaceutical, plastics, paints and paper and pulp industries. Because phenolic compounds are toxic to humans and aquatic organisms, Federal Resolution CONAMA No. 430 of 13.05.2011 limits the maximum content of phenols, in 0.5 mg.L-1, for release in freshwater bodies. In the effluents treatment, the liquid-liquid extraction process is the most economical for the phenol recovery, because consumes little energy, but in most cases implements an organic solvent, and the use of it can cause some environmental problems due to the high toxicity of this compound. Because of this, exists a need for new methodologies, which aims to replace these solvents for biodegradable ones. Some literature studies demonstrate the feasibility of phenolic compounds removing from aqueous effluents, by biodegradable solvents. In this extraction kind called "Cloud Point Extraction" is used a nonionic surfactant as extracting agent of phenolic compounds. In order to optimize the phenol extraction process, this paper studies the mathematical modeling and optimization of extraction parameters and investigates the effect of the independent variables in the process. A 32 full factorial design has been done with operating temperature and surfactant concentration as independent variables and, parameters extraction: Volumetric fraction of coacervate phase, surfactant and residual concentration of phenol in dilute phase after separation phase and phenol extraction efficiency, as dependent variables. To achieve the objectives presented before, the work was carried out in five steps: (i) selection of some literature data, (ii) use of Box-Behnken model to find out mathematical models that describes the process of phenol extraction, (iii) Data analysis were performed using STATISTICA 7.0 and the analysis of variance was used to assess the model significance and prediction (iv) models optimization using the response surface method (v) Mathematical models validation using additional measures, from samples different from the ones used to construct the model. The results showed that the mathematical models found are able to calculate the effect of the surfactant concentration and the operating temperature in each extraction parameter studied, respecting the boundaries used. The models optimization allowed the achievement of consistent and applicable results in a simple and quick way leading to high efficiency in process operation.

Extração enzimática de óleo e produção in situ de biodiesel a partir da Moringa oleífera Lam

With the growth and development of modern society, arises the need to search for new raw materials and new technologies which present the "clean" characteristic, and do not harm the environment, but can join the energy needs of industry and transportation. The Moringa oleifera Lam, plant originating from India, and currently present in the Brazilian Northeast, presents itself as a multi-purpose plant, can be used as a coagulant in water treatment, as a natural remedy and as a feedstock for biodiesel production. In this work, Moringa has been used as a raw material for studies on the extraction and subsequently in the synthesis of biodiesel. Studies have been conducted on various techniques of Moringa oil extraction (solvents, mechanical pressing and enzymatic), being specially developed an experimental design for the aqueous extraction with the aid of the enzyme Neutrase© 0.8 L, with the aim of analyzing the influence variable pH (5.5-7.5), temperature (45-55°C), time (16-24 hours) and amount of catalyst (2-5%) on the extraction yield. In relation to study of the synthesis of biodiesel was initially carried out a conventional transesterification (50°C, KOH as a catalyst, methanol and 60 minutes reaction). Next, a study was conducted using the technique of in situ transesterification by using an experimental design variables as temperature (30-60°C), catalyst amount (2-5%), and molar ratio oil / ethanol (1:420-1:600). The extraction technique that achieved the highest extraction yield (35%) was the one that used hexane as a solvent. The extraction using 32% ethanol obtained by mechanical pressing and extraction reached 25% yield. For the enzymatic extraction, the experimental design indicated that the extraction yield was most affected by the effect of the combination of temperature and time. The maximum yield obtained in this extraction was 16%. After the step of obtaining the oil was accomplished the synthesis of biodiesel by the conventional method and the in situ technique. The method of conventional transesterification was obtained a content of 100% and esters by in situ technique was also obtained in 100% in the experimental point 7, with a molar ratio oil / alcohol 1:420, Temperature 60°C in 5% weight KOH with the reaction time of 1.5 h. By the experimental design, it was found that the variable that most influenced the ester content was late the percentage of catalyst. By physico-chemical analysis it was observed that the biodiesel produced by the in situ method fell within the rules of the ANP, therefore this technique feasible, because does not require the preliminary stage of oil extraction and achieves high levels of esters

Desenvolvimento de um secador spray para obtenção de pós finos de precursores de nióbio

This work presents a spray-dryer designed to oxalate-niobate precursors and suitable for the production of Niobium Carbide. The dryer was intended to produce powders of controlled particle size. First, the precursor is dissolved in water to produce a solution of known concentration and then it is atomized on the spray-dryer to produce the powder. This equipment consists of a 304 stainless steel chamber, 0.48 m x 1.9 m (diameter x length), with a conical shape at the lower portion, which is assembled on a vertical platform. The chamber is heated by three 4 kW electrical resistances. In this process, drying air is heated as it flows inside a serpentine surrounding the chamber, in contrary to more traditional processes in which the hot drying air is used to heat the component. The air enters the chamber at the same temperature of the chamber, thus avoiding adherence of particles on the internal surface. The low speed flow is concurrent, directed from the top to the bottom portion of the chamber. Powders are deposited on a 0.4 m diameter tray, which separates the cylindrical portion from the conical portion of the chamber. The humid air is discharged though a plug placed underneath the collecting tray. A factorial experimental planning was prepared to study the influence of five parameters (concentration, input flow, operation temperature, drying air flow and spray air flow) on the characteristics of the powders produced. Particle size distribution and shape were measured by laser granulometry and scanning electronic microscopy. Then, the powders are submitted to reaction in a CH4 / H2 atmosphere to compare the characteristics of spray-dried powders with powders synthetizided by conventional methods

Avaliação do comportamento de fluidos micelares na recuperação avançada de petróleo

In heavy oil fields there is a great difficulty of the oil to flow from the reservoir to the well, making its production more difficult and with high cost. Most of the original volumes of oil found in the world are considered unrecoverable by the use of the current methods. The injection of micellar solutions has a direct action in the oil interfacial properties, resulting in an enhanced oil recovery. The objective of this research was the study and selection of micellar solutions with ability to decrease the interfacial interactions between fluids and reservoir formation, increasing oil production. The selected micellar solutions were obtained using commercial surfactants and surfactants synthesized in laboratory, based on the intrinsic properties of these molecules, to use in the enhanced oil recovery. Petroleum Reservoirs were simulated using sandstone plugs from Botucatu formation. Experiments with conventional and enhanced oil recovery techniques were accomplished. The obtained results showed that all micellar solutions were able to enhance oil recovery, and the micellar solution prepared with a SB anionic surfactant, at 2% KCl solution, showed the best recovery factor. It was also accomplished an economic analysis with the SB surfactant solution. With the injection of 20% porous volume of micellar solution, followed by brine injection, the increment in petroleum recovery can reach 81% recovery factor in the 3rd porous volume injected. The increment in the total cost by the addition of surfactant to the injection water represents R$ 7.50/ton of injected fluid

Estudo da cristalização de parafinas em sistemas solventes/tensoativos/água

The WAT is the temperature at the beginning of the appearance of wax crystals. At this temperature the first wax crystals are formed by the cooling systems paraffin / solvents. Paraffins are composed of a mixture of saturated hydrocarbons of high molecular weight. The removal of petroleum from wells and the production lines means a surcharge on produced oil, thus solubilize these deposits formed due to modifications of thermodynamics has been a constant challenge for companies of oil exploration. This study combines the paraffin solubilization by microemulsion systems, the determination of WAT systems paraffin / solvent and performance of surfactant in reducing the crystallization. We used the methods: rheological and the photoelectric signal, validating the latter which was developed to optimize the data obtained due to sensitivity of the equipment used. Methods developed for description of wax precipitation are often in poor agreement with the experimental data, they tend to underestimate the amount of wax at temperatures below the turbidity point. The Won method and the Ideal solution method were applied to the WAT data obtained in solvent systems, best represented by the second interaction of Won method using the solvents naphtha, hexane and LCO. It was observed that the results obtained by WAT photoelectric signal when compared with the viscosity occur in advance, demonstrating the greatest sensitivity of the method developed. The ionic surfactant reduced the viscosity of the solvent systems as it acted modifying the crystalline structure and, consequently, the pour point. The curves show that the WAT experimental data is, in general, closer to the modeling performed by the method of Won than to the one performed by the ideal solution method, because this method underestimates the curve predicting the onset of paraffin hydrocarbons crystallization temperature. This occurs because the actual temperature measured was the crystallization temperature and the method proposes the fusion temperature measurement.

Novas alternativas de remoção de enxofre do óleo diesel utilizando tensoativos e microemulsões

The diesel combustion form sulfur oxides that can be discharged into the atmosphere as particulates and primary pollutants, SO2and SO3, causing great damage to the environment and to human health. These products can be transformed into acids in the combustion chamber, causing damage to the engines. The worldwide concern with a clean and healthy environment has led to more restrictive laws and regulations regulating the emission levels of pollutants in the air, establishing sulfur levels increasingly low on fuels. The conventional methods for sulfur removal from diesel are expensive and do not produce a zero-level sulfur fuel. This work aims to develop new methods of removing sulfur from commercial diesel using surfactants and microemulsion systems. Its main purpose is to create new technologies and add economic viability to the process. First, a preliminary study using as extracting agent a Winsor I microemulsion system with dodecyl ammonium chloride (DDACl) and nonyl phenol ethoxylated (RNX95) as surfactant was performed to choose the surfactant. The RNX95 was chosen to be used as surfactant in microemulsioned systems for adsorbent surface modification and as an extracting agent in liquid-liquid extraction. Vermiculite was evaluated as adsorbent. The microemulsion systems applied for vermiculite surface modification were composed by RNX95 (surfactant), n-butanol (cosurfactant), n-hexane (oil phase), and different aqueous phases, including: distilled water (aqueous phase),20ppm CaCl2solution, and 1500ppm CaCl2solution. Batch and column adsorption tests were carried out to estimate the ability of vermiculite to adsorb sulfur from diesel. It was used in the experiments a commercial diesel fuel with 1,233ppm initial sulfur concentration. The batch experiments were performed according to a factorial design (23). Two experimental sets were accomplished: the first one applying 1:2 vermiculite to diesel ratio and the second one using 1:5 vermiculite to diesel ratio. It was evaluated the effects of temperature (25°C and 60°C), concentration of CaCl2in the aqueous phase (20ppm and 1500ppm), and vermiculite granule size (65 and 100 mesh). The experimental response was the ability of vermiculite to adsorb sulfur. The best results for both 1:5 and 1:2 ratios were obtained using 60°C, 1500ppm CaCl2solution, and 65 mesh. The best adsorption capacities for 1:5 ratio and for 1:2 ratio were 4.24 mg sulfur/g adsorbent and 2.87 mg sulfur/g adsorbent, respectively. It was verified that the most significant factor was the concentration of the CaCl2 solution. Liquid-liquid extraction experiments were performed in two and six steps using the same surfactant to diesel ratio. It was obtained 46.8% sulfur removal in two-step experiment and 73.15% in six-step one. An alternative study, for comparison purposes, was made using bentonite and diatomite asadsorbents. The batch experiments were done using microemulsion systems with the same aqueous phases evaluated in vermiculite study and also 20ppm and 1500 ppm BaCl2 solutions. For bentonite, the best adsorption capacity was 7.53mg sulfur/g adsorbent with distilled water as aqueous phase of the microemulsion system and for diatomite the best result was 17.04 mg sulfur/g adsorbent using a 20ppm CaCl2solution. The accomplishment of this study allowed us to conclude that, among the alternatives tested, the adsorption process using adsorbents modified by microemulsion systems was considered the best process for sulfur removal from diesel fuel. The optimization and scale upof the process constitutes a viable alternative to achieve the needs of the market

Síntese e caracterização de tensoativos e estudo de equilíbrio de fase dos sistemas CnH2n+2/H2O/CnH2n+1COONa/But-OH

The growing utilization of surfactants in several different areas of industry has led to an increase on the studies involving solutions containing this type of molecules. Due to its amphiphilic nature, its molecule presents one polar part and one nonpolar end, which easily interacts with other molecules, being able to modify the media properties. When the concentration in which its monomers are saturated, the airliquid system interface is reached, causing a decrease in interfacial tension. The surfactants from pure fatty acids containing C8, C12 and C16 carbonic chains were synthesized in an alcoholic media using sodium hydroxide. They were characterized via thermal analysis (DTA and DTG) and via infrared spectroscopy, with the intention of observing their purity. Physical and chemical properties such as superficial tension, critical micelle concentration (c.m.c), surfactant excess on surface and Gibbs free energy of micellization were determined in order to understand the behaviour of these molecules with an aqueous media. Pseudo-ternary phase diagrams were obtained aiming to limit the Windsor equilibria conditions so it could be possible to understand how the surfactants carbonic chain size contributes to the microemulsion region. Solutions with known concentrations were prepared to study how the surfactants can influence the dynamic light scattering spectroscopy (DLS) and how the diffusion coefficient is influenced when the media concentration is altered. The results showed the variation on the chain size of the studied surfactant lipophilic part allows the conception of surfactants with similar interfacial properties, but dependent on the size of the lipophilic part of the surfactant. This variation causes the surfactant to have less tendency of microemulsionate oil in water. Another observed result is that the n-alcanes molecule size promoted a decrease on the microemulsion region on the obtained phase diagrams