Avaliação mecânica e microestrutural de compósitos de poliéster com adição de cargas minerais e resíduos industriais

With the current growth in consumption of industrialized products and the resulting increase in garbage production, their adequate disposal has become one of the greatest challenges of modern society. The use of industrial solid residues as fillers in composite materials is an idea that emerges aiming at investigating alternatives for reusing these residues, and, at the same time, developing materials with superior properties. In this work, the influence of the addition of sand, diatomite, and industrial residues of polyester and EVA (ethylene vinyl acetate), on the mechanical properties of polymer matrix composites, was studied. The main objective was to evaluate the mechanical properties of the materials with the addition of recycled residue fillers, and compare to those of the pure polyester resin. Composite specimens were fabricated and tested for the evaluation of the flexural properties and Charpy impact resistance. After the mechanical tests, the fracture surface of the specimens was analyzed by scanning electron microscopy (SEM). The results indicate that some of the composites with fillers presented greater Young s modulus than the pure resin; in particular composites made with sand and diatomite, where the increase in modulus was about 168 %. The composites with polyester and EVA presented Young s modulus lower than the resin. Both strength and maximum strain were reduced when fillers were added. The impact resistance was reduced in all composites with fillers when compared to the pure resin, with the exception of the composites with EVA, where an increase of about 6 % was observed. Based on the mechanical tests, microscopy analyses and the compatibility of fillers with the polyester resin, the use of industrial solid residues in composites may be viable, considering that for each type of filler there will be a specific application

Microemulsões aplicadas ao tratamento de Óleos isolantes

Naphthenic lubricating oils are used in transformers with the purpose of promoting electrical insulation and dissipating heat. The working temperature range of these oils typically lies between 60°C and 90°C and their useful life is 40 years in average. In that temperature range, the oils are decomposed during operation, whereby a small fraction of polar compounds are formed. The presence of these compounds may induce failure and loss of physical, chemical and electrical properties of the oil, thus impairing the transformer operation. By removing these contaminants, one allows the oxidized insulating oil to be reused without damaging the equipment. In view of this, an investigation on the use of surfactants and microemulsions as extracting agents, and modified diatomite as adsorbent, has been proprosed in this work aiming to remove polar substances detected in oxidized transformer oils. The extraction was carried out by a simple-contact technique at room temperature. The system under examination was stirred for about 10 minutes, after which it was allowed to settle at 25°C until complete phase separation. In another experimental approach, adsorption equilibrium data were obtained by using a batch system operating at temperatures of 60, 80 and 100°C. Analytical techniques involving determination of the Total Acidity Number (TAN) and infrared spectrophotometry have been employed when monitoring the decomposition and recovery processes of the oils. The acquired results indicated that the microemulsion extraction system comprising Triton® X114 as surfactant proved to be more effective in removing polar compounds, with a decrease in TAN index from 0.19 to 0.01 mg KOH/g, which is consistent with the limits established for new transformer oils (maximal TAN = 0.03 mg KOH/g). In the adsorption studies, the best adsorption capacity values were as high as 0.1606 meq.g/g during conventional adsoprtion procedures using natural bauxite, and as high as 0.016 meq.g/g for the system diatomite/Tensiofix® 8426. Comparatively in this case, a negative effect could be observed on the adsorption phenomenon due to microemulsion impregnation on the surface of the diatomite

Utilização de microemulsões como agentes modificadores de superfícies para remoção de íons metálicos

The heavy metals are used in many industrial processes and when discharged to the environment can cause harmful effects to human, plants and animals. The adsorption technology has been used as an effective methodology to remove metallic ions. The search for new adsorbents motivated the development of this research, accomplished with the purpose of removing Cr (III) from aqueous solutions. Diatomite, chitosan, Filtrol 24TM and active carbon were used as adsorbents. To modify the adsorbent surface was used a bicontinuous microemulsion composed by water (25%), kerosene (25%), saponified coconut oil (10%) and as co-surfactant isoamyl or butyl alcohols (40%). With the objective of developing the best operational conditions the research started with the surfactant synthesis and after that the pseudo-ternary diagrams were plotted. It was decided to use the system composed with isoamyl alcohol as co-surfactant due its smallest solubility in water. The methodology to impregnate the microemulsion on the adsorbents was developed and to prepare each sample was used 10 g of adsorbent and 20 mL of microemulsion. The effect of drying time and temperature was evaluated and the best results were obtained with T = 65 ºC and t = 48 h. After evaluating the efficiency of the tested adsorbents it was decided to use chitosan and diatomite. The influence of the agitation speed, granule size, heavy metal synthetic solution concentration, pH, contact time between adsorbent and metal solution, presence or not of NaCl and others metallic ions in the solution (copper and nickel) were evaluated. The adsorption isotherms were obtained and Freundlich and Langmuir models were tested. The last one correlated better the data. With the purpose to evaluate if using a surfactant solution would supply similar results, the adsorbent surface was modified with this solution. It was verified that the adsorbent impregnated with a microemulsion was more effective than the one with a surfactant solution, showing that the organic phase (kerosene) was important in the heavy metal removal process. It was studied the desorption process and verified that the concentrated minerals acids removed the chromium from the adsorbent surface better than others tested solutions. The treatment showed to be effective, being obtained an increase of approximately 10% in the chitosan s adsorption capacity (132 mg of Cr3+ / g adsorbent), that was already quite efficient, and for diatomite, that was not capable to remove the metal without the microemulsion treatment, it was obtained a capacity of 10 mg of Cr3+ / g adsorbent, checking the applied treatment effectiveness

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

Novos adsorventes para aplicação na remoção de enxofre de combustíveis

Currently the market requires increasingly pure oil derivatives and, with that, comes the need for new methods for obtaining those products that are more efficient and economically viable. Considering the removal of sulfur from diesel, most refineries uses catalytic hydrogenation process, the hydrodesulfurization. These processes needs high energy content and high cost of production and has low efficiency in removing sulfur at low concentrations (below 500 ppm). The adsorption presents itself as an efficient and economically viable alternative in relation to the techniques currently used. With that, the main purpose of this work is to develop and optimize the obtaining of new adsorbents based on diatomite, modified with two non ionic surfactants microemulsions, adding efficiency to the material, to its application on removal of sulfur present in commercial diesel. Analyses were undertaken of scanning electron microscopy (SEM), x-ray diffraction (XRD), x-ray fluorescence (XRF), thermogravimetry (TG) and N2 adsorption (BET) for characterization of new materials obtained. The variables used for diatomite modification were: microemulsion points for each surfactant (RNX 95 and UNTL 90), microemulsion aqueous phase through the use or non-use of salts (CaCl2 and BaCl2), the contact time during the modification and the contact form. The study of adsorption capacity of materials obtained was performed using a statistical modeling to evaluate the influence of salt concentration in the aqueous phase (20 ppm to 1500 ppm), finite bath temperature (25 to 60° C) and the concentration of sulphur in diesel. It was observed that the temperature and the concentration of sulphur (300 to 1100 ppm) were the most significant parameters, in which increasing their values increase the ability of modified clay to adsorb the sulphur in diesel fuel. Adsorption capacity increased from 0.43 to mg/g 1.34 mg/g with microemulsion point optimization and with the addition of salts.

Síntese e caracterização de peneiras moleculares mesoporosas do tipo MCM-41 e AlMCM-41 a partir de fontes alternativas de sílica e de alumínio

The mesoporous molecular sieves of MCM-41 and AlMCM-41 type are considered as promising support for metal in the refining processes of petroleum-based materials as catalysts and adsorbents for environmental protection. In this work the molecular sieves MCM-41 and AlMCM-41 were synthesized by replacing the source of silica conventionally used, for quartz, an alternative and abundant, and the use of waste from the production of diatomaceous earth, an aluminum-silicate, as a source aluminum, due to abundant reserves of diatomaceous earth in the state of Rio Grande do Norte in the city of Ceará-Mirim, with the objective of producing high-value materials that have similar characteristics to traditional commercial catalysts in the market. These materials were synthesized by the method of hydrothermal synthesis at 100 º C for 7 days and subjected to calcination at 500 º C for 2 hours under flow of nitrogen and air. The molecular sieves were characterized by X-ray diffraction (XRD), differential thermal analysis (DTA) and thermogravimetric analysis (TG), adsorption of N2 (BET and BJH methods), spectroscopy in the infra red (FTIR), microscopy scanning electron (SEM) and transmission electron microscopy (TEM). The analysis indicated that the synthesized materials showed characteristic hexagonal structure of mesopores materials with high specific surface area and sort and narrow distribution of size of pores

Estudo de adsorvente obtido de terras diatomáceas para remoção de metais pesados em águas produzidas: processamento, caracterização e dinâmica em leito fixo

The acceleration of industrial growth in recent decades on all continents aroused the interest of the companies to counter the impacts produced on the environment, spurred primarily by major disasters in the petroleum industry. In this context, the water produced is responsible for the largest volume of effluent from the production and extraction of oil and natural gas. This effluent has in its composition some critical components such as inorganic salts, heavy metals (Fe, Cu, Zn, Pb, Cd, ), presence of oil and chemicals added in the various production processes. In response to impact, have been triggered by research alternative adsorbent materials for water treatment and water produced, in order to removing oils and acids and heavy metals. Many surveys of diatomaceous earth (diatomite) in Brazil involve studies on the physico-chemical, mineral deposits, extraction, processing and applications. The official estimated Jazi are around 2.5 million tonnes, the main located in the states of Bahia (44%) and Rio Grande do Norte (37,4%). Moreover, these two states appear as large offshore producers, earning a prominent role in research of adsorbents such as diatomite for treatment of water produced. Its main applications are as an agent of filtration, adsorption of oils and greases, industrial load and thermal insulator. The objective of this work was the processing and characterization of diatomite diatomaceous earth obtained from the municipality of Macaíba-RN (known locally as tabatinga) as a low cost regenerative adsorbent for removal of heavy metals in the application of water produced treatment. In this work we adopted a methodology for batch processing, practiced by small businesses located in producing regions of Brazil. The characterization was made by X-ray diffraction (XRD), scanning electron microscopy (SEM) and specific surface area (BET). Research conducted showed that the improvement process used was effective for small volume production of diatomite concentrated. The diatomite obtained was treated by calcination at temperature of 900 oC for 2 hours, with and without fluxing Na2CO3 (4%), according to optimal results in the literature. Column adsorption experiments were conducted to percolation of the in nature, calcined and calcined fluxing diatomites. Effluent was used as a saline solution containing ions of Cu, Zn, Na, Ca and Mg simulating the composition of produced waters in the state of Rio Grande do Norte, Brazil. The breakthrough curves for simultaneous removal of copper ions and zinc as a result, 84.3% for calcined diatomite and diatomite with 97.3 % for fluxing. The calcined fluxing diatomite was more efficient permeability through the bed and removal of copper and zinc ions. The fresh diatomite had trouble with the permeability through the bed under the conditions tested, compared with the other obtained diatomite. The results are presented as promising for application in the petroleum industry

Formulação e caracterização de pastas espumadas por incorporação de ar e estabilizantes minerais

Cementing operations may occur at various stages of the life cycle of an oil well since its construction until its definitive abandonment. There are some situations in which the interest zones are depleted or have low fracture pressure. In such cases, the adoption of lowdensity cement slurries is an efficient solution. To this end, there are basically three ways to reduce the density of cement slurries: using microspheres, water extending additives or foamed cement. The objective of this study is to formulate, to study and to characterize lowdensity foamed cement, using an air entrainment surfactant with vermiculite or diatomite as water extenders and stabilizers. The methodology consists on preparation and evaluation of the slurries under the American Petroleum Institute (API) and the Brazilian Association of Technical Standards (ABNT) guidelines. Based on calculated densities between 13 and 15 ppg (1.559 and 1.799 g/cm3), the slurries were prepared with fixed surfactant concentration, varying the concentrations of vermiculite and diatomite and were compared with the base slurries. The results of plastic viscosity, yield point and gel strength and the compressive strength for 24 h showed that the slurries presented suitable rheology and mechanical strength for cementing operations in oil wells, and had their densities reduced between 8.40 and 11.89 ppg (1.007 and 1.426 g/cm3). The conclusion is that is possible, under atmospheric conditions, to obtain light weighted foamed cement slurries with satisfactory rheological and mechanical properties by means of air entrainment and mineral additions with extenders and stabilizers effects. The slurries have great potential for cementing operations; applicability in deep wells, in low fracture gradient formations and in depleted zones and bring cost savings by reducing the cementing consumption

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