Utilização do éster de soja como biolubrificante

The lubricants found in the market are of mineral or synthetic origin and harm to humans and the environment, mainly due to their improper discard. Therefore industries are seeking to develop products that cause less environmental impact, so to decrease mainly, operator aggression the Cutting Fluids became an emulsion of oil / water or water / oil. However, the emulsion was not considered the most suitable solution for environmental question, therefore the search for biodegradable lubricants and which no are toxic continues and so vegetable oils are seen, again, as a basis for the production of lubricants. The biggest problem with these oils is their oxidative instability that is intensified when working at high temperatures. The process transesterification decreases the oxidation, however changes some physical and chemical properties. Therefore soybean oil after the transesterification process was subjected to tests of density, dynamic viscosity, kinematic viscosity which is calculated from two parameters mentioned, flash point and acidity. Besides the physico-chemical test the soybean oil was subjected to a dynamic test in a tribometer adapted from a table vise, whose induced wear was the adhesive and ultimately was used as cutting fluid in a process of turning in two different materials, steel 1045 and cast iron. This latter test presented results below the mineral cutting fluid which it was compared in all tests, already in other experiments the result was satisfactory and other experiments not, so that chemical additives can be added to the oil analyzed to try equate all parameters and so formulate a biolubrificante not toxic to apply in machining processes of metalworking industry

Fermentação alcoólica utilizando líquido da casca de coco verde como fonte de nutrientes

The liquid of the rind of green coconut (LCCV), an effluent stream from the industrial processing of green coconut rind, is rich in sugars and is a suitable feedstock for fermentation. The first step of this study was to evaluate the potential of natural fermentation of LCCV. As the literature did not provide any information about LCCV and due to the difficulty of working with such an organic effluent, the second step was to characterize the LCCV and to develop a synthetic medium to explore its potential as a bioprocess diluent. The third step was to evaluate the influence of initial condensed and hydrolysable tannins on alcoholic fermentation. The last step of this work was divided into several stages: in particular to evaluate (1) the influence of the inoculum, temperature and agitation on the fermentation process, (2) the carbon source and the use of LCCV as diluent, (3) the differences between natural and synthetic fermentation of LCCV, in order to determine the best process conditions. Characterization of LCCV included analyses of the physico-chemical properties as well as the content of DQO, DBO and series of solids. Fermentation was carried out in bench-scale bioreactors using Saccharomyces cerevisiae as inoculum, at a working volume of 5L and using 0.30% of soy oil as antifoam. During fermentations, the effects of different initial sugars concentrations (10 - 20%), yeast concentrations (5 and 7.5%), temperatures (30 - 50°C) and agitation rates (400 and 500 rpm) on pH/sugars profiles and ethanol production were evaluated. The characterization of LCCV demonstrated the complexity and variability of the liquid. The best conditions for ethanol conversion were (1) media containing 15% of sugar; (2) 7.5% yeast inoculum; (3) temperature set point of 40°C and (4) an agitation rate of 500 rpm, which resulted in an ethanol conversion rate of 98% after 6 hours of process. A statistical comparison of results from natural and synthetic fermentation of LCCV showed that both processes are similar

Desenvolvimento de um reator fotoquímico aplicável no tratamento de efluentes fenólicos presentes na indústria do petróleo

With water pollution increment at the last years, so many progresses in researches about treatment of contaminated waters have been developed. In wastewaters containing highly toxic organic compounds, which the biological treatment cannot be applied, the Advanced Oxidation Processes (AOP) is an alternative for degradation of nonbiodegradable and toxic organic substances, because theses processes are generation of hydroxyl radical based on, a highly reactivate substance, with ability to degradate practically all classes of organic compounds. In general, the AOP request use of special ultraviolet (UV) lamps into the reactors. These lamps present a high electric power demand, consisting one of the largest problems for the application of these processes in industrial scale. This work involves the development of a new photochemistry reactor composed of 12 low cost black light fluorescent lamps (SYLVANIA, black light, 40 W) as UV radiation source. The studied process was the photo-Fenton system, a combination of ferrous ions, hydrogen peroxide, and UV radiation, it has been employed for the degradation of a synthetic wastewater containing phenol as pollutant model, one of the main pollutants in the petroleum industry. Preliminary experiments were carrier on to estimate operational conditions of the reactor, besides the effects of the intensity of radiation source and lamp distribution into the reactor. Samples were collected during the experiments and analyzed for determining to dissolved organic carbon (DOC) content, using a TOC analyzer Shimadzu 5000A. The High Performance Liquid Chromatography (HPLC) was also used for identification of the cathecol and hydroquinone formed during the degradation process of the phenol. The actinometry indicated 9,06⋅1018 foton⋅s-1 of photons flow, for 12 actived lamps. A factorial experimental design was elaborated which it was possible to evaluate the influence of the reactants concentration (Fe2+ and H2O2) and to determine the most favorable experimental conditions ([Fe2+] = 1,6 mM and [H2O2] = 150,5 mM). It was verified the increase of ferrous ions concentration is favorable to process until reaching a limit when the increase of ferrous ions presents a negative effect. The H2O2 exhibited a positive effect, however, in high concentrations, reaching a maximum ratio degradation. The mathematical modeling of the process was accomplished using the artificial neural network technique

Análise dos Processos de Flotação e Oxidação Avançada para o Tratamento de Efluente Modelo da Indústria do Petróleo

The generation of wastes in most industrial process is inevitable. In the petroleum industry, one of the greatest problems for the environment is the huge amount of produced water generated in the oil fields. This wastewater is a complex mixture and present great amounts. These effluents can be hazardous to the environmental without adequate treatment. This research is focused in the analysis of the efficiencies of the flotation and photo-oxidation processes to remove and decompose the organic compounds present in the produced water. A series of surfactants derivated from the laurilic alcohol was utilized in the flotation to promote the separation. The experiments have been performed with a synthetic wastewater, carefully prepared with xylene. The experimental data obtained using flotation presented a first order kinetic, identified by the quality of the linear data fitting. The best conditions were found at 0.029 g.L-1 for the surfactant EO 7, 0.05 g.L-1 for EO 8, 0.07 g.L-1 for EO 9, 0.045 g.L-1 for EO 10 and 0.08 g.L-1 for EO 23 with the following estimated kinetic constants: 0.1765, 0.1325, 0.1210, 0.1531 and 0.1699 min-1, respectively. For the series studied, the most suitable surfactant was the EO 7 due to the lower reagent onsumption, higher separation rate constant and higher removal efficiency of xylene in the aqueous phase (98%). Similarly to the flotation, the photo-Fenton process shows to be efficient for degradation of xylene and promoting the mineralization of the organic charge around 90% and 100% in 90 min

Preparação e caracterização de um material híbrido, à base de vermiculita modificada com quitosana, para a remoção de íons de chumbo presentes em efluentes sintéticos

Actually, surveys have been developed for obtaining new materials and methodologies that aim to minimize environmental problems due to discharges of industrial effluents contaminated with heavy metals. The adsorption has been used as an alternative technology effectively, economically viable and potentially important for the reduction of metals, especially when using natural adsorbents such as certain types of clay. Chitosan, a polymer of natural origin, present in the shells of crustaceans and insects, has also been used for this purpose. Among the clays, vermiculite is distinguished by its good ion exchange capacity and in its expanded form enhances its properties by greatly increasing its specific surface. This study aimed to evaluate the functionality of the hybrid material obtained through the modification of expanded vermiculite with chitosan in the removal of lead ions (II) in aqueous solution. The material was characterized by infrared spectroscopy (IR) in order to evaluate the efficiency of modification of matrix, the vermiculite, the organic material, chitosan. The thermal stability of the material and the ratio clay / polymer was evaluated by thermogravimetry. To evaluate the surface of the material was used in scanning electron microscopy (SEM) and (BET). The BET analysis revealed a significant increase in surface area of vermiculite that after interaction with chitosan, was obtained a value of 21, 6156 m2 / g. Adsorption tests were performed according to the particle size, concentration and time. The results show that the capacity of removal of ions through the vermiculite was on average 88.4% for lead in concentrations ranging from 20-200 mg / L and 64.2% in the concentration range of 1000 mg / L. Regarding the particle size, there was an increase in adsorption with decreasing particle size. In fuction to the time of contact, was observed adsorption equilibrium in 60 minutes with adsorption capacity. The data of the isotherms were fitted to equation Freundlich. The kinetic study of adsorption showed that the pseudo second- order model best describes the adsorption adsorption, having been found following values K2=0,024 g. mg-1 min-1and Qmax=25,75 mg/g, value very close to the calculated Qe = 26.31 mg / g. From the results we can conclude that the material can be used in wastewater treatment systems as a source of metal ions adsorbent due to its high adsorption capacity

Síntese e caracterização de tungstatos de cério e estrôncio para fins catalíticos

The main goal of this work was to produce nanosized ceramic materials of the family of the tungstates (tungstates of cerium and strontium), and test them for their catalytic activity in processes involving the transformation of methane (CH4). The methodology used for the synthesis of the ceramic powders involved the complexation combining EDTA-citrate. The materials characterization was performed using simple and differential thermogravimetry, x-ray diffraction, transmission electron microscopy, and energy dispersive spectroscopy (EDS). The microstructure analysis was performed using the refinement by the Rietveld method, and the crystallite size and distribution of the materials was elucidate by the Scherrer and Williamson-Hall methods. The conditions of the synthesis process for the three envisaged materials (SrWO4, SrWO4 using tungsten oxide concentrate as raw material, and Ce2(WO4)3) were adjusted to obtain a single phase crystalline material. The catalytic tests were carried out in the presence of methane and synthetic air, which is composed of 21% O2 and 79% N2. The analysis of the conversion of the reaction was done with the aid of an fourier transform infrared device (FTIR). The analysis showed that, structurally, the SrWO4 produced using raw materials of high and poor purity (99% and 92%, respectively) are similar. The ideal parameters of calcination, in the tested range, are temperature of 1000 °C and time of calcination 5 hours. For the Ce2(WO4)3, the ideal calcination time and are temperature 15 hours and 1000°C, respectively. The Williamson-Hall method provided two different distributions for the crystallite size of each material, whose values ranged between the nanometer and micrometer scales. According to method of Scherrer, all materials produced were composed of nanometric crystallites. The analyses of transmission electron microscopy confirmed the results obtained from the Williamson- Hall method for the crystallite size. The EDS showed an atomic composition for the metals in the SrWO4 that was different of the theoretical composition. With respect to the catalytic tests, all materials were found to be catalytically active, but the reaction process should be further studied and optimized.

Remoção do cobre de efluente galvânico aplicando tensoativos derivado de óleos vegetais

Copper is one of the most used metals in platingprocesses of galvanic industries. The presence of copper, a heavy metal, in galvanic effluents is harmful to the environment.The main objective of this researchwas the removal ofcopperfromgalvanic effluents, using for this purpose anionic surfactants. The removal process is based on the interaction between the polar head group of the anionic surfactant and the divalent copper in solution. The surfactants used in this study were derived from soybean oil (OSS), coconut oil (OCS), and sunflower oil (OGS). It was used a copper synthetic solution (280 ppm Cu+2) simulating the rinse water from a copper acid bath of a galvanic industry. It were developed 23and 32 factorial designs to evaluate the parameters that have influence in theremoval process. For each surfactant (OSS, OCS, and OGS), the independent variables evaluated were: surfactant concentration (1.25 to 3.75 g/L), pH (5 to 9) and the presence of an anionic polymer (0 to 0.0125 g/L).From the results obtained in the 23 factorial design and in the calculus for estimatingthe stoichiometric relationship between surfactants and copper in solution, it were developed new experimental tests, varying surfactant concentration in the range of 1.25 to 6.8 g/L (32 factorial design).The results obtained in the experimental designs were subjected to statistical evaluations to obtain Pareto charts and mathematical modelsfor Copper removal efficiency (%). The statistical evaluation of the 23 and 32factorial designs, using saponifiedcoconut oil (OCS), presented the mathematical model that best described the copper removal process.It can be concluded that OCS was the most efficient anionic surfactant, removing 100% of the copper present in the synthetic galvanic solution

Influência da intensidade de aeração na formação do floco de lodo ativado e na eficiência de remoção de matéria orgânica

In wastewater treatment, activated sludge systems have been a technology widely applied as secondary treatment. During this step, which has a strong biological aspect, it is necessary to introduce oxygen supply for the maintenance of metabolic activity of the bacteria through the aerators. Aeration devices are responsible for most of the energy consumption in this stage. In this background, the influence of three aeration intensities (atmospheric air flow 3.5, 7.0 and 10.5 L.min-1) and the concentration of dissolved oxygen (DO) on the dimension of activated sludge flocs as well as on the efficiency of organic matter removal were assessed using a traditional activated sludge system which was fed with synthetic domestic wastewater. Samples were taken weekly from the three units that make up the system feed, aeration and storage tank in order to verify the Chemical Oxygen Demand (COD). It was established the process efficiency through a comparison between the initial and final COD. Besides the parameters already mentioned, this monitoring work on activated sludge batch system was also observed by Mixed Liquor Suspend Solids (MLSS), Volatile Suspend Solids (VSS), pH and temperature measures. The results have showed a maximum removal efficiency around 75% in the first aeration sequence and approximately 85% for the second and third one. For the first aeration, the DO concentration remained higher than 3.0 mg.L-1 and a diameter range from 10 to 60 μm was observed. In the second e third sequence, the DO concentration remained higher than 4.0 mg.L-1 with a diameter range of 10 until 200 μm. Although the sequence 1 and 2 have presented similar performances for organic matter removal, the sequence 2 promoted a regular floc size distribution and with lower values of Sludge Volumetric Index (SVI) meaning a better flocculating ability. In addition, the results reaffirmed what the literature has reported: higher DO concentrations produce flocs with greater dimensions

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

Estudo da influência de compostos recalcitrantes na remoção de matéria orgânica biodegradável no tratamento de efluente de refinarias de petróleo

Petroleum Refinery wastewaters (PRW) have hart-to-degrade compounds, such as: phenols, ammonia, cyanides, sulfides, oils and greases and the mono and polynuclear aromatic hydrocarbons: benzene, toluene and xylene (BTX), acenaphthene, nitrobenzene and naphtalene. It is known that the microrganisms activity can be reduced in the presence of certain substances, adversely affecting the biological process of wastewater treatment. This research was instigated due the small number of studies regarding to this specific topic in the avaiable literature. This body of work ims to evaluate the effect of toxic substances on the biodegradability of the organic material found in PRW. Glucose was chosen as the model substrate due to its biodegradable nature. This study was divided into three parts: i) a survey of recalcitants compounds and the removal of phenol by using both biological and photochemical-biological processes; ii) biomass aclimation and iii) evaluation of the inhibitory effect certain compounds have on glucose biodegradation. The phenol degradation experiments were carried out in an activity sludge system and in a photochemical reactor. The results showed the photochemical-biological process to be more effective on phenol degradation, suggesting the superioruty of a combined photochemical-biological treatment when compared with a simple biological process for phenol removal from industry wastewaters. For the acclimation step, was used an activated sludge from industrial wastewaters. A rapid biomass aclimation to a synthetic solution composed of the main inhibitory compouns fpund in a PRW was obtained using the following operation condition: (pH = 7,0; DO ≥ 2,0 mg/L; RS = 20 days e qH = 31,2 and 20,4 hours), The last part was consisted of using respirometry evaluation toxicity effects of selected compounds over oxygen uptake rate to adaptated and non adaptated biomass in the presence of inhibitory compounds. The adaptated sludge showed greater degration capacity, with lower sensibility to toxic effects. The respirometry has proved to be very practical, as the techiniques used were simple and rapid, such as: Chemical Oxygen Demand (COD), Dissolved Oxygen (DO), and Volatile Suspended Solids (VSS). Using the latter it is possible to perform sludge selection to beggingthe process; thus allowing its use for aerobic treatment system`s behacior prediction

Extração supercrítica do óleo de linhaça: construção do extrator, estudo de parâmetros de processo, avaliação química e antioxidante do produto

The aim of the present study was to extract vegetable oil from brown linseed (Linum usitatissimum L.), determine fatty acid levels, the antioxidant capacity of the extracted oil and perform a rapid economic assessment of the SFE process in the manufacture of oil. The experiments were conducted in a test bench extractor capable of operating with carbon dioxide and co-solvents, obeying 23 factorial planning with central point in triplicate, and having process yield as response variable and pressure, temperature and percentage of cosolvent as independent variables. The yield (mass of extracted oil/mass of raw material used) ranged from 2.2% to 28.8%, with the best results obtained at 250 bar and 50ºC, using 5% (v/v) ethanol co-solvent. The influence of the variables on extraction kinetics and on the composition of the linseed oil obtained was investigated. The extraction kinetic curves obtained were based on different mathematical models available in the literature. The Martínez et al. (2003) model and the Simple Single Plate (SSP) model discussed by Gaspar et al. (2003) represented the experimental data with the lowest mean square errors (MSE). A manufacturing cost of US$17.85/kgoil was estimated for the production of linseed oil using TECANALYSIS software and the Rosa and Meireles method (2005). To establish comparisons with SFE, conventional extraction tests were conducted with a Soxhlet device using petroleum ether. These tests obtained mean yields of 35.2% for an extraction time of 5h. All the oil samples were sterilized and characterized in terms of their composition in fatty acids (FA) using gas chromatography. The main fatty acids detected were: palmitic (C16:0), stearic (C18:0), oleic (C18:1), linoleic (C18:2n-6) and α-linolenic (C18:3n-3). The FA contents obtained with Soxhlet dif ered from those obtained with SFE, with higher percentages of saturated and monounsaturated FA with the Soxhlet technique using petroleum ether. With respect to α-linolenic content (main component of linseed oil) in the samples, SFE performed better than Soxhlet extraction, obtaining percentages between 51.18% and 52.71%, whereas with Soxhlet extraction it was 47.84%. The antioxidant activity of the oil was assessed in the β-carotene/linoleic acid system. The percentages of inhibition of the oxidative process reached 22.11% for the SFE oil, but only 6.09% for commercial oil (cold pressing), suggesting that the SFE technique better preserves the phenolic compounds present in the seed, which are likely responsible for the antioxidant nature of the oil. In vitro tests with the sample displaying the best antioxidant response were conducted in rat liver homogenate to investigate the inhibition of spontaneous lipid peroxidation or autooxidation of biological tissue. Linseed oil proved to be more efficient than fish oil (used as standard) in decreasing lipid peroxidation in the liver tissue of Wistar rats, yielding similar results to those obtained with the use of BHT (synthetic antioxidant). Inhibitory capacity may be explained by the presence of phenolic compounds with antioxidant activity in the linseed oil. The results obtained indicate the need for more detailed studies, given the importance of linseed oil as one of the greatest sources of ω3 among vegetable oils

Estudo da remoção de Ba2+, Ni2+, Cd2+, Cu3+, Cr3+, Sr2+, Zn2+ por eletrocoagulação em água associada à produção de petróleo

Among the waste generated in the petrochemical industry water associated with oil production is the most important. It is considered one of the great challenges due to the presence of considered toxic chemicals present in this composition. The presence of these substances difficult to reuse the water associated with the enhanced recovery processes, so that prior to their reuse or disposal, treatment is necessary. This paper aimed to study the removal efficiency of chemical species: Ba2+, Ni2+, Cd2+, Cu2+, Cr3+, Sr2+ and Zn2+, present in the composition of the water associated with oil production by electrocoagulation. The evaluation of removal of these chemical species was performed by laboratory tests using electrochemical batch reactors and continuous flow. Initial tests were performed with electrocoagulation of synthetic wastewater in batch reactor using iron electrode. Results of removal of Zn2+ and Ni2+ were 78 % and 59 % respectively. While the percentage of removed Ba2+ was 19 % by 30 minutes of treatment and by applying current of 1.10 A. The tests were performed on effluent batch reactor applying the electrochemical technique with stainless steel electrodes 304, the objective was to remove part of the dispersed oil and also of organic compounds in the effluent. Under the experimental conditions used, the maximum result was obtained TOG was 60 % and TOC was approximately 50 % compared to the initial concentration. In the experiments carried out in continuous reactor, with effluent semisynthetic, have been used electrodes of iron and aluminum and the results were 100 % removal of Cd2+, Cu2+, Cr3+ and Zn2+ and 77 % of Sr2+. These percentages were only attainable through the use of the iron electrode. However, when the electrode was replaced by aluminum, there was a reduction in the percentage of removal to 65 %, using the same flow rate and current. Therefore according to the results obtained using the iron electrode was more effective in removing these metals and the conditions of lower current and lower flow rate was satisfactory, as observed in the experimental design adopted

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

Integração dos processos de flotação e foto-fenton para redução de óleos e graxas de água produzida em campos de petróleo

During production of oil and gas, there is also the production of an aqueous effluent called produced water. This byproduct has in its composition salts, organic compounds, gases and heavy metals. This research aimed to evaluate the integration of processes Induced Air Flotation (IAF) and photo-Fenton for reducing the Total Oils and Greases (TOG) present in produced water. Experiments were performed with synthetic wastewater prepared from the dispersion of crude oil in saline solution. The system was stirred for 25 min at 33,000 rpm and then allowed to stand for 50 min to allow free oil separation. The initial oil concentration in synthetic wastewater was 300 ppm and 35 ppm for the flotation and the photo-Fenton steps, respectively. These values of initial oil concentration were established based on average values of primary processing units in Potiguar Basin. The processes were studied individually and then the integration was performed considering the best experimental conditions found in each individual step. The separation by flotation showed high removal rate of oil with first-order kinetic behavior. The flotation kinetics was dependent on both the concentration and the hydrophilic-lipophilic balance (HLB) of the surfactant. The best result was obtained for the concentration of 4.06.10-3 mM (k = 0.7719 min-1) of surfactant EO 2, which represents 86% of reduction in TOG after 4 min. For series of surfactants evaluated, the separation efficiency was found to be improved by the use of surfactants with low HLB. Regarding the TOG reduction step by photo-Fenton, the largest oil removal reached was 84% after 45 min of reaction, using 0.44 mM and 10 mM of ferrous ions and hydrogen peroxide, respectively. The best experimental conditions encountered in the integrated process was 10 min of flotation followed by 45 min of photo-Fenton with overall TOG reduction of 99%, which represents 5 ppm of TOG in the treated effluent. The integration of processes flotation and photo-Fenton proved to be highly effective in reducing TOG of produced water in oilfields

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