Modelagem e simulação da solubilidade de sais em sistemas aquosos com Monoetilenoglicol

Primary processing of natural gas platforms as Mexilhão Field (PMXL-1 ) in the Santos Basin, where monoethylene glycol (MEG) has been used to inhibit the formation of hydrates, present operational problems caused by salt scale in the recovery unit of MEG. Bibliographic search and data analysis of salt solubility in mixed solvents, namely water and MEG, indicate that experimental reports are available to a relatively restricted number of ionic species present in the produced water, such as NaCl and KCl. The aim of this study was to develop a method for calculating of salt solubilities in mixed solvent mixtures, in explantion, NaCl or KCl in aqueous mixtures of MEG. The method of calculating extend the Pitzer model, with the approach Lorimer, for aqueous systems containing a salt and another solvent (MEG). Python language in the Integrated Development Environment (IDE) Eclipse was used in the creation of the computational applications. The results indicate the feasibility of the proposed calculation method for a systematic series of salt (NaCl or KCl) solubility data in aqueous mixtures of MEG at various temperatures. Moreover, the application of the developed tool in Python has proven to be suitable for parameter estimation and simulation purposes

Análise espacial de reservatórios usando DFA de dados geofísicos

This research aims to set whether is possible to build spatial patterns over oil fields using DFA (Detrended Fluctuation Analysis) of the following well logs: sonic, density, porosity, resistivity and gamma ray. It was employed in the analysis a set of 54 well logs from the oil field of Campos dos Namorados, RJ, Brazil. To check for spatial correlation, it was employed the Mantel test between the matrix of geographic distance and the matrix of the difference of DFA exponents of the well logs. The null hypothesis assumes the absence of spatial structures that means no correlation between the matrix of Euclidean distance and the matrix of DFA differences. Our analysis indicate that the sonic (p=0.18) and the density (p=0.26) were the profiles that show tendency to correlation, or weak correlation. A complementary analysis using contour plot also has suggested that the sonic and the density are the most suitable with geophysical quantities for the construction of spatial structures corroborating the results of Mantel test

Obtenção de Mo2C com adição de Co por reação gás-sólido em reator de leito fixo

Sulfur compounds emissions have been, on the late years, subject to more severe environmental laws due to its impact on the environment (causing the acid rain phenomena) and on human health. It has also been object of much attention from the refiners worldwide due to its relationship with equipment’s life, which is decreased by corrosion, and also with products’ quality, as the later may have its color, smell and stability altered by the presence of such compounds. Sulfur removal can be carried out by hydrotreating (HDT) which is a catalytic process. Catalysts for HDS are traditionally based on Co(Ni)-Mo(W)/Al2O3. However, in face of the increased contaminants’ content on crude oil, and stricter legislation on emissions, the development of new, more active and efficient catalysts is pressing. Carbides of refractory material have been identified as potential materials for this use. The addition of a second metal to carbides may enhance catalytic activities by increasing the density of active sites. In the present thesis Mo2C with Co addition was produced in a fixed bed reactor via gas-solid reaction of CH4 (5%) and H2(95%) with a precursor made of a mix of ammonium heptamolybdate [(NH4)6[Mo7O24].4H2O] and cobalt nitrate[Co(NO3)2.6H2O] at stoichiometric amounts. Precursors’ where analyzed by XRF, XRD, SEM and TG/DTA. Carboreduction reactions were carried out at 700 and 750°C with two cobalt compositions (2,5 and 5%). Reaction’s products were characterized by XRF, XRD, SEM, TOC, BET and laser granulometry. It was possible to obtain Mo2C with 2,5 and 5% cobalt addition as a single phase at 750°C with nanoscale crystallite sizes. At 700°C, however, both MoO2 and Mo2C phases were found by XRD. No Co containing phases were found by XRD. XRF, however, confirmed the intended Co content added. SEM images confirmed XRD data. The increase on Co content promoted a more severe agglomeration of the produced powder. The same effect was noted when the reaction temperature was increased. The powder synthesized at 750°C with 2,5% Co addition TOC analysis indicated the complete conversion from oxide material to carbide, with a 8,9% free carbon production. The powder produced at this temperature with 5% Co addition was only partially converted (86%)

Avaliação térmica e desempenho do processo de secagem de misturas de graviola e leite em secador de leito de jorro

The soursop (A. muricata) is a fruit rich in minerals especially the potassium content. The commercialization of soursop in natura and processed has increased greatly in recent years. Drying fruit pulp in order to obtain the powdered pulp has been studied, seeking alternatives to ensure the quality of dehydrated products at a low cost of production. The high concentration of sugars reducing present in fruits causes problems of agglomeration and retention during fruit pulp drying in spouted bed dryers. On the other hand in relation to drying of milk and fruit pulp with added milk in spouted bed, promising results are reported in the literature. Based on these results was studied in this work drying of the pulp soursop with added milk in spouted bed with inert particles. The tests were based on a 24 factorial design were evaluated for the effects of milk concentration (30 to 50% m/m), drying air temperature (70 to 90 °C), intermittency time (10 to 14 min), and ratio of air velocity in relation to the minimum spout (1.2 to 1.5) on the rate of production, of powder moisture, yield, rate of drying and thermal efficiency of the process. There were physical and chemical analysis of mixtures, of powders and of mixtures reconstituted by rehydration powders. Were adjusted statistical models of first order to data the rate of production, yield and thermal efficiency, that were statistically significant and predictive. An efficiency greater than 40% under the conditions of 50% milk mixture, at 70 ° C the drying air temperature and 1.5 for the ratio between the air velocity and the minimum spout has been reached. The intermittency time showed no significant effect on the analyzed variables. The final product had moisture in the range of 4.18% to 9.99% and water activity between 0.274 to 0.375. The mixtures reconstituted by rehydration powders maintained the same characteristics of natural blends.

Extração do corante do fruto de castanhola (Terminalia catappa Linn) e estudos dos seus compostos fenólicos, antocianinas e atividade antioxidante

The Terminalia catappa Linn belonging to Combretaceae family, popularly known as castanets, has fruits consists of a fleshy pulp, rounded seed and a very hard shell. The natural pigmentation existing in the fruit of castanet indicates the presence of anthocyanins, phenolic nature components belonging to the group of flavonoids, which have antioxidant activity. This research was conducted with the castanets and aimed to the study of factors influencing the extraction of dyes from its pulp. The extracts were obtained using a reactor enjaquetado by solid-liquid extraction. The factors were evaluated as temperature, time, solvent ratio and pH extraction. Adopting a factorial design of 24 , with 4 repetitions at the central point, the effects of these factors on the extraction process were analyzed using Statistica 7.0 software. The antioxidant activity (AA), the content of phenolic compounds (CFT) and the total monomeric anthocyanin content (AMT) were evaluated as response variables planning. Statistical analysis of the results, the effects that influenced the extraction were different for each response (CFT, AMT and AA). However, the pH was significant for the extraction of all compounds. The kinetic behavior of the dye extraction was also studied for phenolic compounds, monomeric anthocyanins and antioxidant activity, in which the equilibrium was reached after 90 minutes of extraction. To study the stability of anthocyanins temperature was the factor that most influenced the stability, however the concentration and pH also played a part.

Estudo experimental e modelagem do processo de sacarificação e fermentação simultânea utilizando bagaço de cana-de-açúcar para produção de etanol

Conselho Nacional de Desenvolvimento Científico e Tecnológico - CNPq

Secagem de resíduo de goiaba em secador convectivo de bandejas: modelagem matemática e análise do processo

Actually, Brazil is one of the larger fruit producer worldwide, with most of its production being consumed in nature way or either as juice or pulp. It is important to highlig ht in the fruit productive chain there are a lot lose due mainly to climate reasons, as well as storage, transportation, season, market, etc. It is known that in the pulp and fruit processing industy a yield of 50% (in mass) is usually obtained, with the other part discarded as waste. However, since most this waste has a high nutrient content it can be used to generate added - value products. In this case, drying plays an important role as an alternative process in order to improve these wastes generated by the fruit industry. However, despite the advantage of using this technique in order to improve such wastes, issues as a higher power demand as well as the thermal efficiency limitation should be addressed. Therefore, the control of the main variables in t his drying process is quite important in order to obtain operational conditions to produce a final product with the target specification as well as with a lower power cost. M athematical models can be applied to this process as a tool in order to optimize t he best conditions. The main aim of this work was to evaluate the drying behaviour of a guava industrial pulp waste using a batch system with a convective - tray dryer both experimentally and using mathematical modeling. In the experimental study , the dryin g carried out using a group of trays as well as the power consume were assayed as response to the effects of operational conditions (temperature, drying air flow rate and solid mass). Obtained results allowed observing the most significant variables in the process. On the other hand, the phenomenological mathematical model was validated and allowed to follow the moisture profile as well as the temperature in the solid and gas phases in every tray. Simulation results showed the most favorable procedure to o btain the minimum processing time as well as the lower power demand.

Desenvolvimento de novos biolubrificantes hidráulicos derivados dos óleos de maracujá e de moringa in natura e epoxidados

With the increasing environmental awareness, maximizing biodegradability and minimizing ecotoxicity is the main driving force for new technological developments. Thus, can be developed new biodegradable lubricants for use in environmentally sensitive areas. The aim of this study was to obtain new bio-lubricants from passion fruit (Passiflora edulis Sims f. flavicarpa Degener) and moringa (Moringa oleifera Lamarck) epoxidized oils and develop a new additive package using experimental design for their use as a hydraulic fluid. In the first stage of this work was performed the optimization of the epoxidation process of the oils using fractional experimental design 24-1 , varying the temperature, reaction time, ratio of formic acid and hydrogen peroxide. In the second step was investigated the selectivity, thermodynamics and kinetics of the reaction for obtaining the two epoxides at 30, 50 and 70 °C. The result of the experimental design confirmed that the epoxidation of passion fruit oil requires 2 hours of reaction, 50 °C and a ratio H2O2/C=C/HCOOH (1:1:1). For moringa oil were required 2 hours reaction, 50 °C and a ratio of H2O2/C=C/HCOOH (1:1:1.5). The results of the final conversions were equal to 83.09% (± 0.3) for passion fruit oil epoxide and 91.02 (±0,4) for moringa oil epoxide. Following was made the 23 factorial design to evaluate which are the best concentrations of corrosion inhibitor and anti-wear (IC), antioxidant (BHA) and extreme pressure (EP) additives. The bio-lubricants obtained in this step were characterized according to DIN 51524 (Part 2 HLP) and DIN 51517 (Part 3 CLP) standards. The epoxidation process of the oils was able to improve the oxidative stability and reduce the total acid number, when compared to the in natura oils. Moreover, the epoxidized oils best solubilized additives, resulting in increased performance as a lubricant. In terms of physicochemical performance, the best lubricant fluid was the epoxidized moringa oil with additives (EMO-ADI), followed by the epoxidized passion fruit oil with additives (EPF-ADI) and, finally, the passion fruit in natura oil without additives (PFO). Lastly, was made the investigation of the tribological behavior under conditions of boundary lubrication for these lubricants. The tribological performance of the developed lubricants was analyzed on a HFRR equipment (High Frequency Reciprocating Rig) and the coefficient of friction, which occurs during the contact and the formation of the lubricating film, was measured. The wear was evaluated through optical microscopy and scanning electron microscopy (SEM). The results showed that the addition of extreme pressure (EP) and anti-wear and corrosion inhibitor (CI) additives significantly improve the tribological properties of the fluids. In all assays, was formed a lubricating film that is responsible for reducing the coefficient of metal-to-metal wear. It was observed that the addition of EP and IC additives in the in natura vegetable oils of passion fruit and moringa did not favor a significant reduction in wear. The bio-lubricants developed from passion fruit and moringa oils modified via epoxidation presented satisfactory tribological properties and shown to be potential lubricants for replacement of commercial mineral-based fluids.

Uso de água produzida na formulação de fluidos de perfuração

Drilling fluids have fundamental importance in the petroleum activities, since they are responsible for remove the cuttings, maintain pressure and well stability, preventing collapse and inflow of fluid into the rock formation and maintain lubrication and cooling the drill. There are basically three types of drilling fluids: water-based, non-aqueous and aerated based. The water-based drilling fluid is widely used because it is less aggressive to the environment and provide excellent stability and inhibition (when the water based drilling fluid is a inhibition fluid), among other qualities. Produced water is generated simultaneously with oil during production and has high concentrations of metals and contaminants, so it’s necessary to treat for disposal this water. The produced water from the fields of Urucu-AM and Riacho da forquilha-RN have high concentrations of contaminants, metals and salts such as calcium and magnesium, complicating their treatment and disposal. Thus, the objective was to analyze the use of synthetic produced water with similar characteristics of produced water from Urucu-AM and Riacho da Forquilha-RN for formulate a water-based drilling mud, noting the influence of varying the concentration of calcium and magnesium into filtered and rheology tests. We conducted a simple 32 factorial experimental design for statistical modeling of data. The results showed that the varying concentrations of calcium and magnesium did not influence the rheology of the fluid, where in the plastic viscosity, apparent viscosity and the initial and final gels does not varied significantly. For the filtrate tests, calcium concentration in a linear fashion influenced chloride concentration, where when we have a higher concentration of calcium we have a higher the concentration of chloride in the filtrate. For the Urucu’s produced water based fluids, volume of filtrate was observed that the calcium concentration influences quadratically, this means that high calcium concentrations interfere with the power of the inhibitors used in the formulation of the filtered fluid. For Riacho’s produced water based fluid, Calcium’s influences is linear for volume of filtrate. The magnesium concentration was significant only for chloride concentration in a quadratic way just for Urucu’s produced water based fluids. The mud with maximum concentration of magnesium (9,411g/L), but minimal concentration of calcium (0,733g/L) showed good results. Therefore, a maximum water produced by magnesium concentration of 9,411g/L and the maximum calcium concentration of 0,733g/L can be used for formulating water-based drilling fluids, providing appropriate properties for this kind of fluid.

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.

Remoção de corantes utilizando tensoativos: extração por ponto de nuvem e floculação iônica

The textile sector is one of the main contributors to the generation of industrial wastewaters due to the use of large volumes of water, which has a high organic load content. In these, it is observed to the presence of dyes, surfactants, starch, alcohols, acetic acid and other constituents, from the various processing steps of the textiles. Hence, the treatment of textile wastewater becomes fundamental before releasing it into water bodies, where they can cause disastrous physical-chemical changes for the environment. Surfactants are substances widely used in separation processes and their use for treating textile wastewaters was evaluated in this research by applying the cloud point extraction and the ionic flocculation. In the cloud point extraction was used as surfactant nonylphenol with 9.5 ethoxylation degree to remove reactive dye. The process evaluation was performed in terms of temperature, surfactant and dye concentrations. The dye removal reached 91%. The ionic flocculation occurs due to the presence of calcium, which reacts with anionic surfactant to form insoluble surfactants capable of attracting the organic matter by adsorption. In this work the ionic flocculation using base soap was applied to the treatment of synthetic wastewater containing dyes belonging to three classes: direct, reactive, and disperse. It was evaluated by the influence of the following parameters: surfactant and electrolyte concentrations, stirring speed, equilibrium time, temperature, and pH. The flocculation of the surfactant was carried out in two ways: forming the floc in the effluent itself and forming the floc before mixing it to the effluent. Removal of reactive and direct dye, when the floc is formed into textile effluent was 97% and 87%, respectively. In the case where the floc is formed prior to adding it to the effluent, the removal to direct and disperse dye reached 92% and 87%, respectively. These results show the efficience of the evaluated processes for dye removal from textile wastewaters.

Remoção de metais utilizando o hexadecanoato de sódio

Industrial activities like mining, electroplating and the oil extraction process, are increasing the levels of heavy metals such as Cu, Fe, Mg and Cd in aquatic ecosystems. This increase is related to the discharge of effluents containing trace of this elements above the maximum allowed by law. Methods such as ion exchange, membrane filtration and chemical precipitation have been studied as a means of treatment of these metals contamination. The precipitation of metals using anionic surfactants derived from carboxylic acids emerged as an alternative for the removal of metals from industrial effluents. The reaction between bivalent ions and these types of surfactants in aqueous solution leads to the formation of metal carboxylates, which can precipitate in the form of flakes and are subsequently removed by a process of decantation or simple filtration. In this work the metals extraction is performed by using the surfactant sodium hexadecanoate as extracting agent. The main purpose was to study the effect of temperature, solution pH, and concentration of surfactant in the metal removal process. The statistical design of the process showed that the process is directly dependent to changes in pH and concentration of surfactant, but inversely proportional and somewhat dependent to temperature variation, with the latter effect being considered negligible in most cases. The individual study of the effect of temperature showed a strong dependence of the process with the Kraft point, both for the surfactant used as extracting agent, as for the surfactant obtained after the reaction of this surfactant with the metal. From data of temperatures and concentrations of the surfactant was possible to calculate the equilibrium constant for the reaction between sodium hexadecanoate and copper ions. Later, thermodynamic parameters were determined, showing that the process is exothermic and spontaneous.

Simulação da destilação molecular de filme descendente para o petróleo

The heavy part of the oil can be used for numerous purposes, e.g. to obtain lubricating oils. In this context, many researchers have been studying alternatives such separation of crude oil components, among which may be mentioned molecular distillation. Molecular distillation is a forced evaporation technique different from other conventional processes in the literature. This process can be classified as a special distillation case under high vacuum with pressures that reach extremely low ranges of the order of 0.1 Pascal. The evaporation and condensation surfaces must have a distance from each other of the magnitude order of mean free path of the evaporated molecules, that is, molecules evaporated easily reach the condenser, because they find a route without obstacles, what is desirable. Thus, the main contribution of this work is the simulation of the falling-film molecular distillation for crude oil mixtures. The crude oil was characterized using UniSim® Design and R430 Aspen HYSYS® V8.5. The results of this characterization were performed in spreadsheets of Microsoft® Excel®, calculations of the physicochemical properties of the waste of an oil sample, i.e., thermodynamic and transport. Based on this estimated properties and boundary conditions suggested by the literature, equations of temperature and concentration profiles were resolved through the implicit finite difference method using the programming language Visual Basic® (VBA) for Excel®. The result of the temperature profile showed consistent with the reproduced by literature, having in their initial values a slight distortion as a result of the nature of the studied oil is lighter than the literature, since the results of the concentration profiles were effective allowing realize that the concentration of the more volatile decreases and of the less volatile increases due to the length of the evaporator. According to the transport phenomena present in the process, the velocity profile tends to increase to a peak and then decreases, and the film thickness decreases, both as a function of the evaporator length. It is concluded that the simulation code in Visual Basic® language (VBA) is a final product of the work that allows application to molecular distillation of petroleum and other similar mixtures.

Tratamento de cascalho de perfuração utilizando sistemas microemulsionados

The oil industry is one of the activities that generates more waste to the environment. The drill cuttings is a waste generated in large quantities in the drilling process and that may cause environmental damage such as soil contamination and consequently the contamination of groundwater if disposed of without prior treatment. Arises the need to develop scientific activities and research ways to adapt these wastes the current environmental standards. In the case of solid wastes, the NBR 10004: 2004 of the Brazilian Association of Technical Standards (ABNT) classifies them into class I waste (hazardous) and class II (not dangerous), which determines which wastes may or may not be discarded in the environment without causing environmental impact. This study presents a novel alternative for treating drill cuttings, where this waste was classified as class I (Abreu & Souza, 2005), mainly by removing the n-paraffin present in it, since this arises when using drilling fluids base oil. Using microemulsion systems promotes the removal of this contaminant drill cuttings samples from wells located in Alto do Rodrigues - RN. Initially, we determined the concentration of paraffin using infrared method in samples were extracted with ultrasound, we obtained a paraffin concentration in the range from 36.59 to 43.52 g of paraffin per kilogram of cuttings. Used two microemulsion systems containing two nonionic surfactants from different classes, one is an alcohol ethoxylated (UNTL-90) and the other an nonylphenol ethoxylated (RNX 110). The results indicated that the system UNTL-90 surfactant has better efficiency than the system with RNX 110. The study of the influence of contact time at the extraction showed that for times greater than 25 minutes has a tendency to increase the percentage extraction with increasing contact time. It was also observed that the extraction is fast because at 1 minute contact has 22.7% extraction. The reuse of the microemulsion system without removing the paraffin extracted in previous steps, showed reduction of 29.32 in percentage of extraction by comparing the first and third extraction, but by comparing the first and second extractions reduction is 8.5 in percentage extraction, so the systems reuse optimization can be an option for economically viable removing paraffin from cuttings. The extraction with shaking is more effective in the treatment of cuttings, reaching the extraction percentage of 87.04%, that is, obtaining a drill cuttings with 0.551% paraffin. Using the percentage of paraffin employed in non-aqueous drilling fluids and fluid maximum limit on cuttings for disposal established by the Environmental Protection Agency of the United States (US EPA), one arrives at the conclusion that the level of paraffin on gravel cannot exceed 3.93%. Conclude that the amount of paraffin in the treated cuttings with the microemulsion system with shaking is below the established by US EPA, showing that the system used was efficient in removing the paraffin from the drill cuttings.

Avaliação da biodegradação do dibenzotiofeno utilizando lodos ativados

During the oil refining process a huge discard volume of water occurs, which carries the contaminants from the process. A class of contaminant compounds resulting from the petrochemical industry are the Polyaromatic Hydrocarbons (PAH's). To evaluate the biodegradation of Dibenzothiophene in refinery water a synthetic wastewater was prepared to be treated using activated sludge. For this, a 2 3 Composite Design (plus 3 central points and six axial points) was carried out. The planning had as independent variables (factors) the initial concentration of DBT, pH and time of biodegradation. Biodegradation of DBT was assayed following the parameters COD, pH, temperature, SS, VSS, FVS, SVI. Concerned to the chromatographic conditions, a methodology was validated in order to verify the presence of DBT and its metabolite, 2-HBF, in the final wastewater treated by activated sludge system using a liquid - liquid extraction coupled to HPLC / UV analysis. The parameters used for validation were DL, QL, linearity, recovery and repeatability. As for optimization, the results indicated that the studied methodology can be used in monitoring the DBT degradation and 2- HBF by activated sludge, as they showed excellent linearity values, coefficients of variation, so as satisfactory recovery percentage. COD reduction efficiency tests showed an average percentage of 64.4%. The increasing trend for the results for the TSS and VSS tests showed that the activated sludge was well tailored. The best operating conditions for the reduction of COD were observed when operated with median concentrations of DBT, a higher time to biodegradation, and pH in both the acidic range as the basic one. The biodegradability of the DBT was confirmed by determining the presence of HBF-2. The highest concentrations of HBF-2 were obtained in extreme concentrations of DBT and pH, and higher biodegradation times.