Estudo de um sistema híbrido de destilação solar para polimento de águas produzidas

The oil industry, experiencing a great economic and environmental impact, has increasingly invested in researches aiming a more satisfactory treatment of its largest effluent, i.e., produced water. These are mostly discarded at sea, without reuse and after a basic treatment. Such effluent contains a range of organic compounds with high toxicity and are difficult to remove, such as polycyclic aromatic hydrocarbons, salts, heavy metals, etc.. The main objective of this work was to study the solar distillation of produced water pre-treated to remove salts and other contaminants trough of a hybrid system with a pre-heater. This developed apparatus was called solar system, which consists of a solar heater and a conventional distillation solar still. The first device consisted of a water tank, a solar flat plate collector and a thermal reservoir. The solar distillator is of simple effect, with 1m2 of flat area and 20° of inclination. This dissertation was divided in five steps: measurements in the solar system, i.e. temperatures and distillate flow rate and weather data; modeling and simulation of the system; study of vapor-liquid equilibrium of the synthetic wastewater by the aqueous solution of p-xylene; physical and chemical analyses of samples of the feed, distillate and residue, as well as climatology pertinent variables of Natal-RN. The solar system was tested separately, with the supply water, aqueous NaCl and synthetic oil produced water. Temperature measurements were taken every minute of the thermal reservoir, water tank and distillator (liquid and vapor phases). Data of solar radiation and rainfall were obtained from INPE (National Institute for Space Research). The solar pre-heater demonstrated to be effective for the liquid systems tested. The reservoir fluid had an average temperature of 58°C, which enabled the feed to be pre-heated in the distillator. The temperature profile in the solar distillator showed a similar behavior to daily solar radiation, with temperatures near 70°C. The distillation had an average yield of 2.4 L /day, i.e., an efficiency of 27.2%. Mathematical modeling aided the identification of the most important variables and parameters in the solar system. The study of the vapor-liquid equilibrium from Total Organic Carbon (TOC) analysis indicated heteroazeotropia and the vapor phase resulted more concentrated in p-xylene. The physical-chemical analysis of pH, conductivity, Total Dissolved Solids (TDS), chlorides, cations (including heavy metals) and anions, the effluent distillate showed satisfactory results, which presents a potential for reuse. The climatological study indicates the region of Natal-RN as favorable to the operation of solar systems, but the use of auxiliary heating during periods of higher rainfall and cloud cover is also recommended

Otimização do processo de flotação de emulsão óleo/água através do planejamento fatorial completo

In recent decades, the generation of solid and liquid waste has increased substantially due to increased industrial activity that is directly linked to economic growth. For that is the most efficient process, it is inevitable generation of such wastes. In the oil industry, a major waste generated in oil exploration is produced water, which due to its complex composition and the large amount generated, has become a challenge, given the restrictions imposed by environmental laws regarding their disposal, making if necessary create alternatives for reuse or treatment in order to reduce the content of contaminants and reduce the harmful effects to the environment. This water can be present in free form or emulsified with the oil, when in the form of an emulsion of oil-water type, it is necessary to use chemicals to promote the separation and flotation is the treatment method which has proved to be more efficient, for it can remove much of the emulsified oil when compared to other methods. In this context, the object of this work was to study the individual effects and interactions of some physicochemical parameters of operations, based on previous work to a flotation cell used in the separation of synthetic emulsion oil / water in order to optimize the efficiency of the separation process through of the 24 full factorial design with center point. The response variables to evaluate the separation efficiency was the percentage of color and turbidity removal. The independent variables were: concentration of de-emulsifying, oil content in water, salinity and pH, these being fixed, minimum and maximum limits. The analysis of variance for the equation of the empirical model, was statistically significant and useful for predictive purposes the separation efficiency of the floater with R2 > 90%. The results showed that the oil content in water and the interaction between the oil content in water and salinity, showed the highest values of the estimated effects among all the factors investigated, having great and positive influence on the separation efficiency. By analyzing the response surface was determined maximum removal efficiency above 90% for both measured for turbidity as a measure of color when in a saline medium (30 g/L), the high oil concentrations (306 ppm) using low concentrations of de-emulsifying (1,1 ppm) and at pH close to neutral

Comparação entre planejamento estatístico experimental e análise dimensional em operações de mistura e separação para sistema óleo-água

This work aims to determine a better methodology to help predicting some operational parameters to a new design of mixer-settler on treating wastewater produced by petroleum industry, called MDIF (Misturador-Decantador à Inversão de Fases/ Mixer-Settler based on Phase Inversion MSPI). The data from this research were obtained from the wastewater treatment unit, called MSPI-TU, installed on a wastewater treatment plant (WTP) of PETROBRAS/UO-RNCE. The importance in determining the better methodology to predict the results of separation and extraction efficiency of the equipment, contributes significantly to determine the optimum operating variables for the control of the unit. The study was based on a comparison among the experimental efficiency (E) obtained by operating MSPI-TU, the efficiency obtained by experimental design equation (Eplan) from the software Statistica Experimental Design® (version 7.0), and the other obtained from a modeling equation based on a dimensional analysis (Ecalc). The results shows that the experimental design equation gives a good prediction of the unit efficiencies with better data reliability, regarding to the condition before a run operation. The average deviation between the proposed by statistic planning model equation and experimental data was 0.13%. On the other hand, the efficiency calculated by the equation which represents the dimensional analysis, may result on important relative deviations (up 70%). Thus, the experimental design is confirmed as a reliable tool, with regard the experimental data processing of the MSPI-TU

Tratamento de água de produção de petróleo visando o aproveitamento na obtenção de barrilha

The petroleum production is associated to the produced water, which has dispersed and dissolved materials that damage not only the environment, but also the petroleum processing units. This study aims at the treatment of produced water focusing mainly on the removal of metals and oil and using this treated water as raw material for the production of sodium carbonate. Initially, it was addressed the removal of the following divalent metals: calcium, magnesium, barium, zinc, copper, iron, and cadmium. For this purpose, surfactants derived from vegetable oils, such as coconut oil, soybean oil, and sunflower oil, were used. The investigation showed that there is a stoichiometric relationship between the metals removed from the produced water and the surfactants used in the process of metals removal. It was also developed a model that correlates the hydrolysis constant of saponified coconut oil with the metal distribution between the resulting stages of the proposed process, flocs and aqueous phases, and relating the results with the pH of the medium. The correlation coefficient obtained was 0.963. Next, the process of producing washing soda (prefiro soda ahs ou sodium carbonate) started. The resulting water from the various treatment approaches from petroleum production water was used. During this stage of the research, it was observed that the surfactant assisted in the produced water treatment, by removing some metals and the dispersed oil entirety. The yield of sodium carbonate production was approximately 80%, and its purity was around 95%. It was also assessed, in the production of sodium carbonate, the influence of the type of reactor, using a continuous reactor and a batch reactor. These tests showed that the process with continuous reactor was not as efficient as the batch process. In general, it can be concluded that the production of sodium carbonate from water of oil production is a feasible process, rendering an effluent that causes a great environmental impact a raw material with large scale industrial use

Sistemas microemulsionados aplicados à remoção da cor de efluente têxtil

Effluent color resulting from textile dyeing processes has been one of the biggest environmental problems faced by the textile industry. In particular, reactive dyes are highly resistant to conventional wastewater treatment methods. New technologies have been contemplated, some of which have been applied in industrial treatment plants, but color removal has not been efficiently attained. Since microemulsion systems provide good results in heavy metals and proteins extraction processes, their use in dyes extraction has been suggested and investigated. In this work, a real textile wastewater from an exhaustion dyebath has been treated, which contains the following reactive dyes: Procion Yellow H-E4R (CI Reactive Yellow 84), Procion Blue H-ERD (CI Reactive Blue 160) and Procion Red H-E3B (CI Reactive Red 120), in addition to auxiliary compounds normally found in dyeing processes with reactive dyes. The dyes Remazol Blue RR and Remazol Turquoise Blue G (Reactive Blue 21) have also been examined in view of the presence of heavy metals in these molecules. The microemulsion system comprised dodecyl ammonium chloride (as a cationic surfactant), water or wastewater as aqueous phase, kerosene as oil phase, and one of the following alcohols as cosurfactant: isoamyl alcohol, n-butyl alcohol and n-octyl alcohol. The pseudo-ternary diagrams were constructed in order to define Winsor s equilibrium regions. The influence of parameters such as pH, C/S (cosurfactant/surfactant) ratio, distribution coefficient, initial dye concentration, salinity, temperature, phases relative amounts, loading capacity of the microemulsion phase and dye reextraction rate has also been investigated. An experimental planning (Scheffé Net) was used to optimize the extraction process. The removal of color and metals reached levels as high as 99%

Estudo da influência de tensoativos em sistemas microemulsionados na extração de gálio e alumínio

Gallium is an important material used in the electronic industry whose demand in the world market is increasing in view of its potential applications. A selective technique is required to allow for the production of the metal, separated from aluminium. Due to the fact that microemulsions constitute an attractive alternative to metal extraction procedures, microemulsified systems have been employed as gallium-selective extraction agents. Two surfactants have been synthesized: sodium 12-N,N-diethylamino-9,10-dihydroxyestearate (AMINE) and saponified coconut oil (SCO), both produced from raw materials readily available in Northeastern Brazil. Also, the commercial extraction agent KELEX-100, conventionally used with the same purpose, has been used in this work for comparison. The optimization of the extraction process with microemulsions was carried out by investigating the influence of some parameters, namely the type of cosurfactant, the cosurfactant/surfactant (C/S) ratio, the pH and concentration of metals in the aqueous phase. Pseudoternary diagrams, which are representative of the microemulsified systems under study, have been constructed in order to establish the boundaries of the regions where the several Winsor systems are formed. An experimental planning methodology (Scheffé Net) has been used to optimize the extraction. The extraction percentage values were as high as 100% for gallium and 99.99% for aluminium for the system with KELEX-100; 96.6% for gallium and 98.8% for aluminium for the system containing AMINE; and 88% for gallium and 85% for aluminium for the system with SCO. The microemulsified system chosen for presenting the best results in gallium extraction was composed by SCO/isoamyl alcohol/kerosene/Bayer licquor with a C/S ratio of 28 and pH of the original aqueous phase of 6.0. The selectivity that has not been observed in the extraction stage was accomplished in the reextraction process using HCl. For the KELEX-100 system, gallium was reextracted at 100% with 6M HCl and aluminium was reextracted at 100% with 0.8M HCl. For the AMINE system, the reextraction percentages were also 100% for both metals, using 6M HCl for gallium and 0.5M HCl for aluminium. On the other hand, the reextraction percentages for the system with SCO were as high as 84% for gallium and 92% for aluminium, with HCl in the same concentrations as those used in the AMINE system. Finally, an optimized system was applied in the gallium extraction process employing a reciprocating perforated-plates extractor. As a result, the metal content was extracted at a recovery rate of 95% for gallium and 97% for aluminium

Tratamento de águas oleosas oriundas do processo de produção de óleo de dendê utilizando a flotação por ar dissolvido

This study was developed to evaluate the performance of different coagulant and pH dosages by applying the use of Dissolved Air Flotation (FAD) to enable its use in effluent treatment of the extraction process of palm oil. The study was developed in the laboratory, where studies about emulsions stability were made for the production of a synthetic effluent which best suit the characteristics of raw effluent. The synthetic water that would be used in the tests of FAD was produced, once the stability and characterization which best approached the raw wastewater was obtained. Trials tested three coagulant doses, combined with various pH ranges and five upward velocities (Va), finding an optimal range of this combination. Some operating parameters such as time and gradient of rapid mixing (20 s / 1000 s-1), time and gradient flotation (15 min / 60 s-1), chamber pressure saturation (450 kPa) and recirculation rate (20%) were set. In this way, samples were collected for analysis of the removal of turbidity parameters, suspended solids and oils and greases. This one is obtained by a correlation turbidity x oils and greases, referring to the previous analysis. The degree of removal obtained were 73,97% for turbidity, 51,4% for total suspended solids and 86,2% for oils and greases. Removal rates may be increased in later studies, by ranging the velocity gradient and flocculation parameters and the recirculation ratio, and by using lower flotation speeds to these effluent characteristics.

Teores elevados de metais potencialmente tóxicos em amostras de fertilizantes

A contaminação do solo por metais potencialmente tóxicos constitui um dos principais problemas ambientais. Por meio da lixiviação e percolação das águas, esses metais podem ser mobilizados e vir a contaminar mananciais superficiais e subterrâneos, comprometendo sua qualidade. A biodisponibilização desses metais para as plantas e, a partir dessas, para o homem é outro desfecho negativo dessa situação. O cádmio é um elemento tóxico. Os teores encontrados nos solos costumam não oferecer riscos. Porém, esses teores são potencializados pela utilização de fertilizantes. O níquel pode ser carcinogênico em doses elevadas. Sua presença em fertilizantes fosfatados proporciona maiores concentrações do metal no solo. É amplo o registro sobre efeitos do excesso desses metais, tanto em plantas, quanto em animais e no ser humano. O manganês é um dos elementos mais abundantes na crosta terrestre e se encontra largamente distribuído em solos, sedimentos, rochas, água e materiais biológicos. Contrariamente aos dois metais anteriores, esse micronutriente é um elemento essencial ao ser humano. Sua carência causa inúmeras enfermidades, por outro lado, seu excesso também. Nesse caso, poucos são os relatos sobre o assunto. Nesse estudo foram utilizados métodos de extração de metais de fertilizantes e se constatou que, quando presentes, os metais cádmio e níquel apresentaram concentrações proibitivas o que é motivo de preocupação e demonstra a falta de controle sobre a indústria de insumos agrícolas. Para o manganês não há parâmetros orientadores com limites de teores, mas com certeza, são necessários trabalhos nesse sentido para se evitar seu consumo indiscriminado.

Desenvolvimento de metodologia de extração e pré-concentração utilizando sistema microemulsionado para determinação de Cd, Co, Cu, Ni, Pb e Tl em águas naturais e produzidas por HR-CS AAS

The determination and monitoring of metallic contaminants in water is a task that must be continuous, leading to the importance of the development, modification and optimization of analytical methodologies capab le of determining the various metal contaminants in natural environments, because, in many cases, the ava ilable instrumentation does not provide enough sensibility for the determination of trace values . In this study, a method of extraction and pre- concentration using a microemulsion system with in the Winsor II equilibrium was tested and optimized for the determination of Co, Cd, P b, Tl, Cu and Ni through the technique of high- resolution atomic absorption spectrometry using a continuum source (HR-CS AAS). The optimization of the temperature program for the graphite furnace (HR-CS AAS GF) was performed through the pyrolysis and atomization curves for the analytes Cd, Pb, Co and Tl with and without the use of different chemical modifiers. Cu and Ni we re analyzed by flame atomization (HR-CS F AAS) after pre-concentr ation, having the sample introduction system optimized for the realization of discrete sampling. Salinity and pH levels were also analyzed as influencing factors in the efficiency of the extraction. As final numbers, 6 g L -1 of Na (as NaCl) and 1% of HNO 3 (v/v) were defined. For the determination of the optimum extraction point, a centroid-simplex statistical plan was a pplied, having chosen as the optimum points of extraction for all of the analytes, the follo wing proportions: 70% aqueous phase, 10% oil phase and 20% co-surfactant/surfactant (C/S = 4). After extraction, the metals were determined and the merit figures obtained for the proposed method were: LOD 0,09, 0,01, 0,06, 0,05, 0,6 and 1,5 μg L -1 for Pb, Cd, Tl, Co, Cu and Ni, re spectively. Line ar ranges of ,1- 2,0 μg L -1 for Pb, 0,01-2,0 μg L -1 for Cd, 1,0 - 20 μg L -1 for Tl, 0,1-5,0 μg L -1 for Co, 2-200 μg L -1 and for Cu e Ni 5-200 μg L -1 were obtained. The enrichment factors obtained ranged between 6 and 19. Recovery testing with the certified sample show ed recovery values (n = 3, certified values) after extraction of 105 and 101, 100 and 104% for Pb, Cd, Cu and Ni respectively. Samples of sweet waters of lake Jiqui, saline water from Potengi river and water produced from the oil industry (PETROBRAS) were spiked and the recovery (n = 3) for the analytes were between 80 and 112% confirming th at the proposed method can be used in the extraction. The proposed method enabled the sepa ration of metals from complex matrices, and with good pre-concentration factor, consistent with the MPV (allowed limits) compared to CONAMA Resolution No. 357/2005 which regulat es the quality of fresh surface water, brackish and saline water in Brazil.

Estudo de métodos de tratamento de efluentes (troca iônica e eletroquímico) separados e sequenciais para eliminação de derivados de petróleo

The produce of waste and the amount of the water produced coming from activities of petroleum production and extraction has been a biggest challenge for oil companies with respect to environmental compliance due to toxicity. The discard or the reuse this effluent containing organic compounds as BTEX (benzene, toluene, ethylbenzene and xylene) can cause serious environmental and human health problems. Thus, the objective this paper was study the performance of two process (separately and sequential) in one synthetic effluent for the benzene, toluene and xylene removal (volatile hydrocarbons presents in the produced water) through of electrochemical treatment using Ti/Pt electrode and exchange resin ionic used in the adsorption process. The synthetic solution of BTX was prepared with concentration of 22,8 mg L-1, 9,7 mg L-1 e 9,0 mg L-1, respectively, in Na2SO4 0,1 mol L-1. The experiments was developed in batch with 0.3 L of solution at 25ºC. The electrochemical oxidation process was accomplished with a Ti/Pt electrode with different current density (J = 10, 20 e 30 mA.cm-2). In the adsorption process, we used an ionic exchange resin (Purolite MB 478), using different amounts of mass (2,5, 5 and 10 g). To verify the process of technics in the sequential treatment, was fixed the current density at 10 mA cm-2 and the resin weight was 2.5 g. Analysis of UV-VIS spectrophotometry, chemical oxygen demand (COD) and gas chromatography with selective photoionization detector (PID) and flame ionization (FID), confirmed the high efficiency in the removal of organic compounds after treatment. It was found that the electrochemical process (separate and sequential) is more efficient than absorption, reaching values of COD removal exceeding 70%, confirmed by the study of the cyclic voltammetry and polarization curves. While the adsorption (separately), the COD removal did not exceed 25,8%, due to interactions resin. However, the sequential process (electrochemical oxidation and adsorption) proved to be a suitable alternative, efficient and cost-effectiveness for the treatment of effluents petrochemical.

Dissolução redutiva de minério de ferro por Acidithiobacillus ferrooxidans para a recuperação de metais de interesse econômico

Coordenação de Aperfeiçoamento de Pessoal de Nível Superior (CAPES)

Estudo da utilização de cinzas de biomassa (volantes e de fundo) na remoção de fosfatos

Dissertação para obtenção do Grau de Mestre em Engenharia do Ambiente, perfil Engenharia Sanitária

Estudo da valorização de cinzas de biomassa na produção de materiais para a construção de recifes artificiais

Dissertação para obtenção do Grau de Mestre em Energia e Bioenergia

Identificação e caracterização da repelência à água em alguns solos brasileiros

Desde 1986, vem-se observando o fenômeno de repelência à água, em amostras de horizontes coletadas para levantamentos de solos realizados pelo Departamento de Solos da Universidade Federal Rural do Rio de Janeiro (UFRRJ) e pela EMBRAPA - Centro Nacional de Pesquisa de Solos. Com o objetivo de estudar as causas desse fenômeno, selecionaram-se sete amostras de solo que, inicialmente, foram submetidas à avaliação do grau de repelência à água pelos métodos da molaridade de gotas de etanol e tempo de penetração de gotas de água no laboratório de solos da UFRRJ. A fim de identificar os compostos orgânicos responsáveis pelo fenômeno da repelência, foram empregados dois métodos de extração, os quais foram eficientes na retirada do caráter hidrofóbico das amostras. O primeiro teve por base o uso da partição isopropanol:água destilada, e o outro, desenvolvido pelos autores, empregou extrações simples com n-hexano, éter de petróleo e clorofórmio, além de partições n-hexano:água destilada e clorofórmio:água destilada. As substâncias extraídas foram analisadas no Instituto de Biociências da Universidade de São Paulo (USP). Os resultados indicam que as substâncias isoladas têm sua origem na vegetação local, sendo os alcanos de alto peso molecular os responsáveis pelo caráter hidrofóbico das amostras de solo.

Metais pesados em solos de área de rejeitos de indústria de processamento de zinco

Apesar de a poluição do solo ser amplamente constatada, estudos sobre as concentrações e formas dos metais pesados em solos e seus efeitos no ecossistema são ainda pouco enfatizados, principalmente em condições tropicais. O presente estudo foi desenvolvido em área de rejeitos de uma unidade de extração e industrialização de zinco pertencente à Companhia Mineira de Metais-CMM, em Três Marias (MG), com o objetivo de avaliar as quantidades e formas de metais pesados em sete locais representativos da área. Os locais foram selecionados para amostragem, baseando-se em diferenças na forma de contaminação, aspectos de solo, topografia e vegetação. Realizaram-se análises químicas de fracionamento de metais pesados e extrações simples com DTPA e Mehlich-1, buscando determinar os teores e formas dos metais na superfície e em profundidade e fazer inferências sobre o potencial de risco ambiental desses metais. Os teores totais dos metais nas camadas superficiais dos locais estudados foram, em média, de: 13.533 mg kg-1, para Zn; 170 mg kg-1, para Cd; 865 mg kg-1, para Cu, e 612 mg kg-1, para Pb, enquanto os teores trocáveis (MgCl2) nessas mesmas camadas variaram de 231 a 1.407 mg kg-1, para Zn; 14 a 390 mg kg-1, para Cd, e 11 a 33 mg kg-1, para Pb; o Cu raramente ocorreu nesta forma. Os solos dos locais estudados, com teores excessivos de Zn, Cd, Cu e Pb, são considerados poluídos. Em determinados locais contaminados por escoamento (superficial e subsuperficial) e arraste de material de solo e rejeito, a poluição mostrou-se mais evidente nas camadas superficiais. No local da ustulação, verificou-se maior percentagem de Zn trocável em todos os níveis de profundidade. Nos demais locais, o Cd apresentou também grandes concentrações nas formas trocáveis, razão por que tal elemento oferece maior risco de contaminação ambiental. De modo geral, a ocorrência de Zn foi maior nas formas carbonato e residual, enquanto o Cd predominou nas formas trocáveis e o Cu e Pb nas formas residuais. A extração dos metais por Mehlich-1 e DTPA correlacionou-se significativamente com a soma das extrações com MgCl2 e NaOAc do fracionamento, para praticamente todos os elementos analisados. Por essa razão, recomendam-se futuros estudos com aqueles extratores em termos de mensuração de metais potencialmente disponíveis ao ambiente.