Estudo da eficiência eletroquímica para tratamento de chorume gerado em aterro sanitário brasileiro

This work was performing effluent degradation studies by electrochemical treatment. The electrochemical oxidation (EO) hydroquinone (H2Q) was carried out in acid medium, using PbO2 electrode by galvanostatic electrolysis, applying current densities of 10 and 30 mA/cm2 . The concentration of H2Q was monitored by differential pulse voltammetry (DPV). The experimental results showed that the galvanostatic electrolysis process performance significantly depends on the applied current density, achieving removal efficiencies of 100% and 80 % and 10 applying 30 mA/cm2 , respectively. Furthermore, the electroanalytical technique was effective in H2Q be used as a detection method. In order to test the efficiency of PbO2 electrode, the electrochemical treatment was conducted in an actual effluent, leachate from a landfill. The liquid waste leachate (600ml effluent) was treated in a batch electrochemical cell, with or without addition of NaCl by applying 7 mA/cm2 . The efficiency of EO was assessed against the removal of thermo-tolerant coliforms, total organic carbon (TOC), total phosphorus and metals (copper, cobalt, chromium, iron and nickel). These results showed that efficient removal of coliforms was obtained (100%), and was further decrease the concentration of heavy metals by the cathode processes. However, results were not satisfactory TOC, achieving low total removal of dissolved organic load. Because it is considered an effluent complex were developed other tests with this effluent to monitor a larger number of decontamination parameters (Turbidity, Total Solids, Color, Conductivity, Total Organic Carbon (TOC) and metals (barium, chromium, lithium, manganese and Zinc), comparing the efficiency of this type of electrochemical treatment (EO or electrocoagulation) using a flow cell. In this assay was compared to electro streaming. In the case of the OE, Ti/IrO2-TaO5 was used as the anode, however, the electrocoagulation process, aluminum electrodes were used; applying current densities of 10, 20 and 30 mA/cm2 in the presence and absence of NaCl as an electrolyte. The results showed that EO using Ti/IrO2–TaO5 was anode as efficient when Cl- was present in the effluent. In contrast, the electrocoagulation flow reduces the dissolved organic matter in the effluent, under certain experimental conditions.

Aplicação de tratamentos eletroquímicos integrados para remediação de solos e águas contaminadas com petróleo e pesticidas

Electrochemical technologies have been proposed as a promising alternative for the treatment of effluents and contaminated soils. Therefore, the objective of this work was to study the treatment of contaminated soils and wastewaters using electrochemical technologies. Thus, the study regarding the scale-up of the electrochemical system with continuous flow treatment of wastewater of the petrochemical industry was investigated using platinum electrodes supported on titanium (Ti / Pt), and boron-doped diamond (BDD). The results clearly showed that under the operating conditions studied and electrocatalytic materials employed, the better removal efficiency was achieved with BDD electrode reducing the chemical oxygen demand (COD) from 2746 mg L-1 to 200 mg L-1 in 5 h consuming 56.2 kWh m-3 . The decontamination of soils and effluents by petrochemical products was evaluated by studying the effects of electrokinetic remediation for removal of total petroleum hydrocarbons (HTP) from contaminated soil with diesel. The efficiency of this process was dependent on the electrolyte used Na2SO4 (96.46%), citric acid (81.36%) and NaOH (68.03%) for 15 days. Furthermore, the effluent after treatment of the soil was treated by electrochemical oxidation, achieving a good elimination of the organic polluting load dissolved. Depending on the physical behavior of wastewater contaminated with oil (emulsified state); atrazine emulsified effluents were investigated. The main characteristics of the effluent produced during the washing of contaminated soil were studied, being dependent on the surfactant dosage used; which determined its electrolytic treatment with BDD. The electrochemical oxidation of emulsified effluent of atrazine was efficient, but the key to the treatment is reducing the size of micelles.

Aplicação e otimização de métodos eletroquímicos combinados para remoção e determinação de cromo hexavalente em efluentes simulados

Hexavalent chromium is a heavy metal present in various industrial effluents, and depending on its concentration may cause irreparable damage to the environment and to humans. Facing this surrounding context, this study aimed on the application of electrochemical methods to determine and remove the hexavalent chromium (Cr6+) in simulated wastewater. To determine was applied to cathodic stripping voltammetry (CSV) using ultra trace graphite electrodes ultra trace (work), Ag/AgCl (reference) and platinum (counter electrode), the samples were complexed with 1,5- diphenylcarbazide and then subjected to analysis. The removal of Cr6+ was applied electrocoagulation process (EC) using Fe and Al electrodes. The variables that constituted the factorial design 24, applied to optimizing the EC process, were: current density (5 and 10 mA.cm-2), temperature (25 and 60 ºC), concentration (50 and 100 ppm) and agitation rate (400 and 600 RPM). Through the preliminary test it was possible the adequacy of applying the CSV for determining of Cr6+, removed during the EC process. The Fe and Al electrodes as anodes sacrifice showed satisfactory results in the EC process, however Fe favored complete removal in 30 min, whereas with Al occurred at 240 min. In the application of factorial design 24 and analysis of Response Surface Methodology was possible to optimize the EC process for removal of Cr6+ in H2SO4 solution (0.5 mol.L-1), in which the temperature, with positive effect, was the variable that presented higher statistical significance compared with other variables and interactions, while in optimizing the EC process for removal of Cr6+ in NaCl solution (0.1 mol.L-1) the current density, with positive effect, and concentration, with a negative effect were the variables that had greater statistical significance with greater statistical significance compared with other variables and interactions. The utilization of electrolytes supports NaCl and Na2SO4 showed no significant differences, however NaCl resulted in rapid improvement in Cr6+ removal kinetics and increasing the NaCl concentration provided an increase in conductivity of the solution, resulting in lower energy consumption. The wear of the electrodes evaluated in all the process of EC showed that the Al in H2SO4 solution (0.5 mol.L-1), undergoes during the process of anodization CE, then the experimental mass loss is less than the theoretical mass loss, however, the Fe in the same medium showed a loss of mass greater experimental estimated theoretically. This fact is due to a spontaneous reaction of Fe with H2SO4, and when the reaction medium was the NaCl and Na2SO4 loss experimental mass approached the theoretical mass loss. Furthermore, it was observed the energy consumption of all processes involved in this study had a low operating cost, thus enabling the application of the EC process for treating industrial effluents. The results were satisfactory, it was achieved complete removal of Cr6+ in all processes used in this study.

Estudo da produção eletroquímica de espécies de cloro ativo para tratamento de efluentes sintéticos

The treatment of wastewater is essential to human health. One of the most important steps is the disinfection treatment which uses chlorine to eliminate bacteria as required by environmental agencies. However, the identification of potentially toxic byproducts generated by this method, such as trihalomethanes, has stimulated the development of new alternative disinfection technologies. Among them, heterogeneous photocatalysis, TiO2 photocatalysis and electrochemical disinfection are considered suitable alternatives to the chlorination method. Thus, the present dissertation analyzes the evolution of active chlorine species in a synthetic NaCl solution and it is tested to treat a synthetic solution of the dye Reactive Blue 19 using boron-doped diamond (BDD) and ruthenium oxide (Ti/Ru0.3Ti0.7O2) as anodes. The indirect electrochemical process was discussed in terms of mineralization of the total organic load and percentage of color removal in order to evaluate the applicability of electrochemical technology. Electrochemical experiments were carried out with different current densities (25, 50 and 75 mA.cm-2) during 120 minutes. On the other hand, other important parameter in this study was the influence of the proportion sp3/sp2 on BDD anode on the performance of the evolution of active chlorine species which was investigated by electrolytic techniques (linear polarization), with the intention of determining the related training oxidizing species and consumption energy to chemical or electrochemical reactions. From the results, it can be noted that the BDD electrode showed better efficiency throughout the electrochemical process.

Estudo da produção eletroquímica de espécies de cloro ativo para tratamento de efluentes sintéticos

The treatment of wastewater is essential to human health. One of the most important steps is the disinfection treatment which uses chlorine to eliminate bacteria as required by environmental agencies. However, the identification of potentially toxic byproducts generated by this method, such as trihalomethanes, has stimulated the development of new alternative disinfection technologies. Among them, heterogeneous photocatalysis, TiO2 photocatalysis and electrochemical disinfection are considered suitable alternatives to the chlorination method. Thus, the present dissertation analyzes the evolution of active chlorine species in a synthetic NaCl solution and it is tested to treat a synthetic solution of the dye Reactive Blue 19 using boron-doped diamond (BDD) and ruthenium oxide (Ti/Ru0.3Ti0.7O2) as anodes. The indirect electrochemical process was discussed in terms of mineralization of the total organic load and percentage of color removal in order to evaluate the applicability of electrochemical technology. Electrochemical experiments were carried out with different current densities (25, 50 and 75 mA.cm-2) during 120 minutes. On the other hand, other important parameter in this study was the influence of the proportion sp3/sp2 on BDD anode on the performance of the evolution of active chlorine species which was investigated by electrolytic techniques (linear polarization), with the intention of determining the related training oxidizing species and consumption energy to chemical or electrochemical reactions. From the results, it can be noted that the BDD electrode showed better efficiency throughout the electrochemical process.

Degradação de paracetamol empregando tecnologia oxidativa avançada baseada em fotocatálise heterogênea usando irradiação artificial e solar

In this work, the oxidation and mineralization of paracetamol, based in an advanced oxidative process promoted by heterogeneous photocatalysis, was evaluated. The action of two photocatalysts (titanium dioxide, and a composite based on the association between titanium dioxide and zinc phthalocyanine dye) was studied. First of all, experiments in laboratory scale were performed using as radiation font a 400 W high pressure mercury lamp. The mineralization of paracetamol, promoted by both photocatalysts, was evaluated working with 4L of solution containing 10 mg L-1 of paracetamol and 100 mg L-1 of photocatalyst. To find the best experimental conditions, the influence of hydrogen peroxide concentration and pH was evaluated for the reactions. The best results for the reactions in laboratory scale was obtained using 33,00 mg L-1 of hydrogen peroxide in natural pH (6,80). Under these conditions, 100% oxidation was reached in just 40 minutes of reaction using TiO2 P25, while the mineralization was 78%. Using the composite, the mineralization was 63% in 2 hours of reaction and a oxidation of almost 100% was reached after 60 minutes. A CPC reactor (compound parabolic concentrator) was employed in the expanded work scale, using the sun as irradiation source. In this case the experiments were performed using 50 L of aqueous solution containing 10 mg L-1 of paracetamol and 100 mg L-1 of photocatalyst. The assays were done at pH 3,00 and natural pH (6,80). The used concentration of hydrogen peroxide was 33,00 mg L-1, adopted after laboratory scale studies. The reaction at pH 3,00 shows to be more advantageous, since under natural pH (6,80), the use of deionized water was necessary to prepare the solutions, probably because the deleterious action of carbonate ions, known hydroxyl radical scavengers. Using solar irradiation, the reaction mediated by the composite was more efficient when compared with the assays under laboratory scale since the composite presents the advantage of promoting a better use of visible radiation. Under these conditions, the mineralization increased from 40% to 56% under pH 3,00. At natural pH the oxidation occurred more slowly and the mineralization decreased from 56% to 50%. Thus, the use of pH 3,00 will be more interesting in real scale applications, even if it is necessary the pH correction before the discard of the treated effluent to the environment.

Determinação voltamétrica de zinco empregando eletrodos quimicamente modificados com bismuto

This dissertation presents the development of voltammetric methods to zinc determination in multivitamin commercial samples, talc, and art materials for painting (soft pastel) combining an alkaline extraction with 1.0 mol L-1 NaOH aqueous solution and bismuth modified electrodes. Two electrodes were used to zinc quantification in the samples, bismuth film electrode (BiFE) plated in situ onto glassy carbon and carbon paste electrode chemically modified with strongly acidic ion exchange resin Amberlite® IR 120 and bismuth nanostructures (EPCAmbBi). It was verified that the best concentration of Bi3+ for Bi film deposition onto glassy carbon was 4.0 μmol L-1 using an 0.1 mol L-1 acetate buffer aqueous solution (pH = 4.5) as supporting electrolyte. The best condition to formation of Bi nanostructures in the EPC modified with 10 % Amberlite® IR 120 was the use of 30 s to pre-concentration (open circuit) in 0.5 mmol L-1 Bi3+ aqueous solution (pH 5.5) prepared with supporting electrolyte solution. The obtained analytical curve for Zn2+ using BiFE presented linear range from 0.5 to 5.0 μmol L-1, the limit of detection (LD) was 41 nmol L-1. For EPCAmbBi only one linear range was observed for the analytical curve varying the Zn2+ concentration from 0.05 to 8.2 μmol L-1, LD obtained in this curve it was equal to 10 nmol L-1. The EPCAmbBi presented the most intense and sharp anodic stripping peaks for Zn2+ presenting, therefore, a better voltammetric profile, with sensitivity higher than obtained with the BiFE. Moreover, the EPCAmbBi presented a LD lower than that obtained with the BiFE. Alkaline extraction was an efficient sample pretreatment to extract Zn2+ from solid samples, besides that, this procedure was less susceptible to interferences from Cu2+, since it remains at extracting vessel as insoluble Cu(OH)2. The combination of alkaline extraction with the EPCAmbBi is a simple, fast, efficient and low cost for the zinc determination in pharmaceutical formulations and art materials for painting (soft pastel) samples, which can be employed as a low-cost alternative method to the atomic absorption spectroscopy.

Avaliação das condições de precipitação do azul da Prússia sobre pó de grafite visando o desenvolvimento de eletrodos de pasta de carbono para a quantificação de nitrito

An amperometric FIA method for nitrite quantification based on nitrite electroreduction and employing a carbon paste electrode (CPE) chemically modified with iron hexacyanoferrate (HCF) as an amperometric detector was developed. The influence of experimental conditions on the preparation of the electrode materials was evaluated and the materials obtained in each study were used for the development of modified electrodes. The electrochemical sensors were prepared by a fast, simple, and inexpensive procedure, and the long-term performance of the electrodes were quite satisfactory as the stability was maintained over one year. HCF was an effective redox mediator for nitrite electroreduction in acidic media, allowing nitrite detection at +0.2 V vs. Ag/AgClsat, which is a potential free of possible interfering species that are normally present in food and water samples. The electrochemical cell used in the FIA system was similar to a batch injection analysis cell, enabling recirculation of the carrier solution. This is an attractive feature because it allows the use of a high flow rate (6 mL min-1) leading to high sensitivity and analysis speed, while keeping reagent consumption low. The proposed method had a detection limit of 9 μmol L-1 and was successfully employed for nitrite quantification in spiked water and sausage samples. The obtained results were in good agreement with those provided by the spectrophotometric official method. At a 95 % confidence level it was not observed statistical differences neither in nitrite content nor in the precision provided by both methods. The experimental conditions for the synthesis of HCF were optimized and the best electrode material was prepared by mixing FeCl3, K4[Fe(CN)6] and carbon powder subjected to an acid and thermal treatment (400 ºC), followed by ultrasonic agitation at 4 °C. This material was used to construct an electrode with improved analytical performance to reduce nitrite, which presented greater stability compared to HCF film electrodeposited on the EPC, showing that the preparation procedure of the electrode material is an effective strategy for the development of HCF modified electrodes.

Metal transfer mapping for FCAW process by using near-infrared filming

In the Flux Cored Arc Welding (FCAW) process, the transfer of filler metal (metal transfer modes) to the base material to accomplish the weld bead determines the weld quality and therefore studies of such phenomena is demanded. Thus, in this work, the metal transfer through the FCAW process is investigated by filming the phenomena with the assist of near infrared visualization. During the literature survey, it was found that this technic has not been used so far for analyzing the FCAW process. It must be pointed out that the radiation emitted from the weld arc, fumes and particles (spattering) in this process represent a barrier for these studies based in the process visualization. The monitoring of metal transfer for FCAW process was carried out within the operational envelope of voltage and wire feed speed with the electrode E71T-1 (1.2 mm diameter) and Ar+25%CO2 as a shielding gas. A local developed near infrared filming with frame rate of 300 Hz was employed for metal transfer visualization in order to contribute to a better understanding of this process and evaluating characteristics of metal transfer, unlike previous studies, which used shadowgraph technique. It can clearly be seen how the droplet is created and transferred in this process and also identify the different modes of metal transfer by changing the parameters of voltage and wire feed speed in metal transfer maps. The final result of this study is the metal transfer mode maps, which establish suitable conditions and provide the basis for developing arc control strategies for the FCAW process.

Atividade β-D-N-Acetilglucosaminidásica de enzimas imobilizadas extraídas da Artemia franciscana e possíveis aplicações biotecnológicas

A β-D-N-acetilglucosaminidase extracted and partially isolated from crustacean Artemia franciscana by ammonium sulfate precipitation and filtration gel chromatography Bio Gel A 1.5m. the enzyme was immobilized on ferromagnetic Dacron yielding a insoluble active derivative with 5.0 units/mg protein and 10.35% of the soluble enzyme activity. β-D-N-acetilglucosaminidase-ferromagnetic Dacron was easily removed from the reaction mixture by a magnetic field, it was reused for ten times without loss in its activity. The ferromagnetic Dacron was better activated at pH 5.0. The particles visualized at scanning electron microscope (SEM) had presented different sizes, varying between 721nm and 100µm. Infra red confirmed immobilization on support, as showed by primary amino peaks at 1640 and 1560 cm-1 . The immobilize enzyme presented Km of 2.32 ± 0.48 mM and optimum temperature of 50°C. Bought presented the same thermal stable of the soluble enzyme and larger enzymatic activity at pH 5.5. β-D-N-acetilglucosaminidase-Dacron ferromagnético showed sensible for some íons as the silver (AgNO3), with loss of activity. The β-D-N acetilglucosaminidase activity for mercury chloride (HgCl2), whom is one of the most toxic substance joined in nature, it was presented activity already diminished at 0,01mM and lost total activity at 4mM, indicating sensitivity for this type of metal. β-D-N-acetilglucosaminidase-ferromagnetic Dacron showed degradative capacity on heparan sulfate, the enzyme still demonstrated degradative capacity on heparan sulphate, suggesting a possible application to produce fractions of this glycosaminoglycan

Estudo espectroeletroquímico da eletroredução de CO2 em meio de líquidos iônicos

Tese (doutorado)–Universidade de Brasília, Instituto de Química, Programa de Pós-Graduação em Química, 2015.

Purificação e caracterização de uma ß-N-acetillhexosaminadase extraída do mamífero marinho Sotalia fluviatilis

This report shows 2232 times purification of a βNAcetylhexosaminidase from hepatic extracts from the sea mammal Sotalia fluviatilis homogenate with final recovery of 8,4%. Sequenced steps were utilized for enzyme purification: ammonium sulfate fractionation, Biogel A 1.5 m, chitin, DEAESepharose and hydroxyapatite chromatographies. The protein molecular mass was estimated in 10 kDa using SDSPAGE and confirmed by MALDITOF. It was found to have an optimal pH of 5.0 and a temperature of 60°C. Using pnitrophenylNAcetylβDglycosaminide apparent Km and Vmax values were of 2.72 mM and 0.572 nmol/mg/min, respectively. The enzyme was inhibited by mercury chloride (HgCl2) and sodium dodecil sulfate (SDS)

Microstructural-based approach to the interpretation of clays and transitional soils behaviour

Tese (doutorado)—Universidade de Brasília, Faculdade de Tecnologia, Departamento de Engenharia Civil e Ambiental, 2016.

Análise e avaliação dos elementos de penetração no solo de equipamentos rodoviários após revestimento

The main objective is to analyze the abrasive wear resistance to the low stress of the elements that make up the organs of road machinery that are exposed directly to contact with abrasives. These samples were analyzed after these elements are coated superficially by the process of welding electrode coated with (SAER) and the manual process of coating type LVOF thermal spraying. As well, is to provide suggestions for a better recovery and return of these elements, which are reducing costs and avoiding downtime in the fronts of service. The samples were made from a substrate of carbon ABNT 1045 tempered steel, following the same specifications and composition of metals and alloys of constituents was followed the standard governing the dimensions of these samples and in accordance with the corresponding size. The results were evaluated by testing the hardness, abrasion resistance to wear by the low stress and the loss of volume involving the microstructure of coatings analyzed