Conciliação entre modelos de mecanismos avançados de oxidação eletroquímica

Many pollutants dumped in waterways, such as dyes and pesticides, have become so ubiquitous that they represent a serious threat to human health. The electrochemical oxidation is presented as an alternative clean, efficient and economic degradation of wastewater containing organic compounds and a number of advantages of this technique is to just not make use of chemical reagents, since only electrical energy is consumed during the removal of pollutants organic. However, despite being a promising alternative, still needs some tweaking in order to obtain better efficiency in the elimination of persistent pollutants. Thus, this study sought a relationship between a recently discovered phenomenon that reflects the participation of dissolved oxygen in solution in the electrochemical oxidation process, as an anomaly, present a kinetic model that shows instantaneous current efficiency (ICE) above 100% limited by theory, manifested for some experiments with phenolic compounds with H2SO4 or HClO4 as supporting electrolyte with electrodes under anodic oxidation on boron doped diamond (BDD). Therefore it was necessary to reproduce the data ICE exposes the fault model, and thus the 2-naphthol was used as phenolic compound to be oxidised at concentrations of 9, 12 and 15 mmol L-1, and H2SO4 and HClO4 to 1 mol L-1 as a supporting electrolyte under a current density of 30 mA cm-2 in an electrochemical reactor for continuous flow disk configuration, and equipped with anodes DDB at room temperature (25 oC). Experiments were performed using N2 like as purge gas for eliminate oxygen dissolved in solution so that its influence in the system was studied. After exposure of the anomaly of the ICE model and investigation of its relationship with dissolved O2, the data could be treated, making it possible for confirmation. But not only that, the data obtained from eletranálise and spectroscopic analysis suggest the involvement of other strongly oxidizing species (O3 (ozone) and O radicals and O2 -), since the dissolved O2 can be consumed during the formation of new strong oxidizing species, not considered until now, something that needs to be investigated by more accurate methods that we may know a little more of this system. Currently the performance of the electrocatalytic process is established by a complex interaction between different parameters that can be optimized, so it is necessary to the implementation of theoretical models, which are the conceptual lens with which researchers see

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.

Tecnologia eletroquímica como tratamento alternativo de efluentes têxteis sintéticos utilizando ânodos de platina e diamante

In this work, the treatment of synthetic wastewaters containing Remazol Red BR (RRB) and Novacron Blue C-D (NB) by anodic oxidation using boron doped diamond anodes (BDD) and Novacron Yellow (YN) using BDD and Platinum (Pt) anodes was investigated. Galvanostatic electrolyses of RRB and NB synthetic wastewaters have led to the complete decolorization removal at different operating conditions (current density, pH and temperature). The influence of these parameters was investigated in order to find the best conditions for dyestuff colour removal. According to the experimental results obtained, the electrochemical oxidation process is suitable for decolorizing wastewaters containing these textile dyes, due to the electrocatalytic properties of BDD and Pt anode. Energy requirements for removing colour during galvanostatic electrolyses of RRB, NB and YN synthetic solutions depends mainly on the operating conditions; for example for RRB, it passes from 3.30 kWh m-3 at 20 mA cm-2 to 4.28 kWh m-3 at 60 mA cm-2 (pH = 1); 15.23 kWh m-3 at 20 mA cm-2 to 24.75 kWh m-3 at 60 mA cm-2 (pH = 4.5); 10.80 kWh m-3 at 20 mA cm-2 to 31.5 kWh m-3 at 60 mA cm-2 (pH = 8) (data estimated per volume of treated effluent). In order to verify the Brazilian law regulations of NB and RRB synthetic solutions after electrochemical decolourisation treatment, Hazen Units values were determined and the total colour removal was achieved; remaining into the regulations. Finally, electrical energy cost for removing colour was estimated

Aplicação das técnicas eletroanalíticas (voltametria cíclica e de pulso diferencial) usando o eletrodo de diamante dopado com boro para o estudo da isoniazida, etambutol, rifampicina e pirazinamida

In this work a study was done using electrochemical cyclic voltammetry and differential pulse voltammetry for isoniazida (INH), ethambutol (EMB), rifampicina (RIF) and pyrazinamide (PZA) using the electrode boron-doped diamond (BDD) as working electrode. It also verified the applicability of the technique of differential pulse voltammetry in the quantification of the active compounds used in the treatment of tuberculosis, subsequently applying in samples of pharmaceutical formulation. Among the four active compounds studied, isoniazid showed the best results for the detection and quantification using differential pulse voltammetry. At pH 4 and pH 8, for the calibration curves to INH showed good linearity, with quantification limits of 6.15 mmol L-1 (0,844 ppm) and 4.08 mmol L-1 (0.560 ppm) for the respective pH. The proposed method can be used to determine drug isoniazid, for recovery values were obtained in approximately 100%

Estudo da participação das espécies fortemente oxidantes produzidas durante a oxidação eletroquímica de corantes usando eletrodo de diamante dopado com boro: função das propriedades eletroquímicas do eletrodo e condições experimentais

The textile industry is one of the most polluting in the world (AHMEDCHEKKAT et al. 2011), generating wastewater with high organic loading. Among the pollutants present in these effluents are dyes, substances with complex structures, toxic and carcinogenic characteristics, besides having a strong staining. Improper disposal of these substances to the environment, without performing a pre-treatment can cause major environmental impacts. The objective this thesis to use a technique of electrochemical oxidation of boron doped diamond anode, BDD, for the treatment of a synthetic dye and a textile real effluent. In addition to studying the behavior of different electrolytes (HClO4, H3PO4, NaCl and Na2SO4) and current densities (15, 60, 90 and 120 mA.cm-2 ), and compare the methods with Rhodamine B (RhB) photolysis, electrolysis and photoelectrocatalytic using H3PO4 and Na2SO4. Electrochemical oxidation studies were performed in different ratio sp3 /sp2 of BDD with solution of RhB. To achieve these objectives, analysis of pH, conductivity, UV-visible, TOC, HPLC and GC-MS were developed. Based on the results with the Rhodamine B, it was observed that in all cases occurred at mineralization, independent of electrolyte and current density, but these parameters affect the speed and efficiency of mineralization. The radiation of light was favorable during the electrolysis of RhB with phosphate and sulfate. Regarding the oxidation in BDD anode with different ratio sp3 /sp2 (165, 176, 206, 220, 262 e 329), with lower carbon-sp3 had a longer favoring the electrochemical conversion of RhB, instead of combustion. The greater the carbon content on the anodes BDD took the biggest favor of direct electrochemical oxidation

Tecnologia eletroquímica como tratamento alternativo de efluentes derivados da indústria têxtil e petroquímica

In this work, the treatment of wastewater from the textile industry, containing dyes as Yellow Novacron (YN), Red Remazol BR (RRB) and Blue Novacron CD (NB), and also, the treatment of wastewater from petrochemical industry (produced water) were investigated by anodic oxidation (OA) with platinum anodes supported on titanium (Ti/Pt) and boron-doped diamond (DDB). Definitely, one of the main parameters of this kind of treatment is the type of electrocatalytic material used, since the mechanisms and products of some anodic reactions depend on it. The OA of synthetic effluents containing with RRB, NB and YN were investigated in order to find the best conditions for the removal of color and organic content of the dye. According to the experimental results, the process of OA is suitable for decolorization of wastewaters containing these textile dyes due to electrocatalytic properties of DDB and Pt anodes. Removal of the organic load was more efficient at DDB, in all cases; where the dyes were degraded to aliphatic carboxylic acids at the end of the electrolysis. Energy requirements for the removal of color during OA of solutions of RRB, NB and YN depends mainly on the operating conditions, for example, RRB passes of 3.30 kWh m-3 at 20 mA cm-2 for 4.28 kWh m-3 at 60 mA cm-2 (pH = 1); 15.23 kWh m-3 at 20 mA cm-2 to 24.75 kWh m-3 at 60 mA cm-2 (pH 4.5); 10.80 kWh m-3 at 20 mA cm-2 to 31.5 kWh m-3 at 60 mA cm-2 (pH = 8) (estimated data for volume of treated effluent). On the other hand, in the study of OA of produced water effluent generated by petrochemical industry, galvanostatic electrolysis using DDB led to the complete removal of COD (98%), due to large amounts of hydroxyl radicals and peroxodisulphates generated from the oxidation of water and sulfates in solution, respectively. Thus, the rate of COD removal increases with increasing applied current density (15-60 mAcm-2 ). Moreover, at Pt electrode, approximately 50% removal of the organic load was achieved by applying from 15 to 30 mAcm-2 while 80% of COD removal was achieved for 60 mAcm-2 . Thus, the results obtained in the application of this technology were satisfactory depending on the electrocatalytic materials and operating conditions used for removal of organic load (petrochemical and textile effluents) as well as for the removal of color (in the case of textile effluents). Therefore, the applicability of electrochemical treatment can be considered as a new alternative like pretreatment or treatment of effluents derived from textiles and petrochemical industries.

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.

Remoção de nitratos em água utilizando diferentes materiais e processos

The need to preserve the environment has led to the search for new materials for efficient disposal of chemical compounds that alter the stability of our natural resources. Among these resources, stands in first place the water, as a precious commodity and scarce, leading to the proper use and reuse. As a result, the World Health Organization has established maximum permissible values in drinking water, such as: 50 mg/L, 0, 1 mg/L and 0, 5 mg/L to at-3, at-2, NH 4, respectively. For these reasons, assesses the implementation of new materials and water treatment processes aiming at the removal of these compounds, such as alumina, in the form of powder or as a support for a catalytic system using inorganic membranes capable of supporting more severe conditions of temperature and pressure by opening new possibilities for applications of membrane reactors; and also for electrochemical treatments with doped diamond bobo electrodes (BDD) as anode and copper as cathode. For such purpose, was conducted the study of adsorption of nitrate in different times to assess the time required to achieve equilibrium by employing three commercial alumina called: acidic, basic and neutral alumina, with subsequent treatment only in the acidic alumina impregnating metals (PdCu/Al2O3) for the catalytic reaction. The materials were previously characterized by XRD, SEM techniques and ABET. Aluminas presented a considerable adsortive capacity of nitrate in the first thirty minutes, equivalent to 50% of removal reaching equilibrium in that time. After treatment, using alumina as catalyst for the reaction in batch reactor (Pd-Cu/Al2O3), the results were more favourable, totalling 64% reduction of ion NO3-at the end of three hours. On the other hand, the results for the catalytic reaction using the catalytic support Pd-Cu/TiO2 in membrane reactor proved to be low. -if, in this way, improve the conditions of catalytic system to optimize the process. Already, for the electrochemical tests using DDB1 electrodes as anode, and Cu, as cathode, there was a fairly significant nitrate reduction, approximately 80% of ion removal during three hours and cost viable applications.