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M. Tech. (Chemical Engineering, Faculty of Engineering and Technology), Vaal University of Technology. / A novel technology in the treatment of river water, which involves an electrochemical treatment technique to produce domestic or drinking water is being investigated using aluminium and iron electrodes in an electrochemical circuit. Coagulation and flocculation are traditional methods for the treatment of polluted water. Electrocoagulation presents a robust novel and innovative alternative in which a sacrificial metal anode treats water electrochemically. This has the major advantage of providing mainly active cations required for coagulation and flocculation, without increasing the salinity of the water. Electrocoagulation is a complex process with a multitude of mechanisms operating synergistically to remove pollutants from the water. A wide variety of opinions exist in the literature for key mechanisms. A lack of a systematic approach has resulted in a myriad of designs for electrocoagulation reactors without due consideration of the complexity of the system. A systematic, holistic approach is required to understand electrocoagulation and its controlling parameters. An electrocoagulation-flotation process has been developed for water treatment. This involved an electrolytic reactor with aluminium and/or iron electrodes. The water to be treated (river water) was subjected to coagulation, by Al(III) and Fe(II) ions dissolved from the electrodes, resulting in floes floating after being captured by hydrogen gas bubbles generated at the cathode surfaces. Apparent current efficiencies for AI and Fe dissolution as aqueous Al(III) and Fe(II) species at pH 6.5 and 7.8 were greater than unity. This was due to additional chemical reactions occurring parallel with electrochemical AI and Fe dissolution: oxygen reduction at anodes and cathodes, and hydrogen evolution at cathodes, resulting in net (i.e. oxidation plus reduction) currents at both anodes and cathodes. Investigation results illustrate the feasibility of ferrous and aluminium ion electrochemical treatment as being a successful method of water treatment. Better results were achieved under conditions of relatively high raw water alkalinity, relatively low raw water turbidity, and when high mixing energy conditions were available.

Made available in DSpace on 2014-12-17T15:42:20Z (GMT). No. of bitstreams: 1 JonasAB_DISSERT.pdf: 1695862 bytes, checksum: 814d00e46b0fb400b2ca97afa17cf2f1 (MD5) Previous issue date: 2014-03-31 / Petr?leo Brasileiro SA - PETROBRAS / This work is directed to the treatment of organic compounds present in produced water from oil using electrochemical technology. The water produced is a residue of the petroleum industry are difficult to treat , since this corresponds to 98 % effluent from the effluent generated in the exploration of oil and contains various compounds such as volatile hydrocarbons (benzene, toluene, ethylbenzene and xylene), polycyclic aromatic hydrocarbons (PAHs), phenols, carboxylic acids and inorganic compounds. There are several types of treatment methodologies that residue being studied, among which are the biological processes, advanced oxidation processes (AOPs), such as electrochemical treatments electrooxidation, electrocoagulation, electrocoagulation and eletroredution. The electrochemical method is a method of little environmental impact because instead of chemical reagents uses electron through reactions of oxide-reducing transforms toxic substances into substances with less environmental impact. Thus, this paper aims to study the electrochemical behavior and elimination of the BTX (benzene, toluene and xylene) using electrode of Ti/Pt. For the experiment an electrochemical batch system consists of a continuous source, anode Ti/Pt was used, applying three densities of current (1 mA/cm2, 2,5 mA/cm2 and 5 mA/cm2). The synthetic wastewater was prepared by a solution of benzene, toluene and xylene with a concentration of 5 ppm, to evaluate the electrochemical behavior by cyclic voltammetry and polarization curves, even before assessing the removal of these compounds in solution by electrochemical oxidation. The behavior of each of the compounds was evaluated by the use of electrochemical techniques indicate that each of the compounds when evaluated by cyclic voltammetry showed partial oxidation behavior via adsorption to the surface of the Ti/Pt electrode. The adsorption of each of the present compounds depends on the solution concentration but there is the strong adsorption of xylene. However, the removal was confirmed by UV-Vis, and analysis of total organic carbon (TOC), which showed a percentage of partial oxidation (19,8 % - 99,1 % TOC removed), confirming the electrochemical behavior already observed in voltammetry and cyclic polarization curves / O presente trabalho ? dirigido ao tratamento de compostos org?nicos presentes na ?gua produzida de petr?leo usando a tecnologia eletroqu?mica. A ?gua produzida ? um res?duo da ind?stria do petr?leo de dif?cil tratamento, j? que este efluente corresponde a 98 % do efluente gerado na explora??o do petr?leo e cont?m v?rios compostos, tais como hidrocarbonetos vol?teis (benzeno, tolueno, etilbenzeno e xileno), hidrocarbonetos polic?clicos arom?ticos (HPAs), fen?is, ?cidos carbox?licos e compostos inorg?nicos. Existem v?rios tipos de metodologias de tratamento desse res?duo sendo estudadas, dentre elas est?o os processos biol?gicos, os processos de oxida??o avan?ados (POAS), tratamentos eletroqu?micos como eletroxida??o, eletrocoagula??o, eletroflota??o e eletroredu??o. O tratamento eletroqu?mico ? um m?todo ambientalmente correto, pois em vez de reagentes qu?micos utiliza o el?tron que atrav?s de rea??es de oxido redu??o transforma as subst?ncias t?xicas em subst?ncias de menor impacto ambiental. Assim, este trabalho se prop?e a estudar o comportamento eletroqu?mico e a degrada??o dos BTX (benzeno, tolueno e xileno) usando o eletrodo de Ti/Pt. Para os experimentos foi utilizado um sistema eletroqu?mico em batelada composto por uma fonte de corrente cont?nua, ?nodo de Ti∕Pt, aplicando tr?s densidades de corrente (1,0 mA/cm2, 2,5 mA/cm2 e 5,0 mA/cm2). O efluente sint?tico foi preparado mediante uma solu??o de benzeno, tolueno e xileno com concentra??o de 5 ppm, com objetivo de avaliar o comportamento eletroqu?mico atrav?s de voltametria c?clica e curvas de polariza??o, antes mesmo de avaliar a remo??o desses compostos em solu??o atrav?s de oxida??o eletroqu?mica. O comportamento de cada um dos compostos foi avaliado mediante o uso de t?cnicas eletroqu?micas indicando que cada um dos compostos quando avaliado por voltametria c?clica, mostrou um comportamento de oxida??o parcial via adsor??o na superf?cie do eletrodo de Ti/Pt. A adsor??o de cada um dos compostos depende da concentra??o presente em solu??o, mas destaca-se a forte adsor??o do xileno. Entretanto, a remo??o foi comprovada atrav?s de espectrofotometria UV-Vis, e analises de carbono org?nico total (COT), os quais mostraram um percentual de oxida??o parcial (de 19,8 a 99,1% de COT removido), confirmando o comportamento eletroqu?mico j? observado na voltametria c?clica e curvas de polariza??o

Made available in DSpace on 2014-12-17T15:41:49Z (GMT). No. of bitstreams: 1 JulianaPSDP_DISSERT.pdf: 1777680 bytes, checksum: 11814e53360b103c7198cf617f2a583c (MD5) Previous issue date: 2010-07-06 / The aim of this work is the treatment of produced water from oil by using electrochemical technology. Produced water is a major waste generated during the process of exploration and production in the oil industry. Several approaches are being studied aiming at the treatment of this effluent; among them can be cited the biological process and chemical treatments such as advanced oxidation process and electrochemical treatments (electrooxidation, electroflotation, electrocoagulation, electrocoagulation). This work studies the application of electrochemical technology in the treatment of the synthetic produced water effluent through the action of the electron, in order to remove or transform the toxic and harmful substances from the environment by redox reactions in less toxic substances. For this reason, we used a synthetic wastewater, containing a mixture H2SO4 0,5M and 16 HPAs, which are: naphthalene, acenaphthylene, acenaphthene, fluorene, phenanthrene, anthracene, fluoranthene, pyrene, benzo (a) anthracene, chrysene, benzo(b)fluoranthene, benzo(k) fluoranthene, benzo(a)pyrene, indeno(1,2,3-cd)pyrene, dibenzo(a, h)anthracene, benzo(g, h, i)perylene. Bulk electrochemical oxidation experiments were performed using a batch electrochemical reactor containing a pair of parallel electrodes, coupled with a power supply using a magnetic stirrer for favoring the transfer mass control. As anodic material was used, a Dimensionally Stable Anode (DSA) of Ti/Pt, while as cathode was used a Ti electrode. Several samples were collected at specific times and after that, the analysis of these samples were carried out by using Gas Chromatography Coupled to Mass Spectrometry (GC - MS) in order to determine the percentage of removal. The results showed that it was possible to achieve the removal of HPAs about 80% (in some cases, more than 80%). In addition, as an indicator of the economic feasibility of electrochemical treatment the energy consumption was analyzed for each hour of electrolysis, and based on the value kWh charged by ANEEL, the costs were estimated. Thus, the treatment costs of this research were quite attractive / O presente trabalho ? dirigido ao tratamento de ?gua produzida de petr?leo usando uma tecnologia eletroqu?mica. A ?gua produzida ? um dos principais res?duos gerados durante o processo de explora??o e produ??o na ind?stria petrol?fera, onde corresponde a 98 % de todos os efluentes gerados. V?rias metodologias est?o sendo estudadas visando o tratamento desse efluente, dentre elas est?o os processos biol?gicos, os processos de oxida??o avan?ados (POAs), tratamentos eletroqu?micos como eletrooxida??o, eletrocoagula??o, eletroflota??o e eletroredu??o. Esse trabalho mostra a aplica??o da tecnologia de eletrooxida??o no tratamento da ?gua produzida, pois se trata de uma t?cnica com alta compatibilidade ambiental, onde atrav?s da a??o do pr?prio el?tron, as subst?ncias t?xicas e nocivas ao meio ambiente podem ser removidas ou transformadas atrav?s de rea??es de ?xido-redu??o em subst?ncias menos t?xicas. Para isso, foi utilizado efluente sint?tico contendo uma mistura de H2SO4 0,5M e de 16 hidrocarbonetos polic?clicos arom?ticos (HPAs), que s?o: naftaleno, acenaftileno, acenafteno, fluoreno, fenantreno, antraceno, fluoranteno, pireno, benzo(a)antraceno, criseno, benzo(b)fluoranteno, benzo(k)fluoranteno, benzo(a)pireno, indeno(1,2,3-cd)pireno, dibenzo(a,h)antraceno, benzo(g,h,i)perileno. Utilizou-se o processo de oxida??o eletroqu?mica com um reator eletroqu?mico em batelada contendo um par de eletrodos paralelos, acoplados a uma fonte de corrente cont?nua e usando um agitador magn?tico para favorecer o transporte de massa na solu??o sint?tica. Como material an?dico utilizou-se um eletrodo de ?nodo dimensionalmente est?vel (DSA), constitu?do de Ti/Pt, enquanto o material cat?dico foi o Ti. Para detec??o e quantifica??o dos HPAs utilizou ? t?cnica de cromatografia gasosa acoplada a espectrometria de massa (CG - EM), onde o efluente foi analisado antes e ap?s o tratamento eletroqu?mico. Os resultados se mostraram eficazes, obtendo-se remo??es significativas dos HPAs superiores a 80%. Como indicador da viabilidade econ?mica do tratamento eletroqu?mico foram analisados os consumos energ?ticos do processo para cada hora do tratamento eletroqu?mico com base no valor kWh cobrado pela ANEEL. Os custos dos tratamentos desta pesquisa foram bastantes atrativos

Electrocatalysis is key to both sensitive electrochemical sensing and efficient electrochemical energy conversion. Despite high catalytic activity, traditional metal catalysts have poor stability, low selectivity, and high cost. Metal-free, carbon-based materials are emerging as alternatives to metal-based catalysts because of their attractive features including natural abundance, environmental friendliness, high electrical conductivity, and large surface area. Altering surface functionalities and heteroatom doping are effective ways to promote catalytic performance of carbon-based catalysts. The first chapter of this dissertation focuses on developing electrode modification methods for electrochemical sensing of biomolecules. After electrochemical pretreatment, glassy carbon demonstrates impressive figures-of-merit in detecting small, redox-active biomolecules such as DNA bases and neurotransmitters. The results highlight a simplified surface modification procedure for producing efficient and highly selective electrocatalysts. The next four chapters focus on evaluating nitrogen-doped carbon nano-onions (𝑛-CNOs) as electrocatalysts for oxygen reduction and CO2 reduction. 𝑛-CNOs exhibit excellent electrocatalytic performance toward O2 to H2O reduction, which is a pivotal process in fuel cells. 𝑛-CNOs demonstrate excellent resistance against CO poisoning and long-term stability compared to state-of-the-art Pt/C catalysts. In CO2 electrochemical conversion, 𝑛-CNOs demonstrate significant improvement in catalytic performance toward reduction of CO2 to CO with a low overpotential and high selectivity. The outstanding catalytic performance of 𝑛-CNOs originates from the asymmetric charge distribution and creation of catalytic sites during incorporation of nitrogen atoms. High contents of pyridinic and graphitic N are critical for high catalytic performance. This work suggests that carbon-based materials can be outstanding alternatives to traditional metal-based electrocatalysts when their microstructures and surface chemistries are properly tailored.

Made available in DSpace on 2014-12-17T14:08:31Z (GMT). No. of bitstreams: 1 AdrianaMZR.pdf: 1640551 bytes, checksum: 6e342552b459e9af8b4b603e028a87b3 (MD5) Previous issue date: 2008-08-01 / The production of water has become one of the most important wastes in the petroleum industry, specifically in the up stream segment. The treatment of this kind of effluents is complex and normally requires high costs. In this context, the electrochemical treatment emerges as an alternative methodology for treating the wastewaters. It employs electrochemical reactions to increase the capability and efficiency of the traditional chemical treatments for associated produced water. The use of electrochemical reactors can be effective with small changes in traditional treatments, generally not representing a significant additional surface area for new equipments (due to the high cost of square meter on offshore platforms) and also it can use almost the same equipments, in continuous or batch flow, without others high costs investments. Electrochemical treatment causes low environmental impact, because the process uses electrons as reagent and generates small amount of wastes. In this work, it was studied two types of electrochemical reactors: eletroflocculation and eletroflotation, with the aim of removing of Cu2+, Zn2+, phenol and BTEX mixture of produced water. In eletroflocculation, an electrical potential was applied to an aqueous solution containing NaCl. For this, it was used iron electrodes, which promote the dissolution of metal ions, generating Fe2+ and gases which, in appropriate pH, promote also clotting-flocculation reactions, removing Cu2+ and Zn2+. In eletroflotation, a carbon steel cathode and a DSA type anode (Ti/TiO2-RuO2-SnO2) were used in a NaCl solution. It was applied an electrical current, producing strong oxidant agents as Cl2 and HOCl, increasing the degradation rate of BTEX and phenol. Under different flow rates, the Zn2+ was removed by electrodeposition or by ZnOH formation, due the increasing of pH during the reaction. To better understand the electrochemical process, a statistical protocol factor (22) with central point was conducted to analyze the sensitivity of operating parameters on removing Zn2+ by eletroflotation, confirming that the current density affected the process negatively and the flow rate positively. For economical viability of these two electrochemical treatments, the energy consumption was calculated, taking in account the kWh given by ANEEL. The treatment cost obtained were quite attractive in comparison with the current treatments used in Rio Grande do Norte state. In addition, it could still be reduced for the case of using other alternative energy source such as solar, wind or gas generated directly from the Petrochemical Plant or offshore platforms / A produ??o de ?gua tem sido a maior corrente de res?duos da ind?stria do petr?leo no segmento de Explora??o e Produ??o E&P. O tratamento deste efluente al?m de ser complexo, requer um alto custo. Neste contexto, surge o tratamento eletroqu?mico como uma metodologia alternativa que empregando rea??es de eletr?lise possibilita aumentar a capacidade e a efici?ncia do tratamento f?sico-qu?mico tradicional da ?gua produzida. A implanta??o de reatores eletroqu?micos pode ser efetivada com pequena modifica??o numa esta??o de tratamento tradicional, sem demandar ?rea significativa (tendo em vista o alto custo do metro quadrado nas plataformas em alto mar), aproveitando os equipamentos existentes, podendo realizar tratamento cont?nuo ou em bateladas, sem a necessidade de investimentos elevados. O tratamento eletrol?tico causa baixo impacto ambiental, pois o processo utiliza el?trons como reagente e gera poucos res?duos. Neste trabalho foram estudados dois tipos de reatores eletroqu?micos: um eletrofloculador e um eletroflotador, tendo como objetivo a remo??o de Cu2+, Zn2+ , fenol e BTEX presentes na ?gua produzida. No eletrofloculador aplicou-se um potencial el?trico a uma solu??o aquosa contendo NaCl, atrav?s de eletrodos de ferro, que promovendo a dissolu??o deste metal com a gera??o de ?ons Fe2+ e gases que em pH apropriado formou rea??es de coagula??o-flocula??o removendo Cu2+ e Zn2+. No eletroflotador utilizou-se c?todo de a?o carbono e ?nodo do tipo DSA de Ti/TiO2-RuO2-SnO2, em solu??o contendo NaCl, que atrav?s de uma corrente el?trica produziu agentes oxidantes fortes como Cl2 e HOCl que ajudaram a degradar o BTEX e fenol em diferentes vaz?es; o Zn2+ foi removido por eletrodeposi??o ou pela forma??o de ZnOH devido ao aumento de pH durante a rea??o. Para compreender o processo eletroqu?mico foi realizado um planejamento fatorial 22 com ponto central para avaliar a sensibilidade dos par?metros operacionais que influenciaram no processo de remo??o de Zn2+ na eletroflota??o, de forma que a densidade de corrente influenciou positivamente e a vaz?o negativamente. Como indicador da viabilidade econ?mica do tratamento eletroqu?mico foram analisados os consumos energ?ticos dos reatores tomando como base o valor kWh cobrado pela ANEEL. Os custos dos tratamentos desta pesquisa foram mais atrativos quando comparados ao utilizado atualmente no Rio Grande do Norte, podendo ser reduzidos caso seja utilizada fontes de energia alternativas, como solar, e?lica ou a g?s gerada no pr?prio P?lo Petroqu?mico ou plataformas

Made available in DSpace on 2014-12-17T14:08:56Z (GMT). No. of bitstreams: 1 PatriciaRFC_DISSERT.pdf: 3052706 bytes, checksum: 187fb21e02f9cda7fb573aba65cc8c25 (MD5) Previous issue date: 2014-02-06 / Coordena??o de Aperfei?oamento de Pessoal de N?vel Superior / A polui??o das ?guas decorrentes do contato com os derivados de petr?leo em postos de combust?vel tem se apresentado como um problema agravante. Cada vez mais estudos relacionam problemas ambientais com essas situa??es e procuram propor algumas solu??es para o tratamento das ?guas e solos que s?o contaminados pelos compostos org?nicos: benzeno, tolueno, etilbenzeno e xilenos - BTEX, TPH e HPA S presentes nesses derivados de petr?leo. As t?cnicas eletroqu?micas vem tomando lugar de destaque nesse cen?rio, pela sua efici?ncia, baixo custo e por n?o gerar res?duos. O presente trabalho visa caracterizar o efluente proveniente de caixas separadoras de ?gua e ?leo de postos de combust?veis, bem como analisar a efici?ncia de remo??o de compostos org?nicos com diferentes tipos de pares de eletrodos sendo eles: Ti/Pt e Ti/IrO2-Ta2O5a fim de comprovar, qual par de eletrodo desempenham melhor essa fun??o. As an?lises de Carbono Org?nico Total (COT), Demanda Qu?mica de Oxig?nio (DQO), Cromatografia Gasosa (CG) e Teor de ?leos e Graxas (TOG), na amostra de ?gua coletada na sa?da caixa separadora confirmou a presen?a de compostos org?nicos em altas concentra??es no efluente, bem como comprovou a remo??o dos mesmo ap?s as 4 horas de tratamento com varia??es de corrente de 10,20,30 mA/cm2 efetuadas nesse trabalho, foi poss?vel constatar em alguns casos remo??o superiores a 99,36%