Industrial operations produce a notable amount of wastewaters with high concentration of chemical oxygen demand (COD), mostly consisting of organic carbon compounds. The treatment performance of electrochemical methods for organic removal and the effects of process parameters are the subject of this research. Three research tasks were performed. The first task was the removal of organic pollutants from three different industrial wastewaters using two different electrochemical methods; combined electrocoagulation + electrooxidation (EC+EO) and b) electrochemical peroxidation (ECP). Using only EC process was found to be significantly successful in removing suspended and colloidal pollutants and could remove more than 90% COD and 80% of TOC. The study showed that combined EC+EO process had better removal capability compared to ECP when operated under similar process conditions. The second task was to study the effect of the process parameters; pH, H2O2 dosage, current density, and operation time; and to optimize and estimate the best treatment conditions for the methods using Box-Behnken Design (BBD). For sugar beet wastewater, the results showed that EO could remove 75% of organics at optimum conditions of pH 5.3; current density of 48.5 mA/cm2; and operation time of 393 min. The canola oil refinery wastewater achieved more than 90% pollutant removal when the conditions were optimized at pH 5.8 – 6 with applied current density of 9.2 mA cm-2¬ run for nearly 300 min. The rate of degradation of the wastewater derived organic pollutants followed a first order kinetics for all the wastewaters investigated and the models were validated for goodness of fit with high R2. The final task was to compare treatment efficiency between the electrochemical processes. Based on the energy consumed and the performance efficiency to remove COD, sCOD, TOC and DOC in the three different wastewaters studied, EC+EO process was found suitable for the treatment of canola and sunflower oil wastewater. On the other hand, from the model prediction and the experiments conducted, EO resulted in better removal capability compared to ECP. Also, the consumption of energy by ECP was comparatively higher than EO process while taking longer time of operation for significant removal. / North Dakota Water Resources Research Institute; North Dakota Agricultural Experimental Station; Frank Bain Agricultural Scholarship

No description available.

Many industrial processes would require enormous amounts of water, which could ultimately result in wastewater. Water scarcity in many parts of the world makes this situation unsustainable. In order to reuse wastewater in industrial processes or for other purposes, wastewater must be treated properly. In industrial wastewater treatment, electrocoagulation-flotation (ECF) can be used to dissolve sacrificial electrodes and produce metal coagulant in-situ by applying a current to the electrodes. The reactor design and electrode configuration can profoundly affect the performance of electrocoagulation-flotation (ECF). While most conventional ECF reactors use an open-vertical electrode configuration in rectangular cells, mixing is limited by vertical electrodes that make a barrier and disrupt the flow hydrodynamics. The effects of these factors may influence removal efficiency, flow hydrodynamic, floc formation, and flotation/settling characteristics. The present work aimed to optimize the ECF process by developing an innovative electrode configuration. A variety of parameters were examined to determine the effectiveness of the removal of contaminants from industrial wastewater that had turbidity, emulsified oil, and heavy metals (Si, Zn, Pb, Ni, Cu, Cr, and Cd), as well as stirring speed and foaming. Additionally, the experimental results of the innovative electrode configuration were compared with those of the conventional rectangular cell with plate electrode configuration. Based on the results, the innovative electrode configuration consumed approximately 20% less energy than a conventional ECF for operating times of 10, 20, 30, 32, 48, and 70 minutes. As a result of the enhanced flow hydrodynamic, the formed gas bubbles tilted toward the center, significantly reducing foam formation. There was also an investigation of the dominant operating parameters for electrocoagulation-flotation (ECF) that could affect the removal efficiency, including current density (CD), initial pH, electrolytic conductivity, dosage of coagulant, operating time, initial turbidity concentration, and stirring speed. In addition, a novel approach has been proposed for evaluating EC performance and selecting an appropriate process for removing sludge based on the intake's initial concentration. Keywords: Electrode configuration, electrocoagulation process, electro-flotation, energy consumption, removal efficiency, Electrochemical treatment, Aluminium electrode, Turbidity removal, TOC removal, operating parameters, computational fluid dynamics, Reynolds number, mass transfer, pH evolution.:Table of Contents Abstract 7 1. Introduction 16 1.1. The electrocoagulation process 17 1.2. Problem statement 19 1.3. Objectives 20 1.4. Scope of the work 21 2. Literature survey 23 2.1. Industrial wastewater and treatment methods 24 2.1.1. Impact of industrial growth 24 2.1.2. An analysis of global industrial growth based on statistics 25 2.1.3. Extensive sources of industrial effluent 26 2.1.4. Wastewater and reserve rehabilitation in industry 34 2.1.5. Applied techniques in industrial wastewater treatment 40 2.2. Electrocoagulation (ECF) 50 2.3. Comparison of EC with other treatment methods 50 2.4. Basic concepts and theory of coagulation and electrocoagulation 53 2.5. Electrocoagulation applications 58 2.5.4. Textile industry 60 2.5.5. Leather Tanning Industry 61 2.5.6. Metal-bearing industrial effluents 61 2.5.7. Pulp and paper industry 62 2.5.8. Petroleum refinery 63 2.6. Type and Configuration of the Electrodes 64 2.6.1. Case of Al electrodes 66 2.6.2. Case of Fe electrodes 68 2.7. Reactor design 71 2.6. Modeling 72 2.6.1. Kinetics 73 2.7. Impact of electrocoagulation operating condition on contaminant removal efficiency 75 2.7.1. Effect of current density 75 2.7.2. Effect of initial pH 75 2.7.3. Effect of operating time 76 2.7.4. Effect of electro conductivity 76 2.7.5. Effect of stirring speed 77 2.7.6. Effect of concentration 77 2.7.7. Effect of gap between the electrodes 77 2.7.8. Effect of temperature 78 2.8. Economical aspects and cost analysis 78 3. Material and methods of the tests 80 3.1. Test procedure 1: Impact of operating parameters on removal of turbidity 81 3.1.1. Operating conditions 81 3.1.2. EC cell construction and electrode arrangement 82 3.1.3. Synthetic wastewater 85 3.1.4. Analytical methods and EC procedure 86 3.1.5. Anodic and cathodic reactions 87 3.1.6. Electrical double layer and particle stability 89 3.2. Test procedure 2: Spiral electrode configuration 91 3.2.1. Experimental Setup 91 3.2.2. Sampling and analytical measurements 95 3.2.3. Experimental procedure 95 4. Results and discussion 97 4.1. Test procedure 1: Impact of operating parameters on removal of turbidity 98 4.1.1. Effect of current density (CD) 98 4.1.2. Effect of initial pH 100 4.1.3. Effect of electrolytic conductivity 104 4.1.4. Effect of coagulant dosage, electrode and energy consumption 106 4.1.5. Effect of current density and operating time on initial turbidity concentration 107 4.1.6. Effect of stirring speed 111 4.1.7. Effect of electrode passivation 112 4.2. Test procedure 2: Spiral electrode configuration 115 4.2.1. Removal efficiency of contaminants 115 4.2.2. Effect of stirring speed and ECF configuration on removal efficiency 119 4.2.3. Energy consumption and voltage rise 123 4.2.4. Foaming effect 126 4.3. Computational Fluid Dynamics (CFD) Simulation 128 5. Conclusions and future work 138 5.1. Conclusions 139 5.2. Future works 142 References 143 6. Appendix 159

Poor settling of solids increases land requirement for tailings containment and imposes severe constraints on the water balance. Consequent to these considerations, the alternating current electrocoagulation (AC/EC) technique emerged as a candidate for enhancing the settling behaviour of suspensions in the mineral, coal and oil sands industries. Hence, a fundamental study of AC/EC was undertaken with aluminum electrodes. Ground silica (d50 = 20 m), which formed a stable suspension, served as the model tailings solid at 5.0 wt % in water. The AC/EC process consisted of two developmental stages: coagulation, marked by pH decrease in the silica suspension; and floc growth, characterized by pH increase from the minimum (i.e., the end of coagulation). AC/EC enhanced the initial settling rate of silica by over three orders of magnitude, and exhibited remarkable flexibility by virtue of the wide range of process parameters that could be optimized. For example, AC/EC can be operated in either the indirect or direct mode. The settling behaviour of bentonite (estimated d50 < 1 m) was more enhanced by indirect AC/EC, while that of silica benefited more from direct AC/EC. Any condition that increased aluminum dosage (e.g., current, retention time), increased the initial settling rate of silica. Over the feed water pH range of 3.0 to 9.1, AC/EC was effective in enhancing the settling behaviour of silica. AC/EC was also effective over a wide range of temperatures (23 to 85C). High electrical energy demand by AC/EC was observed throughout this study. Its optimization was beyond the scope of this work. Dilution of a sample of Syncrude mature fine tailings (MFT) to 4.6 wt % solids sustained a stable suspension. Settling occurred after AC/EC treatment, a crystal-clear supernatant resulted and bitumen was recovered as froth. Entrained solids were easily spray-washed from the froth with water. The settling behaviour of a Luscar Sterco fine coal tailings sample was not augmented by AC/EC, possibly due to contamination by the companys own electrocoagulation operation. After having been stored dry for more than a year, electrocoagulated silica was an effective coagulant for as-received silica and Syncrude MFT. / Chemical Engineering

No description available.

L'électrocoagulation (EC) est une méthode électrochimique non spécifique couramment utilisée pour le traitement de l'eau et des eaux usées. Dans ce travail, l’EC est d'abord étudiée comme une technique classique de traitement des eaux usées dédiée à l'élimination des protéines de lactosérum de l'eau pour laquelle les mécanismes d'élimination sont expliqués et un modèle est développé. Ensuite, l'utilisation de l’EC est étendue à la séparation et à la purification d’acides gras volatils issus de la fermentation acidogénique. Dans cette deuxième étude, les effets des paramètres opératoires sur l'efficacité et le coût de l’EC sont discutés. En outre, l’EC est utilisée pour la récolte de deux espèces de microalgues de leur milieu de culture. En ce qui concerne la récolte de Chlamydomonas reinhardtii, la méthodologie de la surface de réponse est utilisée et deux modèles permettant de prédire respectivement l'efficacité de la récupération et le coût opératoire sont développés. La récolte d’une autre espèce de microalgues, Chlorella vulgaris, est étudiée en utilisant l’EC respectivement en mode discontinu et continu. En mode discontinu, les effets des principaux paramètres de fonctionnement sur l'efficacité du processus sont expliqués et les mécanismes de récupération sont discutés. Dans l'étude en mode continu, la méthodologie de la surface de réponse est utilisée et un modèle permettant de prédire l’efficacité de récupération des microalgues est développé. Enfin, la comparaison des performances de l'EC en mode continu avec et sans échange de polarité aux performances de l'EC en mode discontinu est effectuée. / Electrocoagulation (EC) is a non-specific electrochemical method usually used for water and wastewater treatment. In this work, EC is firstly investigated as a conventional wastewater treatment technique for the removal of whey proteins from water, where the mechanisms of removal are explained and a model on whey proteins elimination is developed. Then, EC use is extended for the separation and purification of volatile fatty acids issued from acidogenic fermentation. In this second study, the effects of operating parameters on EC efficiency and cost are discussed. Moreover, EC is used for the harvesting of two microalgae species from their culture medium. In the study that concerns recovering Chlamydomonas reinhardtii, response surface methodology (RSM) is employed and two models for predicting recovery efficiency and operating cost are developed. The harvesting of the other microalgae species Chlorella vulgaris is studied using EC in the batch and continuous modes. In the batch mode, the effects of the main operating parameters on the process effectiveness are explained along with discussing the mechanisms of recovery. In the continuous mode study, response surface methodology (RSM) is applied and a model for predicting microalgae recovery is developed. Finally, comparison of EC performance in continuous mode with and without polarity exchange (PE) to EC performance in batch mode is carried out.

L'électrocoagulation permet d'éliminer simultanément un large spectre de polluants organiques et minéraux, de colorants et de métaux lourds ; de ce fait, il a été beaucoup étudié. En revanche, peu de travaux ont été entrepris pour étudier de façon plus approfondie son fonctionnement. La complexité des effluents pour laquelle il est particulièrement intéressant d'utiliser ce procédé, fait aussi qu'il est difficile d'analyser les résultats. Cette thèse a pour objectif d'apporter une contribution à la compréhension du couplage électrocoagulation - décantation et des interactions liés à des effluents multi-polluants complexes. De plus l'aspect réacteur en continu a été abordé dans le cas d'un effluent synthétique simple pour mieux appréhender les différences par rapport au fonctionnement en discontinu. Cette étude est basée sur une approche systématique qui repose sur les processus élémentaires de l'électrocoagulation: Electrochimie, Coagulation et Séparation physique. Chaque processus fournit une base pour l'étude des interactions qui permettent ensuite la modélisation globale des processus. Afin d'étudier les couplages électrocoagulation-décantation, des effluents textiles industriels ont été traités par électrocoagulation suivie par une étape de décantation en éprouvette, sans agent floculant. L'effet des paramètres d'électrocoagulation sur la décantabilité des effluents traités et l'efficacité d'élimination de la pollution a été étudié en suivant en particulier la vitesse de décantation en éprouvette et en calculant le SVI. Le deuxième objectif de ce notre travail était d'étudier les couplages entre les différents types de pollution à éliminer et plus particulièrement un effluent de papeterie contenant des pollutions organiques et de l'arsenic. Enfin, nous avons réalisé une étude sur les performances du couplage EC-décantation pour le traitement d'un effluent synthétique textile en réacteur continu. Ce dernier est composé de deux éléments, la cellule électrochimique suivie d'une chambre de sédimentation / Electrocoagulation eliminates simultaneously a large spectrum of organic pollutants, dyes and heavy metals; therefore, it has been studied extensively. However, little work has been undertaken to investigate more thoroughly its behaviors. The complexity of the effluent for which it is particularly interesting to use this method also makes it difficult to analyze the results. This thesis aims to contribute to understanding the coupling electrocoagulation - settling and interactions associated with complex effluent multi-pollutants. Also a continuous reactor has been addressed in the case of a simple synthetic sewage to better understand the differences from the batch operation. This study is based on a systematic approach based on the elementary processes of electrocoagulation: Electrochemistry, coagulation and physical separation. Each process provides a basis for studying the interactions that then the overall modeling process. To study the electro-decantation couplings, industrial textile effluents were treated by electrocoagulation followed by a settling step, without flocculent. The effect of parameters on electrocoagulation settleability of treated effluent and removal efficiency of pollution has been studied in particular by following the settling velocity in the test tube and calculating the SVI. The second objective of this our work was to study the coupling between the different types of pollution and to eliminate a particular paper mill effluent containing organic pollutants and arsenic. Finally, we conducted a study on the performance of EC-coupling settling for the treatment of a synthetic textile effluent flow reactor. The latter is composed of two elements, the electrochemical cell followed by a settling chamber

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.

[pt] Efluentes oleosos são gerados de muitas fontes, tais como: indústrias petroquímicas, refinarias, plataformas de petróleo, fabricação de maquinarias, e até mesmo, no transporte, distribuição e armazenagem de óleo. O óleo presente na forma de emulsão é difícil de separar. Para quebrar essas emulsões, geralmente, são usados tratamentos químicos, biológicos, eletroquímicos, ultrafiltração. O processo de eletrocoagulação-flotação se inicia com a dissolução do anodo produzindo espécies aquosas (monoméricas, poliméricas) e precipitadas, espécies que funcionam como coagulantes e floculantes. As mesmas causam a desestabilização das emulsões através de mecanismos como a neutralização de carga superficial, ponte interparticular e coagulação por varredura, formando flocos de gotículas de óleo. A dissolução do metal no anodo é acompanhada da geração do gás hidrogênio no catodo. As bolhas são aderidas aos flocos, carregando-os até a superfície, onde são separados do reator, porém, dependendo da densidade deles, poderiam sedimentar-se. Neste trabalho, é avaliada a remoção de óleo de uma emulsão sintético pelo processo de eletrocoagulação-flotação. Avaliou-se a influência dos principais parâmetros de operação na taxa de redução da demanda química de oxigênio (DQO): concentração inicial do óleo; densidade de corrente; separação entre eletrodos; pH da solução; concentração de eletrólito. O efluente sintético foi preparado a partir de óleo Shell Talpa 30 e Oleáto de sódio como surfatante. Foi adicionado NaCl para aumentar a condutividade da solução. O pH inicial da emulsão foi de 8,70. O potencial zeta nessas condições teve um valor médio de -75mV, valor este que indicou a estabilidade da emulsão. / [en] The separation of emulsions or colloidal particles from wastewater is a major concern for the petroleum, metal manufacturing, food, textile, paper and hydrometallurgy industries. The emulsion present is very stable due to the presence of surfactants, so conventional methods can not be applied and it is necessary to combine one or two treatment processes for highly effective purification. Several techniques have been applied to treat these types of oily wastewater, e.g.: chemical, biological and electrochemical destabilization, ultrafiltration. Electrocoagulation is initiated by the oxidation of sacrificial anodes. The metal ions released combine to the hydroxyl ions produced at the cathode to form the corresponding metal hydroxides and others species, which cause the destabilization of the contaminants or particulate suspensions and form flocs. The bubbles hydrogen gas capturing and floating the flocs formed and separating from the liquid surface by scraping or settling depending on density of the flocs. In this work, the electrocoagulation technique was studied in order to treat concentrated oil-water emulsions chemically stabilized. This study was mainly focused on the effects of operating parameters such as: initial pH, current density, reaction time, NaCl concentration, electrode distance and inlet concentration on the abatement rate of chemical oxygen demand (COD). The synthetic emulsion was prepared from Shell - Talpa 30 oil (3g.L-1) and sodium dodecyl sulfate (1.0 g.L-1), also was added NaCl (3g L-1) for increasing the conductivity of the emulsion. Under those conditions we had a pH value around 8.70 and a zeta potential around -70mV, showing a good stability of the emulsion.

[pt] Compostos de boro são utilizados na indústria metalúrgica, microeletrônica, de vidros, na agricultura, etc. Esse elemento é um micronutriente essencial no desenvolvimento de microrganismos, plantas, animais e humanos. No entanto, pode ser tóxico em grandes concentrações e por isso necessita ser removido de águas e efluentes. No Brasil, o limite padrão é de 0,5mg/L para águas doces de classe I e II, estabelecido pela resolução do Conama 357/2005. Por sua vez, a resolução do Conama 430/2011 estabelece um padrão de lançamento de efluentes de 5mg/L. A presente dissertação tem como objetivo geral estudar a remoção de boro por eletrocoagulação para o tratamento de águas e efluentes contendo boro, utilizando uma célula com um arranjo de 4 eletrodos de alumínio (2 catodos e 2 anodos) monopolares em paralelo. Os resultados obtidos mostram que o processo de eletrocoagulação é uma alternativa viável para a remoção de boro, e alcança eficiências em torno de 70 por cento (em pH inicial igual à 4; densidade de corrente igual à 18,75mA/cm2 e tempo de eletrólise igual à 90min). O modelo cinético que melhor descreve a remoção de boro foi o de pseudo-primeira ordem. O modelo de Langmuir se ajustou muito bem aos dados experimentais obtidos. O valor de qm obtido pelo modelo de Langmuir refletiu a elevada capacidade de adsorção máxima (qm é igual à 334mg/g). Através das análises por Microscopia Eletrônica de Varredura (MEV) e por Espectroscopia de Energia Dispersiva (EDS) na superfície dos eletrodos, observou-se a presença de corrosão do tipo localizada nos catodos e a corrosão do tipo uniforme nos anodos. A morfologia do lodo produzido no processo de eletrocoagulação foi analisada por MEV, indicando a presença de uma morfologia heterogênea na superfície, enquanto que a análise por Difração de Raios-X (DRX) apresentou picos largos característicos de um material amorfo e a fase de alumínio predominante foi a boehmita, AlO(OH), finalmente, através da análise por Espectroscopia por Perda de Energia de Elétrons (EELS) foi possível a detecção do boro no lodo, além da detecção de alumínio e de oxigênio. Diante dos resultados obtidos no estudo de otimização a partir da Metodologia de Superfície de Resposta (RSM) constatou-se que o desenvolvimento de um modelo matemático por análise de regressão possibilitou a avaliação do efeito das variáveis independentes (densidade de corrente, pH inicial e tempo de eletrólise) e as suas interações na remoção de boro. / [en] Boron compounds are used in the metallurgical industry, microelectronics, glassware, agriculture, etc. This element is an essential micronutrient in the development of microorganisms, plants, animals and humans. However, it can be toxic in high concentrations and therefore needs to be removed from water and effluent. In Brazil, the standard limit is 0.5mg/L for Class I and II freshwaters, established by Conama Resolution 357/2005. In turn, the Conama 430/2011 resolution establishes an effluent discharge standard of 5mg/L. The present dissertation aims to study the removal of boron by electrocoagulation for the treatment of water and effluents containing boron, using a cell with an arrangement of 4 monopolar aluminum electrodes (2 cathodes and 2 anodes) in parallel. The results show that the electrocoagulation process is a viable alternative for the removal of boron and reaches efficiencies around 70 per cent (at initial pH equals to 4, current density equals to 18.75mA/cm2 and electrolysis time equals to 90min). The kinetic model that best describes the removal of boron was pseudo-first order. The Langmuir model fitted very well to the experimental data obtained. The value of qm obtained by the Langmuir model reflected the high maximum adsorption capacity (qm equals to 334mg/g). Through the analysis by Scanning Electron Microscopy (SEM) and Energy Dispersive Spectroscopy (EDS) on the surface of the electrodes, it was observed the presence of pitting corrosion in the cathodes and uniform corrosion in the anodes. The morphology of the sludge produced in the electrocoagulation process was analyzed by SEM, indicating the presence of a heterogeneous surface morphology, while the X-ray diffraction (XRD) analysis showed broad peaks characteristic of an amorphous material and the predominant aluminum phase was boehmite, AlO(OH), finally, through the Electron Energy Loss Spectroscopy (EELS) analysis, it was possible to detect boron in the sludge, as well as aluminum and oxygen. In view of the results obtained in the optimization study from the Response Surface Methodology (RSM), it was verified that the development of a mathematical model by regression analysis made possible the evaluation of the effect of the independent variables (current density, initial pH and time of electrolysis) and their interactions in the removal of boron.