Boron is an element distributed widely in environment mainly in the form of boric acid or borate salts. Boron is an element of demand because of its use in many high technology materials. Moreover boron is an essential element for growth of plants, but may also result in toxicity when present in excessive amounts. As the range between a deficient and toxic amount of boron is very narrow, imbalances in boron nutrition are well-known. For the removal of boron from aqueous solutions, various methods exist which are chemical coagulation, adsorption, solvent extraction and ion exchange processes. In this study, an alternative, energy efficient and easily scalable membrane based method, polymer enhanced ultrafiltration (PEUF) was developed for removal of boron from aqueous boron solutions. PEUF process consists of two steps: complexing boron with a water soluble polymer then removing the complex by ultrafiltration. Previously, boron removal from aqueous solutions was studied in a continuous process with a commercial ligand, polyvinyl alcohol (PVA). In our study, three newly developed polymers, which are derivatives of N-methyl-D-glucamine (P1) and iminodipropylene glycol(P2 and P2G) were used as the boron complexing ligand. P1 and P2 are linear polymers, while P2G is cross linked version of P2. The pilot scale system utilized for the PEUF process accommodates a spiral wound cellulose cartridge with 10000 Da molecular weight cutoffs (MWCO). The effects of operating parameters on performance of PEUF were investigated. The experimental parameters studied are metal/polymer ratio (loading) (0.01-1), pH (7-10). Boron analyses of the samples were made by using ICP-AES. Maximum removal (retention) was 90.1 %. The permeate flux remained constant at around 20 L/m2.hr and was not affected by the operating parameters. Decrease in loading caused the retention of boron to increase. Also at high pH values, retentions were relatively higher. Results showed that PEUF could be a successful alternative method for removal of boron.

Conventional desalination plant, municipal water supply and wastewater treatment system are among the most electricity-intensive facilities. Microbial Desalination Cell (MDC) has emerged as a promising technique to capture the chemical energy stored in wastewater directly for desalination, which has the potential to solve the high energy consumption issue in desalination industry as well as wastewater treatment system. The MDC is composed of two critical components, the electrodes (anode and cathode), and the ion-exchange membranes separating the two electrodes which drive anions migrate towards the anode, and cations migrate towards the cathode. The multiple components allow us to manipulate the configuration to achieve most efficient desalination performance. By coupling with Donnan Dialysis or Microbial Fuel Cell, the device can effectively achieve boron removal which has been a critical issue in desalination plants. The uncertainty of water quality of the final desalinated water caused by contaminant back diffusion from the wastewater side can be theoretically explained by two mechanisms, Donnan exchange and molecule transport which are controlled by bioelectricity and concentration gradient. Scaling and fouling is also a factor needs to be taken into consideration when operating the MDC system in real world. With mathematical modeling, we can provide insight to bridge the gap between lab-scale experiments and industrial applications. This study is expected to provide guidance to enhance the efficiency as well as the reliability and controllability of MDC for desalination. / Ph. D.

Le dessalement de l’eau de mer par osmose inverse connait un intérêt croissant depuis une vingtaine d’années afin de répondre aux besoins en eau potable et en eau d’irrigation dans de nombreuses régions dans le monde. Cependant, le bore contenu dans l’eau de mer est incomplètement éliminé par osmose inverse et des concentrations supérieures à la valeur limite de 0,3 mg/ sont obtenues. Dans cette étude, nous présentons des résultats sur l'élimination du bore de l'eau de mer en utilisant une technique hybride de résine échangeuse d'ions/microfiltration sans addition continue de résine. Une membrane de microfiltration en céramique a été utilisée pour retenir la résine échangeuse d'ions dans le réservoir d'alimentation et la boucle de circulation tandis que la solution modèle de bore ou l’eau de mer était continuellement ajoutée. Tout d'abord, des résines fines de taille moyenne 40 - 60 µm ont été obtenues par broyage et tamisage de résines commerciales (Amberlite IRA743, Diaion CRB05 et Purolite S108). Les résines ont ensuite été testées en système batch pour obtenir les cinétiques de sorption et par la technique hybride de sorption/microfiltration pour mesurer les courbes de perçage et le flux de perméat. L'effet de la dose de résine, de la concentration initiale en bore, de la pression transmembranaire et de la taille des pores de la membrane a été étudié. Dans une deuxième partie, l’effet de la taille des particules de résine sur les courbes de perçage en sortie d’une colonne a été déterminé et une comparaison entre les performances d’une colonne et d’un système hybride a été proposée. Dans une dernière partie, les isothermes et cinétiques de sorption expérimentales sont comparées à des équations classiques, et les courbes de perçage en colonne et en système hybride sont modélisées. En conclusion, il est suggéré que le procédé hybride de résine échangeuse d'ions et microfiltration sans ajout continu de résines peut être une technique possible pour l'élimination du bore / The maximum concentration suggested by the World Health Organization is 0.3 mg/L. In this study, we investigated a hybrid process for boron removal from water which associates sorption on ion exchange resin and microfiltration, without continuous resin addition. First, fine resins were obtained by grounding and sieving at 40 and 60 µm commercial resins (Amberlite IRA743, Diaion CRB05 and Purolite S108). The resins were then tested in batch to obtain the kinetics and in the hybrid sorption/microfiltration process to measure breakthrough curves and permeate flux. A ceramic microfiltration membrane was used to retain the ion exchange resin in the feed tank and the circulation loop while the boron solution was continuously added and the permeate collected for analysis. The effect of resin dosage, boron initial concentration, transmembrane pressure and membrane pore size was studied. In a second part, the effect of the size of the resin particles on the breakthrough curves measured at the outlet of a column was determined and a comparison between the performances of a column and a hybrid system are proposed. For the Amberlite IRA743 resin, the overall process was tested: reverse osmosis followed by hybrid sorption/microfiltration. The hybrid process was able to re-duce concentration of bacterial and phytoplankton cells thanks to the steric rejection by the microfiltration membrane, suggesting that the same membrane can be used as a pretreatment before reverse osmosis in a desalination plant. In a final part, the experimental isotherms and kinetics are compared with classical models, and the breakthrough curves obtained with a column and with the hybrid sys-tem are modelised. Overall, it is suggested that the hybrid process of ion exchange resin and microfiltration without continuous addition of resin may be a possible technique for boron removal

[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.

[EN] The present PhD thesis is centred in the design (using concepts of supramolecular chemistry), synthesis and characterization of different hybrid organic-inorganic materials for boron removal from aqueous media. The interaction between boron and organic groups, polyols, used in the development of these new adsorbents is also studied. In the first part of the thesis it is presented a brief review of supramolecular chemistry concepts, chemistry of boron and also the main methods for boron removal (first chapter) and, also, the objectives of this thesis (second chapter). The third chapter exposes the results obtained by using a ceramic foam as macroscopic support for active materials for boron removal. This support is previously "impregnated" with an inorganic silica mesoporous material (UVM-7) and, in a second step, it is functionalized with an organic group with high boron affinity (gluconamide). This organic group, which works as an adsorbent, remains anchored to a macroscopic support, which will facilitate the use of these materials in industrial applications. Once the material is synthetized their boron adsorption and elimination abailability in aqueous media is studied and its ulterior reutilization. The fourth chapter of the PhD thesis is focused on the preparation of low cost materials for boron adsorption from water. In first place, it is used, as inorganic scaffolding, UVM-7 material, a mesoporous silica phase with a bimodal pore system. This material has a high boron adsorption capacity after its functionalization with the polyalcohol (as it is shown in the previous chapter) nevertheless, the reagents used in the synthesis tetraethylorthosilicate, as silica source, and hexadecyltrimethylammonium bromide, as templating agent are so expensive that they induce a high cost of final materials. In this chapter is presented as an alternative another materials which are able to perform as inorganic scaffolds: UVM-11 (surfactant-free mesoporous material), two silica xerogels with pores within the mesoporous range and comercial high surface area silica fume were prepared. Once all the materials are synthetized they are functionalized with gluconamides which are the active compounds for boron adsorption. Finally, a comparative study of the boron adsorption capacities in water is carried out. Low cost materials present comparable boron removal to those of higher cost and comercially abailable materials. Finally, in the fith chapter of this PhD thesis, the adsorption mechanism of boron on the active materials (based on UVM-7 as inorganic support) is studied using solid Nuclear Magnetic Resonance measures of 11B and 13C and using techniques as Magic Angle Sppining, crossed polarization and heteronuclear polarization disacoplament. To do that, a hybrid material composed by UVM-7 matrix grafted with gluconamide is prepared and then the solid is put in contact with different boron quantities. Final solids are characterized through 13C and 11B NMR, showing the formation of boronesters between gluconamide diol groups and boron adsorbed. When low boron concentration is used, bisquelate complexes are formed (B:glucosa = 1:2), however with higher concentrations monoquelate complexes are formed (B:glucosa = 1:1). This work was carried out in collaboration with the research group of "sol-gel materials and NMR", appertaining to the center of "Chimie de la matière condensée de Paris" of the "Université Pierre et Marie Curie". / [ES] La presente tesis doctoral está dedicada al diseño (empleando conceptos de química supramolecular), síntesis y caracterización de diferentes materiales híbridos orgánico-inorgánicos para la eliminación de boro en medios acuosos. También se ha procedido a estudiar detalladamente la interacción del boro con las agrupaciones orgánicas, polialcoholes, empleadas en el desarrollo de estos nuevos adsorbentes. En la primera parte de la tesis de presenta una introducción en la que se revisa los conceptos de química supramolecular, química del boro y los principales métodos de eliminación de boro (primer capítulo) y, también, se exponen los objetivos de la tesis (segundo capítulo). Ya en el tercer capítulo se exponen los resultados obtenidos empleando una esponja cerámica como soporte macroscópico para los materiales activos frente a la eliminación de boro. Este soporte se "impregnan" previamente con un material inorgánico silíceo mesoporoso (UVM-7) y, en una fase posterior, se funcionaliza con un grupo orgánico con alta afinidad hacia el boro (gluconamida). El grupo orgánico que funcionará como adsorbente queda así anclado a un soporte de tamaño macroscópico que facilitará la aplicación de estos materiales a gran escala. Una vez preparado y caracterizado se estudió la capacidad del material para adsorber y eliminar boro de medios acuosos y su posterior reutilización. En el cuarto capítulo de la tesis doctoral se aborda la preparación de materiales adsorbentes de bajo coste económico para la eliminación de boro en medios acuosos. En primer lugar se emplea, como soporte inorgánico, UVM-7 una sílice mesoporosa con un sistema bimodal de poros. Este material tiene una capacidad de adsorción de boro muy elevada una vez funcionalizado con el correspondiente polialcohol (tal y como se expone en el capítulo anterior) sin embargo los reactivos para su síntesis tetraetilortosilicato como fuente de sílice y bromuro de cetiltrimetilamonio como agente director de estructura son muy caros con lo que el material final presenta un elevado coste. En este capítulo se presenta como alternativa otros materiales que puedan actuar como soportes inorgánicos: UVM-11, material mesoporoso que no requiere de agente director de estructura en su síntesis, dos xerogeles con poros en el rango meso y una sílice comercial nanoparticulada de elevada superficie específica. Una vez sintetizados y caracterizados los cinco soportes se funcionalizaron con gluconamidas, que son los componentes activos frente a la adsorción de boro. Finalmente, se realiza un estudio comparativo de la capacidad de eliminación de boro de los cinco materiales preparados. Los materiales de bajo coste estudiados presentan una capacidad de eliminación de boro comparable a los materiales de mayor coste y a los materiales comercialmente disponibles. Por último, en el capítulo cinco de esta tesis doctoral, se aborda el estudio del mecanismo de adsorción del boro en los materiales activos preparados (basados en UVM-7 como soporte inorgánico) mediante medidas de resonancia magnética nuclear de sólidos, tanto de 13C como de 11B empleando las técnicas de rotación en ángulo mágico, polarización cruzada, y el desacoplamiento dipolar heteronuclear. Para ello se prepara un material híbrido formado por una matriz de UVM-7 funcionalizada con gluconamidas y este sólido se pone en contacto con diferentes cantidades de boro. Los sólidos finales se caracterizan mediante RMN de 13C y de 11B, observándose la formación de boroesteres entre los grupos diol de las gluconamidas ancladas y el boro adsorbido. Cuando la concentración de boro empleada es baja se forman complejos bisquelados (B:glucosa = 1:2) mientras que a concentraciones altas empiezan a formarse complejos monoquelados (B:glucosa = 1:1). Este trabajo se llevó a cabo en colaboración con el grupo de investigación de "Materiales sol-gel y RMN", perteneciente al centro "Chimie de la matiè / [CAT] La present tesi doctoral està dedicada al disseny (empleant conceptes de química supramolecular), síntesi i caracterització de diferents materials híbrids orgànico-inorgànics per a la el¿liminació de bor en medi aquòs. També s'ha precedit a estudiar detalladament la interacció del bor amb les agrupacions orgàniques, polialcohols, empreats en el desenvolupament d'aquestos nous adsorbents. En la primera part de la tesi es presenta una introducció en la que es revisen els conceptes de química supramolecular, química del bor i els principals mètodes de el¿liminació de bor (primer capítol) i, també, s'exposen els objectius de la tesi (segon capítol). Ja en el tercer capítol s'exposen els resultats obtinguts empreant una esponja ceràmica com a suport macroscòpic per als materials actius front a l'el¿liminació del bor. Aquest suport s'impregna prèviament amb un material inorgànic de sílice mesoporós (UVM-7) i, en una següent fase, es funcionalitza amb un grup orgànic amb alta afinitat cap al bor (gluconamida). El grup orgànic que funcionarà com a adsorbent queda aixina anclat a un suport de tamany macroscòpic que facil¿litarà l'aplicació d'aquestos materials a gran escala. Una vegada preparat i caracteritzat s'estudia la capacitat del material per a adsorber i el¿liminar bor en medi aquós i la seua posterior reutilització. Al quart capítol de la tesi doctoral s'aborda la preparació de materials adsorbents de baix cost econòmic per a l'eliminació de bor en medi aquòs. En primer lloc, s'empra, com a suport inorgànic, UVM-7 una sílice mesoporosa amb un sistema bimodal de porus. Aquest material té una capacitat d'adsorció molt elevadadeprés de la seua funcionalització amb el corresponent polialcohol (tal i com s'exposa al capítol anterior), no obstant això els reactius que s'utilitzen per a la seua síntesi tetraetilortosilicat com a font de sílice i bromur de cetiltrimetilamoni com agent director d'estructura són molt cars, per tant el material final presenta un elevat cost. En aquest capítol es presenta com alternativa altres materials que puguen actuar com a suports inorgànics: UVM-11, material mesoporòs que no requereix d'agent director d'estructura durant la seua síntesi, dos xerogels en porus en el rang meso i una sílice comercial nanoparticulada amb elevada superficie específica. Una vegada sintetitzats i caracteritzats els cinc suports es funcionalitzen en gluconamides, que són els components actius front a la adsorció de bor. Finalment, es realitza un estudi comparatiu de la capacitat d'el¿liminació de bor dels cinc materials preparats. Els materials de baix cost estudiats presenten una capacitat de eliminació de bor semblant als materials de major cost i als materials comercialment disponibles. Per últim, al capítol cinc d'aquesta tesi doctoral, s'aborda l'estudi del mecanisme d'adsorció de bor als materials actius preparats (basats en UVM-7 com a suport inorgànic) mitjançant medides de resonància magnética nuclear de sólids, tant de 13C com de 11B emprant tècniques de rotació en àngul màgic, polarització creuada, i el desacoplament dipolar heteronuclear. Per a ell es prepara un material híbrid format per una matriu de UVM-7 funcionalitzada amb gluconamides i aquest sòlid es posa en contacte amb diferents quantitats de bor. Els sòlids finals es caracteritzen mitjançant RMN de 13C i de 11B observant-se la formació de borésters entre els grups diol de les gluconamides anclades i el bor adsorbit. Quan la concentració de bor emprada és baixa es formen complexos bisquelats (B:glucosa = 1:2) mentre que a concentracions més altes comencen a formar-se complexos monoquelats (B:glucosa = 1:1). Aquest treball és va realitzar ne col¿laboració amb el grup d'investigació de "Materials sol-gel i RMN", perteneixent al centre "Chimie de la matière condensée de Paris" de la "Université Pierre et Marie Curie". / Sanfeliu Cano, C. (2016). Organic-inorganic hybrid materials for boron removal from aqueous media [Tesis doctoral no publicada]. Universitat Politècnica de València. https://doi.org/10.4995/Thesis/10251/63277 / TESIS

no / In this work, a model based MINLP (mixed integer nonlinear programming) optimisation framework is developed for evaluating boron rejection in a reverse osmosis (RO) desalination process. A mathematical model (for the RU process) based on solution diffusion model and thin film theory is incorporated in the optimisation framework. A superstructure of the RU network is developed which includes two passes: (a) seawater pass containing normal two-stage RU system housing seawater membrane modules and (b) the brackish water pass (BW) accommodating brackish water membrane modules. For fixed freshwater demand, the objective of this work is to demonstrate the effectiveness of the MINLP approach for analyzing and optimizing the design and operation of RU network while attaining desired limit on boron concentration in the freshwater produced. The effect of seasonal variation in seawater temperature and pH on boron removal efficiency is also discussed.

Produced water is the largest waste product by volume in the oil industry and its treatment in onshore or offshore fields poses bigger and different challenges than what water engineers are used to encounter. Process to achieve reuse quality of this water is very expensive with many technical hurdles to overcome making the optimization of the treatment steps necessary. Electrocoagulation (EC) generates coagulants in-situ responsible for destabilizing oil droplets, suspended particles, and common pollutant in produced water. Furthermore, EC is a very efficient technology compared with traditional primary treatments used in the oil & gas industry and has several advantages such as: no hazardous chemical handling (which diminishes the risk of accident and logistic costs), high efficiency potential concerning boron removal, potential small footprint and less sludge generation. In this research, the treatment of produced water using EC was investigated in a practical manner for the oilfield to aim for a cleaner effluent for further processing and help to achieve a reuse quality. For this, an EC cell was designed using different parameters normally used in the literature to fit this scenario. After preliminary tests, the treatment time was set to 3 seconds. Response surface method (RSM) was employed to optimize the operating conditions for TOC removal on a broad quality of synthetic produced water while varying: salinity, initial oil concentration and initial pH. TOC was chosen to be the main response because of its importance in legislation and sensibility on the method. Furthermore, turbidity removal, change of pH value after EC in water with lack of buffer capacity, aluminum concentration and preliminary tests involving boron removal and influence of hydrogen carbonate were also studied. Real produced water was treated with EC to assess the optimum conditions obtained by the RSM showing the results were closely related. Finally, an estimation of volume required and operating cost for EC in the different types of produced water was made to assess how realistic it is for onshore and offshore applications.:ERKLÄRUNG DES PROMOVENDEN I ACKNOLEDGEMENT III ABSTRACT V TABLE OF CONTENT VII LIST OF FIGURES IX LIST OF TABLES X LIST OF EQUATIONS XII ABBREVIATIONS XIV 1. INTRODUCTION 1 2. PRODUCED WATER 6 2.1 Characterization of Oilfield Produced Water 6 2.2 Produced Water Management 10 2.2.1 Discharge and Regulations 10 2.2.2 Efforts on Reuse 11 2.2.3 Cost 14 3. PRODUCED WATER TREATMENT 17 3.1 Most Common Primary Treatment 17 3.1.1 Hydrocyclones 17 3.1.2 Flotation unit 18 3.2 Further Water Treatment Technologies 19 3.2.1 Membrane Process 19 3.2.1.1 Microfiltration 19 3.2.1.2 Ultrafiltration 21 3.2.1.3 Nanofiltration 23 3.2.1.4 Reverse Osmosis 24 3.2.1.5 Forward osmosis 24 3.2.2 Electrodialysis 25 3.2.3 Biological treatment 28 3.2.3.1 Aerobic and anaerobic process 28 3.2.3.2 Combining membrane and bio-reactor 29 3.2.4 Oxidative process 30 3.2.4.1 Oxidation process 30 3.2.4.2 Anodic oxidation 32 3.2.5 Thermal technology 34 3.2.5.1 Evaporation 34 3.2.5.2 Eutectic freeze crystallization 35 3.2.6 Adsorption and ion-exchange 36 3.3 Electrocoagulation 39 3.3.1 Colloidal Stability Theory 39 3.3.2 Theory of Electrocoagulation 40 3.3.3 Mechanism of Abatement of Impurities 44 3.3.4 Operational parameters and efficiency 49 4. MATERIALS AND METHODS 51 4.1 Analytical Techniques and Synthetic Solutions 51 4.1.1 Analytical Techniques 51 4.1.2 Synthetic Produced Water 51 4.2 Design of Experiment and Models 54 4.3 Experimental Protocol for EC 56 4 .4 Development of the new Electrocoagulation cell 57 4.5 Real Produced water 58 5. RESULTS AND DISCUSSION 59 5.1 Designing EC Cell Process 59 5.1.1 Computational Fluid Dynamics for EC manufacturing 59 5.2 Preliminary Experiments 61 5.2.1 TOC Removal and Residence Time Determination 61 5.2.2 Aluminum Concentration 64 5.3 Models Quality and Range of Validity 66 5.3.1 TOC Removal 66 5.3.2 Turbidity Removal 69 5.3.3 Final pH value 71 5.3.4 Ionic Strength and Interpolation for Different Salinities 73 5.3.5 Partial Conclusions 76 5.4 Evolution of the Final pH Value 78 5.5 Operation Region for Effective Treatment of Produced Water with EC 80 5.5.1 Produced Water with Low Salinity 80 Organic Compounds Removal 80 Turbidity Removal 83 5.5.2 Produced Water with Medium Salinity 84 Organic Compounds Removal 84 Turbidity Removal 86 5.5.3 Produced Water with High Salinity 87 Organic Compounds Removal 87 5.6 Influence of Hydrogen Carbonate 90 5.7 Real Produced water 91 5.8 Boron Removal 93 5.9 Estimation of the Size for EC in Full scale 94 5.10 Produced Water with Very Low Salinity and EC 95 5.11 Estimation of Operation Cost 96 6. CONCLUSION AND RECOMMENDATIONS 98 6.1 Conclusion 98 6.2 Recommendations for Future Work 101 Scale up on EC for upstream 101 Further processing and reuse 101 Online optimization for EC 101 Recommendations for any research related to upstream produced water 101 BIBLIOGRAPHY 102 APPENDIX A 117 APPENDIX B 120