Contamination of natural waters due to nitrogenous wastes has become a crucial environmental problem due to deterioration of water quality and eutrophication in aquatic eco-systems. Thus, the reduction of nitrogen accumulation in the natural environment is vital to maintain a healthy eco-system. Bipolar membrane electrodialysis (BMED) is a promising technology for selective ammonia separation from high-strength wastewater, such as liquid digestates of food waste or wastewater sludge. This technology was recently studied for reducing membrane scaling problems associated with conventional electrodialysis (ED) systems due to the water splitting mechanism in the BPM interface. A bench-scale BMED stack was built using 5 pairs of cation exchange membranes (CEMs) and bipolar membranes (BPMs). Using the BMED stack, a simulated food liquid digestate solution was examined to separate ammonia with different voltage applications and inter-membrane distances. The highest ammonia recovery was obtained at a cell pair voltage of 5.83 V (81% separation). Experiments on investigation of optimal inter-membrane distance of BMED operation suggested that the inter-membrane distance could be increased up to 2.46 mm without a significant decrease in nitrogen recovery. The residual Ca2+ and Mg2+ in the CIP (clean-in-place) solution which explains the degree of the scaling problem in the BMED was observed consistently below 2% of the initial mass introduced to the system, indicating that BMED design and regular CIP were effective in scaling control. The ammonia loss through CEMs to the feed cell by back diffusion was minimized due to high pH in the base cell since uncharged free ammonia was dominant over ammonium cation in the base cell. The energy required for BMED operation was comparatively low; 1.93-6.93 kWh/kg-N within 90 mins. Therefore, BMED can be considered as a sustainable candidate for selective ammonia recovery at high energy efficiency with successful scaling control. / Thesis / Master of Civil Engineering (MCE)

Nitrogen pollution in the environment creates challenging problems globally and locally and can be effectively controlled by a significant reduction in nitrogen release into the natural water system. In addition, nutrients in high-strength wastewater can be recovered as valuable resources such as different types of ammonium solutions for industrial and agricultural utilizations. Selective ammonia separation from high-strength wastewater can be achieved by bipolar membrane electrodialysis (BMED), a relatively new ion exchange technology. A series of 8 bench-scale BMED experiments with bipolar membranes and cation exchange membranes were performed under various voltage applications. Ammonia in the wastewater was rapidly separated and recovered as a high purity ammonium hydroxide solution. BMED operation for 30 minutes at 5.0 V per cell pair was found to be ideal for high purity ammonium hydroxide production and low electrical energy consumption. Additionally, effective organic fouling control and low energy consumption were achieved. The experiments showed a decrease in the feed pH making it ideal for applications in solid-state anaerobic digestion with leachate recirculation. The application of leachate recirculation in solid-state anaerobic digestion (SSAD) has proven effective for mobilizing nutrients and diluting toxic byproducts to enhance biogas production. The leachate after recirculation contains accumulated ammonia and an increased pH and requires water and chemicals for dilution and pH adjustment prior to recirculation. The data from the experiments were used to construct a numerical model for a hypothetical lab-scale and pilot-scale bipolar membrane electrodialysis and solid-state anaerobic digestion with leachate recirculation (BMED-SSAD) system. A final ammonia concentration of less than 2000 mg-N/L in the reactor was found to be achievable by lab-scale (6 mA/cm2) and pilot-scale (12 mA/cm2) BMED-SSAD and low electric energy consumption. The results suggest that BMED is an attractive solution for ammonia separation from high-strength wastewater. / Thesis / Master of Applied Science (MASc)

In the 1970s it was discovered that organic polymers, a class of materials otherwise best know as insulating plastics, could be made electronically conductive. As an alternative to silicon semiconductors, organic polymers offer many novel features, characteristics, and opportunities, such as producing electronics at low costs using printing techniques, using organic chemistry to tune optical and electronic properties, and mechanical flexibility. The conducting organic polymers have been used in a vast array of devices, exemplified by organic transistors, light-emitting diodes, and solar cells. Due to their softness, biocompatibility, and combined electronic and ionic transport, organic electronic materials are also well suited as the active material in bioelectronic applications, a scientific and engineering area in which electronics interface with biology. The coupling of ions and electrons is especially interesting, as ions serve as signal carriers in all living organisms, thus offering a direct translation of electronic and ionic signals. To further enable complex control of ionic fluxes, organic electronic materials can be integrated with various ionic components, such as ion-conducting diodes and transistors. This thesis reports a background to the field of organic bioelectronic and ionic devices, and also presents the integration of ionic functions into organic bioelectronic devices. First, an electrophoretic drug delivery device is presented, capable of delivering ions at high spatiotemporal resolution. The device, called the organic electronic ion pump, is used to electronically control amyloid-like aggregation kinetics and morphology of peptides, and offers an interesting method for studying amyloids in vitro. Second, various ion-conducting diodes based on bipolar membranes are described. These diodes show high rectification ratio, i.e. conduct ions better for positive than for negative applied voltage. Simple ion diode based circuits, such as an AND gate and a full-wave rectifier, are also reported. The AND gate is intended as an addressable pH pixel to regulate for example amyloid aggregation, while the full-wave rectifier decouples the electrochemical capacity of an electrode from the amount of ionic charge it can generate. Third, an ion transistor, also based on bipolar membranes, is presented. This transistor can amplify and control ionic currents, and is suitable for building complex ionic logic circuits. Together, these results provide a basic toolbox of ionic components that is suitable for building more complex and/or implantable organic bioelectronic devices.

A couple of processes for electrosynthetic production of expendable reagents, namely acids, bases, and oxidants, from the native salt content of raw waters and industrial wastes were investigated, and the composition of mixed acids and bases made of sodium sulfate or sodium chloride salts were predicted using a model predicated on conservation principles, mass action relations, and Pitzer equations. Electrodialysis with bipolar membranes (BMED) was used to produce acids and bases in a single pass. Product concentration was limited only by the salt content of the feed water. The current efficiency for acid production was slightly higher than that for base, but neither dropped below 75%. Acid and base current utilization showed the same trends with respect to feed salt content and flow velocity, with higher efficiency at higher feed salt concentrations and flow velocities. Operating the BMED stack near the limiting current density of the bipolar membrane (BLCD) or above the limiting current density of the diluate compartment (LCD) decreased current efficiency and increased electrical power dissipation. Electrodialytic acid and base production was approximately10 times cheaper than the chemicals' f.o.b. unit costs as quoted on Alibaba.com. The mechanism and cost of on site peroxodisulfuric acid production by electrolysis of sulfuric acid solutions with boron doped diamond film anodes was investigated experimentally and with molecular dynamics (MD) and density functional theory (DFT) simulations. The cost of on site peroxodisulfate production was approximately 4 times less expensive than purchasing a 25 lb bag. It was shown that direct discharge of sulfate species produces sulfate radicals, which subsequently combined to form peroxodisulfuric acid. The likely hood of these reactions was dependent on electrode surface condition. Sulfate radicals could also be produced in solution by reaction with hydroxyl radicals generated by water discharge.

This work is focused on the preparation of heterogeneous bipolar membranes and studies the influence of different composition on mechanical and physical properties. The main feature of this approach is optimalization of composition following gained data. Theoretical part contains new piece of knowledge in the field of heterogeneous bipolar membranes. Experimental part engages preparation of bipolar ion-exchange membranes on one face cation-selective and on the other one anion-selective. In this case are used variant types of polyethylene.

The removal of lignin in a Kraft pulp mill, with the aim to utilize the lignin as more value added green product than just firing lignin in black liquor, is possible with a LignoBoost plant. The LignoBoost plant uses sulfuric acid in the process and this results in an increased net input of sulfur to the pulp mills recovery cycle. The sodium/sulfur balance in a Kraft pulp mill is an important factor to be able to run a mill optimal. The increased input of sulfur into the mill when implementing a LignoBoost plant is therefore an issue to address. A too high sulfur/sodium ratio in the Kraft pulp mill is often solved by purging electrostatic precipitator dust from the recovery boiler. The major component of the ESP dust is sodium sulfate. When purging ESP dust from the recovery boiler the mill loose sodium and the need of sodium make-up increases. A large extent of the ESP dust that is not purged is returned to the recovery cycle of the mill via the evaporation plant. If the recycled sodium sulfate could be split and returned to the recovery cycle as one controlled sodium- and one controlled sulfur component or at least split into two flows where sulfur is enriched in one flow and sodium in the other flow, the sodium/sulfur balance would be easier controlled. In this master thesis the split of sodium and sulfur in sodium sulfate is addressed. The aim is to study opportunities to: • Enrich sodium and sulfur in two flows from the dissolved ESP dust, which is normally recycled to the evaporation plant. • Produce one sulfur component and one sodium component that can be utilized in the Kraft pulp mill, especially in an integrated LignoBoost process. • Accomplish this by using an electrochemical split of the sodium sulfate from the ESP dust to generate sodium hydroxide and sulfuric acid.   To be able to produce one sulfur component and one sodium component from the dissolved ESP dust an electrodialysis with or without bipolar membranes is the method to use decided after contact with Eka Chemicals research and development department and literature studies. An electrodialysis cell produces sodium hydroxide and sulfuric acid, from the sodium sulfate solution, that can be used in the Kraft pulp mill. The difficulty by using an electrochemical cell with ion selective membranes is the need of a pure feed to the cell. If a high content of contaminations, such as multivalent ions, is present in the feed solution to the cell scaling can be formed. Scaling leads to shorter membrane life that result in higher operational cost for the cell stack. Due to the multivalent ions in the electrostatic dust a pre-treatment such as carbonate- and hydroxide precipitation removal of the ions is suggested, which results in a decrease of the multivalent ions in the feed solution.   In previous work concerning electrochemical split of sodium sulfate the lack of utilization for the produced acid became negative in an economical point of view. The need of sulfuric acid to the LignoBoost plant is an advantage for the economical study. In this master thesis is:   • An economical case study for the implementation of an electrochemical cell, electrodialysis with or without a bipolar membrane, in a Kraft pulp mill performed. • A sensitivity analysis performed and evaluated in the aim of addressing the change in payback time due to alternating: Sodium price Membrane life Utilization of the acid produced from the electrochemical cell. The economical case study concerns a Kraft pulp mill with a LignoBoost plant. Utilization of the acid to the LignoBoost- and tall oil plant is varied, as is the membrane life for the cell stack. The membrane life is varied due to the difficulty of predicting the ESP-feed solutions affect on the membranes. The feed solution has to be tested in a cell to decide the real life for the membrane in this case.   The electrodialysis cell with bipolar membranes indicates promising economical gain for future implementation in a mill with LignoBoost lignin removal compared to the electrodialysis cell that indicates no economical gain for future implementation in a mill. For a mill with both a LignoBoost plant and a tall oil plant, i.e. optimized utilization of acid from the electrodialysis with bipolar membrane, and a five years membrane life in the cell, a payback of one and a half year can be reached. The same case but for an electrodialysis results in nine and a half payback years. The sensitivity analysis show that compared to the electrodialysis with bipolar membrane, the electrodialysis cell is more vulnerable to changes for the acid utilization, sodium hydroxide price and membrane life. The BME cell is most affected by changes in the sodium hydroxide price and the ED cell affects most by changes in the membrane life.

Le présent travail vise à étudier le couplage de l’échange d’ions et de l’électrodialyse. Cette étude est appliquée à la séparation de biomolécules. Un des objectifs est de diminuer la génération d’effluents salins produits par les étapes d’échange d’ions utilisées de façon classique dans les bioséparations. Une première approche a conduit à la conception d’une architecture avec un mode de fonctionnement cyclique en 3 étapes qui permet de purifier certaines familles de peptides sans utiliser de tampon de pH ni générer d’effluents. Le dispositif expérimental est constitué d’une cellule d’électrodialyse dans laquelle sont introduites des résines échangeuses d’anions. Les trois étapes sont les suivantes : fixation des biomolécules sur la résine initialement sous forme carbonate, élution par une solution de dioxyde de carbone dissous dans l’eau, électrorégénération de la résine sous sa forme initiale, conduisant simultanément à la régénération de la solution d’acide carbonique. L’étape d’électrorégénération a été modélisée et les simulations permettent d’améliorer la compréhension des processus couplés mis en jeu comme les équilibres d’échange d’ions, les équilibres en solution, l’électromigration. Une deuxième approche a ensuite consisté à étudier les possibilités de contrôle du pH par voie électrochimique, afin de limiter l’utilisation de solutions tampons. La dissociation de l’eau, conduisant à la formation de protons et d’ions hydroxyles, a été plus particulièrement étudiée en mettant à profit les propriétés des contacts dits « bipolaires » sous l’effet d’un champ électrique. Il s’est alors avéré que les choix du type de résine et de la densité de courant permettent de jouer sur le pH Toutefois ce travail doit être poursuivi par la recherche d’architectures et de modes opératoires qui permettent d’obtenir un pouvoir tampon adéquat / The present work aims to study the coupling of ion exchange and electrodialysis. This study is applied to the separation of biomolecules. One objective is to reduce the generation of saline wastewater produced by the ion exchange steps used conventionally in bioseparations. One approach has led to the design of architecture with a cyclic mode in 3 steps to purify some families of peptides without using a buffer pH or generate wastes. The experimental device consists of an electrodialysis cell in which are introduced anion exchange resins. The three steps are: loading of biomolecules on the resin initially in the carbonate form, elution with a solution of carbon dioxide dissolved in water, electroregeneration of the resin in its original form leading simultaneously to the regeneration of the carbonic acid solution. Using a modelling of the electroregeneration step, simulations can improve the understanding of coupled processes as the ion exchange equilibria, the equilibria in solution, the electromigration. A second approach has then been to study the possibilities of controlling the pH by electrochemical means to limit the use of buffers. The dissociation of water, leading to the formation of protons and hydroxyl ions, has been particularly studied by accounting the properties of contacts called « bipolar » as a result of an electric field. It was established that the choice of resin type and the current density can modify the pH. However this work must be pursued through research of architectures and operating procedures that deliver appropriate buffer capacity

Le présent travail est dédié à l’étude d’un procédé hybride couplant l’électrodialyse à membrane bipolaire et l’échange d’ions. Cette étude est appliquée au traitement de solutions diluées d’acide acétique. L’objectif est double : acquérir une compréhension théorique des processus de transfert et des mécanismes qui impactent la consommation énergétique de ce système hybride et, de façon plus appliquée, proposer une configuration de cellule qui permette d’éliminer l’acide de la solution traitée en la transférant vers un compartiment de concentration. Cette configuration doit permettre d’obtenir le taux de purification le plus élevé possible tout en minimisant la consommation d’énergie. Des critères visant à optimiser le choix des résines échangeuses d’ions (fortes ou faibles) dans les compartiments de dilution sont proposés. L’intérêt de l’utilisation d’une résine cationique forte sous forme H+ dans le compartiment de concentration est par ailleurs mise en évidence, conduisant à une diminution de la résistance du compartiment et de ce fait de la consommation d’énergie. Une étude réalisée sur des systèmes « couplés » et « découplés » a permis d’identifier les contributions résistives des différents éléments de l’empilement. Cette approche a conduit à la détermination des paramètres d’un modèle qui permet de prévoir la résistance électrique d’un lit de résine dans une solution donnée. Les consommations spécifiques d’énergie (kWh/kg d’acide transféré) ont été évaluées en fonction du taux de purification souhaité. L’ensemble de l’étude a permis d’établir des recommandations pour la conception de la cellule et pour le choix des paramètres opératoires. / This work is dedicated to the study of a hybrid separation process involving bipolar membrane electrodialysis and ion exchange. This study is applied to the treatment of diluted effluents. The aim is first to acquire a theoretical understanding of transfer processes and mechanisms that affect energy consumption of this hybrid system. Then, in a more applied way, the objective is to be able to propose a cell configuration that allows to remove the acid from the treated solution by transferring it to a concentration compartment. This configuration must allow to obtain the highest purification rates as possible while minimizing energy consumption. Criteria aiming at optimizing ion exchange resins (strong or weak) in dilution compartment are proposed. The interest of the introduction of strong cationic resin under H+ form in the concentrated compartment is highlighted, as it enables reducing compartment resistance and hence energy consumption. Furthermore, experimental measurements successively conducted with “decoupled” and “coupled” systems identified resistive contributions of the different elements of the stack. This approach led to the determination of parameters of a model which predicts the resin bed electrical resistance in a given solution. Specific energy consumption (kWh/Kg transferred acid) was evaluated as a function of the desired purification rate. All the work led to recommendations for the cell design and for the choice of operating parameters.