Per- and polyfluorinated substances (PFASs) have become an urgent topic in the water treatment industry in recent years as a consequence of new scientific discoveries of the correlation between the ingestion of some PFASs and their toxicity in humans and other organisms. PFASs are synthetic compounds present in a variety of products. Due to their desirable physical and chemical properties, PFASs are found in everything from clothes and furniture to aqueous fire-fighting foams. These compounds have also been identified in food and drinking water. The flourine-carbon bond present in these chemicals are exceptionally strong. Hence PFASs are persistent in nature when leaked to the environment. Additionally, the mobility properties of PFASs in the soil leads to contamination of surface and groundwater, necessitating actions from drinking water treatment plants (DWTP).  Nanofiltration plants have shown to successfully reduce the PFASs content in contaminated waters. The accumulation of PFASs in the concentrate is a potent source of these compounds and requires treatment before leaving the DWTP. Foam fractionation (FF) is an aeration technique that utilizes the hydrophobic properties of the PFASs compounds, in which PFASs adsorbs to the interfaces of introduced rising air-bubbles. The foam forming at the surface is then extracted, reducing the contamination.  In this study, the efficacy of the FF system on a concentrate from a two-stage nanofiltration membrane was evaluated. Also, the ability of surfactants to enhance the PFAS reduction was explored. The study was conducted in two parts. The first part was executed in a laboratory scale environment where five surfactants were added to a batchwise FF system. A minimum dose was determined and four experimental runs were then executed for each surfactant: Zero surfactant, 1x minimum dose, 2x minimum dose and 5x minimum dose. The results were evaluated and the surfactant showing the greatest improvement of PFASs removal, in this study a cationic surfactant, was chosen for further investigations in the second part. A continuous pilot FF system was used in the second part, the inner diameter of the colon was 54 mm, the height of the water column was held at 1 m prior to the aeration, the contact time (CT) was 10 minutes and the air-flow rate was set to be 4 L/min in all runs. Four experimental runs were conducted with different doses of the cationic surfactant: Zero surfactant, 1x minimum dose, 2x minimum dose and 3x minimum dose. Each experiment was repeated three times. A total of 12 runs were performed.  The results showed a removal efficiency of > 99 % of long-chained PFASs in all conducted experimental runs. Without the addition of surfactant, the average removal efficiency of ∑ short-chained PFASs was 61 % whereas maximum removal (77 %) was obtained with the highest surfactant dose applied. The mean reduction of ∑PFASs was 90 % in the zero surfactant run and 94 % in the highest dose experiment. The main findings from the study were that: 1) FF is an efficient method for the removal of long-chained PFASs from concentrate 2) Surfactants can be added to increase the removal of short-chained PFASs, 3) Higher dosing of the surfactant positively correlated with the removal efficiency of ∑short-chained PFASs in the FF system, however the relationship was not linear. / Per- and polyfluorerade ämnen (PFAS) är ett högaktuellt forskningsområde inom dricksvattenproduktion. På senare år har ny forskning påvisat korrelationen mellan intag av vissa PFAS-ämnen och hälsoproblem hos både människor och djur. PFAS är syntetiskt framställda kemikalier som förekommer i flertalet av våra vardagliga produkter på grund av dess fördelaktiga fysiska- och kemiska egenskaper. PFAS används i allt från smink och möbler till brandskum men har också påträffats i dricksvatten och mat. Kol-fluor bindningen som förekommer i alla PFAS-ämnen tillhör den organiska kemins starkaste bindningar. Följaktligen bryts PFAS-ämnen ned extremt långsamt när de hamnar i naturen. PFAS förmåga att mobilisera sig i jorden leder till kontaminering av yt- och grundvatten vilket tvingar dricksvattenverk att vidta åtgärder.  Nanofiltration har visat sig vara en kraftfull metod för att rena vatten från PFAS. I koncentratet, det vill säga det vatten som inte renas genom membranen, ackumuleras PFAS vilket förutsätter en separat reningsprocess innan vattnet kan släppas ut i naturen. Skumfraktionering är en luftbaserad teknik som utnyttjar hydrofobiciteten i PFAS. PFAS-ämnen adsorberas till ytan hos de injicerade luftbubblorna och transporteras till vattenytan där det bildar ett skum. Uppsamling av skummet reduceras således kontamineringen.  I den här studien bedömdes effektiviteten av skumfraktionering på koncentratet från ett två- stegs nanofiltrationsmembran. Därutöver undersöktes effekterna av att tillföra surfaktanter till systemet för att optimera reduceringen. Studien genomfördes i två delar. Den första delen ufördes i en mindre skala där 5 olika surfaktanter adderades till en satsvis- skumfraktioneringsprocess. Initialt bestämdes en minimum dosering för alla surfaktanter. Totalt genomfördes 4 experiment: Ingen surfaktant, 1x minimum dosen, 2x minimum dosen, 5x minimum dosen. Den surfaktant som påvisade bäst effekt på reduceringen av PFAS, i detta fall en katjonisk surfaktant, användes sedan.  I den andra delen av arbetet användes en kontinuerlig skumfraktioneringsprocess. Den inre diametern på kolonnen var 54 mm, vattenkolumnen hölls konstant på 1 m innan luftningen, kontakttiden var 10 min och lufthastigheten var satt till 4 L/min. Totalt genomfördes 4 experiment: Ingen surfaktant, 1x minimum dosen, 2x minimum dosen, 3x minimum dosen. Varje experiment upprepades tre gånger.  Resultatet visade att > 99 % av ∑långkedjiga PFAS-ämnen reducerades i alla genomförda experiment. Den genomsnittliga reduktionen av ∑kortkedjiga PFAS-ämnen var 63 % i experimenten utan surfaktant, medan i experimenten med den högsta doseringen var reduktionen 77 %. Den genomsnittliga reduktionen av ∑11 PFAS var 94 % för den högsta doseringen medans den var 90 % i experimentet utan surfaktant. Studien visade att:  1) Skumfraktionering är en effektiv metod för att rena koncentrat från långkedjiga-PFAS 2) Surfaktanter kan fördelaktigen användas för att optimera reningen av kortkedjiga-PFAS ämnen. 3) Högre dosering av surfaktanter korrelerade med högre reduktion av ∑kortkedjiga PFAS i skumfraktioneringsprocessen, ökningen var dock inte linjär.

Die vorliegende Arbeit beschäftigt sich mit dem Einsatz eines Membranverfahrens zur Extraktabtrennung unter Hochdruckbedingungen. Die in einem zu koppelnden Prozess extrahierten Naturstoffsubstanzen sollen dabei ohne große Energieverluste, wie sie bei der herkömmlichen Methode der Druckentspannung entstehen, in nahezu isobarer und isothermer Fahrweise aus dem verdichteten Lösungsmittel gewonnen werden. Für den Einsatz oxid-keramischer, integral-asymmetrisch aufgebauter Einkanal-Rohrmembranen wurden vor allem grundlegende Daten zum Transportverhalten hinsichtlich der beiden eingesetzten Gase CO2 und dem Frigen Tetrafluorethan ermittelt. Dies geschah für zwei Nanofiltrationsmembranen mit trennaktiven Schichten aus TiO2 und SiO2. Die Filtrationsleistung der Membranen wurde für drei beispielhafte Wertstoffe (Koffein, Aescin, Inulin), deren Extraktionsverhalten im Vorfeld untersucht wurde, u.a. anhand von Rückhalt und Deckschichtbildung bewertet.

Die vorliegende Arbeit beschäftigt sich mit dem Einsatz eines Membranverfahrens zur Extraktabtrennung unter Hochdruckbedingungen. Die in einem zu koppelnden Prozess extrahierten Naturstoffsubstanzen sollen dabei ohne große Energieverluste, wie sie bei der herkömmlichen Methode der Druckentspannung entstehen, in nahezu isobarer und isothermer Fahrweise aus dem verdichteten Lösungsmittel gewonnen werden. Für den Einsatz oxid-keramischer, integral-asymmetrisch aufgebauter Einkanal-Rohrmembranen wurden vor allem grundlegende Daten zum Transportverhalten hinsichtlich der beiden eingesetzten Gase CO2 und dem Frigen Tetrafluorethan ermittelt. Dies geschah für zwei Nanofiltrationsmembranen mit trennaktiven Schichten aus TiO2 und SiO2. Die Filtrationsleistung der Membranen wurde für drei beispielhafte Wertstoffe (Koffein, Aescin, Inulin), deren Extraktionsverhalten im Vorfeld untersucht wurde, u.a. anhand von Rückhalt und Deckschichtbildung bewertet.

In this study, the implementation of membrane technology at Anglo Platinum’s base metals refinery to separate acid from metal containing solutions was investigated. The refinery includes a circuit known as the “sulphur removal section”, where the acid in the spent nickel electrolyte is neutralized with caustic soda to remove the excess sulphur from the overall process. Reagent costs associated with acid neutralisation, result in high operating expenditures. An alternative process route is required to improve efficiencies and stay competitive. Nanofiltration was investigated to separate acid from nickel, with the aim of recovering the acid and thereby reducing the need for expensive neutralisation. The objectives of this study were twofold: (1) investigate and simulate the current base metals refinery, and (2) use the understanding and process know-how to investigate the use of nanofiltration by modifying the simulation to include for this technology. The modified process simulation was then used to evaluate the type of membrane required for technical viability. The process investigation of the refinery proceeded with literature studies done on base metals recovery process, chemical reactions and design criteria applicable to the process. A simulation of the base metals refinery was undertaken in Aspen Plus using the information established in the process investigation. The simulation provided insight into the operational issues across the flowsheet, and identified key areas of the process which were sensitive to parameter changes in the sulphur removal section. Areas which were impacted were the electrowinning and copper removal section. The simulation therefore provided a useful tool to predict process variabilities as a result of plant modifications. The investigation into nanofiltration found that it can successfully be used to separate metal ions from acid, subject to the constraints of metal ion concentrations. Pre-treatment of the nickel spent electrolyte was required to remove most of the sodium sulphate in solution, since this can cause fouling and thereby degrade membrane performance. For this reason, a cold crystallization process was introduced for the removal of sodium sulphate. However the sodium removal process caused the sodium sulphate levels in the electrowinning feed to drop below 100 g/l. Therefore minor modifications had to be made to the electrowinning pre-treatment process. The nanofiltration process itself consisted of a series of six nanofiltration stages with dilution of the interstage feed to allow the system to operate below osmotic pressure and wash out all the acid from the system. The modified simulation including the new sulphur removal circuit (nanofiltration process) was completed by integrating the current base metals refinery simulation with the new sulphur removal process, thereby providing a tool where different membrane characteristics could be varied to enable the performance of the overall process to be evaluated. The membrane parameters varied were the nickel rejection, the sodium rejection and the acid rejection. The simulation predicted that each of the cases which varied the mentioned parameters would be technically feasible, although not necessarily economically feasible. The process was most sensitive to acid rejection. The key variables were the amount of water used for dilution, and the membrane size. An exponential distribution was present for the sensitivity of membrane size versus acid rejection; thus realistic membrane sizes can only be achieved if the acid rejection is -100% or less. Furthermore, the addition of dilution water results in the nickel being washed out with the acid, despite nickel rejection being in the region of 99.5%. This demonstrates the importance of the membrane nickel rejection to be as high as possible. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2014

In this study, the implementation of membrane technology at Anglo Platinum’s base metals refinery to separate acid from metal containing solutions was investigated. The refinery includes a circuit known as the “sulphur removal section”, where the acid in the spent nickel electrolyte is neutralized with caustic soda to remove the excess sulphur from the overall process. Reagent costs associated with acid neutralisation, result in high operating expenditures. An alternative process route is required to improve efficiencies and stay competitive. Nanofiltration was investigated to separate acid from nickel, with the aim of recovering the acid and thereby reducing the need for expensive neutralisation. The objectives of this study were twofold: (1) investigate and simulate the current base metals refinery, and (2) use the understanding and process know-how to investigate the use of nanofiltration by modifying the simulation to include for this technology. The modified process simulation was then used to evaluate the type of membrane required for technical viability. The process investigation of the refinery proceeded with literature studies done on base metals recovery process, chemical reactions and design criteria applicable to the process. A simulation of the base metals refinery was undertaken in Aspen Plus using the information established in the process investigation. The simulation provided insight into the operational issues across the flowsheet, and identified key areas of the process which were sensitive to parameter changes in the sulphur removal section. Areas which were impacted were the electrowinning and copper removal section. The simulation therefore provided a useful tool to predict process variabilities as a result of plant modifications. The investigation into nanofiltration found that it can successfully be used to separate metal ions from acid, subject to the constraints of metal ion concentrations. Pre-treatment of the nickel spent electrolyte was required to remove most of the sodium sulphate in solution, since this can cause fouling and thereby degrade membrane performance. For this reason, a cold crystallization process was introduced for the removal of sodium sulphate. However the sodium removal process caused the sodium sulphate levels in the electrowinning feed to drop below 100 g/l. Therefore minor modifications had to be made to the electrowinning pre-treatment process. The nanofiltration process itself consisted of a series of six nanofiltration stages with dilution of the interstage feed to allow the system to operate below osmotic pressure and wash out all the acid from the system. The modified simulation including the new sulphur removal circuit (nanofiltration process) was completed by integrating the current base metals refinery simulation with the new sulphur removal process, thereby providing a tool where different membrane characteristics could be varied to enable the performance of the overall process to be evaluated. The membrane parameters varied were the nickel rejection, the sodium rejection and the acid rejection. The simulation predicted that each of the cases which varied the mentioned parameters would be technically feasible, although not necessarily economically feasible. The process was most sensitive to acid rejection. The key variables were the amount of water used for dilution, and the membrane size. An exponential distribution was present for the sensitivity of membrane size versus acid rejection; thus realistic membrane sizes can only be achieved if the acid rejection is -100% or less. Furthermore, the addition of dilution water results in the nickel being washed out with the acid, despite nickel rejection being in the region of 99.5%. This demonstrates the importance of the membrane nickel rejection to be as high as possible. / MIng (Chemical Engineering), North-West University, Potchefstroom Campus, 2014

Approximately 35% of the population of the Navajo Nation does not have direct access to the electric grid and public water supply. Tribal members haul their potable and livestock water from public water systems that are located great distances from their homes. The Navajo Nation Solar Desalination Research Pilot Demonstration Project is designed to provide residents affordable livestock water. The same technology can later be adopted to provide potable water. The project has deployed an off-grid, prototype water purification unit at a demonstration site north of Leupp, AZ utilizing membrane distillation (MD) technology. A second prototype for the same purposes utilizing nanofiltration (NF) membrane technology has been designed, built, and operated at The University of Arizona. Through experimentation I confirmed information provided the manufacturer of the NF membrane, calculated the production rate to be 636 gallons per day, and calculated the cost of desalinated water to be $0.003 per gallon. Both systems use solar energy to desalinate brackish ground water and the second prototype will later be deployed at the same site for side-by-side comparison. A critical part of the project is the development of technology transfer methods that will help the community take ownership of the project. To accomplish this goal I have written a comprehensive manual that will be given to the Navajo Department of Water Resources. The demonstration site will act as an applied research site for investigation, demonstration, and training related to sustainable water and energy systems designed to address the needs of remote, rural communities in arid and semi-arid regions. The aim is to inform a regional plan for Southwestern Navajo Nation Chapters to address chronic water and energy shortages, demonstrate renewable energy application for water treatment of brackish ground water, evaluate trade-offs in energy and water supplies, and foster community development. The research and demonstration site has been developed by an interdisciplinary and collaborative effort between the Bureau of Reclamation, Apex Applied Technology, Inc., and The University of Arizona.

L'objectif de cette thèse est d'évaluer le concept d'un dispositif intégré comprenant un bioréacteur à biofilm fluidisé bio-augmenté, couplé à une membrane de nanofiltration de type polyelectrolyte multicouche, destiné à éliminer les micropolluants en traitement tertiaire des eaux usées domestiques, traitées conventionnellement. Les résultats montrent que, pour des micropolluants ciblés, chacun des procédés est efficace comme traitement tertiaire. Les mécanismes biologiques et de rétention membranaires sont explicités. Cependant des challenges restent à relever en particulier pour l'étape de bio augmentation (survie et implantation de la souche apportée) pour une exploitation de cette étape. D'autre part, des investigations plus poussées sont nécessaires à l'élaboration d'une membrane fiable et robuste. Un tel procédé couplé MBBR-NF pourra alors être entièrement justifié dans le contexte d'une élimination performante de micropolluants ciblés. Il aura toute sa place dans le panel des technologies vertes pour la préservation de l'environnement. / This thesis aims at answering whether the concept of an integrated layout comprised of a coupled "bioaugmented moving bed biofilm reactors (bMBBRs) - polyelectrolyte multilayer (PEM)-based nanofiltration (NF) membrane" can be considered as a promising technology to eliminate target MPs from conventionally-treated municipal wastewater. Results presented herein indicate that each given component of the layout is efficient in the tertiary removal of MPs. Still, several challenges ahead of the process bioaugmentation (such as the survival and maintenance of inoculated strains) must be in-depth studied to find convenient operating solutions. On the other hand, further investigations are definitely needed to achieve a robust PEM-based membrane as a long-lasting technology. Even though a coupled bMBBR-NF system for enhanced MPs removal can be experimentally justified is, however, practically questionable. "The tale of bMBBR-NF" deserves much more scientific endeavors as plenty of environmental considerations are placed in, whereby achieving a future Green technology will not be far from our expectation.

Gram-negative bacterial cells are surrounded by a cell membrane which protects the cell and controls the transport of nutrients and waste products in and out of the cells at a fast rate. This rapid transport of nutrients and wastes through the cell membrane is made possible by channel proteins called porins. Various types of porins present in the cell membrane have specific functions depending on their selectivity towards different nutrients, and channel proteins selective towards water are called aquaporins. These proteins restrict the passage of all entities except water molecules and they provide a fast transport rate of water molecules at 109 molecules/second per channel. The high selectivity of porins has led to their incorporation into synthetic systems, and one example is the addition of porins to separations membranes in order to enhance their performance in terms of selectivity and permeability, in a field called biomimetics. The concept of incorporating aquaporins into synthetic membranes has been studied for the last 10 years in order to enhance the water permeability and selectivity of membranes for water purification; however, there are still limitations such as high costs, difficulties in fabrication of aquaporins, their alignment into synthetic membrane assembly, low stability, and limitations on number of aquaporin molecules that can be introduced into synthetic membranes limit their applicability. In recent years, concurrent with the work on aquaporin-based biomimetic membranes, there has been an increase in the study of synthesizing molecules with similar structure-function relationships of aquaporins. These artificial channels attempt to mimic the high-water permeability and selectivity of aquaporins, while being synthesized using simple chemistry, being solvent compatible, and requiring less space on the membrane surface which helps to incorporate more channels into the membrane assembly. The objectives of this study were to first incorporate aquaporins into synthetic nanofiltration membranes without chemical alteration them to prevent flattening or denaturing of aquaporins; then, the second objective was to install functional groups on aquaporins and align them in the direction of water flow; lastly, the third objective was to synthesize artificial channels in order to overcome the issues with aquaporin stability, alignment, and efficient packing of water channels onto the membrane surface. For the first objective, aquaporins were treated with a polysaccharide, gum Arabic, and incorporated into an amphiphilic polymer, polyvinyl alcohol with alkyl side chains (PVA-alkyl), in order to simulate the natural housing of lipid bilayer for aquaporins and to protect them from denaturing. Long alkyl chains provided the hydrophobic component, while PVA provided the hydrophilic component of the amphiphilic polymer. Membranes modified with aquaporins displayed lower flux declines and higher flux recoveries after reverse flow filtration, along with improved rejection values for both protein and salt solutions as compared to PBI and PBI-PVA-alkyl membranes. However, there was leakage of ions between channels. Therefore, in order to improve the rejection of protons, ions and other impurities, the channels were aligned with the direction of water flow. Functional groups were installed on Aquaporins using site-directed mutagenesis for covalent attachment to the polymer matrix so that the proteins could be immobilized to the membranes and aligned in the direction of the flow. Aquaporin constructs were modified to bear affinity tags or unique amino acids at the N-terminus of the aquaporin molecule, which was used to facilitate directional immobilization. Each aquaporin monomer was modified with a unique amino acid Cys group at the N-terminus right after the first Met, and due to the aquaporin tetrameric nature, these Cys groups became four anchors for attachment. The presence of these four Cys anchors per aquaporin tetramer was used to attach on the membrane surface in alignment with the feed water flow direction. Membranes modified with mutated aquaporins showed consistently higher salt rejection values of ~70% irrespective of feed concentration, along with higher flux recoveries and lower flux declines. Commercial NF-270 membranes provide a monovalent salt (NaCl) rejection of ~50% and divalent salt (MgCl2) rejection of 97%. Also, approximate coverage of membrane surface with attached aquaporins was calculated using simulation studies. Simulation studies showed that immobilized aquaporins with PVA-alkyl provided a diffusion rate equivalent to 64% coverage on the membrane surface. This showed that aquaporins didn’t cover the entire surface area of the membrane. However, immobilized aquaporins were responsible for the rejection of a portion of ions passing through the membrane. In order to overcome the limitations of aquaporin incorporation into polymer membranes, artificial organic frameworks were added as surface modification on PBI membranes. Organic frameworks were synthesized as derivatives of hybrid bisamides. The series of bisamides 1-4 consist of 6-amino-pyridine-2-dicarboxylic acid, 6-hydroxymethyl-pyridine-2-carboxylic acid and ethylenediamine, trimethylenediamine, putrescine, and cadaverine depending on the length of carbon chain. These frameworks are amphiphilic in nature and have strong chemical attachment due to the presence of amines and carboxylic acids into each building block. These molecules were introduced into the membrane matrix using carbodiimide chemistry. FTIR results showed the attachment of these bisamide molecules onto the surface of a modified PBI membrane. Also, modified membranes showed a reduced molecular weight cut off (MWCO) for neutral organic molecules. Overall, membranes modified with aquaporins have shown a potential to provide consistently high salt rejections with increasing feed solutions. Also, preliminary results have shown that bisamide molecules can be attached onto the membrane surface as organic frameworks and have a potential to be an alternative for aquaporins based biomimetic membranes.

Membrane processes are increasingly used in water treatment. Experiments were performed using stirred cell equipment, polymeric membranes and synthetic surface water containing natural organics, inorganic colloids and their aggregates, and cations. All processes could remove a significant amount of natural organics. Pretreatment with ferric chloride was required to achieve significant organic removal with MF and high MWCO UF. Additionally, fouling mechanisms for the three processes were investigated. Crucial parameters were aggregate characteristics (fractal structure, stability, organic-colloid interactions), solubility of organics and calcium, and hydrodynamics. In MF, fouling by pore plugging was most severe. Variations in solution chemistry changed the aggregation state of the colloids and/or natural organic matter and dramatically affected rejection and fouling behaviour. UF membrane fouling was mainly influenced by pore adsorption and could improve natural organics rejection significantly. Coagulant addition shifted fouling mechanism from pore adsorption to cake formation. Aggregate structure was most significant for flux decline. In NF, rejection of natural organics involved both size and charge exclusion. Fouling was caused by precipitation of a calcium-organic complex. Fouling could be avoided by pretreatment with metal salt coagulants. Thorough chemical characterisation of the organics used demonstrated that only size and aromaticity can be related to fouling. The study is concluded with a process comparison based on a water quality parameter and a cost comparison. Treatment cost of microfiltration with chemical pretreatment was similar to that of nanofiltration at a comparable natural organics rejection.

Thesis (Ph.D. (Chemical Engineering))--North-West University, Potchefstroom Campus, 2009.