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Thesis (Ph. D.)--University of Missouri-Columbia, 2007. / The entire dissertation/thesis text is included in the research.pdf file; the official abstract appears in the short.pdf file (which also appears in the research.pdf); a non-technical general description, or public abstract, appears in the public.pdf file. Title from title screen of research.pdf file (viewed on March 6, 2008) Includes bibliographical references.

Recently a large amount of interest has developed around separating out impurities of small size; pertinent examples are found within fuel and solvent processing. For such applications a leading candidate process is nanofiltration. This thesis focuses on SRNF (solvent resistant nanofiltration) composite membranes consisting of a dense polymer active layer bonded to a stronger, but ultimately more porous, support layer. The composite membranes that have been produced during the course of this work consist of a PDMS (polymdimethylsiloxane) active layer bonded to a commercially available support layer of PAN (polyacrylonitrile). To create the membrane a monomer was spread over the support layer and then polymerised to form the matrix which was responsible for separation. Commercially, either heat or radiation is often applied to cause polymerisation, however the membranes in the current work have been formed by the used of a homogeneous catalyst. This thesis investigates the transport and separation dynamics of the produced membranes for a series of fuel simulants composed of organometallics and poly-nuclear aromatic solutes dissolved in aromatic and alkane solvents. Membrane composition and the extent of polymer swelling were found to be the two key factors which had the greatest influence on solvent flux and solute rejection. By increasing catalyst concentration it was found that the dual effects of increased rejection and reduced flux occurred, with the converse also being true. The effective pore size of the membrane could also be controlled by varying the catalyst amount during manufacture as this directly affected the limit of crosslinking which formed. Polymer swelling was the most pronounced using solvents with a solubility parameter close to that of the polymer. The membrane transport mechanism was most accurately forecast by the solution diffusion model for flux predictions and the convection diffusion model for rejection predictions, however all the models tried were in close agreement. This was postulated to be due to the swelled polymer matrix which allows for both convective and diffusive transport to occur.

Perfluoroalkylated substances (PFASs) are a group of synthetic compounds that have gained growing attention due to their environmental persistence, toxicity and their potential to bioaccumulate. Even though PFASs are not occurring naturally in our environment, they are globally distributed and can be found ubiquitously in air, water, soil, wildlife as well as in humans. PFASs have primarily been used, due to their unique properties of being both hydrophilic and hydrophobic, as surfactants in numerous products such as firefighting foams, paint, leather and textile coating. The occurrence of PFASs in drinking water as well as in wastewater makes it important to develop effective techniques to remove these compounds from drinking water sources and wastewater. To be able to effectively remove PFASs from drinking water and wastewater it is important to understand which treatment process is most efficient and how the removal efficiency is affected by the physicochemical properties of PFASs and characteristics of water. In this study, the removal efficiency of PFASs was investigated using six different water types with varying dissolved organic carbon (DOC) character. Four different treatment techniques were evaluated including anion exchange using MIEX® resins, coagulation with iron (III) chloride (FeCl3), adsorption using powdered activated carbon (PAC) and nanofiltration (NF) membrane. The batch experiments were performed in laboratory-scale for 14 individual PFASs including C3-11, C13 perfluoroalkyl carboxylic acids (PFCAs), C4, C6, C8 perfluoroalkyl sulfonic acids (PFSAs) and perfluorooctane sulfonamide (FOSA). The results showed that the removal efficiency of PFASs was dependent on both perfluorocarbon chain length as well as functional group, with an increase in removal efficiency with increased perfluorocarbon chain length. Short-chained PFASs (C!6) were removed in less extent than the long chained PFASs for all treatment techniques. Amongst the four treatment techniques investigated, NF membrane exhibited the best removal efficiency for both short- and long chained PFASs (on average, 51%). Lower removal efficiencies for PFASs were observed for MIEX (33%) < FeCl3 (16%) < PAC (14%). However, all tested treatment techniques used in this study exhibited generally low removal efficiency (< 78%), in particular for the short-chained PFASs (C!6, < 41%) Results using three different doses of PAC (i.e. 20, 50, 100 mg L-1) showed an increase in removal (i.e. 2.2-41%, 8.0-78% and 12-92% respectively) with increasing dose. No significant trends were found between PFAS removal and DOC removal for any of the treatments (p<0.05, student t-test). However, the removal efficiency was different of the six different water types, which indicates that the DOC characteristics (i.e. Freshness, humification index, pH and absorbance) have an influence on the removal efficiency of PFASs in water. / Perfluoroalkylerade ämnen (PFASer) är en grupp syntetiska ämnen som har fått allt större uppmärksamhet den senaste tiden då de har visat sig vara persistenta, toxiska och bioackumulerande. Även om PFASer inte förekommer naturligt i vår miljö är de globalt fördelade och kan återfinnas i luft, vatten, mark, djur och hos människor. PFASer har främst använts, på grund av sina unika egenskaper att vara både hydrofila och hydrofoba, som tensider i många produkter såsom brandsläckningsskum, färg, läder och textil. Förekomsten av PFASer i dricksvattentäkter och i många reningsverk gör det viktigt att utveckla effektiva metoder för att ta bort dessa föreningar i vattenreningsverk. För att effektivt kunna avlägsna PFASer från dricks- och avloppsvatten är det viktigt att ha kunskap om vilken behandlingsmetod som är effektivast och hur reningseffektiviteten påverkas av ämnenas fysikalisk-kemiska egenskaper och vattnets karaktär.   Syftet med denna studie var att undersökta reningseffektiviteten för PFASer i sex olika vatten innehållande olika typer av löst organiskt kol (DOC). Detta undersöktes för fyra olika behandlingsteknikert; jonbyte med MIEX®, koagulering med järnklorid (FeCl3), adsorption med hjälp av pulveriserat aktivt kol (PAC) och nanofiltrering. Försöken gjordes små skaligt i laboratorie och 14 olika PFASer undersöktes; C3-11,13  perfluoralkyl karboxylsyror (PFCAer), C4, C6, C8, perfluoralkyl sulfonsyror (PFSAer) och perfluoroktan sulfonamid (FOSA). Resultaten visar att reningseffektiviteten för PFASer var beroende av både den perfluorerade kolkedjans längd och funktionell grupp, med en ökning av reningseffektivitet med längre perfluorerad kolkedja. PFASer med kort perfluorerad kolkedja (C≤6) renades i mindre utsträckning än PFASer med lång perfluorerad kolkedjade; detta gällde för alla behandlingstekniker. Bland de fyra behandlingstekniker som undersöktes uppvisade nanofiltreringen den bästa reningseffektiviteten för PFASer med både korta och långa kolkedjor (i genomsnitt, 51%.). Lägre reningseffektivitet för PFASer observerades för MIEX®(33%), < FeCl3(16%) < PAC (14%). Totalt sett erhölls en relativt låg reningseffektivitet (<78%) för samtliga reningstekniker, speciellt för de kortkedjade PFASer (C£6, < 41%). Resultat från försök med tre olika doser PAC (e.g. 20, 50, 100 mg L-1) visade på en ökad reningseffektivitet (2,2-41%, 8,0-78% och 12-92%) med ökad dos PAC. Inga signifikanta trender kunde urskiljas vad gäller reningseffektivitet av PFASer och rening av DOC (p<0.05, student t-test), detta gällde för samtliga behandlingstekniker. Det fanns dock tydliga skillnader i reningseffektivitet mellan de sex olika vattentyperna vilket indikerar på att DOC egenskaperna (Freshnessindex, humifieringsindex, pH, absorbans) har en påverkan på reningseffektiviteten för PFASer i vatten.

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.

This thesis describes the rejection efficiency and the fouling behaviour of calcium sulphate solutes in a 1 nm tubular ceramic titanium dioxide nanofiltration membrane. Calcium sulphate is considered as one of the greatest scaling potential inorganic salts that responsible for membrane fouling which represents a main challenge in the expansion of membrane processes for desalination of brackish and saline water. The surface charge type and magnitude for the composite amphoteric TiO_2 membrane were characterised using streaming potential measurements. Electrokinetic membrane experiments were conducted in a background electrolyte comprising 0.01 M (NaCl). The zeta potential was estimated from the measured streaming potential using the Helmoholtz-Smoluchowski equation and the surface charge density was subsequently calculated using the Gouy-Chapman and Graham equations. The experimental results showed that the membrane was negatively charged at neutral pH and its iso-electrical point (i.e.p) was at pH of 4.0. The rejection behaviour of calcium sulphate at three different initial concentrations (0.001, 0.005 and 0.01 M) were investigated compared to other naturally occurring minerals (NaCl, Na_2 SO_4, CaCl_2) in single salt solutions. The rejection experiments were conducted at five different applied trans-membrane pressures ranged from 1.0 to 5.0 bars. Salt retention measurements showed that the rejection sequence was R (CaSO_4) > R (Na_2 SO_4) > R (CaCl_2) > R (NaCl). This rejection sequence behaviour showed an inverse relationship with the diffusion coefficients of the four salts. The salt with the lowest diffusion coefficient (CaSO_4) showed the highest rejection (43.3%), whereas that with the highest diffusion coefficient showed the lowest rejection. The rejection of calcium sulphate solution at saturation concentration was also conducted after a suspension solution of 0.015 M (CaSO_4) was prepared and filtered. The ionic analysis for calcium sulphate permeates indicated that, for the negatively charged TiO_2 membrane, the rejection for bivalent anion (SO_4^(2-) ) was higher than that of the bivalent cation (Ca^(2+) ).The critical flux (CF) experiments were carried out at six trans-membrane pressure ranged from 1.0 to 6.0 bars to identify the form and the onset of calcium sulphate fouling (as gypsum) using different concentrations below saturation concentration (0.001, 0.005, 0.01 M) and at saturation concentration. Two different flux-pressure techniques have been applied and compared to determine the critical flux values; these are: step by step technique and standard stepping technique. The obtained critical flux results from both measuring techniques (for all the four sessions) confirmed that the critical flux was reached and exceeded. The present work indicated that the resulting critical flux values from both measuring procedures were decreased as the ionic strengths of the calcium sulphate solutes were increased. A mathematical model has been proposed to identify the key parameters that affect the transport performance inside the TiO_2 nanofiltration membrane. The original Donnan steric pore model (DSPM) was used to simulate the rejection of 0.01 M sodium chloride as a reference solution. The membrane effective pore radius was estimated using two different transport models, both of these models depend on the permeation test of uncharged solute (glucose). The Donnan potential was determined based on the membrane effective fixed charge density which was determined by supposing that the membrane surface charge was uniformly distributed in the void volume of cylindrical pores. The theoretical rejection of NaCl solute for the present DSPM model was found to be in agreement with the experimental data.

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.