Yes / Phenol and phenolic derivatives found in different industrial effluents are highly toxic and extremely harmful to human and the aquatic ecosystem. In the past, trickle bed reactor (TBR), reverse osmosis (RO) and other processes have been used to remove phenol from wastewater. However, each of these technologies has limitations in terms of the phenol concentration in the feed water and the efficiency of phenol rejection rate. In this work, an integrated hybrid TBR-RO process for removing high concentration phenol from wastewater is suggested and model-based simulation of the process is presented to evaluate the performance of the process. The models for both TBR and RO processes were independently validated against experimental data from the literature before coupling together to make the hybrid process. The results clearly show that the combined process significantly improves the rejection rate of phenol compared to that obtained via the individual processes.

Yes / Reverse Osmosis (RO) processes are readily used for removing pollutants, such as dimethylphenol from wastewater. A number of operating parameters must be controlled within the process constraints to achieve an efficient removal of such pollutants. Understanding the process dynamics is absolutely essential and is a pre-step for designing any effective controllers for any process. In this work, a detailed distributed two-dimensional dynamic (x and y dimensions and time) model for a spiral-wound RO process is developed extending the 2-D steady state model of the authors published earlier. The model is used to capture the dynamics of the RO process for the removal of dimethylphenol from wastewater. The performance of the 2-D model is compared with that obtained using 1-D dynamic model before the model is being used to investigate the performance of the RO process for a range of operating conditions.

Yes / The Reverse Osmosis (RO) input parameters have key roles in mass transport and performance indicators. Several studies can be found in open literature. However, an experimental research on evaluating the brackish water RO input parameters influence on the performance metrics with justifying the interference between them via a robust model has not been addressed yet. This paper aims to design, construct, and experimentally evaluate the performance of a 50 m3/d RO pilot-plant to desalinate brackish water in Shahid Chamran University of Ahvaz, Iran. Water samples with various salinity ranging from 1000 to 5000 ppm were fed to a semi-permeable membrane under variable operating pressures from 5 to 13 bar. By evaluating permeate flux and brine flowrate, permeate and brine salinities, membrane water recovery, and salt rejection, some logical relations were derived. The results indicated that the performance of an RO unit is largely dependent on feed pressure and feed salinity. At a fixed feed concentration, an almost linear relationship was found to relate feed pressure and both permeate and brine flowrates. Statistically, it was found that 13 bar feed pressure results in a maximum salt rejection of 98.8% at a minimum permeate concentration of 12 ppm. Moreover, 73.3% reduction in permeate salinity and 30.8% increase in brine salinity are reported when feed pressure increases from 5 to 13 bar. Finally, it is concluded that the water transport coefficient is a function of feed pressure, salinity, and temperature, which is experimentally estimated to be 2.8552 L/(m2 h bar).

Yes / Brackish water can be considered an important source of fresh water, via desalination, especially for arid districts. Reverse Osmosis (RO) process has been successfully used to produce fresh water from brackish water sources. However, there is still the challenge of improving the performance of multistage RO desalination plants. From the selection of the RO configurations to the selection of the appropriate type of membranes and the operating conditions at the end determines the performance of RO process in terms of recovery, salt rejection, energy consumptions and ultimately the cost of production of freshwater. Using model-based simulation, this work attempts to investigate the most suitable types of membranes for an industrial scale RO plant from a set of different membrane brands that would attain the highest-performance at lowest specific energy consumption (SEC). As a case study, we considered a multistage multi-pass medium-scale RO plant (1200 m3/day) of Arab Potash Company (APC, Jordan) which produces high quality water for the boilers after pre-treatment stage. The simulation results confirmed that employment of the Filmtec BW30LE-440 would increase water recovery by about 22% besides reducing the product salinity and SEC by about 15% and 10%, respectively compared to the existing membrane.

Yes / The reverse osmosis (RO) process is one of the best desalination methods, using membranes to reject several impurities from seawater and brackish water. To systematically perceive the transport phenomena of solvent and solutes via the membrane texture, several mathematical models have been developed. To date, a large number of simulation and optimisation studies have been achieved to gauge the influence of control variables on the performance indexes, to adjust the key variables at optimum values, and to realise the optimum production indexes. This paper delivers an intensive review of the successful models of theROprocess and both simulation and optimisation studies carried out on the basis of the models developed. In general, this paper investigates the scope and limitations of the RO process, as well as proving the maturity of the associated perspective methodologies.

Understanding transport of water molecules and salt ions from a molecular level up to macroscopic length scales is critical to the design of novel materials for many applications, including separations membranes for fuel cell and desalination applications, as well as rechargeable battery technology. This work aims to investigate and develop new models correlating the dynamics and structure of polymeric materials, to the transport of small molecules within them, using a variety of Nuclear Magnetic Resonance (NMR) techniques. We present three studies through which we utilize two chemically similar membranes: hydroxyethyl acrylate-co-ethyl acrylate (HEA-co-EA) and hydroxymethyl methacrylate-co-methyl methacrylate (HEMA-co-MMA), which greatly differ in glass transition temperature, in order to understand the fundamental relationships from polymer chain dynamics and small molecule diffusion. From observations of the micron scale diffusion of these materials we find that the more dynamic, rubbery HEA-co-EA exhibits lower water to salt selectivity than HEMA-co-MMA, and that this difference arises from nanoscale morphology of the materials. From this, we propose a new model for hydrophilic pathways inside polymeric materials consisting of nanometer scale interconnected pathways are interrupted by micron scale arrangements of so-called "dead ends". We also for the first time show the separation of material tortuosity into two regimes, ranging from the nanometer-bulk and micron-bulk length scales. We further separate the contributions of structure from chemical interactions in the chemically similar desalination materials by investigating the local activation energy of diffusion in both materials, as well as aqueous solutions of the hydrophilic monomers analogous to the internal membrane environment. We find that the effects of local geometric confinement are very similar between the two materials, however the intermolecular interactions between water and the hydrophilic monomers, with respect to water transport, are significantly different between the two hydrophilic species. Geometric confinement accounts for a 5 ± 1 kJ/mol increase in diffusive activation energy from solution to membrane for both chemistries, and a 4 ± 1 kJ/mol difference in activation energy is seen between the two chemistries in both solution and membrane form. We propose that the entropic contributions to transport, are strongly impacted by the rigid environment of the HEMA material, and is related to the increased water-salt selectivity, as well as the increasing selectivity with increased ionic size observed compared to the HEA system. Using Dynamic NMR spectroscopy, we further investigate the differences seen in water-monomer intermolecular proton exchange by NMR. We utilize an iterative least-squares solving method to fit our exchange lineshape to a model of an uncoupled, two-site exchange lineshape in order to obtain rate and equilibrium population data from -50 to 70 °C. We find that, similar to the diffusive activation energy, the HEA-water system shows reduced enthalpy and entropy of the transition state compared to HEMA-water, such that there is faster exchange between HEMA and water at all temperatures measured, in addition to more biased populations in the HEA-water system. / Doctor of Philosophy / Understanding transport of water molecules and salt ions from a molecular level up to macroscopic length scales is critical to the design of novel materials for many applications, including separations membranes for fuel cell and desalination applications, as well as rechargeable battery technology. This work aims to investigate and develop new models correlating the dynamics and structure of polymeric materials, to the transport of small molecules within them, using a variety of Nuclear Magnetic Resonance (NMR) techniques. We will present three studies in which we seek to further understand the relationships between a material's physical and chemical properties, with the behavior of small molecules like water absorbed within the material. NMR spectroscopy, while not the standard method for characterizing desalination membranes, allows us to specifically probe direct effects on molecular motion of polymer structure from the microscopic level to the bulk, a feat not easily achieved by any other single technique. The first study presented within focuses on the differences in micrometer scale structure in two near identical sets of materials; differing only in that one is rubbery with flexible polymer chains, and the other is rigid with relatively immobile polymer chains. The second study takes these two materials and investigates them through a different lens, probing the molecular scale differences in water motions imparted by the flexible versus rigid polymer chains. The third and final study looks into the fundamental differences seen in how the two chemistries used to create the polymers in the first two studies interact with water molecules through a different NMR technique. These three studies together represent a series of methods and techniques that can be applied to many other classes of polymer materials, such as those destined for use in fuel cells and rechargeable batteries, in order to better understand the fundamental forces at work in those systems to aid in the design of the next generation's materials.

Over 30% of the world's population does not have access to safe drinking water, and the need for clean water spans further than just for human consumption. Currently, we use freshwater for growing agriculture, raising livestock, generating power, sanitizing waste, mining resources, and fabricating consumer goods. With that being said, the world is beginning to feel pressure from the excessive freshwater withdrawal compared to the current freshwater supply. This water stress is causing a water crisis. Places including Australia, South Africa, and California in the United States, just to name a few, are beginning to run out of fresh water to support daily societal demands. This is a phenomenon that is indiscriminately observed in all ranges of economically and politically developed countries and environments. However, it is important to note that less politically and economically developed countries especially those in arid climates, experience higher water stress than countries without such qualities. With only 2.5% of the world's water being freshwater and 30% of it being accessible as either ground or surface water, freshwater is a scarce resource, especially with the growing population and society's demand for water. Since the remaining 97.5% of water is composed of either brackish or seawater (saline water sources), one way to overcome the water stress would be to convert saline water into freshwater. As a result, various desalination techniques have been developed in the last 80 years that employ either membrane technology or temperature alterations to desalinate either brackish or seawater. One of the fastest growing methods for producing freshwater is reverse osmosis. Reverse osmosis uses an externally applied pressure, in the form of a cross flow back pressure, to overcome the osmotic pressure produced by the saline gradient across a semi-permeable membrane. The semi permeable membrane commercially consists of an interfacially polymerized aromatic polyamide thin film composite with a polysulfone porous backing that allows water to pass through while barring the transport of salt ions. This research focuses on the development of sulfonated poly(arylene ether sulfone) derivatives with differing amounts of sulfonation and with the ions placed at different structural positions. Previously, such materials were tested as potential high performance fuel cell membranes, but they are also of interest as potential high performance water desalination membranes, specifically for reverse osmosis. Two different methods were used to synthesize the sulfonated polysulfone derivatives: direct polymerization and post-modification of a non-sulfonated active polysulfone. The polysulfones from direct polymerization incorporated specialty sulfonated monomers, which were stoichiometrically controlled during the polymerization. Sulfonated polysulfones that were synthesized from post sulfonation incorporated biphenol and hydroquinone monomer units randomly throughout the polysufone backbones. These units could be sulfonated selectively because of their activation towards electrophilic aromatic substitution with sulfuric acid. Each of the polymers were cast into films ranging between 20-100 microns in thickness and tested for water uptake, hydrated uniaxial tensile properties, crossflow water and salt transport properties, and for crosslinked samples, gel fractions. The water uptakes from all the polysulfones were tuned by the degree of sulfonation or disulfonation present in the polymer. This was either controlled via the presence of a sulfonated monomer or a monomer that was active toward electrophilic aromatic substitution after polycondensation of the polysulfone. All polymers exhibited increases in their water uptake as the degree of sulfonation increased. We also observed a decreasing trend in the hydrated mechanical properties of the films for all the high molecular weight linear polymers as the water uptake was increased. The directly polymerized sulfonated polysulfones were found to have high hydrated elastic moduli ranging between 400 and 1000 MPa, while the post sulfonated counterparts (with either hydroquinone or biphenol incorporated in their structures) exhibited elastic moduli ranging between 1000 and 1500 MPa. It is important to note that the structures of the polymers were slightly different from one another because of the technique used to synthesize them. Thus, the increases in hydrated moduli among polymers synthesized via different routes may have influences from differences in chemical structures. Some of the polymers with higher degrees of sulfonation were synthesized as amine terminated oligomers with varying controlled molecular weights. The two targeted molecular weights were 5 and 10 kDa. Those oligomers were then crosslinked with a tetra-functional epoxide agent. The increases in sulfonation allowed for increases in water uptake and in theory, the water throughput through the sulfonated polysulfone membrane. Decreases in hydrated mechanical performance of the crosslinked networks with increasing degrees of sulfonation were also observed, similar to their high molecular weight linear counterparts. The directly polymerized crosslinked networks had salt permeabilities that plateaued at 70% disulfonation for both the 5 and 10 kDa polymers. Thus, we expect disulfonation content greater than 70% would lead to higher water throughput without significant increases in salt transport. / Doctor of Philosophy / A worldwide shortage of freshwater is becoming more problematic by each passing day. The World Health Organization and the United Nation's World Water Assessment Program predict that by 2025, 50-66% of the world's population will be living in a water-stressed area. This includes any area that experiences higher clean water withdrawals than are available. This includes but is not limited to areas that are politically unstable, technologically disadvantaged, resource deficient, located in arid climates, and highly populated. To put this further into perspective, only 2.5% of the available water on earth is freshwater. Freshwater typically has low concentrations of dissolved salts that are safe for human consumption and use. Of the available freshwater, only 30% of it is actually accessible for use through either surface or groundwater reservoirs, making the amount of clean water available for usage already a scarce resource. On the other hand, 97.5% of the world's water is composed of saline water reservoirs in the form of brackish and seawater. Through harnessing, seawater and removing the excess dissolved salt ions, the salt water can be converted to freshwater. Two major methods have been developed to remove the dissolved ions from water through either membrane filtration or thermal phase changes. One of the fastest growing membrane filtration techniques used worldwide is reverse osmosis. Reverse osmosis refers to the use of applied pressure across a semipermeable membrane to desalinate saline water. The semipermeable membrane prevents the migration of salt ions through the membrane while allowing transport of water. This work has focused on developing new polymers that can increase the overall efficiency of water desalination. Different types of high performance sulfonated polysulfone derivative polymers were synthesized and used to make membranes that were subsequently tested for performance. Relationships between the polymer structure, process, and properties were quantified through different analytical techniques. This study showed how the properties of sulfonated polysulfone membranes may be manipulated depending on structural modifications and processing to increase both the material's water throughput and salt rejection.

Inorganic nano- and micromaterials (NMMs) exhibit unique properties including high surface areas, tunable optical and electronic properties, low densities, thermal and chemical robustness, and catalytic capabilities, among others. One of the more novel subclasses of NMMs, metal-organic frameworks (MOFs), are crystalline porous coordination polymers consisting of metal nodes connected by organic linkers to form one-, two-, or three-dimensional frameworks. While the mechanism of MOF formation is complex, tuning the metal:ligand ratios, reaction temperature and vessel pressure, ligand concentration, modulator concentration, and H+ activity impacts particle size, morphology, dispersity, and isotropy of these materials. MOFs also exhibit post-synthetic modification capabilities, which, along with their tunable synthetic nature, make them promising candidates for composite materials such as functionalized nanofillers for reverse osmosis (RO) desalination. The work described herein investigates synthetic parameters of a zirconium-based porphyrinic MOF, PCN-222, to selectively control its crystal size, aspect ratio, and dispersity. Size-constrained PCN-222 was post-synthetically modified with fatty acids and zwitterions to be used as RO thin-film composite (TFC) membranes with improved membrane flux, salt rejection, and anti-fouling properties. The synthetic parameters of MOFs were also considered for the commercial scale-up of CO2 direct air capture (DAC) solid sorbents, including UiO-66, MIL-101-Cr, and Mg-MOF-74, to preserve CO2 uptake capacities between lab and industrial scales. / Doctor of Philosophy / Metal-organic frameworks (MOFs) are unique, highly porous materials that have garnered attention for their potential in many applications, including catalysis, drug delivery, energy, and gas storage. In this work, MOFs were produced for environmental applications, particularly for the conversion of salt water to drinkable water in a process known as reverse osmosis (RO) desalination. RO uses a thin membrane to separate dissolved salt, as well as organic materials such as decomposed organisms, from water. Though RO membranes are widely used commercially, they suffer from high costs and short lifetimes; however, their performance is improved through the incorporation of extremely small materials known as nanoparticles. MOF nanoparticles were grown small enough to be dispersed in the polymer matrix of the thin membrane, then functionalized to improve salt rejection and flux, or the speed at which clean water is produced from RO processes. They were also modified to improve lifetimes by preventing the build-up of organic materials on the surface. Besides clean water, MOFs were also prepared for capturing the greenhouse gas, CO2, directly from the air. Because MOFs can be made with many different functionalities, they are promising materials for many different research fields.

Sulfonated poly(arylene ether sulfone)s can exhibit several ideal features as potential desalination membranes for reverse osmosis applications, including chlorine resistance, low surface fouling, and high water flux. However, this class of polymer membranes has suffered from two major drawbacks that jeopardize effective levels of salt rejection in order to achieve high water flux. In mixed salt feed sources, monovalent salt rejection decreases when divalent cations such as Ca2+ bind with the anionic sulfonate groups to cause charge screening, and this can lead to too much salt passage for the membranes to be competitive with interfacially produced polyamides. Sulfonate fixed charge concentration must be high enough for sufficient membrane water uptake to obtain high membrane water flux, but if the water uptake is too high, this permits increased salt passage. The research described in this dissertation attempts to address both of these challenges through the design of a sulfonated monomer that strategically spaces the ionic groups along the polymer backbone chains to inhibit divalent ion binding. Free radical crosslinking further tunes the hydrated free volume in the RO membranes. A mono-sulfonated comonomer, sodium 3-sulfonate-4,4'-dichlorodiphenylsulfone (ms-DCDPS), was synthesized by stoichiometrically controlled electrophilic aromatic sulfonation of 4,4'-dichlorodiphenylsulfone (DCDPS). HPLC-UV revealed complete isolation of ms-DCDPS free of by-products after the 1st recrystallization and 1H NMR analysis confirmed the structure. A standard calibration curve was developed to accurately determine the leftover quantity of excess NaCl that was used for precipitation during the work-up procedures. A series of linear sulfonated poly(arylene ether sulfone)s with varying ms-DCDPS incorporation was synthesized. 1H NMR confirmed the structure of the polymers and size-exclusion chromatography confirmed that the intended molecular weights were achieved. The copolymers were cast into dense films and the mechanical and transport properties were measured in their fully hydrated states. Tensile tests revealed mechanically robust, tough membranes with glassy elastic moduli and high strains at break. The dense membrane prepared from sulfonated poly(arylene ether sulfone) with 51% of the repeat units sulfonated had NaCl rejection = 99.3% measured at 400 psi and 2000 ppm NaCl with a water permeability coefficient of 0.57 x 10-6 cm2/s. The salt rejection remained greater than 99% when a mixed salt feed source containing Ca2+ in the 0-200 ppm range together with the 2000 ppm NaCl was introduced. Crosslinked mono-sulfonated oligomers were synthesized with targeted molecular weights by utilizing stoichiometric quantities of monomers with the desired degrees of sulfonation, and the endgroups were functionalized with tetrafluorostryene. These end-functionalized sulfonated oligomers were crosslinked by both thermal and UV free radical methods in the presence of initiators without any additional crosslinking agents. Reaction conditions were thoroughly investigated and optimized to produce highly crosslinked membranes that yielded gel fractions greater than 87%, as measured by solvent extraction in dimethylacetamide. The hydrated crosslinked membranes were tested for both mechanical and transport properties, and the results were compared to their linear membrane counterparts. Crosslinking decreased the hydrated free volume and reduced water uptakes when compared to linear sulfonated membranes. Tensile tests of the fully hydrated crosslinked membranes showed good mechanical properties. The transport properties of a dense UV crosslinked membrane prepared with a 10,000 g/mol oligomer having 50% of the repeat units sulfonated was tested under RO cross-flow conditions at 400 psi and 2000 ppm NaCl in the feed. The membrane demonstrated a salt rejection = 98.4% with a water permeability coefficient of 0.49 x 10-6 cm2/s. / Doctor of Philosophy / Billions of individuals across the world lack clean, affordable drinking water, and the unavailability of fresh drinking water can be attributed to both physical and economic reasons. Several techniques have been utilized to produce potable water for human consumption that include both water desalination and recycling procedures. Water desalination is a process that allows for purifying salt contaminated water into drinking water. The two major desalination processes involve either distillation or passage through polymer membranes. Distillation separates water from salt by heating liquid water to form a gas, and collecting the vapor as condensate while impurities remain in the heated bulk material. Polymer membranes separate impurities through filtration where membranes allow water to pass through a physical barrier while rejecting the unwanted contaminants, including salt. Reverse osmosis desalination is the most common membrane separation process. Reverse osmosis membranes are comprised of either short-chain crosslinked oligomers or long-chain linear polymers. Commercial reverse osmosis membranes are largely poly(amide)s where a thin film is formed in an interfacial reaction. The membranes allow for almost quantitative salt rejection with high water fluxes. But, these membranes degrade over time from periodic cleaning with chlorine disinfectants. This dissertation primarily focuses on the implementation of an alternative polymer membrane material known as a mono-sulfonated polysulfone that strategically distributes the fixed sulfonate charged groups along the polymer backbone. Theses reverse osmosis mono-sulfonated polysulfones display comparable salt rejection with better chemical resistance than commercial poly(amide)-based membranes, and could potentially offer a replacement in the market.

This thesis research focused on the synthesis and characterization of disulfonated poly(arylene ether sulfone) hydrophilic-hydrophobic segmented and multiblock copolymers for application as proton exchange membranes (PEMs) in fuel cells or as reverse osmosis (RO) membranes for water desalination. The first objective was to demonstrate that synthesizing blocky copolymers using a one oligomer, two monomer segmented copolymerization afforded copolymers with similar properties to those which used a previous approach of coupling two preformed oligomers. A 4,4′-biphenol based hydrophilic block of disulfonated poly(arylene ether sulfone) oligomer of controlled number average molecular weight (Mn) with phenoxide reactive end groups was first synthesized and isolated. It was then reacted with a calculated amount of hydrophobic monomers, forming that block in-situ. Copolymer and membrane properties, such as intrinsic viscosity, tensile strength, water uptake, and proton conductivity, were consistent with those of multiblock copolymers synthesized via the oligomer-oligomer approach. The segmented polymerization technique was then used to synthesize a variety of other copolymers for PEM applications. The well known bisphenol phenolphthalein was explored as a comonomer for either the hydrophilic and hydrophobic blocks of the copolymer. Membrane properties were explored as a function of block length for both series of copolymers. Both series showed that as block length increases, proton conductivity increases across the entire range of relative humidity (30-100%), as does, water uptake. This was consistent with earlier research which showed that the water self-diffusion coefficient scaled with block length. Copolymers produced with phenolphthalein had higher tensile strength, but lower ultimate elongation than the 4,4′-biphenol based copolymers. Multiblock copolymers were also synthesized and characterized to assess their feasibility as RO membranes. A new series of multiblock copolymers was synthesized by coupling hydrophilic disulfonated poly(arylene ether sulfone) (BisAS100) oligomer with hydrophobic unsulfonated poly(arylene ether sulfone) (BisAS0) oligomer. Both oligomers were derived using 4,´-isopropylidenediphenol (Bis-A) as the bisphenol. Phenoxide-terminated BisAS100 was end-capped with decafluorobiphenyl and reacted at relatively low temperatures (~ 100 oC) with phenoxide-terminated BisAS0. Basic properties were characterized as a function of block length. The initial membrane characterization suggested these copolymers may be suitable candidates for reverse osmosis applications, and water and salt permeability testing should be conducted to determine desalination properties. The latter measurements are being conducted at the University of Texas, Austin and will be reported separately. / Ph. D.