Positively charged nanofiltration membrane synthesis, transport models, and lanthanides separation.

The design and understanding of rejection mechanisms for both positively and negatively charged nanofiltration (NF) membranes are needed for the development of highly selective separation of multivalent ions. In this study, positively charged nanofiltration membranes were created via an addition of commercially available polyallylamine hydrochloride (PAH) by conventional interfacial polymerization technique. Demonstration of real increase in surface zeta potential, along with other characterization methods, confirmed the addition of weak basic functional groups from PAH. Both positively and negatively charged NF membranes were tested for evaluating their potential as a technology for the recovery or separation of lanthanide cations (neodymium and lanthanum chloride as model salts) from aqueous sources. Particularly, the NF membranes with added PAH performed high and stable lanthanides retentions, with values around 99.3% in mixtures with high ionic strength (100 mM, equivalent to ~6,000 ppm), 99.3% rejection at 85% water recovery (and high Na+/La3+ selectivity, with 0% Na+ rejection starting at 65% recovery), and both constant lanthanum rejection and permeate flux at even pH 2.7. Donnan steric pore model with dielectric exclusion elucidated the transport mechanism of lanthanides and sodium, proving the potential of high selective separation at low permeate fluxes using positively charged NF membranes.

Naphthenic acids removal from high TDS produced water by persulfate mediated iron oxide functionalized catalytic membrane, and by nanofiltration.

Oil industries generate large amounts of produced water containing organic contaminants, such as naphthenic acids (NA) and very high concentrations of inorganic salts. Recovery of potable water from produced water can be highly energy intensive is some cases due to its high salt concentration, and safe discharge is more suitable. Here, we explored catalytic properties of iron oxide (FexOy nanoparticles) functionalized membranes in oxidizing NA from water containing high concentrations of total dissolved solids (TDS) using persulfate as an oxidizing agent. Catalytic decomposition of persulfate by FexOy functionalized membranes followed pseudo-first order kinetics with an apparent activation energy of 18 Kcal/mol. FexOy functionalized membranes were capable of lowering the NA concentrations to less than discharge limits of 10 ppm at 40 °C. Oxidation state of iron during reaction was quantified. Membrane performance was investigated for extended period of time. A coupled process of advanced oxidation catalyzed by membrane and nanofiltration was also evaluated. Commercially available nanofiltration membranes were found capable of retaining NA from water containing high concentrations of dissolved salts. Commercial NF membranes, Dow NF270 (Dow), and NF8 (Nanostone) had NA rejection of 79% and 82%, respectively. Retentate for the nanofiltration was further treated with advanced oxidation catalyzed by FexOy functionalized membrane for removal of NA.

Engineered Iron/Iron Oxide Functionalized Membranes for Selenium and Other Toxic Metal Removal from Power Plant Scrubber Water.

The remediation of toxic metals from water with high concentrations of salt has been an emerging area for membrane separation. Cost-effective nanomaterials such as iron and iron oxide nanoparticles have been widely used in reductive and oxidative degradation of toxic organics. Similar procedures can be used for redox transformations of metal species (e.g. metal oxyanions to elemental metal), and/or adsorption of species on iron oxide surface. In this study, iron-functionalized membranes were developed for reduction and adsorption of selenium from coal-fired power plant scrubber water. Iron-functionalized membranes have advantages over iron suspension as the membrane prevents particle aggregation and dissolution. Both lab-scale and full-scale membranes were prepared first by coating polyvinylidene fluoride (PVDF) membranes with polyacrylic acid (PAA), followed by ion exchange of ferrous ions and subsequent reduction to zero-valent iron nanoparticles. Water permeability of membrane decreased as the percent PAA functionalization increased, and the highest ion exchange capacity (IEC) was obtained at 20% PAA with highly pH responsive pores. Although high concentrations of sulfate and chloride in scrubber water decreased the reaction rate of selenium reduction, this was shown to be overcome by integration of nanofiltration (NF) and iron-functionalized membranes, and selenium concentration below 10 µg/L was achieved.

Composite Membranes Derived from Cellulose and Lignin Sulfonate for Selective Separations and Antifouling Aspects.

Cellulose-based membrane materials allow for separations in both aqueous solutions and organic solvents. The addition of nanocomposites into cellulose structure is facilitated through steric interaction and strong hydrogen bonding with the hydroxy groups present within cellulose. An ionic liquid, 1-ethyl-3-methylimidazolium acetate, was used as a solvent for microcrystalline cellulose to incorporate graphene oxide quantum dots into cellulose membranes. In this work, other composite materials such as, iron oxide nanoparticles, polyacrylic acid, and lignin sulfonate have all been uniformly incorporated into cellulose membranes utilizing ionic liquid cosolvents. Integration of iron into cellulose membranes resulted in high selectivity (>99%) of neutral red and methylene blue model dyes separation over salts with a high permeability of 17 LMH/bar. With non-aqueous (alcohol) solvent, iron-cellulose composite membranes become less selective and more permeable, suggesting the interaction of iron ions cellulose OH groups plays a major role in pore structure. Polyacrylic acid was integrated into cellulose membranes to add pH responsive behavior and capacity for metal ion capture. Calcium capture of 55 mg Ca2+/g membrane was observed for PAA-cellulose membranes. Lignin sulfonate was also incorporated into cellulose membranes to add strong negative charge and a steric barrier to enhance antifouling behavior. Lignin sulfonate was also functionalized on the commercial DOW NF270 nanofiltration membranes via esterification of hydroxy groups with carboxyl group present on the membrane surface. Antifouling behavior was observed for both lignin-cellulose composite and commercial membranes functionalized with lignin. Up to 90% recovery of water flux after repeated cycles of fouling was observed for both types of lignin functionalized membranes while flux recovery of up to 60% was observed for unmodified membranes.

High Total Dissolved Solids Water Treatment by Charged Nanofiltration Membranes Relating to Power Plant Applications.

Selective desalination through nanofiltration (NF) is of great interest for many industrial applications including reuse of power plant scrubber wastewater and treatment of water containing high concentrations of TDS (total dissolved solids). This work seeks to understand the effect ion interactions at the membrane interface have on rejection and flux performance of charged NF membranes. NF membranes were also effective for low energy desalination of scrubber wastewater from Georgia Power Plant Bowen, composed primarily of Ca2+, Mg2+, Cl-, and SO4 2-. As NF membranes have the capability for selective separations, 80% water recovery was achieved experimentally while maintaining an overall rejection of over 60% for Ca2+ and Cl-. The occurrence of CaSO4 precipitation at high water recovery was observed. The effect of precipitation on osmotic pressure and the effect of Cl- counterions on increasing gypsum solubility were explored for water recovery operation. This work expands on a previous work on the topics of desalination of multi-ionic solutions by incorporating the use of large scale membrane modules (0.59 m2) with several synthetic solutions as well as actual scrubber water containing precipitating elements, Ca2+ and SO4 2-. It was observed that the spiral wound membrane modules maintained a stable water permeability over the 144 day course of tests.