Machine Learning for Polymer Design to Enhance Pervaporation-Based Organic Recovery.

Pervaporation (PV) is an effective membrane separation process for organic dehydration, recovery, and upgrading. However, it is crucial to improve membrane materials beyond the current permeability-selectivity trade-off. In this research, we introduce machine learning (ML) models to identify high-potential polymers, greatly improving the efficiency and reducing cost compared to conventional trial-and-error approach. We utilized the largest PV data set to date and incorporated polymer fingerprints and features, including membrane structure, operating conditions, and solute properties. Dimensionality reduction, missing data treatment, seed randomness, and data leakage management were employed to ensure model robustness. The optimized LightGBM models achieved RMSE of 0.447 and 0.360 for separation factor and total flux, respectively (logarithmic scale). Screening approximately 1 million hypothetical polymers with ML models resulted in identifying polymers with a predicted permeation separation index >30 and synthetic accessibility score <3.7 for acetic acid extraction. This study demonstrates the promise of ML to accelerate tailored membrane designs.

The Future of Municipal Wastewater Reuse Concentrate Management: Drivers, Challenges, and Opportunities.

Water reuse is rapidly becoming an integral feature of resilient water systems, where municipal wastewater undergoes advanced treatment, typically involving a sequence of ultrafiltration (UF), reverse osmosis (RO), and an advanced oxidation process (AOP). When RO is used, a concentrated waste stream is produced that is elevated in not only total dissolved solids but also metals, nutrients, and micropollutants that have passed through conventional wastewater treatment. Management of this RO concentrate─dubbed municipal wastewater reuse concentrate (MWRC)─will be critical to address, especially as water reuse practices become more widespread. Building on existing brine management practices, this review explores MWRC management options by identifying infrastructural needs and opportunities for multi-beneficial disposal. To safeguard environmental systems from the potential hazards of MWRC, disposal, monitoring, and regulatory techniques are discussed to promote the safety and affordability of implementing MWRC management. Furthermore, opportunities for resource recovery and valorization are differentiated, while economic techniques to revamp cost-benefit analysis for MWRC management are examined. The goal of this critical review is to create a common foundation for researchers, practitioners, and regulators by providing an interdisciplinary set of tools and frameworks to address the impending challenges and emerging opportunities of MWRC management.

Multistage Surface-Heated Vacuum Membrane Distillation Process Enables High Water Recovery and Excellent Heat Utilization: A Modeling Study.

Surface-heated membrane distillation (MD) enhances the energy efficiency of desalination by mitigating temperature polarization (TP). However, systematic investigations of larger scale, multistage, surface-heated MD system with high water recovery and heat recycling are limited. Here, we explore the design and performance of a multistage surface-heated vacuum MD (SHVMD) with heat recovery through a comprehensive finite difference model. In this process, the latent heat of condensation is recovered through an internal heat exchanger (HX) using the retentate from one stage as the condensing fluid for the next stage and an external HX using the feed as the condensing fluid. Model results show that surface heating enhances the performance compared to conventional vacuum MD (VMD). Specifically, in a six-stage SHVMD process, 54.44% water recovery and a gained output ratio (GOR) of 3.28 are achieved with a surface heat density of 2000 W m-2, whereas a similar six-stage VMD process only reaches 18.19% water recovery and a GOR of 2.15. Mass and energy balances suggest that by mitigating TP, surface heating increases the latent heat trapped in vapor. The internal and external HXs capture and reuse the additional heat, which enhances the GOR values. We show for SHVMD that the hybrid internal/external heat recovery design can have GOR value 1.44 times higher than that of systems with only internal or external heat recovery. Furthermore, by only increasing six stages to eight stages, a GOR value as high as 4.35 is achieved. The results further show that surface heating can reduce the energy consumption of MD for brine concentration. The multistage SHVMD technology exhibits a promising potential for the management of brine from industrial plants.

High-Efficiency Recovery of Acetic Acid from Water Using Electroactive Gas-Stripping Membranes.

Recovery of carbon-based resources from waste is a critical need for achieving carbon neutrality and reducing fossil carbon extraction. We demonstrate a new approach for extracting volatile fatty acids (VFAs) using a multifunctional direct heated and pH swing membrane contactor. The membrane is a multilayer laminate composed of a carbon fiber (CF) bound to a hydrophobic membrane and sealed with a layer of polydimethylsiloxane (PDMS); this CF is used as a resistive heater to provide a thermal driving force for PDMS that, while a highly hydrophobic material, is known for its ability to rapidly pass gases, including water vapor. The transport mechanism for gas transport involves the diffusion of molecules through the free volume of the polymer matrix. CF coated with polyaniline (PANI) is used as an anode to induce an acidic pH swing at the interface between the membrane and water, which can protonate the VFA molecule. The innovative multilayer membrane used in this study has successfully demonstrated a highly efficient recovery of VFAs by simultaneously combining pH swing and joule heating. This novel technique has revealed a new concept in the field of VFA recovery, offering promising prospects for further advancements in this area. The energy consumption was 3.37 kWh/kg for acetic acid (AA), and an excellent separation factor of AA/water of 51.55 ± 2.11 was obtained with high AA fluxes of 51.00 ± 0.82 g.m-2hr-1. The interfacial electrochemical reactions enable the extraction of VFAs without the need for bulk temperature and pH modification.

Simple and Low-Cost Electroactive Membranes for Ammonia Recovery.

Ammonia is considered a contaminant to be removed from wastewater. However, ammonia is a valuable commodity chemical used as the primary feedstock for fertilizer manufacturing. Here we describe a simple and low-cost ammonia gas stripping membrane capable of recovering ammonia from wastewater. The material is composed of an electrically conducting porous carbon cloth coupled to a porous hydrophobic polypropylene support, that together form an electrically conductive membrane (ECM). When a cathodic potential is applied to the ECM surface, hydroxide ions are produced at the water-ECM interface, which transforms ammonium ions into higher-volatility ammonia that is stripped across the hydrophobic membrane material using an acid-stripping solution. The simple structure, low cost, and easy fabrication process make the ECM an attractive material for ammonia recovery from dilute aqueous streams, such as wastewater. When paired with an anode and immersed into a reactor containing synthetic wastewater (with an acid-stripping solution providing the driving force for ammonia transport), the ECM achieved an ammonia flux of 141.3 ± 14.0 g.cm-2.day-1 at a current density of 6.25 mA.cm-2 (69.2 ± 5.3 kg(NH3-N)/kWh). It was found that the ammonia flux was sensitive to the current density and acid circulation rate.

Nanostructured Graphene Oxide Composite Membranes with Ultrapermeability and Mechanical Robustness.

Graphene oxide (GO) membranes have great potential for separation applications due to their low-friction water permeation combined with unique molecular sieving ability. However, the practical use of deposited GO membranes is limited by the inferior mechanical robustness of the membrane composite structure derived from conventional deposition methods. Here, we report a nanostructured GO membrane that possesses great permeability and mechanical robustness. This composite membrane consists of an ultrathin selective GO nanofilm (as low as 32 nm thick) and a postsynthesized macroporous support layer that exhibits excellent stability in water and under practical permeability testing. By utilizing thin-film lift off (T-FLO) to fabricate membranes with precise optimizations in both selective and support layers, unprecedented water permeability (47 L·m-2·hr-1·bar-1) and high retention (>98% of solutes with hydrated radii larger than 4.9 Å) were obtained.

Mineral Scale Prevention on Electrically Conducting Membrane Distillation Membranes Using Induced Electrophoretic Mixing.

The growth of mineral crystals on surfaces is a challenge across multiple industrial processes. Membrane-based desalination processes, in particular, are plagued by crystal growth (known as scaling), which restricts the flow of water through the membrane, can cause membrane wetting in membrane distillation, and can lead to the physical destruction of the membrane material. Scaling occurs when supersaturated conditions develop along the membrane surface due to the passage of water through the membrane, a process known as concentration polarization. To reduce scaling, concentration polarization is minimized by encouraging turbulent conditions and by reducing the amount of water recovered from the saline feed. In addition, antiscaling chemicals can be used to reduce the availability of cations. Here, we report on an energy-efficient electrophoretic mixing method capable of nearly eliminating CaSO4 and silicate scaling on electrically conducting membrane distillation (ECMD) membranes. The ECMD membrane material is composed of a percolating layer of carbon nanotubes deposited on porous polypropylene support and cross-linked by poly(vinyl alcohol). The application of low alternating potentials (2 Vpp,1Hz) had a dramatic impact on scale formation, with the impact highly dependent on the frequency of the applied signal, and in the case of silicate, on the pH of the solution.

Scalable antifouling reverse osmosis membranes utilizing perfluorophenyl azide photochemistry.

We present a method to produce anti-fouling reverse osmosis (RO) membranes that maintains the process and scalability of current RO membrane manufacturing. Utilizing perfluorophenyl azide (PFPA) photochemistry, commercial reverse osmosis membranes were dipped into an aqueous solution containing PFPA-terminated poly(ethyleneglycol) species and then exposed to ultraviolet light under ambient conditions, a process that can easily be adapted to a roll-to-roll process. Successful covalent modification of commercial reverse osmosis membranes was confirmed with attenuated total reflectance infrared spectroscopy and contact angle measurements. By employing X-ray photoelectron spectroscopy, it was determined that PFPAs undergo UV-generated nitrene addition and bind to the membrane through an aziridine linkage. After modification with the PFPA-PEG derivatives, the reverse osmosis membranes exhibit high fouling-resistance.

On the Disproportionate Contribution of Membrane Electron Donor Functionality in Membrane Biofouling.

This study set out to uncover which interfacial properties have the greatest impact on membrane organic fouling, biofouling, and fouling resistance. A relatively simple manipulation of the basic equations used in determining Lifshitz-van der Waals (LW) and Lewis acid-base (AB) surface tensions for solid materials reveals that the high electron accepticity of water makes the electron donicity of membrane and biofouling materials the key component governing their interfacial free energy of adhesion (ΔG132), which defines the favorability (or unfavorability) of one material (1) adhering to another (2) when immersed in a liquid (3). Various biofoulant and membrane LW and AB surface tensions were systematically characterized. Static bacterial adhesion, alginic acid filtration, and wastewater filtration tests were conducted to determine the fouling propensities of three different polymeric membrane materials. Experimental results of microbial adhesion, alginate fouling, and biofouling tests all correlated well with membrane electron density, where higher electron density produced less organic fouling or biofouling. These combined theoretical and experimental results confirm the importance of surface electron donicity in determining the fouling propensity of polymeric membranes.

Molecular dynamics of equilibrium and pressure-driven transport properties of water through LTA-type zeolites.

We consider an atomistic model to investigate the flux of water through thin Linde type A (LTA) zeolite membranes with differing surface chemistries. Using molecular dynamics, we have studied the flow of water under hydrostatic pressure through a fully hydrated LTA zeolite film (~2.5 nm thick) capped with hydrophilic and hydrophobic moieties. Pressure drops in the 50-400 MPa range were applied across the membrane, and the flux of water was monitored for at least 15 ns of simulation time. For hydrophilic membranes, water molecules adsorb at the zeolite surface, creating a highly structured fluid layer. For hydrophobic membranes, a depletion of water molecules occurs near the water/zeolite interface. For both types of membranes, the water structure is independent of the pressure drop established in the system and the flux through the membranes is lower than that observed for the bulk zeolitic material; the latter allows an estimation of surface barrier effects to pressure-driven water transport. Mechanistically, it is observed that (i) bottlenecks form at the windows of the zeolite structure, preventing the free flow of water through the porous membrane, (ii) water molecules do not move through a cage in a single-file fashion but rather exhibit a broad range of residence times and pronounced mixing, and (iii) a periodic buildup of a pressure difference between inlet and outlet cages takes place which leads to the preferential flow of water molecules toward the low-pressure cages.

Bacteria-polymeric membrane interactions: atomic force microscopy and XDLVO predictions.

Atomic force microscopy (AFM) in conjunction with a bioprobe developed using a polydopamine wet adhesive was used to directly measure the adhesive force between bacteria and different polymeric membrane surfaces. Bacterial cells of Pseudomonas putida and Bacillus subtilis were immobilized onto the tip of a standard AFM cantilever, and force measurements made using the modified cantilever on various membranes. Interaction forces measured with the bacterial probe were compared, qualitatively, to predictions by the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory with steric interactions included. The XDLVO theory predicted attractive interactions between low energy hydrophobic membranes with high energy hydrophilic bacterium (P. putida). It also predicted a shallow primary maximum with the most hydrophilic bacterium, B. subtilis . Discrepancies between predictions using the XDLVO theory and theory require involvement of factors such as bridging effects. Differences in interaction between P. putida and B. subtilis are attributed to acid-base interactions and steric interactions. P. putida is Gram negative with lipopolysaccharides present in the outer cell membrane. A variation in forces of adhesion for bacteria on polymeric membranes studied was interpreted in terms of hydrophilicity and interfacial surface potential calculated from physicochemical properties.

Thermodynamic analysis of osmotic energy recovery at a reverse osmosis desalination plant.

Recent years have seen a substantial reduction of the specific energy consumption (SEC) in seawater reverse osmosis (RO) desalination due to improvements made in hydraulic energy recovery (HER) as well as RO membranes and related process technologies. Theoretically, significant potential for further reduction in energy consumption may lie in harvesting the high chemical potential contained in RO concentrate using salinity gradient power technologies. Herein, "osmotic energy recovery" (OER) is evaluated in a seawater RO plant that includes state-of-the-art RO membranes, plant designs, operating conditions, and HER technology. Here we assume the use of treated wastewater effluent as the OER dilute feed, which may not be available in suitable quality or quantity to allow operation of the coupled process. A two-stage OER configuration could reduce the SEC of seawater RO plants to well below the theoretical minimum work of separation for state-of-the-art RO-HER configurations with a breakeven OER CAPEX equivalent to 42% of typical RO-HER plant cost suggesting significant cost savings may also be realized. At present, there is no commercially viable OER technology; hence, the feasibility of using OER at seawater RO plants remains speculative, however attractive.

Supercomputing and machine learning-aided optimal design of high permeability seawater reverse osmosis membrane systems.

Concentration polarization (CP) should limit the energy and cost reducing benefits of high permeability seawater reverse osmosis (SWRO) membranes operating at a water flux higher than normal one. Herein, we propose a multiscale optimization framework coupling membrane permeability, feed spacer design (sub-millimeter scale) and system design (meter scale) via computational fluid dynamics and system level modeling using advanced supercomputing in conjunction with machine learning. Simulation results suggest energy consumption could be reduced by 27.5% (to 1.66 kWh m-3) predominantly through the use of high permeability SWRO membranes (12.2%) and a two-stage design (14.5%). Without optimization, CP approaches 1.52 at the system inlet, whereas the optimized CP is limited to 1.20. This work elucidates the optimized permeability, module design, operating scheme and benefits of high permeability SWRO membranes in seawater desalination.

Carbon/nitrogen ratios determine biofilm formation and characteristics in model microbial cultures.

The influence of growth medium water chemistry, specifically carbon/nitrogen (C/N) molar ratios, on the characteristics and development of biofilms of the model microorganism Pseudomonas aeruginosa was investigated. C/N = 9 had a unique effect on biofilm composition as well as quorum sensing (QS) pathways, with higher concentrations of carbohydrates and proteins in the biofilm and a significant upregulation of the QS gene lasI in planktonic cells. The effect of C/N ratio on total attached biomass was negligible. Principal component analysis revealed a different behavior of most outputs such as carbohydrates and QS chemicals at C/N = 9, and pointed to correlations between parameters of biofilm formation and steady state distribution of cells and extracellular components. C/N ratio was also shown to influence organic compound utilization by both planktonic and sessile organisms, with a maximum chemical oxygen demand (COD) removal of 83% achieved by biofilms at C/N = 21. Planktonic cells achieved higher COD removal rates, but greater overall rates after six days occurred in biofilms. The development of a dual-species biofilm of P. aeruginosa and Nitrobacter winogradskyi was also influenced by C/N, with increase in the relative abundance of the slower-growing N. winogradskyi above C/N = 9. These results indicate that altering operational parameters related to C/N would be relevant for mitigating or promoting biofilm formation and function depending on the desired industrial application or treatment configuration.

Biological treatment of perfluorooctanesulfonic acid (PFOS) using microbial capsules of a polysulfone membrane.

Perfluorooctanesulfonic acid (PFOS) is a persistent organic substance that has been extensively applied in many industries and causes severe, widespread adverse health impacts on humans and the environment. The development of an effective PFOS treatment method with affordable operational costs has been expected. This study proposes the biological treatment of PFOS using microbial capsules enclosing a PFOS-reducing microbial consortium. The objective of this study was to evaluate the performance of the polymeric membrane encapsulation technique for the biological removal of PFOS. First, a PFOS-reducing bacterial consortium, composed of Paracoccus (72%), Hyphomicrobium (24%), and Micromonosporaceae (4%), was enriched from activated sludge by acclimation and subsequent subculturing with PFOS containing media. The bacterial consortium was first immobilized in alginate gel beads, then enclosed in membrane capsules by coating the gel beads with a 5% or 10% polysulfone (PSf) membrane. The introduction of microbial membrane capsules could increase PFOS reduction to between 52% and 74% compared with free cell suspension, which reduced by 14% over three weeks. Microbial capsules coated with 10% PSf membrane demonstrated the highest PFOS reduction at 80% and physical stability for six weeks. Candidate metabolites including perfluorobutanoic acid (PFBA) and 3,3,3- trifluoropropionic acid were detected by FTMS, suggesting the possible biological degradation of PFOS. In microbial membrane capsules, the initial adsorption of PFOS on the shell membrane layer enhanced subsequent biosorption and biological degradation by PFOS-reducing bacteria immobilized in the core alginate gel beads. The 10%-PSf microbial capsules exhibited a thicker membrane layer with the fabric structure of a polymer network, which maintained longer physical stability than 5%-PSf microbial capsules. This outcome suggests the potential application of microbial membrane capsules to PFOS-contaminated water treatment.

Tuning structure and properties of graded triblock terpolymer-based mesoporous and hybrid films.

Despite considerable efforts toward fabricating ordered, water-permeable, mesoporous films from block copolymers, fine control over pore dimensions, structural characteristics, and mechanical behavior of graded structures remains a major challenge. To this end, we describe the fabrication and performance characteristics of graded mesoporous and hybrid films derived from the newly synthesized triblock terpolymer, poly(isoprene-b-styrene-b-4-vinylpyridine). A unique morphology, unachievable in diblock copolymer systems, with enhanced mechanical integrity is evidenced. The film structure comprises a thin selective layer containing vertically aligned and nearly monodisperse mesopores at a density of more than 10(14) per m(2) above a graded macroporous layer. Hybridization via homopolymer blending enables tuning of pore size within the range of 16 to 30 nm. Solvent flow and solute separation experiments demonstrate that the terpolymer films have permeabilities comparable to commercial membranes, are stimuli-responsive, and contain pores with a nearly monodisperse diameter. These results suggest that moving to multiblock polymers and their hybrids may open new paths to produce high-performance graded membranes for filtration, separations, nanofluidics, catalysis, and drug delivery.

Carbon nanotube/polyaniline composite nanofibers: facile synthesis and chemosensors.

An initiator is applied to synthesize single-walled carbon nanotube/polyaniline composite nanofibers for use as high-performance chemosensors. The composite nanofibers possess widely tunable conductivities (10(-4) to 10(2) S/cm) with up to 5.0 wt % single-walled carbon nanotube (SWCNT) loadings. Chemosensors fabricated from the composite nanofibers synthesized with a 1.0 wt % SWCNT loading respond much more rapidly to low concentrations (100 ppb) of HCl and NH(3) vapors compared to polyaniline nanofibers alone (120 s vs 1000 s). These nanofibrillar SWCNT/polyaniline composite nanostructures are promising materials for use as low-cost disposable sensors and as electrodes due to their widely tunable conductivities.

Impacts of Operating Conditions and Solution Chemistry on Osmotic Membrane Structure and Performance.

Herein, we report on changes in the performance of a commercial cellulose triacetate (CTA) membrane, imparted by varied operating conditions and solution chemistries. Changes to feed and draw solution flow rate did not significantly alter the CTA membrane's water permeability, salt permeability, or membrane structural parameter when operated with the membrane skin layer facing the draw solution (PRO-mode). However, water and salt permeability increased with increasing feed or draw solution temperature, while the membrane structural parameter decreased with increasing draw solution, possibly due to changes in polymer intermolecular interactions. High ionic strength draw solutions may de-swell the CTA membrane via charge neutralization, which resulted in lower water permeability, higher salt permeability, and lower structural parameter. This observed trend was further exacerbated by the presence of divalent cations which tends to swell the polymer to a greater extent. Finally, the calculated CTA membrane's structural parameter was lower and less sensitive to external factors when operated in PRO-mode, but highly sensitive to the same factors when the skin layer faced the feed solution (FO-mode), presumably due to swelling/de-swelling of the saturated porous substructure by the draw solution. This is a first attempt aimed at systematically evaluating the changes in performance of the CTA membrane due to operating conditions and solution chemistry, shedding new insight into the possible advantages and disadvantages of this material in certain applications.

Desalinating a real hyper-saline pre-treated produced water via direct-heat vacuum membrane distillation.

Membrane distillation (MD) is an emerging thermal desalination technology capable of desalinating waters of any salinity. During typical MD processes, the saline feedwater is heated and acts as the thermal energy carrier; however, temperature polarization (as well as thermal energy loss) contributes to low distillate fluxes, low single-pass water recovery and poor thermal efficiency. An alternative approach is to integrate an extra thermal energy carrier as part of the membrane and/or module assembly, which can channel externally provided heat directly to the membrane-feedwater interface and/or along the feed channel length. This direct-heat delivery has been demonstrated to increase single-pass water recovery and enhance the overall thermal efficiency. We developed a bench-scale direct-heated vacuum MD (DHVMD) process to desalinate pre-treated oil and gas "produced water" with an initial total dissolved solids of 115,500 ppm at a feed temperature ranging between 24 and 32 °C. We evaluated both water flux and specific energy consumption (SEC) as a function of water recovery. The system achieved a 50% water recovery without significant scaling, with an average flux >6 kg m-2 hr-1 and a SEC as low as 2,530 kJ kg-1. The major species of mineral scales (i.e., NaCl, CaSO4, and SrSO4) that limited the water recovery to 68% were modeled in terms of thermodynamics and identified by scanning electron microscopy and energy-dispersive X-ray spectroscopy. In addition, we further developed and employed a physics-based process model to estimate temperature, salinity, water transport and energy flows for full-scale vacuum MD and DHVMD modules. Model results show that a direct-heat input rate of 3,600 W can increase single-pass water recovery from 2.1% to 3.1% while lowering the thermal SEC from 7,800 kJ kg-1 to 6,517 kJ kg-1 in an unoptimized module. Finally, the scaling up potential of DHVMD process is briefly discussed.