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At least 19 records

Effect of Polyphenylsulfone and Polysulfone Incompatibility on the Structure and Performance of Blend Membranes for Ultrafiltration

This study deals with the modification of polyphenylsulfone ultrafiltration membranes by introduction of an incompatible polymer polysulfone to the polyphenylsulfone casting solution to improve the permeability. The correlation between properties of the blend polyphenylsulfone/polysulfone solutions and porous anisotropic membranes for ultrafiltration prepared from these solutions was revealed. The blend polyphenylsulfone/polysulfone solutions were investigated using a turbidity spectrum method, optical microscopy and measurements of dynamic viscosity and turbidity. The structure of the prepared blend flat sheet membranes was studied using scanning electron microscopy. Membrane separation performance was investigated in the process of ultrafiltration of human serum albumin buffered solutions. It was found that with the introduction of polysulfone to the polyphenylsulfone casting solution in N-methyl-2-pyrrolidone the size of supramolecular particles significantly increases with the maximum at (40–60):(60:40) polyphenylsulfone:polysulfone blend ratio from 76 nm to 196–354 nm. It was shown that polyphenylsulfone/polysulfone blend solutions, unlike the solutions of pristine polymers, are two-phase systems (emulsions) with the maximum droplet size and highest degree of polydispersity at polyphenylsulfone/polysulfone blend ratios (30–60):(70–40). Pure water flux of the blend membranes passes through a maximum in the region of the most heterogeneous structure of the casting solution, which is associated with the imposition of a polymer-polymer phase separation on the non-solvent induced phase separation upon membrane preparation. The application of polyphenylsulfone/polysulfone blends as membrane-forming polymers and polyethylene glycol (Mn = 400 g·mol -1 ) as a pore-forming agent to the casting solutions yields the formation of ultrafiltration membranes with high membrane pure water flux (270 L·m -2 ·h -1 at 0.1MPa) and human serum albumin rejection of 85%.

36 MATERIALS SCIENCE↗

Evaluation of Ultrafiltration for Spacecraft Water Reuse

Ultrafiltration is examined for use as the first stage of a primary treatment process for spacecraft wastewater. It is hypothesized that ultrafiltration can effectively serve as pretreatment for a reverse osmosis system, removing the majority of organic material in a spacecraft wastewater. However, it is believed that the interaction between the membrane material and the surfactant found in the wastewater will have a significant impact on the fouling of the ultrafiltration membrane. In this study, five different ultrafiltration membrane materials are examined for the filtration of wastewater typical of that expected to be produced onboard the International Space Station. Membranes are used in an unstirred batch cell. Flux, organic carbon rejection, and recovery from fouling are measured. The results of this evaluation will be used to select the most promising membranes for further study.

Pickering, Karen D.↗

Complete coverage fouling model for constant flux crossflow ultrafiltration and experimental validation

A complete coverage model is proposed to describe fouling in constant flux crossflow ultrafiltration. Constant flux crossflow fouling experiments were conducted using dilute latex bead suspensions and commercial poly(ether sulfone) flat sheet ultrafiltration membranes to investigate the influence of operating conditions on evolution of transmembrane pressure (ΔP, TMP) with time. Changes in permeate flux or crossflow rate had little influence on the normalized TMP profile at high latex bead concentration (i.e., above 25 ppm) because the membrane surface was covered with latex beads. At low concentration (i.e., below 25 ppm), increases in permeate flux or foulant concentration increased normalized ΔP. However, this increase in normalized ΔP with permeate flux or foulant concentration diminishes when the permeate flux/concentration is high enough to overwhelm particle removal due to crossflow. Furthermore, these results are in good agreement with the new complete coverage model which describes the influence of operating parameters on fouling better than the previous model.

36 MATERIALS SCIENCE↗

Fabrication of model ultrafiltration membranes with uniform, high aspect ratio pores

Here, in this manuscript, we report the facile fabrication of large-area model membranes with highly uniform and high aspect ratio pores with diameters <20 nm. These membranes are useful for fundamental investigations of separation by size exclusion in the ultrafiltration regime, where species to be separated from solution have dimensions of 1–100 nm. Such investigations require membranes with narrow pores and high aspect ratios such that the Hagen–Poiseuille equation is followed, enabling well-known models such as the hindered transport model to be evaluated and other affecting factors to be ignored. We demonstrate that the sub-20 nm pores in the membrane are of sufficiently high aspect ratio such that water flux through the membrane is consistent with the Hagen–Poiseuille equation. The fabrication relies on self-assembling block copolymers to form uniform, densely packed patterns with sub-20 nm resolution, sequential infiltration synthesis to convert the block copolymer in situ into a mask with adequate contrast to etch pores with an aspect ratio >5, and low-resolution photolithography to transfer the pattern over a large area into a silicon nitride membrane. Model membranes with narrow pore-size distribution fabricated in this way provide the means to investigate parameters that impact size-selective ultrafiltration separations such as the relationships between solute or particle size and pore size, their distributions, and rejection profiles, and, therefore, test the validity or limits of separation models.

Chen, Wen↗

Integrated Electrocoagulation, Ultrafiltration, Membrane Distillation, and Crystallization for Treating Produced Water

Produced water (PW) generated from hydraulic fracturing operations was treated using an integrated electrocoagulation, ultrafiltration, membrane distillation, and crystallization process (EC UF MDC). The aim was to determine the viability of this integrated process for maximizing water recovery. The results obtained here indicate that optimizing the various unit operations could lead to increased recovery of PW. Membrane fouling limits all membrane separation processes. A pretreatment step to suppress fouling is essential. Here, removal of total suspended solids (TSS) and total organic carbon (TOC) was achieved by electrocoagulation (EC) followed by ultrafiltration (UF). The hydrophobic membrane used in membrane distillation may be fouled by dissolved organic compounds. Reducing membrane fouling is essential to increase the long-term durability of the membrane distillation (MD) system. In addition, combining membrane distillation with crystallization (MDC) can help reduce scale formation. By inducing crystallization in the feed tank, scale formation on the MD membrane was suppressed. The integrated EC UF MDC process can impact Water Resources/Oil & Gas Companies. Conservation of surface and groundwater is possible by treating and reusing PW. Additionally, treating PW reduces the amount of PW disposed in Class II disposal wells and promotes more environmentally sustainable operations.

42 ENGINEERING↗

Ultrafiltration by a compacted clay membrane. I - Oxygen and hydrogen isotopic fractionation. II - Sodium ion exclusion at various ionic strengths.

Laboratory experiments were carried out to determine the magnitude of the isotopic fractionation of distilled water and of 0.01N NaCl forced to flow at ambient temperature under a hydraulic pressure drop of 100 bars across a montmorillonite disk compacted to a porosity of 35% by a pressure of 330 bars. The ultrafiltrates in both experiments were depleted in D by 2.5% and in O-18 by 0.8% relative to the residual solution. No additional isotopic fractionation due to a salt-filtering mechanism was observed at NaCl concentrations up to 0.01N. Adsorption is most likely the principal mechanism which produces isotopic fractionation, but molecular diffusion may play a minor role. The results suggest that oxygen and hydrogen isotopic fractionation of ground water during passage through compacted clayey sediments should be a common occurrence, in accord with published interpretations of isotopic data from the Illinois and Alberta basins. It is shown how it is possible to proceed from the ion exchange capacity of clay minerals and, by means of the Donnan membrane equilibrium concept and the Teorell-Meyer-Siever theory, develop a theory to explain why and to what extent ultrafiltration occurs when solutions of known concentration are forced to flow through a clay membrane.

Coplen, T. B.↗

Analysis of fouling mechanism in ultrafiltration of produced water

Flux decline measurements provided insight into the fouling behavior of ultrafiltration (UF) membranes for produced water (PW) treatment. Three UF membranes were compared in terms of the rate and the intensity of fouling. The flux decline analysis showed the fouling transition from blocking mechanisms (i.e., complete and intermediate blocking as well as standard blocking) to cake formation occurs earlier for more permeable membranes. Lower trans-membrane pressure (TMP) of 0.1 bar led to particle accumulation on the membrane surface leading to cake formation as the predominant fouling mechanism. In higher TMP experiments, standard and intermediate blocking followed by cake formation were found to be apparent fouling mechanisms. Overall, for the membranes with higher permeabilities and for the filtrations with pre-filtered feed, faster transition to cake formation was observed primarily due to crowd out effect. By understanding membrane fouling and behavior, it is possible to mitigate performance losses in membrane-based technologies that could be used for the treatment of PW. Furthermore, this study provides information to identify blocking rate and intensity in various conditions for UF membranes when treating PW.

42 ENGINEERING↗

Analysis of backwash settings to maximize net water production in an engineering-scale ultrafiltration system for water reuse

Ultrafiltration (UF) has been widely utilized as water pretreatment for different applications especially in water reuse. The UF system operation is characterized by a filtration phase, where particles accumulate on the membrane surface resulting in an increase in the transmembrane pressure (TMP) and a cleaning phase, where foulants are removed through cleaning cycles including physical backwash and chemical-enhanced backwash (CEB). In this study, data from an engineering-scale UF system treating reclaimed wastewater were used to assess the impact of backwashing on the filtration process. TMP backwash trigger, backwash duration, and CEB frequency were purposely varied for a cycle-by-cycle investigation on the net water production, water recovery, initial operating TMP, and filtration cycle duration. As the TMP backwash trigger was varied between 62 and 145kPa, the maximum net water production (63 m 3 /d) was achieved at 103kPa and water recovery remained relatively constant at approximately 92%. Backwash durations of 45, 65, and 85s were performed where both net water production and water recovery yielded similar results (~63 m 3 /d and ~ 91%) compared with 103kPa TMP backwash trigger. The CEB frequency was also lowered from one every three backwashes (1/3) to 1/6 and 1/12 and resulted in decreased net water production and water recovery while the initial TMP increased. Interestingly, the total number of CEBs remained approximately constant regardless of their frequency. In conclusion, results suggest that CEB is an important fouling control process to maximize water production.

42 ENGINEERING↗

Thermoresponsive antifouling ultrafiltration membranes from mesophase templating

Nanostructured polymers synthesized by lyotropic liquid crystal (LLC) templates with normal hexagonal (H 1 ) structure exhibit a 3D-continuous transport path, which makes them ideal for membrane separation application. Incorporating additional functionality, especially stimuli-responsiveness, in such an ordered structure provides even more application opportunities. Here, in this work, we present the first successful synthesis of H 1 -structured thermoresponsive ultrafiltration (UF) membranes via LLC templating. The membrane contains thermoresponsive Pluronic P84 diacrylate (P84DA) which not only acts as the monomer and structure-directing amphiphile, but also enables the pore size change with temperature. Experimental studies reveal that the swelling capacity of H 1 -templated polymer as well as permeability and selectivity of the obtained membrane can be altered by changing the temperature. Increasing the temperature from 25 to 45 °C increases the normalized flux from 28 to 68 L m -2 h -1 μm and molecular weight cut-off (MWCO) from 2200 to 3900 Da. Furthermore, the membrane shows an outstanding fouling resistance against different solutes.

36 MATERIALS SCIENCE↗

Insights into determining pore size properties of ultrafiltration membranes

The selectivity of porous membranes is often characterized using solute rejection tests, where membranes are challenged with dilute aqueous solutions of neutral solutes at operating conditions that minimize concentration polarization and fouling. In single solute tests, a membrane is challenged with one molecular weight (MW) solute at a time from low to high MW. Since single solute methods are time-intensive, mixed solute tests have become more common, where a mixture of several MW solutes challenges a membrane at once. However, the presence of large solutes in a mixture increases the rejection of smaller solutes. Furthermore, there are no universally accepted operating conditions or standard methods used by membrane manufacturers or researchers for the experiments, leading to difficulty in pore size and pore characteristic comparisons. In this paper, commercial ultrafiltration membranes were challenged with single and mixed solute polyethylene glycol (PEG) and dextran aqueous solutions. First, rejection values determined using total organic carbon (TOC) and high-performance liquid chromatography (HPLC) from single solute filtration experiments are compared. Differences in rejection curves obtained by the two techniques are attributed to solute polydispersity. Mixed solute filtration experiments with binary mixtures of solutes showcased co-solute interactions, which increase with both the size and weight percent of large solute in the mixture. Mixed solute filtration experiments at varying operating conditions (i.e., stir speed and flux) were conducted to determine operating conditions that mitigate co-solute interactions. Stir speed had a minimal effect on co-solute interactions. In contrast, low flux conditions can help minimize co-solute interactions, leading to pore size distributions that closely resemble results observed in single solute filtration using narrowly dispersed solutes. Additionally, at low flux conditions, the predicted membrane pore size distributions utilizing mixed solute experiments with PEG and dextran were similar.

36 MATERIALS SCIENCE↗

Removal of As(III) by Electrically Conducting Ultrafiltration Membranes

As(III) species are the predominant form of arsenic found in groundwater. However, nanofiltration (NF) and reverse osmosis (RO) membranes are often unable to effectively reject As(III). In this study, we fabricate highly conducting ultrafiltration (UF) membranes for effective As(III) rejection. Here, these membranes consist of a hydrophilic nickel-carbon nanotubes layer deposited on a UF support, and used as cathodes. Applying cathodic potentials significantly increased As(III) rejection in synthetic/real tap water, a result of locally elevated pH that is brought upon through water electrolysis at the membrane/water interface. The elevated pH conditions convert H 3 ASO 3 to H 2 AsO 3 – /HAsO 3 2– that are rejected by the negatively charged membranes. In addition, it was found that Mg(OH) 2 that precipitates on the membrane can further trap arsenic. Importantly, almost all As(III) passing through the membranes is oxidized to As(V) by hydrogen peroxide produced on the cathode, which significantly decreased its overall toxicity and mobility. Although the high pH along the membrane surface led to mineral scaling, this scale could be partially removed by backwashing the membrane. To the best of our knowledge, this is the first report of effective As(III) removal using low-pressure membranes, with As(III) rejection higher than that achieved by NF and RO, and high water permeance.

42 ENGINEERING↗

Long-Term Statistical Process Monitoring of an Ultrafiltration Water Treatment Process

As water treatment technology has improved, the amount of available process data has substantially increased, making real-time, data-driven fault detection a reality. One shortcoming of the fault detection literature is that methods are usually evaluated by comparing their performance on hand-picked, short-term case studies, which yields no insight into long-term performance. In this work, we first evaluate multiple statistical and machine learning approaches for detrending process data. Then, we evaluate the performance of a PCA-based fault detection approach, applied to the detrended data, to monitor influent water quality, filtrate quality, and membrane fouling of an ultrafiltration membrane system for indirect potable reuse. Based on two short case studies, the adaptive lasso detrending method is selected, and the performance of the multivariate approach is evaluated over more than a year. The method is tested for different sets of three critical tuning parameters, and we find that for long-term, autonomous monitoring to be successful, these parameters should be carefully evaluated. However, in comparison with industry standards of simpler, univariate monitoring or daily pressure decay tests, multivariate monitoring produces substantial benefits in long-term testing.

ammonia↗

Predicting initial trans-membrane pressure across cycles in the ultrafiltration process using random forest

With growing freshwater scarcity, direct potable reuse (DPR) systems that reclaim wastewater for drinking are becoming increasingly important for sustainable water supply. Reliable operation requires minimizing downtime in ultrafiltration (UF) units, where membrane fouling leads to elevated trans-membrane pressure (TMP). This study develops data-driven regression models based on random forest (RF) and autoregressive (AR) approaches to forecast the initial TMP at the start of each UF filtration cycle in a pilot-scale DPR system. The RF model consistently outperforms baseline methods, including historical mean, last observation carried forward, and AR models, across multiple forecast horizons, achieving the lowest root mean square error. To evaluate how different classes of process variables contribute to TMP dynamics over time, we examine the feature importance of independent input variables across multiple forecast horizons. This analysis provides insight into the temporal relevance of operational and sensor-derived features, guiding control and monitoring strategies. Additionally, the impact of hyperparameter tuning on TMP prediction performance is assessed for both direct and recursive RF modelling approaches. The proposed RF framework establishes a robust foundation for predictive monitoring and real-time optimization of UF operations, supporting sustainable and reliable water reuse.

direct potable reuse↗

Maximizing the grafting of zwitterions onto the surface of ultrafiltration membranes to improve antifouling properties

Superhydrophilic zwitterions have been extensively exploited for surface modification to improve antifouling properties. However, it remains challenging to form layers of <20 nm with high zwitterion content on the surfaces with different degrees of hydrophilicity. We demonstrate that amine-functionalized sulfobetaine (SBAm) can be co-deposited with dopamine on ultrafiltration (UF) membranes, leading to a thickness of 10 nm to 50 nm and an SBAm content of up to 31 mass% in the coating layers. The covalently grafted SBAm is stable underwater and improves the antifouling properties, as evidenced by the lower trans-membrane pressure required to retain targeted water fluxes than that required for the pristine membranes. Finally, the SBAm is also more effective than conventionally used sulfobetaine methacrylate (SBMA) for the zwitterion grafting on the surface to improve antifouling properties

42 ENGINEERING↗

Ionic liquid mediated one-step perpendicular assembly in block copolymer thin films for ultrafiltration membrane applications

The rapid rise of oil and gas, petrochemical, food processing, and pharmaceutical industries has added a complex mixture of contaminants like oil, particulates, metals, and other organic compounds to wastewater. Multipurpose membranes with precise pore structure can offer a solution to this problem and block copolymers (BCP) can be used to achieve such structures. Achieving vertical assembly of BCP domains provides a perfect template for developing uniform through film channels for separation and transport of material, besides being useful for the rectification of defects in photolithography patterns. Producing such morphologies may require extensive film/substrate processing and is not always feasible for scale-up. With this article, we demonstrate a facile solution casting method to induce vertical domain assembly in as-cast diblock copolymer thin films in the presence of an ionic liquid (IL) additive that preferentially segregates to one block and neutralizes interfacial interactions. We also show the tunability of domain sizes by controlling the additive concentration. These vertically aligned morphologies are important for the development of next-generation lithographic techniques and form excellent templates for ultrafiltration membranes with uniform pore sizes. In conclusion, this article demonstrates how IL additives can be used to obtain stable non-equilibrium morphologies in as-cast BCP films and the effect of BCP molecular mass, block volume fractions, and IL content on self-assembly.

59 BASIC BIOLOGICAL SCIENCES↗

Two-Step Thermoresponsive Ultrafiltration Membranes from Polymerization of Lyotropic Liquid Crystals

Here, in this study, we present the fabrication of a two-step thermoresponsive ultrafiltration (UF) membrane through polymerization of a lyotropic liquid crystal (LLC). A mixture of commercially available Pluronic F 127 block copolymer, water (containing ammonium persulfate as the initiator), and polymerizable oil (n-butyl acrylate/ethylene glycol dimethacrylate) is used to create an LLC with a lamellar structure, as characterized by cross-polarized light microscopy and atomic force microscopy. Differential scanning calorimetry is employed to evaluate the thermoresponsive behavior of the polymerized LLC (polyLLC). Two-step thermoresponsiveness (~35 and ~50 °C) of the polyLLC is observed due to the lower critical solution temperature (LCST) of F 127 and melting of the crystalline structure of the polyethylene oxide (PEO) chains of the F 127 surfactant. In the next step, the obtained mesophase is cast on a nonwoven polyester support sheet followed by thermal polymerization. The hydration capacity, water flux, water flux recovery after fouling, and molecular weight cutoff (MWCO) of the obtained membrane are evaluated at different temperatures to examine its thermoresponsiveness. The experimental results reveal that the UF membrane has a reversible thermoresponsive behavior at the LCST and PEO melting of polyLLC. Additionally, the cleaning efficiency of the fouled membrane can be enhanced by using its thermoresponsive behavior, resulting in an extended lifetime of the product. Furthermore, the MWCO of the membrane can be altered with temperature due to the pore size change with temperature stimulus.

36 MATERIALS SCIENCE↗

Electrocoagulation Combined with Ultrafiltration Membranes as Pretreatment for RO Desalination of Synthetic Cooling Tower Blowdown Water

Electrocoagulation (EC), an electrochemical water treatment process, is commonly used to remove particulate and colloidal matter from water. Here, in this study, we demonstrate that EC, when coupled with membrane filtration, is also capable of removing dissolved species, such as Ca + , Mg 2+ , and SiO x . The removal of such species is important for downstream membrane-based desalination treatment of the water that can suffer from reduced performance due to membrane scaling. Here, we describe how EC can be combined with a low-pressure membrane (LPM) system to offer efficient (and potentially universal) pretreatment for downstream membrane desalination. Synthetic water, simulating cooling tower blowdown (CTBD) with elevated concentrations of hardness and silicates (Ca: 418 ppm, Mg: 63 ppm, SiO 2 : 50 ppm) is treated using EC coupled to ultrafiltration (UF) to remove Mg up to 30 ± 1%, Ca up to 29 ± 1%, and silica up to 99 ± 1%. We evaluated the effectiveness of the EC-UF pretreatment system in reducing downstream RO scaling using thermodynamic modeling to predict the saturation index (SI) at the RO membrane/water interface. An SI value below zero (SI < 0) indicates under-saturated conditions (with respect to a particular mineral) where mineral scaling does not take place, which correlates with improved water recovery. Our findings suggest that the EC-UF pretreatment system was able to increase water recovery by up to 30%, compared to 0% recovery without pretreatment, under optimal conditions (feed solution pH of 7 and an EC charge loading of 1800 C/L). Finally, we conducted an economic analysis showing that implementing an EC-UF system for CTBD water could yield a cost benefit of up to $\$$14.13 per m 3 compared to direct brine disposal.

cooling tower blowdown↗

Ultrafiltration separation of Am(VI)-polyoxometalate from lanthanides

Partitioning of americium from lanthanides (Ln) present in used nuclear fuel plays a key role in the sustainable development of nuclear energy. This task is extremely challenging because thermodynamically stable Am(III) and Ln(III) ions have nearly identical ionic radii and coordination chemistry. Oxidization of Am(III) to Am(VI) produces AmO 2 2+ ions distinct with Ln(III) ions, which has the potential to facilitate separations in principle. However, the rapid reduction of Am(VI) back to Am(III) by radiolysis products and organic reagents required for the traditional separation protocols including solvent and solid extractions hampers practical redox-based separations. Herein, we report a nanoscale polyoxometalate (POM) cluster with a vacancy site compatible with the selective coordination of hexavalent actinides ( 238 U, 237 Np, 242 Pu and 243 Am) over trivalent lanthanides in nitric acid media. To our knowledge, this cluster is the most stable Am(VI) species in aqueous media observed so far. Ultrafiltration-based separation of nanoscale Am(VI)-POM clusters from hydrated lanthanide ions by commercially available, fine-pored membranes enables the development of a once-through americium/lanthanide separation strategy that is highly efficient and rapid, does not involve any organic components and requires minimal energy input.

12 MANAGEMENT OF RADIOACTIVE AND NON-RADIOACTIVE W↗