Journal of Membrane Science Letters最新文献

The solution-diffusion (SD) model has been instrumental in the advancement of membrane science, due to its simplicity, transparency, and utility in process engineering. However, some doubts have recently been raised, concerning the fundamental validity of SD. These have largely been based on apparent discrepancies between molecular dynamics simulations and several features, deemed inherent to SD, that appeared in early reports — namely, the exact nature of the pressure and concentration distributions within the membrane. Herein, we re-visit the underlying physics of SD in the context of composite membranes, making no a-priori assumptions and, particularly, highlighting the role of polymer thermodynamics and the mechanics of a loaded, swollen film, supported by a porous substrate. The analysis provides a coherent view, linking the solvent concentration profile within the film and the resultant flux-pressure relations with the polymer rigidity and, importantly, the way in which the film is supported. It is shown that, although the flux may generally vary non-linearly with the feed pressure and depend on the film-support geometry, for rigid films – most common in real operations – SD predicts a linear behavior, virtually independent of specific geometry and pressure distribution. Moving forward, we stress the importance and need for further refinements of the SD model, driven by insight from molecular dynamics, thermodynamics and mechanics, while maintaining its applicability to process design.

Background

Superabsorbent polymers (SAPs) have a remarkable ability to absorb significant quantities of water. However, their absorption capacity is significantly reduced when exposed to saline solutions, such as urine, due to the polyelectrolyte effect and charge screening.

Methods

In this study, we demonstrate a zwitterionic superabsorbent polymer (ZSAP) with excellent salt-water absorption and retention capacities. ZSAP was synthesized by grafting a copolymer of p(sulfobetaine methacrylate-co-2-hydroxyethyl methacrylate) (p(SBMA-co-HEMA)) onto an acrylic acid (AA)-based hydrogel via free-radical polymerization. The introduction of zwitterionic SBMA significantly enhances the hydrophilicity of the polymer, particularly in a saline solution due to the anti-polyelectrolyte effect, thereby accelerating the rate of salt absorption. Additionally, the hydroxyl groups from HEMA facilitate the formation of covalent bonds with the AA network membrane through esterification, effectively mitigating polymer leaching. The hydration/dehydration behaviors of linear polymers were measured using the dynamic vapor sorption (DVS) method. Moreover, the salt-water absorption capacity, centrifuge retention capacity (CRC), and absorbency under load (AUL) of ZSAP with various SBMA moieties and copolymer dosages were comprehensively evaluated in a 0.9 wt% sodium chloride solution. Additionally, the water retention under different temperatures and polymer leaching of ZSAP were investigated.

Significant Findings

The copolymer p(SBMA-co-HEMA) not only demonstrates a high salt-water absorption rate at 90% RH in a 0.9 wt% NaCl solution but also exhibits superior water retention at 0% RH compared to the AA polymer. Moreover, the ZSAP exhibits superior salt-water absorption capacity and AUL in a 0.9 wt% NaCl solution compared to conventional AA-based SAP. Additionally, the introduction of the hydroxyl moiety from the p(SBMA-co-HEMA) copolymer reduces free polymer leaching from ZSAP. This work presents an approach for the development of new SAP with high salt-water absorption and retention.

Understanding salt and water transport mechanisms in reverse osmosis (RO) under high pressures and salinities is critical to advancing RO-based brine management technologies. In this study, we investigate the dependence of salt permeance and partitioning on feed salinity and applied pressure. Salt partitioning coefficients were determined using a novel high-pressure quartz crystal microbalance (QCM), and salt permeances were collected using a lab-scale high-pressure dead-end cell. Our results show that salt permeance decreases with respect to feed concentration, in contrast to conventional theories for charged RO membranes. We further show salt partitioning coefficients do not change with applied hydrostatic pressure but are dependent on feed salt concentration. We use non-equilibrium molecular dynamics simulations to show that these trends are explained by salinity and pressure-induced changes to the structure of the polyamide layer, namely osmotic deswelling and compaction. Changes in the polyamide layer thickness and pore size alter the frictional interactions of ions, affecting membrane performance at larger salinities and pressures. These results provide new insights on how structure-performance relationships affect salt transport at higher pressures.

Surfactant-induced wetting impedes the practical implementation of membrane distillation (MD). Addressing this issue demands the development of an effective membrane cleaning strategy that can eliminate surfactants adhering to the membrane surface and restore the membrane hydrophobicity. However, current cleaning methods, such as direct drying and pressurized air backwashing, encounter challenges in thoroughly removing surfactants trapped within the pores while preserving the structural integrity of the membrane. This work presents a refined approach to conquer surfactant-induced wetting in MD by water flushing. Utilizing ultrasonic time domain reflectometry and optical coherence tomography techniques, we identified a critical cleaning depth and showed that the hydrophobicity of a partially wetted membrane can be fully recovered by water flushing when the wetting depth is below the critical threshold. Theoretical models evidenced that in instances of low water temperature and low flow rate conditions, relatively high critical cleaning depths can be realized, thereby expanding the operational scope for achieving complete hydrophobicity recovery. Our results demonstrated the applicability of water flushing to commercial membrane modules without necessitating any modification, emphasizing its substantial potential for advancing MD applications.

Pore wetting is a major constraint to the performance of membrane distillation (MD) for hypersaline brine treatment. Despite the existence of surfactants with diverse properties, an explicit relationship between the properties of surfactants and their capabilities of inducing pore wetting has yet to be established. In this study, we perform a comparative analysis of the wetting behaviors of various surfactants with different charges and molecular weights in MD desalination. The induction time of surfactants to initiate pore wetting was correlated to the apparent contact angle and surface tension of the feedwater. Our results show that different surfactants resulting in similar feedwater surface tensions can lead to drastically different wetting potential, suggesting that both charge of the head group and molecular weight of surfactants have a significant influence on membrane pore wetting. Further, we demonstrate that parameters that have been commonly used to indicate wetting potential, including apparent contact angle and solution surface tension, are not reliable in predicting the wetting behavior of MD membranes, which is intricately linked with surfactant properties such as charge and molecular size. We envision that our results not only improve our fundamental understanding of surfactant-induced wetting but also provide valuable insights that necessitate thorough consideration of surfactant properties in evaluating wetting potential and membrane wetting resistance for MD desalination.