Physico-chemical characterization of polyamide NF/RO membranes: Insight from streaming current measurements

International audienceTangential streaming current measurements were performed to investigate the surface charge properties and the charge formation mechanism of various NF/RO membranes. Unlike what is usually done in electrokinetic studies of membranes, experiments were conducted with degassed background solutions under a controlled atmosphere by means of nitrogen gas in order to get accurate electrokinetic measurements even in the basic range of pH. It was demonstrated that the streaming current technique implemented with these rigorous experimental conditions is a reliable tool to verify the presence of an additional coating on a commercial TFC membrane. It was also shown that these electrokinetic measurements allow a more clear discrimination between coated and uncoated membranes than the ATR-FTIR technique. Moreover, experiments performed with and without a nitrogen environment revealed specific adsorption of bicarbonate and carbonate ions coming from the dissolution of carbon dioxide in the air onto the surface of RO polyamide membranes containing hexafluoroalcohol functional groups

The effect of cross-contamination in the sequential interfacial polymerization on the RO performance of polyamide bilayer membranes

International audienceIn this study, hexafluoroalcohol-containing polyamide layer (HFAPA) was prepared on top of a conventional polyamide under-layer (REFPA) via sequential interfacial polymerization (SIP) to improve RO separation behavior, and the performance of the resulting bilayer membrane was thoroughly optimized by investigating the effect of cross-contamination in the SIP process. When several coupons of the polyamide bilayer membrane were prepared by SIP of MPD(aq), TMC(hx) and hexafluoroalcohol-containing diamine (HFAMDA)(aq) in the manner of subsequent membrane dipping, unreacted MPD monomer (mostly captured in the porous PSF support) carried over from the 1st interfacial reaction dissolved and accumulated in the 2nd aqueous solution as verified by UV spectroscopic analysis. The MPD contaminant then participated in the 2nd interfacial reaction, forming copolyamide with HFAMDA monomer onto the REFPA. Depending on the amount of MPD contaminant accumulated in the 2nd aqueous solution, the composition of the resulting co-polyamide in the top-layer varied, causing a significant variation of RO performance; the flux was gradually decreased with the increase of MPD contaminants while the salt rejection slightly increased (from 1st coupon toward 4th coupon). This result indicated that a trace amount of MPD contaminant may be necessary to maximize RO separation behavior. Through in-depth performance evaluation of polyamide bilayer membranes prepared by adding various known-amount of MPD into 2nd HFAMDA solution, and also by applying a frame process (2nd amine solution was applied only top surface of membrane) to eliminate uncontrollable MPD contamination, we have successfully demonstrated consistent RO performance, and identified an optimum material composition to provide superior separation performance. The bilayer membrane prepared by adding 1.2 mol% of MPD to the total amount of HFAMDA in the 2nd aqueous solution showed 99.8% NaCl rejection with the water flux of 45 LMH under the cross-flow filtration performed with 2000 ppm NaCl solution at 400 psi, 25 °C

Phenomenological prediction of desalination brines nanofiltration through the indirect determination of zeta potential

The prediction of nanofiltration (NF) performance at environmentally relevant conditions, e.g.: highly saline brine solutions, is becoming of increasing interest for the recovery of waste materials in the water desalination industry. In this work, the prediction of the separation of sulfate and chloride contained in the retentate of reverse osmosis brackish water desalination by means of the commercial NF270 membrane is studied. Prior to theoretical modelling, streaming potential measurements were performed for aqueous single and binary mixtures of NaCl and Na2SO4 within the range of ionic strengths 1-100 mol/m3. Zeta potential values were obtained applying an extrapolation method from recent literature to allow the calculation of surface charge density under higher ionic strengths found in reverse osmosis desalination brines (100-1200 mol/m3). Then, the obtained surface charge density was used to simulate sulfate, chloride and sodium rejections by means of the Donnan steric pore model (DSPM), in the pressure range 2-20 bar. The good agreement between experimental and simulated rejection values allows validating the approach that enables the prediction of NF performance for the separation of monovalent and divalent anions, of interest for the purification of desalination brines before their further exploitation as a source of sodium chloride concentrated solutions.The authors gratefully acknowledge the funding for the projects CTM2016-75509-R and CTQ2015-66078-R

Study of charge and transport properties of nanofiltration membranes

Aujourd'hui, la nanofiltration (NF) est perçue comme un procédé de séparation efficace et propre permettant d’extraire ou de concentrer des solutés ioniques ou neutres. Son développement à l’échelle industrielle n’est cependant pas encore optimal car les différents mécanismes de séparation sont encore mal compris. Cette thèse a porté d’une part sur l’étude des propriétés charge de surface des membranes de NF/OI et d’autre part sur les mécanismes de transport à travers des membranes de NF. Il a tout d’abord été montré, grâce à des mesures électrocinétiques réalisées sous atmosphère contrôlée, que certaines membranes commerciales subissent un post-traitement afin d’améliorer leurs performances de filtration. La détermination du potentiel zêta, grandeur caractéristique de la charge de surface, s’est révélée être une méthode adaptée pour mettre en évidence la présence d’une couche de post-traitement à la surface d’une membrane. La suite de l’étude a été consacrée à la compréhension des mécanismes de transport lors de la NF de mélanges ternaires contenant deux cations différents (Na+ et Ca2+) et un anion commun (Cl-). L’utilisation du modèle de transport SEDE a permis de montrer que les performances des membranes de NF résultent de la combinaison d’effets stériques, électriques et diélectriques. La dernière partie de ce travail a été consacrée à la NF d’un coproduit de l’industrie agro-alimentaire, le produit fermenté de soja (PFS). Il a été montré que la NF est potentiellement adaptée au dessalement du PFS (réduction de la teneur en cations monovalents) sans perte des sucres d’intérêt.Today, nanofiltration (NF) is acknowledged as an efficient and environmentally-friendly separation process suited to extract or to concentrate neutral or ionic solutes. However, its development at industrial scale is not yet optimal because separation mechanisms are still poorly understood. This thesis focused on studying surface charge properties of NF/RO membranes and transport mechanisms through NF membranes as well. Firstly it was shown through electrokinetic measurements performed under controlled atmosphere that some commercial membranes undergo a post-treatment to improve their filtration performance. Determining the zeta potential, a physical quantity representative of the membrane surface charge, was shown to be a reliable method to highlight the presence of a post-treatment layer on the membrane surface. The second part of the study dealt with the understanding of transport mechanisms involved in NF of ternary mixtures containing two different cations (Na+ and Ca2+) and a common anion (Cl-). Using the SEDE transport model it was shown that the performance of NF membranes results from the combination of steric, electric and dielectric effects. The last part of this work was concerned with nanofiltration of a food industry co-product, the fermented soy product (PFS). It was shown that NF is potentially suitable for PFS desalination (reduction in the monovalent cation concentration) without loss of the sugars of interest