Development of Thin-Film Composite Membranes for Nanofiltration at Extreme pH
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ABSTRACT:
SUBMITTER: Asadi Tashvigh A
PROVIDER: S-EPMC8593864 | biostudies-literature |
REPOSITORIES: biostudies-literature
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Project description:The successful synthesis of poly(aryl cyanurate) nanofiltration membranes via the interfacial polymerization reaction between cyanuric chloride and 1,1,1-tris(4-hydroxyphenyl)ethane (TPE), atop a polyethersulfone ultrafiltration support, is demonstrated. The use of cyanuric chloride allows for the formation of a polymer that does not contain hydrolysis-susceptible amide bonds that inherently limit the stability of polyamide nanofiltration membranes. In order to achieve a thin defect-free cross-linked film via interfacial polymerization, a sufficient number of each monomer should react. However, the reactivities of the second and third chloride groups of the cyanuric chloride are moderate. Here, this difficulty is overcome by the high functionality and the high reactivity of TPE. The membranes demonstrate a typical nanofiltration behavior, with a molecular weight cutoff of 400 ± 83 g·mol-1 and a permeance of 1.77 ± 0.18 L·m-2 h-1 bar-1. The following retention behavior Na2SO4 (97.1%) > MgSO4 (92.8%) > NaCl (51.3%) > MgCl2 (32.1%) indicates that the membranes have a negative surface charge. The absence of amide bonds in the membranes was expected to result in superior pH stability as compared to polyamide membranes. However, it was found that under extremely acidic conditions (pH = 1), the performance showed a pronounced decline over the course of 2 months. Under extremely alkaline conditions (pH = 13), after 1 month, the performance was lost. After 2 months of exposure to moderate alkaline conditions (pH = 12), the MgSO4 retention decreased by 14% and the permeance increased by 2.5-fold. This degradation was attributed to the hydrolysis of the aryl cyanurate bond that behaves like an ester bond.
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Project description:Thin-film composite (TFC) structure has been widely employed in polymeric membrane fabrication to achieve superior performance for desalination and water treatment. In particular, TFC membranes with a thin active polyamide (PA) selective layer are proven to offer improved permeability without compromising salt rejection. Several modifications to TFCs have been proposed over the years to enhance their performance by altering the selective, intermediate, or support layer. This study proposes the modification of the membrane support using nanozeolites prepared by a unique ball milling technique for tailoring the nanofiltration performance. TFC membranes were fabricated by the interfacial polymerization of Piperazine (PIP) and 1,3,5-Benzenetricarbonyl trichloride (TMC) on Polysulfone (PSf) supports modified with nanozeolites. The nanozeolite concentration in the casting solution varied from 0 to 0.2%. Supports prepared with different nanozeolite concentrations resulted in varied hydrophilicity, porosity, and permeability. Results showed that optimum membrane performance was obtained for supports modified with 0.1% nanozeolites where pure water permeance of 17.1 ± 2.1 Lm-2 h-1 bar-1 was observed with a salt rejection of 11.47%, 33.84%, 94%, and 95.1% for NaCl, MgCl2, MgSO4, and Na2SO4 respectively.
| S-EPMC9610575 | biostudies-literature
Project description:This work addresses a key challenge of tailoring the ion selectivity of a thin-film composite nanofiltration membrane to a specific application, such as water softening, without altering the water permeability. We modified the active surface of a commercial NF270 membrane by molecular layer deposition (MLD) of ethylene glycol-Al (EG-alucone). With increasing deposition cycles, we found that the MLD precursors first infiltrated and deposited in the active layer of NF270, then inflated the active layer, and finally deposited on the surface as a distinct EG-alucone layer. The deposition process changed the morphology of the membrane active layer and decreased the overall density of its fixed negative charge by embedding the positively charged EG-alucone. Filtration experiments revealed that these modifications affected the ion separation properties of the membrane without significantly hindering the water permeability. Specifically, the permeation of Na+ increased relative to that of Mg2+, as indicated by the permselectivity of Na+ salts over Mg2+ salts. The changes in permselectivities with an increasing number of MLD cycles were rationalized using the dielectric, steric, and electrostatic ion exclusion mechanisms, which are related to the membrane material, pore size, and fixed charge, respectively. These relations open a path for the rational design of nanofiltration membranes with tailored selectivity by tuning the properties of the MLD layer. Filtration results of natural brackish groundwater using the MLD modified membranes agreed with the single salt experiments. As a result, water hardness was 26% lower for the permeate obtained using the MLD-modified membranes, which were found stable even during a 24 h filtration run. These results highlight the practical potential of this approach in enhancing water softening efficiency.
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Project description:In this study, the basal spacing of montmorillonite (MMT) was modified through ion exchange. Two kinds of MMT were used: sodium-modified MMT (Na-MMT) and organo-modified MMT (O-MMT). These two particles were incorporated separately into the thin-film nanocomposite polyamide membrane through the interfacial polymerization of piperazine and trimesoyl chloride in n-hexane. The membrane with O-MMT (TFNO-MMT) has a more hydrophilic surface compared to that of membrane with Na-MMT (TFNNa-MMT). When various types of MMT were dispersed in the n-hexane solution with trimesoyl chloride (TMC), O-MMT was well-dispersed than Na-MMT. The poor dispersion of Na-MMT in n-hexane led to the aggregation of Na-MMT on the surface of TFNNa-MMT. TFNO-MMT displayed a uniform distribution of O-MMT on the surface, because O-MMT was well-dispersed in n-hexane. In comparison with the pristine and TFNNa-MMT membranes, TFNO-MMT delivered the highest pure water flux of 53.15 ± 3.30 L∙m-2∙h-1 at 6 bar, while its salt rejection for divalent ions remained at 95%-99%. Furthermore, it had stable performance in wide operating condition, and it exhibited a magnificent antifouling property. Therefore, a suitable type of MMT could lead to high separation efficiency.
| S-EPMC7281585 | biostudies-literature
Project description:Given the huge significance of organic solvents in several industrial processes, the use of membranes for recovering the solvents has evolved into an industrially viable process. The current work has been focused on studying the effect of minor changes in the chemistry of the reacting monomers on the organic solvent nanofiltration/solvent resistance nanofiltration (OSN/SRNF) performance of the membranes. The two aliphatic amines with varying aliphatic chain lengths between primary and secondary amines were selected for this purpose. Based on the structure of the resultant active layer, the Janus nanofiltration performance of the membrane was evaluated. The two membranes, 4A-TPC@crosslinked PAN and 4A-3P@crosslinked PAN were fabricated by using two different tetra-amines, 4A (N,N'-bis(3-aminopropyl)ethylenediamine) and 4A-3P (N,N'-Bis(2-aminoethyl)-1,3-propanediamine) crosslinked with terephthaloyl chloride (TPC) on a crosslinked polyacryonitrile (PAN) support through interfacial polymerization (IP). The presence of multiple hydrophobic -CH2- groups in the structures of the aliphatic amines 4A and 4A-3P develops hydrophobic sites in the hydrophilic polyamide active layers of the membranes. In addition, 4A has two secondary amino groups separated by ethylene (-CH2-CH2-) groups, whereas in 4A-3P, the two secondary amino groups are separated by propylene (-CH2-CH2-CH2-) leading to variation in the structural features and performance of the two membranes. Both membranes were fully characterized by several membrane characterization techniques and applied for OSN/SRNF using both polar (methanol, ethanol, and isopropanol) and non-polar (n-hexane and toluene) solvents. Different dyes (Congo red, Eriochrome black T, and Methylene blue) were used as model solutes during the filtration experiment. The 4A-3P-TPC@crosslinked PAN showed n-hexane and toluene flux of 109.9 LMH and 95.5 LMH, respectively. The Congo red (CR) showed the highest rejection, reaching 99.1% for the 4A-TPC@Crosslinked PAN membrane and 98.8% for the 4A-3P-TPC@Crosslinked PAN membrane.
| S-EPMC10359244 | biostudies-literature
Project description:The development of membrane-based technologies for the treatment of wastewater streams and resources containing heavy metal ions is in high demand. Among various technologies, nanofiltration (NF) membranes are attractive choices, and the continuous development of novel materials to improve the state-of-the-art NF membranes is highly desired. Here, we report on the synthesis of poly(homopiperazine-amide) thin-film composite (HTFC)-NF membranes, using homopiperazine (HP) as a monomer. The surface charge, hydrophilicity, morphology, cross-linking density, water permeation, solute rejection, and antifouling properties of the fabricated NF membranes were evaluated. The fabricated HTFC NF membranes demonstrated water permeability of 7.0 ± 0.3 L/(m2 h bar) and rejected Na2SO4, MgSO4, and NaCl with rejection values of 97.0 ± 0.6, 97.4 ± 0.5, and 23.3 ± 0.6%, respectively. The membranes exhibit high rejection values of 98.1 ± 0.3 and 96.3 ± 0.4% for Pb2+ and Cd2+ ions, respectively. The fouling experiment with humic acid followed by cross-flow washing of the membranes indicates that a flux recovery ratio (FRR) of 96.9 ± 0.4% can be obtained.
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Project description:To address trade-off and membrane-fouling challenges during the development of nanofiltration membranes, a thin-film composite membrane was prepared on the basis of interfacial polymerization regulated by adjusting the capsaicin-derived self-polymer poly N-(2-hydroxy-5-(methylthio) benzyl) acrylamide (PHMTBA) on the polysulfone substrate in this study. Through the self-polymerization of the monomer HMTBA with varied contents, microwave-assisted technology was employed to develop a variety of PHMTBAs. It was discovered that PHMTBA is involved in the interfacial polymerization process. Piperazine and PHMTBA competed for the reaction with trimesoyl chloride, resulting in a flatter and looser membrane surface. The PHMTBA-modified membrane presented a typical double-layer structure: a thicker support layer and a thinner active layer. The addition of PHMTBA to membranes improved their hydrophilicity and negative charge density. As a result, the PHMTBA-modified membrane showed dependable separation performance (water flux of 159.5 L m-2 h-1 and rejection of 99.02% for Na2SO4) as well as enhanced anti-fouling properties (flux recovery ratio of more than 100% with bovine serum albumin-fouling and antibacterial efficiency of 93.7% against Escherichia coli). The performance of the prepared membranes was superior to that of most other modified TFC NF membranes previously reported in the literature. This work presents the application potential of capsaicin derivatives in water treatment and desalination processes.
| S-EPMC9103837 | biostudies-literature
Project description:MOF-based mixed-matrix membranes (MMMs) have attracted considerable attention due to their tremendous separation performance and facile processability. In large-scale applications such as CO2 separation from flue gas, it is necessary to have high gas permeance, which can be achieved using thin membranes. However, there are only a handful of MOF MMMs that are fabricated in the form of thin-film composite (TFC) membranes. We propose herein the fabrication of robust thin-film composite mixed-matrix membranes (TFC MMMs) using a three dimensional (3D) printing technique with a thickness of 2-3 μm. We systematically studied the effect of casting concentration and number of electrospray cycles on membrane thickness and CO2 separation performance. Using a low concentration of polymer of intrinsic microporosity (PIM-1) or PIM-1/HKUST-1 solution (0.1 wt%) leads to TFC membranes with a thickness of less than 500 nm, but the fabricated membranes showed poor CO2/N2 selectivity, which could be attributed to microscopic defects. To avoid these microscale defects, we increased the concentration of the casting solution to 0.5 wt% resulting in TFC MMMs with a thickness of 2-3 μm which showed three times higher CO2 permeance than the neat PIM-1 membrane. These membranes represent the first examples of 3D printed TFC MMMs using the electrospray printing technique.
| S-EPMC9037021 | biostudies-literature
Project description:Positively charged nanofiltration (NF) membranes show great potential in the fields of water treatment and resource recovery. However, this kind of NF membrane usually suffers from relatively low water permeance. Herein, a positively charged NF membrane with a porous interlayer is developed, where the interlayer is formed by assembling dendritic mesoporous silica nanoparticles (DMSNs) after the formation of a polyamide layer. This post-assembly strategy avoids the adverse effect of the interlayer on the formation of positively charged NF membranes. The porous DMSN interlayer provides abundant connected channels for water transport, thus endowing the NF membrane with enhanced water permeance. A series of DMSNs with different sizes was synthesized, and their influence on membrane formation and membrane performance was systematically investigated. The optimized membrane exhibits a CaCl2 rejection rate of 95.2% and a water flux of 133.6 L·h-1·m-2, which is 1.6 times that of the control group without an interlayer. This work represents an approach to the fabrication of a positively charged NF membrane with porous interlayers for high-efficiency cation rejection.
| S-EPMC10574978 | biostudies-literature
Project description:Polyamide (PA) thin-film composite (TFC) membranes are commonly applied in reversed osmosis (RO) and nanofiltration (NF) applications due to their thin, dense top-layer, and high selectivity. Recently, the conventional organic phase (i.e., hexane) during interfacial polymerization (IP) was replaced by less toxic ionic liquids (ILs) which led to excellent membrane performances. As the high price of most ILs limits their up-scaling, the potential use of inexpensive Aliquat was investigated in this study. The thin-film composite (TFC) membranes were optimized to remove flavor compounds, i.e., ethyl acetate (EA) and isoamyl acetate (IA), from a fermentation broth. A multi-parameter optimization was set-up involving type of support, reaction time for IP, water content of Aliquat, and concentration of both monomers m-phenylenediamine (MPD) and trimesoylchloride (TMC). The membranes prepared using Aliquat showed similar fluxes as those prepared from a reference IL 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide ([C4mpyr][Tf2N]) but with better EA and IA retentions, even better than for a commercial RO membrane (GEA type AF). Finally, the recently introduced epoxide-curing of Bisphenol A diglycidyl ether (BADGE) with 1,6-hexanediamine (HDA) was investigated using Aliquat as organic phase. It is the first time this type of IP was performed in combination with an IL as organic phase. The resulting membrane was used in the filtration of a 35 µM Rose Bengal (RB) in 20 wt% dimethylformamide/ water (DMF/H2O) feed mixture. A well-crosslinked poly(β-alkanolamine) film was obtained with a > 97% retention.
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