High-performance multi-functional reverse osmosis membranes obtained by carbon nanotube·polyamide nanocomposite.
ABSTRACT: Clean water obtained by desalinating sea water or by purifying wastewater, constitutes a major technological objective in the so-called water century. In this work, a high-performance reverse osmosis (RO) composite thin membrane using multi-walled carbon nanotubes (MWCNT) and aromatic polyamide (PA), was successfully prepared by interfacial polymerization. The effect of MWCNT on the chlorine resistance, antifouling and desalination performances of the nanocomposite membranes were studied. We found that a suitable amount of MWCNT in PA, 15.5 wt.%, not only improves the membrane performance in terms of flow and antifouling, but also inhibits the chlorine degradation on these membranes. Therefore, the present results clearly establish a solid foundation towards more efficient large-scale water desalination and other water treatment processes.
Project description:Chlorine resistant reverse osmosis (RO) membranes were fabricated using a multi-walled carbon nanotube-polyamide (MWCNT-PA) nanocomposite. The separation performance of these membranes after chlorine exposure (4800 ppm·h) remained unchanged (99.9%) but was drastically reduced to 82% in the absence of MWCNT. It was observed that the surface roughness of the membranes changed significantly by adding MWCNT. Moreover, membranes containing MWCNT fractions above 12.5 wt.% clearly improved degradation resistance against chlorine exposure, with an increase in water flux while maintaining salt rejection performance. Molecular dynamics and quantum chemical calculations were performed in order to understand the high chemical stability of the MWCNT-PA nanocomposite membranes, and revealed that high activation energies are required for the chlorination of PA. The results presented here confirm the unique potential of carbon nanomaterials embedded in polymeric composite membranes for efficient RO water desalination technologies.
Project description:The antiscaling properties of multiwalled carbon nanotube (MWCNT)-polyamide (PA) nanocomposite reverse-osmosis (RO) desalination membranes (MWCNT-PA membranes) were studied. An aqueous solution of calcium chloride (CaCl<sub>2</sub>) and sodium bicarbonate (NaHCO<sub>3</sub>) was used to precipitate in situ calcium carbonate (CaCO<sub>3</sub>) to emulate scaling. The MWCNT contents of the studied nanocomposite membranes prepared by interfacial polymerization ranged from 0 wt % (plain PA) to 25 wt %. The inorganic antiscaling performances were compared for the MWCNT-PA membranes to laboratory-made plain and commercial PA-based RO membranes. The scaling process on the membrane surface was monitored by fluorescence microscopy after labeling the scale with a fluorescent dye. The deposited scale on the MWCNT-PA membrane was less abundant and more easily detached by the shear stress under cross-flow compared to other membranes. Molecular dynamics simulations revealed that the attraction of Ca<sup>2+</sup> ions was hindered by the interfacial water layer formed on the surface of the MWCNT-PA membrane. Together, our findings revealed that the observed outstanding antiscaling performance of MWCNT-PA membranes results from (i) a smooth surface morphology, (ii) a low surface charge, and (iii) the formation of an interfacial water layer. The MWCNT-PA membranes described herein are advantageous for water treatment.
Project description:A hydrophilic, hydrostable porous metal organic framework (MOF) material-MIL-101 (Cr) was successfully doped into the dense selective polyamide (PA) layer on the polysulfone (PS) ultrafiltration (UF) support to prepare a new thin film nanocomposite (TFN) membrane for water desalination. The TFN-MIL-101 (Cr) membranes were characterized by SEM, AFM, XPS, wettability measurement and reverse osmosis (RO) test. The porous structures of MIL-101 (Cr) can establish direct water channels in the dense selective PA layer for water molecules to transport through quickly, leading to the increasing water permeance of membranes. With good compatibility between MIL-101 (Cr) nanoparticles and the PA layer, the lab made TFN-MIL-101 (Cr) membranes integrated tightly and showed a high NaCl salt rejection. MIL-101 (Cr) nanoparticles increased water permeance to 2.2 L/m²·h·bar at 0.05 w/v % concentration, 44% higher than the undoped PA membranes; meanwhile, the NaCl rejection remained higher than 99%. This study experimentally verified the potential use of MIL-101 (Cr) in advanced TFN RO membranes, which can be used in the diversified water purification field.
Project description:Forward osmosis (FO) is a promising alternative to reverse osmosis (RO) in membrane-based water desalination. In the current study, carboxylated multiwalled carbon nanotubes (MWCNTs) were incorporated in a polyamide (PA) layer formed on top of a polysulfone porous support, resulting in a thin film nanocomposite (TFN) membrane. The amount of MWCNTs was varied (0.01, 0.05, 0.1, and 0.2 wt/vol %). The FO performance was investigated using deionized water as the feed solution and 2 M NaCl as the draw solution. It was found that the carboxylated MWCNTs enhanced the membrane hydrophilicity, surface roughness, and porosity. Such combined effects are believed to have led to enhanced FO water flux. TFN 0.2 showed the highest FO water flux of 73.15 L/m<sup>2</sup> h, an improvement of 67% compared to the blank thin-film composite (TFC) membrane and significantly better than the values reported in the literature. Direct observation by transmission electron microscopy revealed the presence of some open-ended CNTs favorably oriented across the PA layer. Those are believed to have facilitated the transport of water through their inner cores and contributed to the increase in water flux. However, this was at the expense of salt rejection and reverse solute flux performance. The best performing membrane was found to be TFN 0.01. It exhibited a salt rejection of 90.1% with a FO water flux of 50.23 L/m<sup>2</sup> h, which is 13% higher than the TFC membrane, and a reverse solute flux of 2.76 g/m<sup>2</sup> h, which is 21% lower than the TFC membrane. This TFN 0.01 membrane also outperformed the TFN membranes reported in the literature.
Project description:Enhancing the water flux while maintaining the high salt rejection of existing reverse osmosis membranes remains a considerable challenge. Herein, we report the use of a porous carbon nitride (C3N4) nanoparticle to potentially improve both the water flux and salt rejection of the state-of-the-art polyamide (PA) thin film composite (TFC) membranes. The organic-organic covalent bonds endowed C3N4 with great compatibility with the PA layer, which positively influenced the customization of interfacial polymerization (IP). Benefitting from the positive effects of C3N4, a more hydrophilic, more crumpled thin film nanocomposite (TFN) membrane with a larger surface area, and an increased cross-linking degree of PA layer was achieved. Moreover, the uniform porous structure of the C3N4 embedded in the "ridge" sections of the PA layer potentially provided additional water channels. All these factors combined provided unprecedented performance for seawater desalination among all the PA-TFC membranes reported thus far. The water permeance of the optimized TFN membrane is 2.1-folds higher than that of the pristine PA-TFC membrane, while the NaCl rejection increased to 99.5% from 98.0%. Our method provided a promising way to improve the performance of the state-of-art PA-TFC membranes in seawater desalination.
Project description:Forward osmosis (FO) is a promising membrane technology to combine seawater desalination and water reuse. More specifically, in a FO-reverse osmosis (RO) hybrid process, high quality water recovered from the wastewater stream is used to dilute seawater before RO treatment. As such, lower desalination energy needs and/or water augmentation can be obtained while delivering safe water for direct potable reuse thanks to the double dense membrane barrier protection. Typically, FO-RO hybrid can be a credible alternative to new desalination facilities or to implementation of stand-alone water reuse schemes. However, apart from the societal (public perception of water reuse for potable application) and water management challenges (proximity of wastewater and desalination plants), FO-RO hybrid has to overcome technical limitation such as low FO permeation flux to become economically attractive. Recent developments (i.e., improved FO membranes, use of pressure assisted osmosis, PAO) demonstrated significant improvement in water flux. However, flux improvement is associated with drawbacks, such as increased fouling behaviour, lower rejection of trace organic compounds (TrOCs) in PAO operation, and limitation in FO membrane mechanical resistance, which need to be better considered. To support successful implementation of FO-RO hybrid in the industry, further work is required regarding up-scaling to apprehend full-scale challenges in term of mass transfer limitation, pressure drop, fouling and cleaning strategies on a module scale. In addition, refined economics assessment is expected to integrate fouling and other maintenance costs/savings of the FO/PAO-RO hybrid systems, as well as cost savings from any treatment step avoided in the water recycling.
Project description:Smooth, durable, ultrathin antifouling layers are deposited onto commercial reverse osmosis membranes without damaging them and they exhibit a fouling reduction. A new synergistic approach to antifouling, by coupling surface modification and drinking-water-level chlorination is enabled by the films' unique resistance against chlorine degradation. This approach substantially enhances longer-term fouling resistance compared with surface modification or chlorination alone, and can reduce freshwater production cost and its collateral toxicity to marine biota.
Project description:In the current study, the poly (amide-urethane) (PAUt) membranes were successfully fabricated by interfacial polymerization of m-phenylenediamine (MPD) and 5-choroformyloxyisophaloyl chloride (CFIC) on the polysulfone substrates. Two modification methods based on layer-by-layer assembly were applied to modify the PAUt membrane surface to achieve antifouling property: 1. Chitosan (CS) was directly self-assembled on the PAUt membrane (i.e., PAUt-CS); and 2. polydimethyl diallyl ammonium chloride (PDDA), polystyrene sulfonate (PSS), and CS were successively self-assembled on the membrane surface (i.e., PAUt-PDDA/PSS/CS). The resultant membranes were symmetrically characterized by Attenuated Total Reflection Fourier Transform Infrared Spectroscopy (ATR-FTIR), X-ray Photoelectron Spectroscopy (XPS), Scanning Electron Microscopy (SEM), Atomic Force Microscopy (AFM) and Contact Angle Meter (CAM), respectively. The results indicated that the modified membranes had much smoother and more hydrophilic surfaces as compared to the nascent PAUt membrane. Meanwhile, the modified membranes exhibited better reverse osmosis performance in terms of water permeability and salt rejection. After the modified membranes were fouled by lake water, the PAUt-PDDA/PSS/CS membrane presented the best antifouling performance among the three types of membranes. Combining the reverse osmosis performance with the anti-fouling property obviously, the PAUt-PDDA/PSS/CS membrane behaved as a promising candidate to be used in real applications.
Project description:Thin-film nanocomposites (TFN) functionalized with tunable molecular-sieving nanomaterials have been employed to tailor membranes, with an enhanced permeability and selectivity. Herein, water-soluble hollow cup-like macrocyclic molecules, sulfothiacalixarene (STCAss) and sulfocalixarene (SCA), are ionically bonded into the polyamide network to engineer the molecular-sieving properties of TFN membranes for organic solvent forward osmosis (OSFO). Introducing both STCAss and SCA into the polyamide network not only increases the free volume, but also reduces the thickness of the TFN layers. Combining with their molecularly tunable size of the lower cavities, both STCAss and SCA enable the TFN membranes to size exclusively reject the draw solutes, but only STCAss-functionalized membrane has an ethanol flux doubling the pristine one under the FO and PRO modes in OSFO processes; leading the functionalized polyamide network with remarkable improvements in OSFO performance. This study may provide insights to molecularly functionalize TFN membranes using multifunctional nano-fillers for sustainable separations.
Project description:In this study, modification of polysulfone (PSf)/sulfonated polysulfone (SPSf) blended porous ultrafiltration (UF) support membranes was proposed to improve the reverse osmosis (RO) performance of aromatic polyamide thin film composite (TFC) membranes. The synergistic effects of solvent, polymer concentration, and SPSf doping content in the casting solution were investigated systematically on the properties of both porous supports and RO membranes. SEM and AFM were combined to characterize the physical properties of the membranes, including surface pore natures (porosity, mean pore radius), surface morphology, and section structure. A contact angle meter was used to analyze the membrane surface hydrophilicity. Permeate experiments were carried out to evaluate the separation performances of the membranes. The results showed that the PSf/SPSf blended porous support modified with 6 wt % SPSf in the presence of DMF and 14 wt % PSf had higher porosity, bigger pore diameter, and a rougher and more hydrophilic surface, which was more beneficial for fabrication of a polyamide TFC membrane with favorable reverse osmosis performance. This modified PSf/SPSf support endowed the RO membrane with a more hydrophilic surface, higher water flux (about 1.2 times), as well as a slight increase in salt rejection than the nascent PSf support. In a word, this work provides a new facile method to improve the separation performance of polyamide TFC RO membranes via the modification of conventional PSf porous support with SPSf.