Synthesis and characterization of flat-sheet thin film composite forward osmosis membranes

Forward osmosis (FO) is an emerging membrane separation technology. It is different from the well-studied pressure-driven membrane separation processes. The FO process is based on water transport under an osmotic pressure difference across a semi-permeable membrane. The distinct operating conditions lead to unique technical challenges during the exploitation of FO technology. According to a comprehensive literature investigation, one of the stringent barriers is lacking of effective FO membranes. The objectives of this research were to develop high performance FO membranes, and furthermore, to systematically study the mass transport and the governing mechanisms in FO process. Thin film composite (TFC) FO membranes with a tailored support structure were developed in this study. The membranes consisted of a highly porous substrate with finger-like pore structure, which was prepared via phase inversion, and a polyamide rejection layer synthesized by interfacial polymerization. The TFC FO membranes had small structural parameters due to the thin cross-section, low tortuosity, and high porosity of the substrates. The membrane rejection layers exhibited superior separation properties (higher water permeability and excellent selectivity) relative to commercial FO membranes. Under FO testing conditions, these membranes achieved high water flux while maintaining relatively low solute reverse diffusion. Comparison of the synthesized TFC FO membranes with commercial FO and reverse osmosis (RO) membranes revealed the critical importance of the substrate structure, with a straight finger-like pore structure preferred over a spongy pore structure to minimize internal concentration polarization (ICP), a unique and critical problem resulting in low water flux in the osmotically driven membrane processes. In addition, membranes with high water permeability and excellent selectivity are preferred to achieve both high FO water flux and low solute flux. The results proved that TFC membranes with a tailored porous substrate and rejection layer are promising for FO applications. In the study of polyamide rejection layer synthesis, the influence of monomer concentrations (i.e., m-phenylenediamine (MPD) and trimesoyl chloride (TMC) concentrations) on the membrane separation properties as well as the FO performance was systematically investigated. A strong trade-off between the water permeability and salt rejection of the membranes was observed, where reducing the MPD concentration or increasing the TMC concentration may result in a higher membrane permeability but a lower salt rejection. In FO tests, membranes with poor salt rejection had severe solute reverse diffusion, which enhanced the severity of ICP. It was found that the FO water flux was governed by both the membrane water permeability and solute rejection. For a membrane with higher water permeability but lower solute rejection, the reduced membrane frictional resistance was compensated simultaneously by the more severe solute-reverse-diffusion-induced ICP. The net effect on the FO water flux depends on the competition of these two opposing mechanisms. Under conditions where solute reverse diffusion may cause severe ICP (e.g., high draw solution concentration and high water flux level), membranes need to be optimized to achieve a high salt rejection even if this is at the expense of lower water permeability. In view of the importance of the water permeability and salt permeability on FO performance, a systematic comparison study of prevailing semi-permeable FO membranes with nanofiltration (NF)-like and RO-like separation properties in terms of flux performance and fouling behavior was conducted. Due to the crucial influence of solute reverse diffusion on FO water flux, the high-rejection RO-like FO membranes generally performed better than the NF-like counterparts in sodium chloride based FO tests. On the other hand, the high permeability of NF-like FO membranes could achieve higher water flux, when proper draw solutes were used to minimize draw solute leakage. Fouling tests suggested that the NF-like TFC FO membranes tended to be more fouling resistant due to their relatively smooth membrane surface. This work further elucidated the major mechanisms that govern the FO performance. These mechanisms were summarized as a frictional resistance loss mechanism (MR), solute-reverse-diffusion-induced ICP (MICP-Js), concentration of feed solutes (concentrative ICP or MICP-feed in the active-layer-facing-draw-solution orientation) and dilution of draw solutes (dilutive ICP or MICP-draw in the active-layer-facing-feed-solution orientation). These mechanisms are related to the properties of membrane, draw and feed solutions. This work led to a set of systematic criteria for the selection of FO membranes, draw solution and optimization of other operating conditions, of which the practicability was demonstrated in potential FO applications.

Middle support layer formation and structure in relation to performance of three-tier thin film composite forward osmosis membrane

Hydrophilic polyvinyl alcohol coating on hydrophobic electrospun nanofiber membrane for high performance thin film composite forward osmosis membrane

Thin film composite forward osmosis membranes based on polydopamine modified polysulfone substrates with enhancements in both water flux and salt rejection

Polydopamine coating on a thin film composite forward osmosis membrane for enhanced mass transport and antifouling performance

Forward Osmosis (FO) process is driven by osmotic energy, which is arisen from the osmotic pressure difference between the draw solution (high concentration) and the feed solution (low concentration) separated by a semi-permeable membrane. Combining anaerobic digestion with FO membrane to retain influent organic waste, this research aims to develop the integrated biological wastewater treatment technology: Anaerobic Osmosis-Membrane Reactor (AnOMBR). In the preliminary study, mixed organic fouling of the FO membrane in submerged mode was systematically investigated. Fouling behavior of cellulose triacetate (CTA) FO membrane and thin film composite (TFC) polyamide FO membranes were studied and compared. It was interesting to find under mild FO fouling conditions, TFC FO membranes could have greater fouling tendency as compared to CTA FO membranes due to their greater surface roughness. Although FO is believed to have superior fouling resistance in the AL-FS orientation, severe fouling could occur even at moderate flux levels, especially for TFC membranes or for unstable feed solutions. In this case, solution chemistries such as pH and presence of calcium ions posed remarkable effect on the cake layer composition due to the effect of foulant-foulant interaction(s); In contrast, the foulant composition was not strongly affected by the membrane type (CTA versus TFC) nor the testing mode (pressure-driven NF mode versus osmosis-driven FO mode). With the understanding of FO organic fouling mechanisms, a novel submerged AnOMBR utilizing CTA FO membrane in anaerobic bioreactor was developed and feasibility of using the AnOMBR to treat low-strength synthetic wastewater at mesophilic temperature was evaluated. Flux declined under the effect of both feed conductivity build-up and membrane fouling. Generally fouling on membrane was mild, while both organic fouling and inorganic scaling could still be observed at the edge of membrane. Bulk pH could be sustained within neutral to slightly alkaline due to the retention of alkalinity by FO membrane. The AnOMBR showed good and stable soluble chemical oxygen demand (sCOD) removal and perfect total phosphorous removal. However the removal of total nitrogen and ammonia still needed improvements. The elevated salt environment had marginal effect on bioactivity of methanogens and methane production of AnOMBR system was stable. Based on the promising results, the AnOMBR was operated at both mesophilic temperature and room temperature to compare the performance in terms of membrane flux level and mixed liquor conductivity, nutrient removal and methane production. At room temperature, the flux decreased and conductivity increased both at a slower speed than at mesophilic temperature. The membrane durability was also better and tap water cleaning was practical at room temperature with 90% flux recovery. At both temperatures, the AnOMBR showed good rejection to nutrients. However, at higher temperature, the nutrient concentration in supernatants was relatively lower, indicating the faster and efficient nutrient degradation by microbial at higher temperature. Methane production rate at mesophilic temperature was also significant higher than at room temperature.

Preparation of polyamide thin film composite forward osmosis membranes using electrospun polyvinylidene fluoride (PVDF) nanofibers as substrates

In this study, a thin-film composite (TFC) forward osmosis membrane was synthesized and characterized with various concentrations (15%, 16%, 17% and 18%) of polysulfone for the removal of two organic micro-pollutants, namely phenol and benzene from the aqueous solutions. Synthesis of a thin-film composite membrane with a support layer carried out by dissolving an amount of polysulfone polymer and polyvinyl pyrrolidone in N-methyl,2-pyrrolidone via phase inversion process and a thin-film layer of the polyamide M-phenylenediamine (MPD) and 1,3,5-benzene trichloride by interfacial polymerization reaction for the fabrication of the TFC were examined. Water flux and reverse salt flux decreased with increasing the concentration of polysulfone polymer. The composite membranes with polysulfone at 16% and 17% had even higher efficiencies. Also, by increasing the concentration of the draw solution, further phenol and benzene could be removed. The highest rejection rates of phenol (polar) and benzene (nonpolar) were found to be 79% and 90%, respectively. The results showed the capability of the thin-film composite forward osmosis (TFC-FO) membranes for removing organic micro-pollutants from the aqueous solutions under different operating conditions, with the efficiency of removing nonpolar compounds being higher.

Fouling and cleaning of thin film composite forward osmosis membrane treating municipal wastewater for resource recovery

Novel CA/PVDF nanofiber supports strategically designed via coaxial electrospinning for high performance thin-film composite forward osmosis membranes for desalination

Characterization and control of membrane fouling during dewatering of activated sludge using a thin film composite forward osmosis membrane

Electrospun nanofiber with interconnected porous structure has been studied as a promising support layer of polyamide (PA) thin-film composite (TFC) forward osmosis (FO) membrane. However, its rough surface with irregular pores is prone to the formation of a defective PA active layer after interfacial polymerization, which shows high reverse salt leakage in FO desalination. Heat-curing is beneficial for crosslinking and stabilization of the PA layer. In this work, a nanofiber-supported PA TFC membrane was conceived to be cured on a hot water surface with preserved phase interface for potential “defect repair”, which could be realized by supplementary interfacial polymerization of residual monomers during heat-curing. The resultant hot-water-curing FO membrane with a more uniform superhydrophilic and highly crosslinked PA layer exhibited much lower reverse salt flux (FO: 0.3 gMH, PRO: 0.8 gMH) than that of oven-curing FO membrane (FO: 2.3 gMH, PRO: 2.2 gMH) and achieved ∼4 times higher separation efficiency. It showed superior stability owing to mitigated reverse salt leakage and osmotic pressure loss, with its water flux decline lower than a quarter that of the oven-curing membrane. This study could provide new insight into the fine-tuning of nanofiber-supported TFC FO membrane for high-quality desalination via a proper selection of heat-curing methods.

Thin film composite forward osmosis membranes based on thermally treated PAN hydrophilized PVDF electrospun nanofiber substrates for improved performance

Improved thin-film-composite forward-osmosis membrane for coal mine water purification

Effect of sulphonated polyethersulfone substrate for thin film composite forward osmosis membrane