聚酰胺复合正渗透膜的制备及其脱盐性能研究

通过溶液相转化法制备四种基膜,然后采用界面聚合法制备不同基膜的聚酰胺复合正渗透(FO)膜,并对其结构与性能进行表征。结果表明,正渗透膜基膜表面开孔率高、孔径分布均匀,且纯水通量大;在基膜中引入聚酯(PET)筛网使其厚度增大、孔隙率和纯水通量降低。基膜材料为聚砜(PSF)时,复合膜聚酰胺分离层较为疏松,以聚偏氟乙烯(PVDF)为基膜材料,形成的分离层较为致密且具有典型峰谷结构,从而使反向盐通量更小。四种复合膜的正渗透纯水通量均大于10 L/m2·h,最高达20 L/m2·h。120 min连续正渗透脱盐实验表明,复合膜截盐率及其稳定性优于商用膜,尤其PET筛网支撑PVDF基复合膜的截盐率基本稳定在97. 5%左右,表现出良好的运行可靠性。     

Molecular design of the cellulose ester-based forward osmosis membranes for desalination

This work has investigated the fundamental science of phase inversion and formation mechanism of cellulose ester membranes at the interface between polymer and casting substrate. It also explores the desired membrane preparation conditions for forward osmosis (FO) applications. With the aid of positron annihilation lifetime spectroscopy (PALS), the similarity in physicochemical properties between the polymer and the substrate was found to play a significant role in determining the porosity of the bottom interfacial layer. The structure of the dense interfacial layer was also strongly dependent on membrane thickness and solvent composition. Experimental results surprisingly reveal that the original pore size of the as-cast membrane plays a critical role determining the final performance of the subsequent annealed membrane independently of annealing temperature and time. In addition, since a threshold pore size exists during annealing above which pores become difficult to downsize, we have found that a thin dense selective layer integrated in an asymmetric membrane may not always be the best option for FO. A balanced membrane structure consisting of a thin porous support and a thin dense selective layer has been developed for FO, which shows a low internal concentration polarization (ICP) and a relatively high water flux when seawater was employed as the feed.     

Multi-functional forward osmosis draw solutes for seawater desalination

Forward osmosis (FO), as one of the emerging desalination technologies, has the potential to produce freshwater from a variety of water sources by utilizing the osmotic pressure gradient across a semi-permeable membrane. Drawsolution, as an essential component of any FO process, can extract watermolecules fromseawater orwastewater. An ideal draw solution should meet three essential requirements, namely high osmotic pressure, low reverse flux, and facile regeneration mechanism. The selection of proper draw solutes is especially critical for an energy-efficient FO process since the energy consumption mostly arises from the separation or regeneration of the draw solution. Recently, we developed a few multi-functional FO draw solutes, mainly aiming to enhance the FO water flux and to explore facile re-concentration methods. This review summarizes these draw solutes, including Na⁺-functionalized carbon quantum dots, thermoresponsive copolymers, hydrophilic magnetic nanoparticles, and thermoresponsive magnetic nanoparticles.     

Selection of substrate manufacturing techniques of polyamine-based thin-film composite membranes for forward osmosis process

This paper is a comparative study on the preparation techniques used to make the support layer of polyamide-thin-film composite forward osmosis (TFC-FO) membranes. The role played by the support layer preparation technique in membrane performance is thoroughly investigated in this study. Electrospinning is shown to produce membranes of lower structural parameter compared to those obtained by conventional phase inversion techniques. The electrospun polyamide selective layer can also be tailored with the required properties. This makes electrospinning a promising process to design efficient FO membrane substrates. It is shown in this work that the FO water flux is more dependent on the internal structure of the support layer than the preparation materials. The main challenge remaining for substrates to operate in FO is to achieve simultaneously a low structural parameter, a high surface porosity, and the required mechanical properties. As most of today's approaches are not suitable, further materials development is essential in future investigations on TFC-FO membranes.     

Forward osmosis water desalination: Fabrication of graphene oxide-polyamide/polysulfone thin-film nanocomposite membrane with high water flux and low reverse salt diffusion

This paper investigates the synthesis of graphene oxide (GO)-incorporated polyamide thin-film nanocomposite (TFN) membranes on polysulfone substrate for forward osmosis applications. The GO nanosheets were embedded into polyamide layer using different concentrations (0.05?0.2 wt%). The results represented the alteration of polyamide surface by GO nanosheets and enhancing the surface hydrophilicity by increasing the GO loading. The results showed that the water flux for 0.1 wt% GO embedded nanocomposite (TFN) membrane was 34.7 L/m² h, representing 90% improvement compared to the thin-film composite, while the salt reverse diffusion was reduced up to 39%.     

Composite membranes for seawater desalination by reverse osmosis

A composite reverse-osmosis membrane has been developed for seawater desalination having a 400-Å semipermeable barrier. The membrane is prepared by directly forming a very thin film of a polymer, generally cellulose triacetate, upon the finely porous surface of a supporting membrane. The composite membrane, capable of desalinating seawater in a single pass, has demonstrated improved flux stability at high pressures over modified membranes currently used to desalinate brackish water.     

Enhanced chlorine-resistant and low biofouling reverse osmosis polyimide-graphene oxide thin film nanocomposite membranes for water desalination

The effect of graphene oxide (GO) loading (0.03, 0.06, 0.09, 0.12, and 0.30 wt%) in the aqueous phase on the performance of reverse osmosis (RO) polyimide (PI) thin film composite (TFC) membrane was investigated. TFC and thin film nanocomposite (TFN) membranes were produced through interfacial polymerization and the imide linkage was confirmed by attenuated total reflection Fourier transform infrared spectroscopy. The spongy-like structure with vertical fingers of RO PI-GO TFN membranes was explored by top-surface and cross-sectional field emission scanning electron microscope (FE-SEM). The roughness of the membranes was determined. All PI-GO TFN membranes exhibited enhanced desalination performance in comparison with PI membranes. Samples with 0.06 wt% GO performed the best with a water flux of 31.80 L/m²/h, salt rejection of 98.8%, and very good antibiofouling properties. This hydrophilic membrane displayed significantly enhanced chlorine-resistance with water flux of 36.3 L/m²/h and salt rejection of 98.5%. This work provides a promising start for designing rapid water permeation PI-GO TFN membranes in water desalination.     

Fabrication of polyamide thin film nanocomposite reverse osmosis membrane incorporated with a novel graphite-based carbon material for desalination

The properties of polyamide (PA) thin film composite (TFC) membranes are affected by many variables, especially the additives in the process of interfacial polymerization that play an important role in the properties of membranes. In this study, a new type graphite carbon was added into organic phase containing trimesoyl chloride for interfacial polymerization with aqueous phase containing m-phenylenediamine to prepare modified polyamide thin film nanocomposite (TFN) membranes for reverse osmosis (RO) adhibition. Polysulfone ultrafiltration membranes were used as the carrier of the interfacial polymerization. The concentration of graphite carbon was selected from 0.002 to 0.01 wt%. The polyamide nanocomposite membrane prepared with the concentration of 0.004 wt% graphite carbon showed the best RO desalination performance, which the water flux of this TFN membrane is over 2.3 times as much as pristine TFC membrane, and the salt rejection is over 99%. This article provides a well-performing polyamide thin film nanocomposite membrane modified by a new-type carbon nanoparticles consequently.     

Fabrication of innovative forward osmosis membranes via multilayered interfacial polymerization on electrospun nanofibers

Practical application of forward osmosis (FO) membranes is beset by low water flux and vulnerability of selective polyamide (PA) layers. Herein, novel composite membranes were fabricated with multilayered PA via cyclic interfacial polymerization (IP) on electrospun polyethersulfone (PES) nanofiber substrates to realize high performance FO. The membrane fabrication conditions were optimized detailedly with respect to the morphologies, physicochemical properties, and FO performances. It is indicated that the PES concentration has great impacts on the morphology, thickness, and fiber diameter of the electrospun substrates and the optimal concentration is proved to be 26 wt %. After multilayered IP, the membrane thickness, surface hydrophilicity, and mechanical strength increased with IP cycles. The optimized FO membranes with two PA layers show much higher water flux and membrane selectivity compared with the commercial thin film composite membranes, holding great promise for water purification and seawater desalination. © 2018 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47247.     

Substrate matters:The influences of substrate layers on the performances of thin-film composite reverse osmosis membranes

Thin-film composite (TFC) reverse osmosis (RO) membranes are playing the dominating role in desalination.Tremendous efforts have been put in the studies on the polyamide selective layers. However, the effect of the substrate layers is far less concerned. In this review, we summarize the works that consider the impacts of the substrates, including pore sizes, surface hydrophilicity, on the processes of interfacial polymerization and consequently on the morphologies of the active layers and on final RO performances of the compositemembranes. All the works indicate that the pore sizes and surface hydrophilicity of the substrate evidently influence the RO performances of the composite membranes. Unfortunately, we find that the observations and understandings on the substrate effect are frequently varied from case to case because of the lack of substrates with uniform pores and surface chemistries.We suggest using track-etchedmembranes or anodized aluminamembranes having relatively uniformpores and functionalizable porewalls asmodel substrates to elucidate the substrate effect.Moreover, we argue that homoporous membranes derived from block copolymers have the potential to be used as substrates for the large-scale production of high-performances TFC RO membranes.     

Effects of polyethylene glycol on the structure and filtration performance of thin-film PA-Psf composite forward osmosis membranes

In forward osmosis, internal concentration polarization is related to the properties (e.g., hydrophilicity, porosity, structural resistant) of membrane support layer. In this work, polyethylene glycol with a low molecular weight of 400 Da was introduced as a support layer additive during the fabrication of thin-film polyamide-polysulfone composite forward osmosis membranes. The forward osmosis performances including water flux and reverse salt flux of the membranes were tested in the mode of AL-FS where the membrane active layer faced toward feed solution. Results showed that the addition of polyethylene glycol would reduce internal concentration polarization and improve membrane performance in forward osmosis by means of enhancing membrane hydrophilicity and changing pore morphologies of membrane support layer. The membrane prepared with 6 wt.% polyethylene glycol was found to exhibit the highest water flux of 47.4 Lm^?2h^?1 with a reverse salt flux of 7.6 gm^?2h^?1 when using DI water and 2.0 M NaCl as the feed and the draw solution, respectively, indicating an optimal polyethylene glycol dosage of 6 wt.% in this work.     

Polyacrylic desalination membranes. II. Reverse osmosis performance

A new class of polyacrylic membranes has been tested under reverse osmosis conditions on dilute (1%–4%) salt solutions. Fluxes up to 0.2 gal-mil/ft²-day at greater than 98% rejection have been achieved. The effect of membrane composition on product flux and salt rejection is discussed. Increased fluxes at even higher rejection should be possible by proper selection of the type and concentration of hydrophilic, hydrophobic, and crosslinking monomers. It is concluded that improved membranes should have as high as possible a concentration of hydrophilic groups, distributed randomly through a lightly crosslinked, rubbery polymer matrix.     

硼掺杂二氧化硅杂化膜的制备及渗透汽化脱盐性能

以1,2-双（三乙氧基硅基）乙烷（BTESE）和硼酸为前体,通过溶胶-凝胶法制备了硼掺杂的二氧化硅（B-BTESE-SiO₂）杂化膜。采用FTIR、XRD、XPS、TEM、SEM等系列表征手段对合成溶胶及膜的结构和形貌进行了分析,结果表明：硼元素成功掺杂进入SiO₂骨架中,形成了水热稳定的B—O—Si键,能明显影响膜表面的微观结构、亲疏水性、膜孔径大小从而提高膜的脱盐性能和稳定性。当溶胶中的H₃BO₃/BTESE比为0.25时所优化制备SiO₂膜的亲水性最强,脱盐过程中活化能最低,传质阻力最小,膜孔径约为0.61 nm,故表现出最佳的脱盐性能。在60℃以3.5%（质量） NaCl溶液为进料液时,该膜的水通量高达16.5 kg·m^-2·h^-1,盐截留率近乎100%,并且表现出优异的长时间稳定性（>168 h）和高浓度盐水溶液[4.2%~15.0%（质量） NaCl]脱盐性能,在海水淡化和高盐废水处理等领域具有潜在的应用前景。     

具有三维聚酰胺脱盐网络结构的无纺布复合正渗透膜

利用间苯二胺（MPD）和均苯三甲酰氯（TMC）,直接在聚酯无纺布（NV）织物的多孔空间中进行界面聚合,形成大通量无纺布复合正渗透（NVC-FO）膜。NVC-FO膜在无纺布内部形成的多层次三维（3-D）聚酰胺结构,分布在30~50μm深的聚对苯二甲酸乙二醇酯支撑材料的内部。这种相对松散的有深度的3-D聚酰胺网络,不仅透水表面积大,而且可以避免薄层聚酰胺缺陷导致的高漏盐性,有较低的反向盐通量。进一步研究发现,在一定范围内降低单体质量分数（MPD 1%~0.01%,TMC 0.5%~0.005%）,可以形成更宽广的3-D聚酰胺网络结构,在保持较低的反向盐通量的同时得到更高的水通量。使用1mol/L NaCl作为汲取溶液,优化的NVC-FO膜水通量最高可以达到193.54L/(m²·h),反向盐通量为0.047mol/(m²·h)。采用加压正渗透实验,发现这些高通量NVC-FO膜的盐穿透破裂压力在200~1400Pa之间,而且证实了降低单体质量分数会导致膜的耐压性能显著降低。尽管NVC-FO膜的耐压性能有待提高,但是该研究有可能为构建高脱盐性能的FO膜提供一条新的思路。     

Crosslinked poly(hydroxyethyl methacrylate) membranes for desalination by reverse osmosis

A series of crosslinked hydroxyethyl methacrylate (HEMA) membranes for reverse osmosis desalination has been prepared. The crosslinkers used were trimethylol propane trimethacrylate (TPT) or ethylene glycol dimethacrylate (EGD). Membranes were synthesized by polymerizing the monomers as a thin homogeneous film. In addition to reverse osmosis tests, the membranes were also characterized by osmosis experiments and sorption measurements. The reverse osmosis water flux (1500 psi applied pressure, 4% NaCl brine, pH = 5) for these membranes decreases from 0.6 gallonmil/ft²-day (GMFD) to 0.055 GMFD and salt rejection increase from 78% to a maximum of 94% as the amount of TPT is increased from 0 to 11 mole-%. Water contents decrease from 42% to 15% over the same range of crosslinker, but the preferential sorption of water to salt does not vary. Thus, rises in reverse-osmosis semipermeability were found to result from changes in water–salt diffusivity ratios. The mechanism of permselectivity has been interpreted in terms of parallel diffusive fluxes across the membrane of primary H-bonded water and secondary water plus salt ions.     

双胺“可逆”溶剂强化正渗透脱盐及过程优化

正渗透作为非压力驱动膜脱盐技术,具有能耗低、膜污染轻、水回收率高等优点,其中汲取液的分离回收是整个正渗透技术的关键。本文提出采用双胺(TEPDA,N,N,N’,N’-四乙基-1,3-丙二胺)“可逆”溶剂经质子化-脱碳可逆循环作为正渗透汲取液进行脱盐的策略。首先,使用TEST软件预测发现,相比传统有机溶剂及单胺溶剂(如DMCHA,N,N-二甲基环己胺),TEPDA具有较低的挥发性、较高的安全性和低生育毒性。正渗透实验发现在两种模式下TEPDA的反向通量选择性均高于DMCHA,证明TEPDA具有更好的正渗透效果。同时发现TEPDA汲取液在PRO模式下效果要优于FO模式。通过对操作条件的优化得到TEPDA汲取液的最优操作温度为30℃,最佳流速为500mL/min。在最优条件下对1%(质量分数)的氯化钠溶液进行5h的连续运行发现,TEPDA汲取液在5h后仍能保持6.09L/(m²·h)的正向渗透通量,具有连续运行的稳定性。循环实验也证明了TEPDA具有较好的循环稳定性。上述结果为双胺(TEPDA)“可逆”溶剂应用于正渗透脱盐领域提供了基础的理论指导。     

Preparation of novel magnetic nanoparticles as draw solutes in forward osmosis desalination

Novel magnetic nanoparticles (MNPs), Fe₃O₄@SiO₂ and Fe₃O₄@SiO₂@PEG-(COOH)₂, were prepared by loading different amounts of SiO₂ or/and PEG-(COOH)₂ onto Fe₃O₄ nanoparticles, and their feasibility to be used as forward osmosis (FO) draw solutes was investigated. The characterization of the materials showed that, compared to normal Fe₃O₄ nanoparticles, the modified MNPs exhibited enhanced dispersity and high osmotic pressure in aqueous solution. The FO experiment indicated that the synthesized draw solutes could obtain a water flux as high as 10 L·m^-2·h^-1 with an aquaporin FO membrane. The optimal concentration of the added tetraethyl orthosilicate was 30% during the synthesis. The novel MNPs could be easily recovered from draw solutions by magnetic field, and the recovery rate of Fe₃O₄@SiO₂ and Fe₃O₄@SiO₂@PEG-(COOH)₂ was 83.95% and 63.37%, respectively. Moreover, after 5 recycles of reuse, the water flux of Fe₃O₄@SiO₂ and Fe₃O₄@SiO₂@PEG-(COOH)₂ as draw solutes still remained 64.36% and 85.26%, respectively. The experimental results demonstrated that the synthesized core–shell magnetic nanoparticles are promising draw solutes, and the Fe₃O₄@SiO₂@PEG-(COOH)₂ was more suitable to be used as draw solute in FO process.     

Development and performance of some porous cellulose acetate membranes for reverse osmosis desalination

The effects of casting solution composition and evaporation period on the performance of resulting porous cellulose acetate membranes have been studied, and the results are discussed in terms of casting solution structure, solvent evaporation rate during film formation, and the film shrinkage temperature profile. The development of Batch 316-type porous cellulose acetate membranes is reported. At 90% level of solute separation and feed flow conditions corresponding to a mass transfer coefficient of 45 × 10^?4 cm/sec, the productivities of the above membranes are 21.5 gallons/day/ft² at 250 psig using 3500 ppm of NaCl in the feed, and 53.9 gallons/day/ft² at 600 psig using 5000 ppm of NaCl in the feed.