商业正渗透膜的改性及其用于处理焦化废水的研究

正渗透技术是一种新兴的膜分离技术，在处理有机废水方面具有广阔的应用前景。分别对Poten以及HTI商业正渗透膜进行改性，并用于对焦化废水中难降解毒性小分子(吲哚和吡啶)的截留测试。探究了水相单体PIP浓度、膜朝向、汲取液浓度对改性前后两种膜水通量、J_s/J_w比值、有机物截留率的影响，以及改性前后两膜特征参数的变化。结果表明：对Poten膜和HTI膜进行界面聚合改性后，膜水通量以及J_s/J_w比值都不同程度地降低；改性后的两正渗透膜水渗透系数A、盐渗透系数B均降低，而膜结构参数S以及对NaCl和有机物的截留率均提高；其中HTI-IP复合膜对有机物的截留率(81%)明显高于IP-2(改性Poten膜)复合膜；与FO模式相比，IP-2复合膜在PRO模式下(汲取液面向活性层)具有更高的水通量及反向盐通量。此外，在两种膜朝向下，水通量及反向盐通量都随汲取液浓度的增大而增大，但是在FO模式下(料液面向活性层)，通量呈现非线性增长。     

Potential use of nanofiltration like-forward osmosis membranes for copper ion removal

The discharge of industrial effluent containing heavy metal ions would cause water pollution if such effluent is not properly treated. In this work, the performance of emerging nanofiltration(NF) like-forward osmosis(FO)membrane was evaluated for its efficiency to remove copper ion from water. Conventionally, copper ion is removed from aqueous solution via adsorption and/or ion-exchange method. The engineered osmosis method as proposed in this work considered four commercial NF membranes(i.e., NF90, DK, NDX and PFO) where their separation performances were accessed using synthetic water sample containing 100 mg·L~(-1) copper ion under FO and pressure retarded osmosis(PRO) orientation. The findings indicated that all membranes could achieve almost complete removal of copper regardless of membrane orientation without applying external driving force.The high removal rates were in good agreement with the outcomes of the membranes tested under pressuredriven mode at 1 MPa. The use of appropriate salts as draw solutes enabled the NF membranes to be employed in engineered osmosis process, achieving a relatively low reverse solute flux. The findings showed that the best performing membrane is PFO membrane in which it achieved N 99.4% copper rejection with very minimum reverse solute flux of 1 g·m~(-2)·h~(-1).     

Thin-film composite forward osmosis membranes with substrate layer composed of polysulfone blended with PEG or polysulfone grafted PEG methyl ether methacrylate

To advance commercial application of forward osmosis (FO), we investigated the effects of two additives on the performance of polysulfone (PSf) based FO membranes: one is poly(ethylene glycol) (PEG), and another is PSf grafted with PEG methyl ether methacrylate (PSf-g-PEGMA). PSf blended with PEG or PSf-g-PEGMA was used to form a substrate layer, and then polyamide was formed on a support layer by interfacial polymerization. In this study, NaCl (1 mol?L⁻¹) and deionized water were used as the draw solution and the feed solution, respectively. With the increase of PEG content from 0 to 15 wt-%, FO water flux declined by 23.4% to 59.3% compared to a PSf TFC FO membrane. With the increase of PSf-g-PEGMA from 0 to 15 wt-%, the membrane flux showed almost no change at first and then declined by about 52.0% and 50.4%. The PSf with 5 wt-% PSf-g-PEGMA FO membrane showed a higher pure water flux of 8.74 L?m⁻²?h⁻¹ than the commercial HTI membranes (6–8 L?m⁻²?h⁻¹) under the FO mode. Our study suggests that hydrophobic interface is very important for the formation of polyamide, and a small amount of PSf-g-PEGMA can maintain a good condition for the formation of polyamide and reduce internal concentration polarization.     

Thin-film composite forward osmosis membrane prepared from polyvinyl chloride/cellulose carbamate substrate and its potential application in brackish water desalination

Synthesized by the reaction between α-cellulose and m-tolyl isocyanate (MTI), cellulose carbamate (CC) was blended with polyvinyl chloride (PVC) to fabricate substrates for thin-film composite (TFC) forward osmosis (FO) membranes. The introduction of CC into substrates improved both membrane structure and performance. The substrates exhibited higher porosity and hydrophilicity, and better connective pore structure; while rejection layer exhibited better morphology but limited cross-linked degree decrease after the introduction of CC. According to the results, the CC blend ratio of 10% was the optimal ratio. With this blend ratio, the TFC-10 membrane presented favorable water permeability (1.86 LMH/bar) and structure parameter (337 μm), which resulted in excellent FO performance (water flux with a value of 40.40 LMH and specific salt flux with a value of 0.099 g/L under rejection layer faces draw solution [DS] mode when 1 M NaCl and deionized water were utilized as DS and feed solution). In addition, the TFC-10 membrane showed good water flux and low-sulfate ion leakage in the potential application of brackish water desalination.     

Recent advances in polymer and polymer composite membranes for reverse and forward osmosis processes

Semipermeable membranes are the core elements for membrane water desalination technologies such as commercial reverse osmosis (RO) process and emerging forward osmosis (FO) process. Structural and chemical properties of the semipermeable membranes determine water flux, salt rejection, fouling resistance, and chemical stability, which greatly impact energy consumption and costs in osmosis separation processes. In recent years, significant progress has been made in the development of high-performance polymer and polymer composite membranes for desalination applications. This paper reviews recent advances in different polymer-based RO and FO desalination membranes in terms of materials and strategies developed for improving properties and performances.     

RO membrane solute rejection behavior at the initial stage ofcolloidal fouling

This study investigated the rejection of salt and inert organic compounds by reverse osmosis membranes during the initial stage of colloidal fouling. Results of laboratory-scale experiments showed that colloidal fouling caused a marked decrease in flux, salt rejection and rejection of organics with molecular weight (MW) smaller than about 100 g/mol. Removal of neutrally charged organics was mainly by size or steric exclusion. Rejection of xylose, which has MW >100 g/mol, was not affected much by colloidal fouling. The decrease in salt and low MW organic rejections during the initial stage of colloidal fouling was attributed to cake-enhanced concentration polarization, whereby the colloidal cake layer hindered back diffusion of solutes from the membrane surface to the bulk solution, resulting in higher solute concentration gradient across the membrane. At higher channel wall shear rate, the rates of colloidal deposition, flux decline, decrease in salt rejection, and decrease in low MW organic rejection were lower.     

Optimization of the Forward Osmosis Process Using Aquaporin Membranes in Chromium Removal

Due to the lack of affordable and feasible wastewater treatment technologies, various industries in developing countries are discharging chromium (Cr) without meeting the environmental standards. Here, the aim was to employ forward osmosis (FO) using aquaporins (AQP)-based biomimetic membranes and optimize the Cr rejection through response surface methodology (RSM). The initial concentration of draw solution, feed solution, and time was selected as independent variables in order to optimize Cr rejection and water flux. A high Cr rejection efficiency and water flux were achieved under the optimal conditions. These results revealed that the FO process applying an AQP membrane beside the RSM could be considered to treat wastewaters containing heavy metals.     

Nanofiltration thin-film-composite polyesteramide membranes based on bulky diols

Polyesteramide thin-film-composite (TFC) membranes have promise for diafiltration applications due to their relatively good oxidative resistance coupled with the ability to tailor the membrane rejection profile by varying the ester/amide ratio. The incorporation ofester linkages in interfaciallyprepared polyesteramide TFC membranes has been previously shown to increase the oxidation resistance of the membrane. It was also found that polyesteramide TFC membranes incorporating hydroquinone (HQ) or bisphenol-A (Bis-A) had high rejection for monovalent salts, i.e., their rejection profiles matched those of reverse osmosis rather than nanofiltration membranes. We report the properties of polyesteramide TFC membranes incorporating bulky diols such as phenolphthalein (Phe) and terabromobisphenol-A (TBrBis-A). The data were used to correlate the influence of different ester fanctionalities on membrane flux and rejection characteristics. Membranes incorporating TBrBis-A had relativelyhigh rejections for monovalent salts coupled with low water permeance. By contrast, membranes incorporating Phe showed 10 times higher flux and a rejection profile which appears to be of interest for diafiltration applications involving the separation of organics with molecular weight >400 grnol⁻¹ from low-molecular-weight organics and salts. The Phe-based membranes show rejection characteristics for monovalent and multivalent salts typical of negatively charged membranes.     

操作条件对正渗透分离性能的影响

正渗透是以渗透压差为驱动力的新型膜分离过程。采用水流分布较佳的膜池结构,研究了膜朝向、流动方式对正渗透水通量性能的影响,结果表明PRO模式（当膜的活性层朝向驱动液时）的水通量明显高于FO模式（当膜的活性层朝向原料液时）,但其衰减程度较大;在溶液浓度差相同的条件下,逆流操作更利于水通量的提高。针对FO模式和逆流条件,探讨了溶液温度对水通量和反向盐通量的影响,结果表明：膜两侧溶液温度同步升高时,正渗透过程的水通量和反向盐通量均增加,且水通量的增加幅度大于反向盐通量;单侧增加溶液的温度时,驱动液侧温度升高对水通量性能的提升效果优于原料液侧。综合考虑过程能耗和系统性能,认为单独升高驱动液温度更具实用价值。     

Thin film composite forward osmosis membranes with poly(2‐hydroxyethyl methacrylate) grafted nano‐TiO2 as additive in substrate

The poly(2‐hydroxyethyl methacrylate) grafted titanium dioxide nanoparticles were synthesized and added to the substrate of flat‐sheet thin film composite forward osmosis (TFC‐FO) membranes. The hydrophilicity of substrate was improved, which was advantageous to enhance the water flux of TFC‐FO membranes. The membranes containing a 3 wt % TiO₂‐PHEMA in the substrate exhibited a finger‐like structure combined with sponge‐like structure, while those with lower or without TiO₂‐PHEMA content showed fully finger‐like structures. As for FO performance, the TFC‐FO membranes with 3 wt % TiO₂‐PHEMA content achieved the highest water flux of 42.8 LMH and 24.2 LMH against the DI water using 2M NaCl as the draw solution tested under the active layer against draw solution (AL‐DS) mode and active layer against feed solution (AL‐FS) mode, respectively. It was proven that the hydrophilic property of membrane substrates was a strong factor influencing the water flux in FO tests. Furthermore, the structural parameter was remarkably decreased with an increase of TiO₂‐PHEMA content in membrane substrate, indicating the reducing of internal concentration polarization. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43719.     

Facile modification of aliphatic polyketone-based thin-film composite membrane for three-dimensional and comprehensive antifouling in active-layer-facing-draw-solution mode

The application of “active-layer-facing-draw-solution” (AL-DS) mode, which allows a considerably high water flux in forward osmosis (FO) processes, is hindered by severe fouling occurring within the porous support of the FO membranes. We designed a series of “three-dimensionally” antifouling FO membranes by an extremely convenient and scalable approach, by using in situ reduced aliphatic polyketone (PK) membranes (rPK) and the silver-nanoparticles-immobilized rPK-Ag membranes as the substrates for thin-film composite (TFC) FO membrane preparation. This modification imparted enhanced hydrophilicity compared with the original PK-TFC membrane, without affecting the morphology and transport properties. Benefiting from the three-dimensional antifouling structure, the modified TFC membranes (i.e., rPK-TFC and rPK-Ag-TFC membranes) demonstrated excellent and comprehensive fouling resistance towards a variety of organic foulants, as well as biofouling resistance towards Escherichia coli. These results provide useful insights into the fabrication of antifouling FO membranes for water purification purposes and pressure retarded osmosis (PRO) process.     

Fabrication of fullerenol-incorporated thin-film nanocomposite forward osmosis membranes for improved desalination performances

Development and use of novel membranes for forward osmosis (FO) applications have gained popularity throughout the world. To enhance FO membrane performance, a novel thin-film nanocomposite membrane was fabricated by interfacial polymerization incorporating Fullerenol (C₆₀(OH)_n) nanomaterial, having n in the range of 24–28 into the active layer. Different concentrations of fullerenol loading (100, 200, 400, and 800 ppm) were added to the top skin layer. The structural and surface properties of the pure thin-film composite membrane (TFC) and fullerenol-incorporated thin-film nanocomposite (FTFC) membranes, were characterized by ATR-FTIR, SEM, and AFM. FO performance and separation properties were evaluated in terms of water flux, reverse salt flux, antifouling propensity, water permeability and salt permeability for all TFC and FTFC membranes. Osmotic performance tests showed that FTFC membranes achieved higher water flux and reverse salt flux selectivity compared with those of TFC membranes. The FTFC membrane with a fullerenol loading of 400 ppm exhibited a water flux of 26.1 L m^?2 h^?1 (LMH), which is 83.03% higher than that of the TFC membrane with a specific reverse salt flux of 0.18 g/L using 1 M sodium chloride draw solution against deionized water in FO mode. The fullerenol incorporation in FTFC membranes also contributed to a decreased fouling propensity.     

Reverse osmosis of lactic acid fermentation broths

Lactic acid model solutions and fermentation broths were concentrated using a tubular thin-film composite reverse osmosis membrane. Flux increased linearly with applied transmembrane pressure and was relatively unaffected by flow rate. Osmotic pressures of 1% lactate solutions were 280–560 kPa, depending on the pH or degree of dissociation. Rejections increased with applied pressure. Higher pH caused a slight decrease in flux (due in part to the higher osmotic pressure) and a significant increase in rejection. Above pH 5·6, rejections of lactate and residual sugars were > 97%. In contrast, with cellulose acetate membranes, flux was generally lower and lactate rejection was proportional to the degree of dissociation at lower pressures.     

聚苯乙烯磺酸钠掺杂正渗透膜的制备及其性能

通过两步无皂乳液聚合法,改变第二步对苯乙烯磺酸钠的加入量,制备表面携带磺酸根基团量不同的纳米粒子（PSS）,并将其应用于正渗透（FO）膜的制备。采用红外光谱仪（FTIR）和光电子能谱仪（XPS）表征粒子组成,通过扫描电子显微镜（SEM）表征膜的表面和断面形貌,测定膜孔隙率和亲水性,考察表面磺酸根量不同的聚合物粒子对膜结构性能的影响。结果表明,PSS的引入能提高膜的孔隙率,改善膜的亲水性,且随着粒子表面携带的磺酸根基团量增多,膜的孔隙率与亲水性也随之提高。这是因为PSS粒子可以支撑内部孔道,且表面携带的亲水基团-SO3Na可以提高膜的亲水性,影响活性层的形成。所制备的FO膜性能也得到相应改善,水通量达到了61.1L/(m²·h),为纯聚砜膜的2.8倍,盐截留率达到93.2%,J_s/J_v值仅为0.31g/L,性能得到极大提升。     

Developing thin‐film‐composite forward osmosis membranes on the PES/SPSf substrate through interfacial polymerization

A new scheme has been developed to fabricate high‐performance forward osmosis (FO) membranes through the interfacial polymerization reaction on porous polymeric supports. p‐Phenylenediamine and 1,3,5‐trimesoylchloride were adopted as the monomers for the in‐situ polycondensation reaction to form a thin aromatic polyamide selective layer of 150 nm in thickness on the substrate surface, a lab‐made polyethersulfone (PES)/sulfonated polysulfone (SPSf)‐alloyed porous membrane with enhanced hydrophilicity. Under FO tests, the FO membrane achieved a higher water flux of 69.8 LMH when against deionized water and 25.2 LMH when against a model 3.5 wt % NaCl solution under 5.0 M NaCl as the draw solution in the pressure‐retarded osmosis mode. The PES/SPSf thin‐film‐composite (TFC)‐FO membrane has a smaller structural parameter S of 238 μm than those reported data. The morphology and topology of substrates and TFC‐FO membranes have been studied by means of atomic force microscopy and scanning electronic microscopy. © 2011 American Institute of Chemical Engineers AIChE J, 2012     

An agent-based simulation with NetLogo platform to evaluate forward osmosis process (PRO Mode)

Forward osmosis (FO), as an emerging technology, is influenced by different factors such as operating conditions, module characteristics, and membrane properties. The general aim of this study was to develop a suitable (flexible, comprehensive, and convenient to use) computational tool which is able to simulate osmosis through an asymmetric membrane oriented in pressure retarded osmosis (PRO) mode in a wide variety of scenarios. For this purpose, an agent-based model was created in NetLogo platform, which is an easy-to-use application environment with graphical visualization abilities and well suited for modeling a complex system evolving over time. The simulation results were validated with empirical data obtained from literature and a great agreement was observed. The effect of various parameters on process performance was investigated in terms of temperature, cross-flow velocity, length of the module, pure water permeability coefficient, and structural parameter of the membrane. Results demonstrated that the increase in all parameters, except structural parameter of the membrane and the length of module led to the increase of average water flux. Moreover, nine different draw solutes were selected in order to assess the influence of net bulk osmotic pressure difference between the draw solution (DS) and feed solution (FS) (known as the driving force of FO process) on water flux. Based on the findings of this paper, the performance of FO process (PRO mode) can be efficiently evaluated using the NetLogo platform.     

A novel ammonia—carbon dioxide forward (direct) osmosis desalination process

A novel forward (direct) osmosis (FO) desalination process is presented. The process uses an ammonium bicarbonate draw solution to extract water from a saline feed water across a semi-permeable polymeric membrane. Very large osmotic pressures generated by the highly soluble ammonium bicarbonate draw solution yield high water fluxes and can result in very high feed water recoveries. Upon moderate heating, ammonium bicarbonate decomposes into ammonia and carbon dioxide gases that can be separated and recycled as draw solutes, leaving the fresh product water. Experiments with a laboratory-scale FO unit utilizing a flat sheet cellulose tri-acetate membrane demonstrated high product water flux and relatively high salt rejection. The results further revealed that reverse osmosis (RO) membranes are not suitable for the FO process because of relatively low product water fluxes attributed to severe internal concentration polarization in the porous support and fabric layers of the RO membrane.     

三乙酸纤维素正渗透膜的制备与性能

以三乙酸纤维素（CTA）为膜材料,1,4-二氧六环、丙酮为溶剂,甲醇、乳酸为添加剂,采用相转换法制备了三乙酸纤维素正渗透膜。研究了不同1,4-二氧六环/丙酮配比、添加剂乳酸含量、挥发时间、膜厚度、热处理温度条件下正渗透膜性能的变化规律。研究表明,当采用纯水为原料液,0.56mol/L CaCl2为汲取液时,优化制备的CTA正渗透膜的水通量达到14.10L/(m2?h),溶质反扩散量为0.031mol/(m2?h);采用0.1mol/L NaCl为原料液,4mol/L葡萄糖为汲取液时,优化制备的CTA正渗透膜的水通量保持在5L/(m2?h)以上,对NaCl的截留率大于99%。CTA正渗透膜相比于HTI膜,具有较高的亲水性、水通量、截留率,稳定性更好。     

Poly(ethylene glycol) crosslinked sulfonated polysulfone composite membranes for forward osmosis

Forward osmosis (FO) membranes were prepared by a coating method with poly(ethylene glycol) crosslinked sulfonated polysulfone (SPSf) as a selective layer. The poly(ether sulfone)/SPSf substrate was prepared by phase inversion. The composite membranes were characterized with respect to membrane chemistry (by attenuated total reflectance/Fourier transform infrared spectroscopy and X‐ray photoelectron spectroscopy), hydrophilicity (by static contact angle measurement), and surface morphology (by scanning electron microscopy and atomic force microscopy). The FO performance was also characterized. The effects of the crosslinker concentration on the hydrophilicity and FO performance were investigated. The crosslinked membrane exhibited a high hydrophilicity with a lowest contact angle of 15.5°. Under FO tests, the membranes achieved a higher water flux of 15.2 L m^?2 h^?1 when used against deionized water as the feed solution and a 2 mol/L sodium chloride (NaCl) solution as the the draw solution. The membranes achieved a magnesium sulfate rejection of 96% and an NaCl rejection of 55% when used against a 1 g/L inorganic salt solution as the feed solution and a 2 mol/L glucose solution as the draw solution. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43941.     

温度对正向渗透的影响机制与数值模拟

正向渗透(FO)是一种以溶液自身渗透压作为推动力的膜分离技术。温度对溶液、膜的性质以及溶液与膜之间的相互作用有很大影响,进而影响FO的水通量。利用数值模拟与试验研究了温度对FO性能的影响。结果表明,当膜两侧等温时,FO水通量随着温度的升高而增大;当膜两侧不等温时,原液(FS)一侧温度的影响比提取液(DS)一侧更大,主要是因为温度升高降低了溶液黏度,强化了过膜扩散过程,而温度对DS渗透压的影响不明显。在不同温度条件下,FO水通量和热通量随流量的增大而增大,主要是由于流速的增大压缩膜表面的流体边界层,强化了传质和传热过程。