Lithium-based draw solute for forward osmosis to treat wastewater discharged from lithium-ion battery manufacturing

As draw solute is the core element of forward osmosis (FO) technology, here Li-Bet-Tf₂N synthesized from a customized ionic liquid betainium bis(trifluoromethylsulfonyl)imide ([Hbet][Tf₂N]) and Li₂CO₃ recovered from lithium-ion battery (LIB) wastes is proposed as a novel draw solute to treat Li⁺-containing wastewater from LIB manufacturing through FO filtration. Having high dissociation ability and an extended structure, Li-Bet-Tf₂N generates a sufficiently high osmotic pressure to drive the FO filtration efficiently along with insignificant reverse solute diffusion. Li-Bet-Tf₂N produces a water flux of 21.3 L·(m²·h)⁻¹ at 1.0 mol∙L^–1 against deionized water, surpassing conventional NaCl and MgCl₂ draw solutes with a higher water recovery efficiency and a smaller solute loss. Li-Bet-Tf₂N induces a more stable and higher water permeation flux with a 10.0% water flux decline than NaCl and MgCl₂ for which the water fluxes decline 16.7% and 16.4%, respectively, during the treatment of 2000 mg∙L^–1 Li⁺-containing wastewater for 12 h. More remarkably, unlike other draw solutes which require intensive energy input and complicated processes in recycling, Li-Bet-Tf₂N is easily separated from water via solvent extraction. Reproducible results are achieved with the recycled Li-Bet-Tf₂N. Li-Bet-Tf₂N thus demonstrates a novel class of draw solute with great potentials to treat wastewater economically.     

正渗透过程中汲取质反向渗透研究进展

正渗透(FO)作为一种浓度驱动的膜技术,因其膜污染轻、能耗低和回收率高等优点而逐渐成为膜技术领域的研究热点之一。汲取质的反向渗透是正渗透过程中不可忽视的现象,但其研究相对比较滞后。本文主要介绍了汲取质反渗模型的研究进展,分析了渗透压差、膜表面流速、膜结构与膜材料、温度、汲取质种类、膜取向、离子水力半径等因素对汲取质反向渗透的影响情况,并发现汲取质的反向渗透通量可由其浓度或汲取液渗透压的一元多项式表达。总体而言,FO模式的汲取质反渗模型经过不断发展已相对比较完善,而压力阻尼渗透(PRO)模式的反渗模型则缺陷较大,有待进一步研究;此外,关于汲取质反渗过程影响因素及其影响机制的研究对于汲取质、膜材料的选择与开发,以及正渗透过程的优化均具有重要的指导作用,因此会引起越来越多的关注。     

Performance evaluation of polyamide nanofiltration membranes for phosphorus removal process and their stability against strong acid/alkali solution

In this study,a quantitative performance of three commercial polyamide nanofiltration(NF) membranes(i.e.,NF,NF90,and NF270) for phosphorus removal under different feed conditions was investigated.The experiments were conducted at different feed phosphorus concentrations(2.5,5,10,and 15 mg·L~(-1)) and elevated pHs(pH 1.5,5,10,and 13.5) at a constant feed pressure of 1 MPa using a dead-end filtration cell.Membrane rejection against total phosphorus generally increased with increasing phosphorus concentration regardless of membrane type.In contrast,the permeate flux for all the membranes only decreased slightly with increasing phosphorus concentration.The results also showed that the phosphorus rejections improved while water flux remained almost unchanged with increasing feed solution pH.When the three membranes were exposed to strong pHs(pH 1.5 and 13.5) for a longer duration(up to 6 weeks)it was found that the rejection capability and water flux of the membranes remained very similar throughout the duration,except for NF membrane with marginal decrement in phosphorus rejection.Adsorption study also revealed that more phosphorus was adsorbed onto the membrane structure at alkaline conditions(pH 10 and 13.5) compared to the same membranes tested at lower pHs(pH 1.5 and 5).In eonelusion,NF270 membrane outperformed Nf and NF90 membranes owing to its desirable performance of water flux and phosphorus rejection particularly under strong alkali solution.The NF270 membrane achieved 14.0 L·m~(-2)·h~(-1) and 96.5% rejection against 10 mg·L~(-1) phosphorus solution with a pH value of 13.5 at the applied pressure of 1 MPa.     

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。     

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.     

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。     

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。     

氧化石墨烯掺杂反渗透混合基质膜制备及性能

由于芳香族聚酰胺反渗透膜在抗污染性以及耐氯性方面存在不足,限制了其在海水淡化等方面的应用。采用往油相中添加氧化石墨烯（GO）的二次界面聚合法改性了商业反渗透膜,评价了GO掺杂反渗透混合基质膜的分离性能和耐氯性能,并用接触角仪、Zeta电位仪、扫描电镜和原子力显微镜等仪器表征了膜的亲水性能、荷电性能以及膜表面形貌。结果表明,GO的添加提高了膜的分离性能、耐氯性能和亲水性能;当GO添加量为30 mg·L^-1时,膜的通量为（77.7±0.9） L·m^-2·h^-1,膜的截留率为97.6%±0.5%,相比商业膜分别提高了38.4%和4.5%。当氯化强度低于4800 mg·L^-1·h时,膜的水通量和盐截留率变化不明显。     

The application of polyethyleneimine draw solution in a combined forward osmosis/nanofiltration system

The objective of this study is to investigate the effect of solution chemistry of branched polyethyleneimine (PEI) draw solute and to evaluate the PEI draw solute in a combined forward osmosis (FO)/nanofiltration (NF) system. Pure water was extracted from feed solution using the FO process, and the separation of pure water was achieved by the NF process. Lower molecular weight PEI showed higher water flux than higher molecular weight PEI, due to the lower internal concentration polarization caused by a higher diffusion rate and the easy permeation of pure water by lower viscosity of the draw solution (DS). The FO water flux was determined by the osmotic pressure induced by protonation/deprotonation of PEI, and the reverse draw solute flux was determined by the combination of PEI size due to the speciation and electrostatic interaction between the membrane and PEI. This study shows that the J_s/J_w value of PEI at pH 7 was smaller than those of sodium chloride and magnesium sulfate. The recovery of PEI DS using NF has a higher value (99.4%) than of sodium chloride (20.6%) and magnesium sulfate (97.0%); this means that PEI would be a promising draw solute in an FO–NF combined system for the saline water desalination. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 42198.     

界面聚合中空纤维正渗透膜的制备和表征

以聚砜为原料,通过浸没沉淀法制备中空纤维基膜,然后采用界面聚合法制备出中空纤维正渗透膜。考察了制膜参数、基膜结构和FO性能三者之间的关系。结果表明基膜的厚度为影响FO性能的主要因素之一。基膜的厚度越厚,FO过程中渗透效率越低。制得PSF中空纤维正渗透膜的厚度为0.129 mm,断裂拉伸力为2.48 N,FO通量为10.3 L·m^-2·h^-1,逆向盐扩散性能为0.15 g·L^-1。     

High performance forward osmosis cellulose acetate (CA) membrane modified by polyvinyl alcohol and polydopamine

Cellulose acetate (CA) is a low cost and readily available material widely used in forward osmosis (FO) membranes. However, the performance of pure CA membranes is not good enough in salt separation and the traditional modification methods are generally multistep and difficult to control. In this paper, we reported high performance cellulose acetate (CA) composite forward osmosis (FO) membranes modified with polyvinyl alcohol (PVA) and polydopamine (PDA). PVA was first cross-linked onto the surface of CA membranes, and then PDA was coated with a rapid deposition method. The membranes were characterized with respect to membrane chemistry (FTIR and XPS), surface properties comprising wettability (by water contact angle), and osmosis performance. The modified membrane coated by PVA and PDA shown better hydrophilicity and exhibited 16.72 LMH osmotic water flux and 0.14 mMH reverse solute flux with DI water as feed solution and 2.0 M NaCl as draw solution and active layer facing the feed solution. This simple and highly effective modification method makes it as an excellent candidate for further exploration for FO.     

新型准对称无机膜的正渗透去除Cd2+的效能

正向渗透(forward osmosis, FO)是一种以溶液渗透压差为驱动力的新型膜技术。课题组在先前研究中使用微界面溶胶凝胶法制备了一种全新的准对称结构无机薄膜(QSTFI膜), 与传统的有机聚合FO膜相比具有更大的优势。本文考察了QSTFI膜分离去除水中重金属Cd²⁺的效能, 讨论了Cd²⁺浓度、提取液浓度以及膜表面带电性对Cd²⁺去除的影响机制。采用扫描电子显微镜(SEM)表征了QSTFI膜的微观形貌, 使用能量色散光谱(EDS)、傅里叶变换红外光谱(FTIR)表征了膜的化学组成, 并使用原子力显微镜(AFM)表征膜表面带电特性。结果表明, QSTFI膜表面带负电荷, 能够与液相主体中的Cd²⁺通过静电引力形成双电层结构, 双电层的Debye厚度越大越有利于膜对Cd²⁺的截留。FO实验测试中原液Cd²⁺浓度为10 mg·L^-1的条件下, QSTFI膜对Cd²⁺截留率超过99%, 水通量最大值可达到69 L·m^-2·h^-1(提取液为2.0 mol·L^-1 NaCl)。本研究为拓展FO技术在含重金属废水处理的潜在应用前景提供了理论依据和指导。     

Novel polyethyleneimine/TMC-based nanofiltration membrane prepared on a polydopamine coated substrate

Most commercial NF membranes are negatively charged at the pH range of a typical feed solution. In order to enhance the removal of cations (such as Mg²⁺ or Ca²⁺), we utilized polyethyleneimine (PEI) and trimesoyl chloride (TMC) to perform interfacial polymerization reaction on a polydopamine coated hydrolyzed polyacrylonitrile substrate to obtain a positively charged nanofiltration membrane. Effects of polydopamine coating time, PEI concentration, TMC reaction time and concentration on the membrane physicochemical properties and separation performance were systematically investigated using scanning electron microscopy, streaming potential and water contact angle measurements. The optimal NF membrane showed high rejection for divalent ions (93.6±2.6% for MgSO₄, 92.4±1.3% for MgCl₂, and 90.4±2.1% for Na₂SO₄), accompanied with NaCl rejection of 27.8±2.5% with a permeation flux of 17.2±2.8 L·m⁻²·h⁻¹ at an applied pressure of 8 bar (salt concentrations were all 1000 mg·L⁻¹). The synthesized membranes showed promising potentials for the applications of water softening.     

纳滤/反渗透膜处理重金属废水的性能

The performance of different nanofiltration （NF） and reverse osmosis （RO） membranes was studied in treating the toxic metal effluent from metallurgical industry. The characteristics and filtration behavior of the processes including the wastewater flux, salt rejection and ion rejection versus operating pressure were evaluated. Then the wastewater flux of RO membrane was compared with theoretical calculation using mass transfer models, and good consistency was observed. It was found that a high rejection rate more than 95% of metal ions and a low Chemical Oxygen Demand （COD） value of 10 mg·L^-1 in permeate could be achieved using the RO composite membrane, while the NF rejection of the salt could be up to 78.9% and the COD value in the permeate was 35 mg·L^-1. The results showed that the product water by both NF and RO desalination satisfied the State Reutilization Qualification, but NF would be more suitable for large-scale industrial practice, which offered significantly higher permeate flux at low operating pressure.     

正渗透膜生物反应器运行过程中溶质反渗对微生物群落的影响

以氯化钠为驱动溶质,采用正渗透膜生物反应器(forward osmosis membrane bioreactor, FOMBR)处理生活污水,考察其在运行过程中溶质反渗对系统内微生物群落造成的影响。稳定运行状态下的第7、14、20天的混合液污泥样品分别称为A1、A2、A3,并对微生物群落物种丰度、群落结构、聚类等进行了分析。结果表明：正渗透膜生物反应器运行20 d内水通量从9.5 L/(m²·h)下降到8.17 L/(m²·h),反向盐通量从29.52 g/(m²·h)增加到35.06 g/(m²·h)。整个运行过程中溶质反渗对微生物群落结构的变化有着一定的影响,3个样品共产生1496个OTUs,各样品间共享的OTUs不尽相同;溶质反渗对3种样品的微生物群落多样性、菌群丰度等影响较小。PCA分析中A2和A3两个样品距离更近,组成更相似,热图聚类分析再次验证A2与A3相似性更高;3个样品斜率较小且非常接近,并且A1和A3两个样品所含物种的丰富程度和均匀程度几乎一样;3个样品的活性污泥群落结构在门、纲、目分类水平上均具有较高的多样性,各分类水平上的菌群丰度存在一定的差异。     

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.     

Highly permeable reverse osmosis membranes incorporated with hydrophilic polymers of intrinsic microporosity via interfacial polymerization

Enhancing the water permeation while maintaining high salt rejection of existing reverse osmosis (RO) membranes remains a considerable challenge. Herein, we proposed to introduce polymer of intrinsic microporosity, PIM-1, into the selective layer of reverse osmosis membranes to break the trade-off effect between permeability and selectivity. A water-soluble a-LPIM-1 of low-molecular-weight and hydroxyl terminals was synthesized. These designed characteristics endowed it with high solubility and reactivity. Then it was mixed with m-phenylenediamine and together served as aqueous monomer to react with organic monomer of trimesoyl chloride via interfacial polymerization. The characterization results exhibited that more “nodule” rather than “leaf” structure formed on RO membrane surface, which indicated that the introduction of the high free-volume of a-LPIM-1 with three dimensional twisted and folded structure into the selective layer effectively caused the frustrated packing between polymer chains. In virtue of this effect, even with reduced surface roughness and unchanged layer thickness, the water permeability of prepared reverse osmosis membranes increased 2.1 times to 62.8 L·m^-2·h^-1 with acceptable NaCl rejection of 97.6%. This attempt developed a new strategy to break the trade-off effect faced by traditional polyamide reverse osmosis membranes.     

Investigation on removing recalcitrant toxic organic polluters in coking wastewater by forward osmosis

Investigation was made on the efficiency of two commercial membranes in removing via forward osmosis (FO) the low molecular weight organic compounds typical of coking wastewater. The membranes were supplied by Poten and HTI companies. The organics in the simulated coking water were indole and pyrridine. Under FO mode, the rejection to the organics by Poten membrane was around 50%, whereas that for HTI membrane was obviously higher, ranging from 65% to 74%. The response of the two membranes in terms of Water flux and reverse salt flux (RSF) towards changing feed/draw solution (DS) flow rates in FO mode showed similar tendency, but different degree. Generally, the flux in FO using HTI membranes was lower. For HTI membrane, FO operated with pressure retarded osmosis (PRO) mode was also performed and the overall rejection of the organics was slightly lower than that in FO mode. In the long term FO test within 15 days, both Poten and HTI membranes displayed flux reduction and rejection enhancement. But the variation with Poten membrane was much more obvious. Discussion was carried out about the reasons and the mechanisms behind the FO performance difference between two membranes and the variation in flux and rejection with operation conditions. Characterizations by SEM, FTIR, AFM, XRD and XPS were tried to support the proposed explanations.     

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.     

反渗透膜法处理磷酸铁生产废水的零排放工艺研究

以硫酸亚铁为原料生产电池级磷酸铁过程中产生大量的含硫酸根、磷酸根、钠离子的废水。为减少废水排放并使之得到循环利用,采用反渗透膜技术对中试生产电池级磷酸铁的废水处理进行了零排放设计和实验研究,考察了进水压力、进水浓度、温度、pH等因素对硫酸根和磷酸根的截留率、膜通量和产水率的影响。实验结果表明所采用的反渗透膜对硫酸根、磷酸根的截留率达99.15%以上,进水压力、进水浓度、温度、pH等因素对截留率影响较小,但对膜通量和产水率影响较大。截留率随着进水压力的增加略有增加,随进水浓度增加和温度的升高而略有减小,膜通量和产水率随进水压力和温度的升高而增大,随进水浓度的增大而减小,pH=6.5时截留率、膜通量和产水率最高。同时采用生产废水制备了硫酸钙晶须,实现了废水零排放。