聚电解质静电沉积改性制备高性能反渗透膜

利用次氯酸钠溶液对商品反渗透膜表面进行氯化处理,然后将聚阳离子电解质壳聚糖通过静电吸附作用沉积在RO膜的表面,系统地研究了氯化过程的p H、氯化时间、次氯酸钠浓度、壳聚糖浓度及其沉积时间对膜性能的影响,以制备出高通量、高截留率的RO膜。在压力1.55 MPa、原料液温度(298±1)K的条件下,测定RO膜处理2000μg·g-1氯化钠溶液的水通量和截留率。结果表明,当p H=9、氯化时间为30 min、次氯酸钠浓度为1000mg·L-1时,水通量较原膜提高了约19.89%,截留率略有提高;当壳聚糖浓度为0.1%(质量分数)、沉积时间为30 min时,改性膜的接触角降低到34.88°,亲水性提高,水通量较氯化后的RO膜几乎保持不变,为60.55 L·m-2·h-1,截留率达到了99.56%。经过氯化和沉积改性后的RO膜水通量和截留率均得到了提高。     

聚酰胺反渗透复合膜的多巴胺改性研究

采用多巴胺对聚酰胺反渗透复合膜(RO)进行表面改性来提高膜的亲水性和耐污染性能。考察了不同改性条件(如多巴胺浓度、沉积时间、氧化剂添加)对膜水通量、盐截留、牛血清白蛋白(BSA)吸附的影响。研究结果表明,在碱性环境(pH=8.5)下多巴胺可以在RO表面发生氧化自聚、沉积形成聚多巴胺超薄层,适量氧化剂-过硫酸铵的加入可以加快多巴胺在RO表面的沉积;多巴胺改性后的RO膜水通量和盐截留均未有明显降低;水接触角测试结果显示,RO膜经多巴胺改性后的亲水性明显得到改善;X光电子能谱结果证明,多巴胺改性的RO膜成功引入了聚多巴胺层;扫描电镜对聚多巴胺改性的RO膜表面形态结构进行了表征;BSA吸附实验表明,聚多巴胺改性的RO膜能有效减少BSA的吸附。     

原位修饰DAT提升哌嗪基聚酰胺纳滤膜耐氯性能研究

为了提高哌嗪基聚酰胺纳滤膜的耐氯性,通过原位改性的方法在膜表面修饰了对氯稳定的3,5-二氨基-1,2,4-三唑(DAT)。DAT引入后,改性膜表面出现了更大、更多的结节结构,膜表面变得更加粗糙和亲水。在DAT质量分数为0.1%、交联时间为2 min的条件下,改性膜的纯水通量高达55.9 L/(m²·h),对无机盐的截留顺序为Na₂SO₄(96.7%)>MgSO₄(79.5%)>MgCl₂(33.7%)>NaCl(27.3%)。经不同pH次氯酸钠溶液浸泡后,未改性膜的表面结构被严重破坏,形成了巨大的聚合物颗粒,堵塞了水的传递路径,水通量下降了20%以上,分离性能恶化。而改性膜受到活性氯攻击很小,表面形貌较完整地保存下来,并且在保持较高盐截留率的同时,其水通量还有所上升,这对于构建耐氯脱盐纳滤膜具有很大的吸引力。     

ZrO2-TiO2复合纳滤膜在模拟放射性废水中的应用

核工业、核研究及医疗等过程会产生大量的放射性废水,会对环境和生物体造成严重伤害,必须经过合适的处理后才能排放。采用高性能陶瓷纳滤膜处理模拟放射性废水,考察了跨膜压差、pH和离子浓度等操作参数对Co²⁺和Sr²⁺截留性能的影响,并对操作参数进行了优化。所用陶瓷纳滤膜材料为ZrO₂-TiO₂复合材料,截留分子量为500,纯水渗透率为270 L·m^-2·h^-1·MPa^-1。研究表明,陶瓷纳滤膜对Co²⁺和Sr²⁺两种离子的截留率随着跨膜压差的升高而增大,膜的渗透通量随着跨膜压差的增大呈线性增加。pH变化时,截留率在一定pH范围内先降低后升高,在等电点（pH=7）附近达到最小值;pH=3的情况下,两种离子的截留率均达到最高,Co²⁺和Sr²⁺的截留率均在99%以上,而纳滤膜渗透通量保持稳定。离子截留率和渗透通量均随进料浓度的增大而减小,在2000 min的连续循环操作过程中,陶瓷纳滤膜材料的渗透通量及其对Co²⁺和Sr²⁺的截留率均维持在较高水平。陶瓷纳滤膜在放射性废水处理方面展现出了良好的应用前景。     

正渗透膜污染影响因素的研究与分析

以海藻酸钠（ALG）为典型有机污染物,采用TFC FO膜,以水通量下降率和污染阻力作为膜污染的评价指标,探究了正渗透（FO）过程中的膜摆向（FO模式和PRO模式）、原料液（FS）和驱动液（DS）的浓度、原料液中Ca²⁺浓度和pH对FO膜污染的影响规律,并提出适宜的膜清洗方案。结果表明,在PRO模式下,膜污染阻力为3.38×10¹¹m^-1,而在FO模式下仅为3.88×10¹⁰m^-1,表明FO模式污染轻;FS或者DS浓度的增大均会导致污染阻力增大,使得污染更加严重;当FS中不含Ca²⁺和含Ca²⁺浓度分别为1mmol/L和2mmol/L时,相较于初始通量,其通量降低率分别15.40%、18.49%和24.93%,当Ca²⁺浓度从1mmol/L增大到2mmol/L过程中,膜污染阻力增大1.6倍;当FS的pH为4.2、7.0和10.7时,水通量降低率依次增加,分别为14.56%、14.82%和18.78%。分别采用去离子水、pH为3.0的HCl溶液、pH为11.8的NaOH溶液以及十二烷基硫酸钠（SDS,pH=11.0）溶液对膜进行清洗,得到SDS溶液清洗效果较好,通量恢复率可达90.70%。     

4nm孔径陶瓷膜去除水中钙离子研究

采用孔径为4 nm的陶瓷膜去除水中的Ca2+,考察了不同Ca2+含量、跨膜压差、溶液pH和温度对陶瓷膜渗透通量和Ca2+截留率随时间的变化情况。结果表明,溶液中的Ca2+含量越低,膜渗透通量越高,Ca2+截留率也越高;跨膜压差升高,膜渗透通量增大,Ca2+截留率降低;降低溶液pH及升高温度能够提高膜渗透通量及对Ca2+的截留率。对Ca2+的质量浓度为10 mg/L的水溶液,在TMP为0.1 MPa、溶液pH为3、温度为50℃时、孔径为4 nm陶瓷膜渗透通量稳定在80 L/(m2.h),Ca2+截留率为85%左右。研究结果可为金属离子微污染水的净化提供方法。     

国产纳滤膜脱除硝酸盐的试验研究

采用国产纳滤膜脱除水环境中的硝酸根离子,研究进液浓度、浓水流量、压力、温度等对纳滤膜的截留性能和通量的影响。结果表明,压力的升高有利于提高纳滤膜的截留率和产水通量,最佳压力为0.7 MPa,此时截留率和产水通量可达75.0%和153.7 L/(m²·h);适当的提升进水温度可以提高纳滤过程的截留率,最佳进水温度为39.3℃;进料浓度对截留过程有着显著的影响,进料浓度越低,纳滤膜的截留效果越好。     

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。     

低温水等离子体活化和表面接枝DMAE聚氯乙烯中空纤维膜研究

采用低温水等离子体技术，在三通道聚氯乙烯(PVC)膜表面接枝了甲基丙烯氧基苄基二甲基氯化铵(DMAE)单体，增强了膜亲水和抗菌性能。通过红外分析，表明DMAE成功接枝到了PVC膜上，水通量提高两倍，PVC-ir-H₂O膜(通过水等离子体处理的膜)对牛血清蛋白(BSA)的吸附能力下降67%，对BSA溶液的通量从7.7提高至40 kg?m^-2?h^-1，并且对BSA的截留能力不变。通过静态及动态抗菌实验，接枝后的PVC膜（PVC-g-PMAE膜）抗菌率达到100%，膜组件运行中的抗菌率也达到82%以上。在保证细菌截留率100%的同时，其渗透通量提高三倍。该膜表面修饰工程技术能实现膜表面的均一化改性，且绿色环保、操作简便、成本低，改性膜在饮用水处理领域，尤其是家用净水器中展现了很好的应用前景。     

氧化石墨烯-陶瓷复合纳滤膜的层层自组装制备及其性能

氧化石墨烯（GO）的片层边缘含有 COOH等含氧官能团,因而带负电荷,可以在带正电荷多孔基体上通过层层自组装实现快速沉积。以由3-氨丙基三乙氧基硅烷（APTES）修饰的多孔氧化铝管式陶瓷膜为基膜,令GO和聚乙烯亚胺（PEI）以溶液形态在其表面交替沉积实现自组装,继以环氧氯丙烷（ECH）交联之,制备新型氧化石墨烯-陶瓷复合纳滤膜。最佳制备工艺是,PEI浓度5 g·L^-1、pH=9,NaCl浓度0.3 mol·L^-1,GO浓度0.6 mg·ml^-1、pH 4.5,层数2层,ECH用量6.25 ml·L^-1,50℃条件下处理70 min。层数为1～4层的自组装膜在0.6 MPa操作压力下对2 g·L^-1的MgCl₂的截留率分别为90.16%、93.71%、97.54%、92.93%,其中1层自组装膜的渗透通量为21.92 L·m^-2·h^-1。氧化石墨烯-陶瓷复合纳滤膜对4种无机盐的截留率大小为MgCl₂ >MgSO₄ > NaCl >Na₂SO₄,符合典型正电荷纳滤膜的特征。     

Flux enhancement of thin film composite RO membrane by controlled chlorine treatment

A major stumbling block in polyamide thin film composite RO membrane performance is its incompatibility with chlorine and oxidizing agents. The amide bond of the membrane is highly vulnerable to chlorine attack. Two reactions are possible with chlorine exposure i.e. N-H bond chlorination and/or aromatic ring chlorination. In this way, chlorine may cause degradation/modification in the membrane leading to deterioration in performance.However, low concentration of chlorine up to a certain time may give synergistic effect on membrane and improve its performance. Chlorine solution, if exposed to membrane for certain time gives enhancement in trans-membrane flux of the membrane.The same solution if exposed for more time deteriorates ultra-thin polyamide layer of TFC membrane. Conspicuously, the membrane with poor salt rejection and flux benefited more as compared to the membrane with better performance. In the present study, membranes with different salt rejection and flux were taken and exposed to the inorganic chlorine solution. The inorganic chlorine solutions were made by dissolving sodium hypochlorite in pH buffer. The different solutions were made by varying pH to investigate the pH dependence. The membrane samples were kept in solution for different time durations. The exposure time was monitored and the exposure level was taken in terms of ppm h (ppm chlorine solution exposed to membrane for a fixed time in h). With the same chlorine concentration, effect of varying pH was studied. Spiral wound TFC membrane modules were also subjected to chlorine solution to study its effect.     

A novel high‐flux thin film composite reverse osmosis membrane modified by polysaccharide supramolecular assembly

Thin film composite reverse osmosis (TFC RO) membrane is widely used in desalination and water reuse applications. With increasing capacity of Reverse Osmosis desalination all over the world, the increasing green‐house gas emission for the required power is a cause of concern. TFC RO membrane is composed of the top polyamide layer over which, the linear polysaccharide such as chitosan can bind after activating the surface with oxidizing agent. The present paper analyzes the novel protocol of controlled oxidation of TFC RO membrane by exposing the same to potassium per sulfate with varying concentration of chitosan followed by sodium hypochlorite and sodium hypochlorite followed by potassium per sulfate with varying concentration of chitosan. The optimum performance was obtained when TFC RO membrane was exposed to 1% potassium persulfate with 1000 mg/L chitosan solution followed by 1000 mg/L sodium hypochlorite. Reversing order of the treatment resulted in the decline in permeance of the membrane. The reason of improvement in permeance is super‐hydrophilic surface formed by oxidation of chitosan over polyamide surface. Thus, this article demonstrates the novel protocol of significantly improving the flux of TFC RO membrane and thereby reducing the energy consumption. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45026.     

Change of membrane performance due to chlorination of crosslinked polyamide membranes

A systematic investigation of the relationship between chlorine exposure of a thin film composite crosslinked polyamide membrane (LE membrane, FilmTec©) and changes in membrane performance (water flux and salt rejection) is discussed here. Performance change of crosslinked polyamide membranes due to chlorination depended on pH and concentration of chlorine in the soaking bath. Membranes chlorinated at low pH and high chlorine concentration showed flux decreases at an early stage of filtration and then increases with filtration time. On the other hand, membranes chlorinated at high pH and low chlorine concentration showed flux increases at an early stage and then decreases with filtration time. Performance of chlorinated polyamide membranes was determined by the balance between rearrangement of polymer chains and the distortion of the chains due to chlorination. A conceptual model of performance change was proposed consistent with the chlorination of polyamide membranes. © 2006 Wiley Periodicals, Inc. J Appl Polym Sci 102: 5895–5902, 2006     

Forward-osmosis strategy and chemical cleaning of seawater desalination reverse osmosis membranes

In order to settle the membrane fouling of reverse osmosis membranes in seawater desalination process, this study reported a novel strategy based on forward-osmosis process and discussed the effects of different factors like different cleaning combination among reverse osmosis product, simulated reverse osmosis concentrate and simulated seawater, as well as cleaning time on the membrane permeate flux and salt rejection. For irreversible fouling, the effects of different chemical cleaning agents, immersion time and concentration were also investigated in this study. The results exhibited that the cleaning combination between diluted water and simulated reverse osmosis concentrate possessed the best cleaning performance in the process of forward-osmosis cleaning. Such approach also enhanced normalized flux from 9.48 L/(m²·h·MPa) to 13.6 L/(m²·h·MPa) and enhanced NaCl rejection from 80.59% to 92.80%. Furthermore, the normalized flux was enhanced from 9.48 L/(m²·h·MPa) to 14.3 L/(m²·h·MPa) and NaCl rejection was also enhanced from 80.59% to 96.27% after soaking in 2%(mass) citric acid solution for 2h, soaking with 1%(mass) ethylenediamine tetra-acetic acid tetrasodium salt and 0.3%(mass) sodium tripolyphosphate solution for 1.5 h. According to the result of SEM images and AFM images, the forward-osmosis cleaning strategy could not cause the damage of selective layer of membrane surface and caused the drop of inorganic and organic fouling on the membrane surface. Hence, cleaning fouled RO membranes by such approach could prolong the chemical cleaning cycle and reduce the amount of chemical cleaning agent, which has certain industrial application perspectives.     

正渗透策略和化学清洗海水淡化反渗透膜

为解决海水淡化过程中反渗透膜的污染问题，研究了基于正渗透策略的反渗透产水、模拟反渗透浓水、模拟海水不同的组合清洗和清洗时间对膜通量和截留率的影响。针对不可逆污染，研究了不同化学清洗药剂、浸泡时间、浓度对膜通量和截留率的影响。结果表明，正渗透策略清洗方式中，淡水/模拟反渗透浓水的组合清洗方式效果最佳，其归一化通量从9.48 L/(m²·h·MPa)提升至13.6 L/(m²·h·MPa)，截留率从80.59%提升至92.80%。此外，经质量分数为2%的柠檬酸溶液浸泡2 h后，再使用质量分数为1%的乙二胺四乙酸四钠盐和0.3%的三聚磷酸钠溶液浸泡1.5 h，其归一化通量从9.48 L/(m²·h·MPa)提升至14.3 L/(m²·h·MPa)，截留率从80.59%提升至96.27%。从SEM和AFM图可以看出，正渗透清洗策略并未对膜表面选择层造成损坏，且可以清洗膜表面的有机污染物和无机污染物，因此，应用这种方法对污染的反渗透膜进行清洗，可延长化学清洗周期，减少化学清洗剂用量，具有一定的工业应用前景。     

Fabrication of high-performance pervaporation composite membrane for alkaline wastewater reclamation

Pervaporation desalination has a unique advantage to recycle concentrated salt solutions. The merit can be applied to treat alkaline wastewater if the membrane has superior alkali-resistance. In this paper, we used polyethylene microfiltration membrane as the substrate and deposited a glutaraldehyde crosslinked sodium carboxymethylcellulose layer by spray-coating. Pervaporation flux of the composite membrane reached 35 ± 2 kg·m^–2·h^–1 with a sodium chloride rejection of 99.9% ± 0.1% when separating a 3.5 wt-% sodium chloride solution at 70 °C. The desalination performance was stable after soaking the membrane in a 20 wt-% NaOH solution at room temperature for 9 d and in a 10 wt-% NaOH solution at 60 °C for 80 h. Moreover, the membrane was stable in 4 wt-% sulfuric acid and a 500 mg·L⁻¹ sodium hypochlorite solution. In a process of concentrating a NaOH solution from 5 to 10 wt-% at 60 °C, an average water flux of 23 kg·m^–2·h^–1 with a NaOH rejection over 99.98% was obtained.     

A novel ultra‐low energy reverse osmosis membrane modified by chitosan with glutaraldehyde crosslinking

The energy consumption of reverse osmosis (RO) has declined significantly since inception and to further decrease the energy consumption is a challenging task. The present article demonstrates the novel method to increase the membrane productivity and reduce energy consumption of desalination. Thin film composite RO (TFC RO) membrane was subjected to 2000 mg/L sodium hypochlorite for 1 h followed by varying concentrations of chitosan and glutaraldehyde for 1 h each to make a hydrophilic supra‐molecular assembly of linear polysaccharide over the polyamide layer. RO membrane exposed to 1000 mg/L chitosan and glutaraldehyde each reported 180% increase in water‐flux with about 2.7% increase in divalent ion rejection as compared to virgin TFC RO membrane. The superior performance of the membrane was explained by increased hydrophilicity as shown by decline in contact angle from 46.37° to 29.87°, increase in surface area ratio from atomic force microscope image analysis, and modification in chemical structure of polyamide from attenuated total reflectance Fourier transform infrared spectroscopy. It was further investigated that curing of glutaraldehyde treated membrane resulted in decreased water‐flux because of increase in crosslink density. Thus, an ultra‐low energy RO process can be developed based on polyamide–chitosan–glutaraldehyde membrane. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2018 , 135, 45971.     

The chlorination and chlorine resistance modification of composite polyamide membrane

Membrane‐based separation technology is one of the most active separation technologies being employed in water treatment. Polyamides (PA) are widely used membrane materials because they exhibit excellent performance, such as high flux with high salt rejection, and enhanced stability against wide range of pH and temperature. Unfortunately, PA membranes exhibit extremely poor resistance to chlorine leading to increased operation costs and decreased membrane lifetime. In this study, we find new ways for prolonging membrane lifetime and reducing the operating costs by investigating the chlorination and modification of PA membranes. Varying concentrations of hypochlorite were used to chlorinate a commercial reverse osmosis membrane (BW‐30, DOW). The results showed that short‐time exposure to high concentrations of hypochlorite could cause more serious problems to membranes than long‐time exposure to low concentrations under the similar total exposure. The performance of the chlorinated membranes was recovered to some extent after treatment with NaOH solution (pH 10), indicating that the alkali treatment could initiate the reversible regeneration of chlorinated membranes. Furthermore, an industrial grade epoxy resin was used to modify the membranes to enhance the chlorine resistance via the reaction between the amide nitrogen and epoxy bond. The successful modifications were confirmed by attenuated total reflectance Fourier transform infrared spectroscopy, X‐ray photoelectron spectroscopy, scanning electron microscopy, and atomic force microscopy. Moreover, the chlorination tests showed that the modifications performed in these experiments enhanced the chlorine resistance of the membranes, especially for the membranes exposed to low concentration of chlorine. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41584.     

Some experimental parameters affecting performance of composite reverse osmosis membranes produced by plasma polymerization

Reverse osmosis (RO) composite polymer membranes were prepared from the organic monomers 3-butenenitrile, propyleneimine, 4-vinylpyridine, and allylamine by plasma polymerization in a radio-frequency discharge. RO performance data (water flux and salt rejection) were obtained as a function of discharge power and deposition time. Membranes were subject to RO testing at 45°C for up to 150 hr to investigate membrane deterioration. No appreciable degradation was observed. Water flux increased significantly with time at 45°C, and improved salt rejection at 45°C was observed in most cases.     

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。