反渗透膜脱硼技术研究进展

硼是生命体中必不可少的微量元素，但是摄入过量的硼会危害动植物的生长发育。在现有脱硼技术中，反渗透膜脱硼被认为最具应用前景，但受硼酸分子的分子直径小和不带电荷等影响，反渗透膜对硼的脱除仍不能满足实际要求，因此制备高脱硼反渗透膜具有重要意义。本文综述了近年来反渗透膜脱硼技术的研究进展，重点阐述了提高反渗透膜脱硼率的机制，主要思路包括优化反渗透膜结构和利用硼酸特殊性质；改善反渗透膜脱硼性能的有效途径包括开发新型膜材料，优化界面聚合工艺和物理化学法改性等；制备高脱硼反渗透膜的主要障碍是水硼传输的trade-off现象和缺少针对水和硼传输的模型。另外，硼酸分子具有独特的物理化学性质，可以借助硼酸分子研究聚酰胺反渗透膜的网络结构、水硼在膜内的传输机制和引起trade-off现象的因素。     

溶剂改性聚酰胺膜的研究

实验选用聚酰胺(PA)的良溶剂醋酸作为PA膜的改性剂。改性膜对不同醇的溶胀率是随着醇中碳原子数的增加而增加。溶剂改性条件(改性时间、改性剂浓度)对改性膜的吸着性能有明显影响。随着改性时间的延长，改性膜对水的溶胀率都呈下降趋势，而对异丙醇(IPA的溶胀率基本上是先增大后减小。随着改性剂浓度的增大，改性膜对水和IPA的溶胀率都是先上升后下降，而且当醋酸浓度为6％～8％时，都达到最大值。红外光谱分析表明，醋酸改性对PA的化学结构并没有产生影响，吸着性能的变化主要来自于改性过程PA膜物理结构的变化。     

基于聚异丁烯胺改性的耐甲醇溶胀新型薄膜复合膜

聚合物膜可以在甲醇/染料废液处理中发挥重要作用。为了保证膜在甲醇处理过程中的高性能，提高膜的耐甲醇溶胀性是必要的。然而，关于耐甲醇溶胀膜的研究相对较少。在此，提出将活性聚合物（聚异丁烯胺，PIBA）引入分离层，制备新型耐甲醇溶胀聚酰胺（PA）薄膜复合（TFC）膜。PIBA的掺入增加了膜的表面粗糙度、活性层厚度和活性层背面的致密性。PIBA提高了膜的耐甲醇溶胀性能：当PIBA的添加量从0增加到1g/L时，溶胀率从46.81%下降到15.00%。因此，PA/PIBA膜表现出比PA膜更高的染料（藏红T）截留率（99.53%与94.62%）。此外，在20bar（1bar=0.1MPa）的操作压力下，PA/PIBA膜保持了高通量[84.62L/(m²·h)]和良好的长期运行稳定性。最后，由于聚异丁烯（PIB）在先前的工作中同样用于提高膜的耐甲醇溶胀性，本工作将PIBA与PIB进行了比较，得出PIBA优于PIB。这项工作为开发一种用于甲醇流出物处理的分离膜提供了新途径。     

苦咸水反渗透膜脱硼性能研究

对商业化的苦咸水反渗透膜片的脱硼性能进行研究,考察了进水pH值、压力、温度、NaCl浓度、硼浓度以及膜表面流速等对苦咸水膜脱硼性能的影响.结果表明:不同测试条件下苦咸水反渗透膜元件和膜片脱硼性能影响基本一致.在各种影响因素中,进水pH值影响最明显,脱硼率随着pH值的增加而大幅增大.在pH值小于10的条件下,脱硼率随进水...     

硅藻土膜的疏水改性及其膜蒸馏脱盐性能研究

以大孔径硅藻土膜为基体,对其表面喷涂SiO_2溶胶制备得到非对称结构的硅藻土膜。吸水率法测得其孔隙率为46%,泡点法测得其表面平均孔径为0.78μm。采用辛基三乙氧基硅烷对其进行疏水改性,获得疏水性硅藻土膜。真空膜蒸馏实验表明,改性后的硅藻土膜有较好的脱盐性能,当膜的外侧与温度80℃、质量分数为3.5%的NaCl溶液接触,膜的内侧用抽真空至5 kPa,膜的水渗透通量为10.33 L/(m~2·h),截盐率大于99.9%。     

表面改性对反渗透膜的抗污染和性能的影响

Gilron，J．等Drsalination 2001，140(2)，167～179(英文)研究了商业聚酰胺反渗透膜表面改性对通量／截留率和表面性能的影响。结果表明改性的膜比未改性膜对有机物的吸附少，易清洗，通量和截留率都保持不变。     

表面改性纳米二氧化钛-芳香聚酰胺复合反渗透膜的制备与表征

采用TMC对亲水纳米TiO2进行表面改性,然后添加在复合反渗透膜的聚酰胺层中,制备了改性纳米TiO2-聚酰胺复合反渗透膜。改性纳米TiO2使用红外光谱法(FTIR)和粒径分析仪进行表征;采用渗透试验,扫描电镜(SEM)、静态接触角仪、原子力显微镜等对复合膜的性能和结构分别测试和表征。结果表明,改性TiO2的表面接枝上酰氯基团,在有机溶剂中的分散性得到提高;SEM和AFM照片证实,TiO2在膜表面分布均匀,膜表面粗糙度增加;杂化复合膜亲水性也有一定程度的提高;膜性能测试结果证实了添加TiO2的复合膜水通量均高于纯聚酰胺膜,同时脱盐率变化很小。当改性TiO2的添加量为0.05%(m/v)时,水通量由11.21 L/(m2.h)提升到32.61 L/(m2.h),对NaCl截留率达到98.9%。试验结果表明,改性TiO2很好地分散在聚酰胺层,提高了水通量,还保持了高脱盐率,膜性能得到提高。     

部分嵌入式静电自组装改性聚酰胺反渗透膜

针对聚酰胺反渗透膜(RO)抗阳离子表面活性剂污染能力差的难点,提出改变反渗透膜表面荷电性方法,以聚乙烯亚胺(PEI)的乙醇溶液为电解质溶液,利用部分嵌入式静电自组装法对聚酰胺反渗透膜进行改性。采用场发射扫描电子显微镜(FE-SEM)、X射线光电子能谱(XPS)、接触角和固体表面Zeta电位对改性反渗透膜的结构和性能进行表征。结果表明,FE-SEM图像显示膜表面形态没有发生变化;XPS元素分峰和含量分析证明了PEI成功组装在反渗透膜上;接触角验证了改性后膜的亲水性增加,Zeta电位证实了改性后膜的荷负电性减小。改性后膜通量和脱盐性能均增加,抗污染性能得到显著改善,并具有耐酸碱稳定性(pH 2～11)。     

MOF-199@GO改性PVDF荷电纳滤膜的制备及其性能

采用原位生长法制备了MOF-199@氧化石墨烯（GO）纳米复合材料，并对聚偏氟乙烯（PVDF）支撑膜进行表面改性，以克服PVDF膜表面疏水性。通过界面聚合反应，制备了基于MOF-199@GO改性PVDF的聚酰胺复合荷电纳滤膜。采用XRD、SEM、TEM、AFM和zeta电位等手段表征了MOF-199@GO复合材料及MOF-199@GO改性PVDF聚酰胺复合纳滤膜的结构及微观形貌，并测试了MOF-199@GO改性PVDF聚酰胺复合纳滤膜的脱盐性能。结果表明：通过MOF-199@GO复合材料对PVDF支撑膜的表面改性，有效克服了PVDF支撑膜的疏水性，实现了表面聚酰胺薄层的均匀连续生长，荷电纳滤膜表面荷负电性能显著增强，其中经MOF-199@GO充分改性的复合荷电纳滤膜表现出优异的脱盐性能，对MgSO₄、Na₂SO₄、NaCl和MgCl₂四种盐的截留率分别达到了93.56%、93.04%、87.48%和87.11%。     

环丙胺改性正渗透膜的制备及耐氯性能研究

采用界面聚合的方法,将环丙胺接枝到复合膜表面制备出高耐氯性能的聚酰胺正渗透膜。采用扫描电子显微镜(SEM),原子力显微镜(AFM),傅里叶红外光谱(FTIR)对复合膜进行表征。并以去离子水为进料液,2.0 mol/L的氯化钠溶液为汲取液,对膜进行正渗透实验。研究发现,相比于原始膜,当环丙胺的添加量为1.0wt%和1.5wt%时,膜的表面开始变得更加光滑,其Ra由48.7 nm降至41.4 nm和34.8 nm。同时表现出了很好的分离性能和耐氯性能,改性后膜的盐截留率从99.0%分别增加到99.3%和99.7%;在pH为9的条件下,经过20 000 mg/(L·h)的氯化后,2种改性膜的盐截留率要比未改性膜高出15.1%和19.7%;即使在pH为4的酸性条件下,经过20 000 mg/(L·h)的氯化后,2种改性膜的盐截留率依然比未改性膜高出15.9%和24.4%。     

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.     

Using nanocomposite materials technology to understand and control reverse osmosis membrane compaction

Composite reverse osmosis (RO) membranes were formed by interfacial polymerization of polyamide thin films over pure polysulfone and nanocomposite-polysulfone support membranes. Nanocomposite support membranes were formed from amorphous non-porous silica and crystalline microporous zeolite nanoparticles. For each hand-cast membrane, water flux and NaCl rejection were monitored over time at two different applied pressures. Nanocomposite-polysulfone supported RO membranes generally had higher initial permeability and experienced less flux decline due to compaction than pure polysulfone supported membranes. In addition, observed salt rejection tended to increase as flux declined from compaction. Cross-sectional SEM images verified significant reduction in thickness of pure polysulfone supports, whereas nanocomposites better resisted compaction due to enhanced mechanical stability imparted by the nanoparticles. A conceptual model was proposed to explain the mechanistic relationship between support membrane compaction and observed changes in water flux and salt rejection. As the support membrane compacts, skin layer pore constriction increased the effective path length for diffusion through the composite membranes, which reduced both water and salt permeability identically. However, experimental salt permeability tended to decline to a greater extent than water permeability; hence, the observed changes in flux and rejection might also be related to structural changes in the polyamide thin film.     

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。     

用于反渗透复合膜的海绵状结构支撑膜制备研究

通过调节铸膜液中聚砜浓度和非溶剂含量,浸没沉淀法制备海绵状结构的支撑膜,并在支撑膜上界面聚合制备聚酰胺反渗透复合膜。分别对支撑膜及反渗透复合膜的结构和性能进行表征,考察聚砜浓度对支撑膜结构和性能的影响,以及不同结构支撑膜对反渗透复合膜结构和性能的影响。结果显示,随着聚砜浓度的增加,支撑膜表面孔径和孔隙率下降,断面结构变致密,耐压性增强。在不同支撑膜上制备的反渗透复合膜具有不同的通量和脱盐率。综合考虑支撑膜及反渗透复合膜的性能,以聚砜浓度为15%制备的海绵状结构支撑膜更适于作为制备反渗透复合膜的支撑层。     

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。     

沸石/聚酰胺反渗透复合膜的制备

为了提高反渗透膜的通量,通过在界面聚合反应过程中添加NaA型纳米沸石分子筛制备了沸石/聚酰胺反渗透复合膜,采用SEM及复合膜性能测试的方法比较了沸石分子筛添加在水相或者油相中时对膜结构及分离性能的影响.SEM图谱结果表明:沸石分子筛添加在油相中时,沸石在聚酰胺基质中分散均匀,膜结构比较均一;但当沸石分子筛添加在水相中时...     

Study on Potassium Permanganate Chemical Treatment of Discarded Reverse Osmosis Membranes Aiming their Reuse

Membrane-based industrial desalination/demineralization plants generate a considerable amount of discarded membranes. This work studies the effects of the chemical treatment with potassium permanganate solutions in combination with chemical cleaning of three years old composite polyamide/polysulfone reverse osmosis membranes (8″ modules) in order to make them reusable in other applications than reverse osmosis and to increase their life cycles. The performance of membranes with 60 cm² was evaluated in terms of water permeate flux and salt rejection, two properties that can be easily measured in industrial systems. Potassium permanganate treatment degraded the selective layer, improving the water permeate flux of at least 15% from its initial value at the expense of decreased salt rejection. The formation of a manganese oxide layer was detected which reduced subsequent oxidative treatment efficacy. Citric acid was used as a cleaning agent after the oxidation steps, removing part of the manganese oxide layer; the result was an enhanced oxidative process, which increased the permeate flux even more and decreased the loss of salt rejection. Furthermore, to verify the stability of the treatment, the membrane was submitted to a long-term oxidizing experiment.     

Ionic reverse osmosis membranes of grafted polyethylene

Membranes of graft copolymers of polyethylene with poly(sodium styrene sulfonate), poly(4-vinylpyridinium methyl bromide), and poly(sodium acrylate) were prepared by using the technique of peroxide grafting. The reverse osmosis characteristics of the membranes were examined as a function of grafting yield. In these membranes, the grafting can be considered as a process of introducing ionic sites, and it depends on the conditions of the grafting reaction, such as monomer concentration and temperature. However, the overall reverse osmosis characteristic is not only dependent on the number of ionic sites introduced but also on the swelling capability of the membrane. Consequently, the salt rejection of grafted membrane of a fixed graft yield depends on the conditions of the grafting reaction. All grafted membranes which have grafting yields above a certain value behave as normal ionic polymer membranes, and their interrelationship of salt rejection and water permeability follow the general dependence found for ionic polymer membranes.     

Temperature Effects on Concentration Polarization Thickness in Thin‐Film Composite Reverse Osmosis Membranes

Continuous research and development of reverse osmosis (RO) technologies has led to the production of membranes that are very effective with high salt rejection abilities. As temperature is one of the factors that affects salt rejection capabilities in membranes, this paper investigates the effect of temperature on the thickness of the concentration polarization layer (CPL) deposited on thin‐film composite seawater RO membranes. Two types of membranes were studied: those with ex situ macromolecules and those with in situ macromolecules. FilmTec's reverse osmosis system analysis design software was used to predict the variation of salt rejection and permeate flow rate with temperature. The impact of these variations on the thickness of the CPL was analyzed for different polyamide concentrations in the membrane.