纳滤膜盐水溶液软化过程中膜面动态结垢机理研究进展

膜面结垢是纳滤(NF)膜盐水溶液软化过程中遇到的最主要问题之一。尽管已有大量的研究者对NF膜面结垢趋势预测和膜面污染物形貌的先进科学表征进行了深入广泛的研究,但对NF膜面动态结垢机制和过程还没有系统的报道。本文详细描述了包括膜阻力、浓差极化阻力、滤饼层阻力和膜孔堵塞阻力在内的NF膜结垢阻力理论模型;综述了包括膜面浓差极化、构晶离子成核和膜面结晶沉淀的NF膜面动态结垢过程的研究进展,重点阐述了表面结晶和主体结晶两种NF膜面结晶生长机制的研究概况,并展望了NF膜面结垢机理的研究前景。     

从防垢剂对碳酸钙晶形分布影响的角度研究防垢机理

为研究防垢剂的作用机理, 收集了不同防垢剂加入前后出现的碳酸钙垢. SEM分析表 明, 加入防垢剂前, 碳酸钙垢的SEM表现为方解石的六方柱和菱面体; 加入防垢剂后, 碳酸钙垢的形态发生变化, 且防垢剂的效果越好, 垢的形态改变程度越大. 进一步通过FT-IR, XRD对碳酸钙垢进行了定性、定量分析, 发现加入防垢剂后, 垢中除方解石外, 出现了六方方解石和文石, 且防垢率越大, 垢中六方方解石的含量越高. 上述结果说明, 加入防垢剂后垢形态改变的本质原因是垢中碳酸钙晶型分布发生了变化. 结垢过程主要包括不稳定相的生成和消失、介稳相的生成和消失、稳定相的生长三个阶段. 不出现防垢剂时, 介稳相可以转变为稳定相, 碳酸钙垢的主要成分为方解石; 加入防垢剂后, 防垢剂阻止了介稳相的生成和转化, 导致碳酸钙垢中出现了六方方解石和文石. 防垢率越大, 碳酸钙垢中六方方解石含量越高, 说明防垢剂主要通过将结垢过程控制在第二阶段或第一阶段而起到防垢作用.     

水质稳定剂聚丙烯酸的合成

目前,在大型石油化工企业、大型合成氨厂、大型轧钢厂、油井、气井等工业领域中,水质处理已成为极重要的课题。以冷却水为例,由于冷却过程的蒸发,水中溶解的无机盐被浓缩,随之而来的是产生结垢。结垢后设备传热系数下降,结果导致产量下降,因此对冷却水的缓蚀防垢研究引起了极大的注意。六十年代以前,防结垢剂主要使用无机化合物,如聚     

有机-无机复合多孔膜制备与应用

日益严重的水污染问题引起了越来越多的科学家对水处理技术,特别是新型的分离膜材料及其分离技术的关注。有机-无机复合分离膜因同时具备有机聚合物与无机物的特点而逐渐成为研究的热点之一。本文综述了近年来有机-无机复合多孔膜研究领域的主要进展。在材料制备方面,着重介绍了基于本体掺杂过程(膜相镶嵌模型)与基于界面复合过程(界面复合模型)制备的有机-无机复合膜,其制备方法包括共混法、原位生成法、表面化学修饰、原子层沉积和仿生矿化法等。在实际应用方面,本文介绍了有机-无机复合膜在抗污染、抗菌、油水分离、催化、吸附、电池隔膜及酶固定化领域的应用。随着膜科学的进一步发展,具有多功能与高性能的分离膜将成为研究的主要方向,而具有更高表面无机覆盖率的“界面复合模型”将成为较优的复合膜构建策略。     

燃料电池用填孔型质子交换膜

填孔型质子交换膜是一种将电解质填充到多孔的基底膜中形成的新型质子交换膜。与传统的全氟磺酸膜相比,填孔型质子交换膜具有不溶胀、甲醇渗透率低、质子传导率高、价格低廉以及材料选择范围广等优点。本文介绍了分别以聚合物多孔膜,有机/无机多孔膜和无机多孔膜为基底的三种填孔型质子交换膜的研究现状,并对质子交换膜的发展方向和趋势进行了预测。     

有机无机杂化膜材料的制备技术

有机无机杂化膜兼有机膜韧性和无机膜耐高温性能,具有优良的气体渗透选择性,成为高分子化学和材料科学等领域的研究热点.本文综述了近年来有机无机杂化膜材料的制备技术进展,着重探讨了溶胶-凝胶法制备聚酰亚胺类杂化膜材料的研究状况,并作了简要述评。     

三元复合驱硅垢防垢剂SY-KD的合成及应用

通过分析三元复合驱油体系下硅垢的形成机理,设计合成了新型硅防垢剂SY-KD.SY-KD是由丙烯酸(AA)和对甲基烯丙基氧基苯磺酸(MBS)共聚形成的高分子(CAABS)与2-膦酸丁烷-1,2,4-三羧酸(PBTC)复配的混合物.SY-KD中羧基官能团通过氢键相互作用与原硅酸分子或其二聚体发生键合,由于SY-KD分子链的空间位阻效应,阻止了原硅酸分子或二聚体进一步聚合形成二氧化硅.室内研究结果表明,SY-KD各组分对于硅垢的阻垢能力主要是通过阻聚、吸附分散以及对不溶性SiO2的溶蚀作用来实现的,是一种很好的三元复合驱阻垢剂.SY-KD防垢剂使结垢油井平均检泵周期由50 d左右增加到300 d.     

杂化离子膜的制备和应用*

杂化离子膜（包括有机-无机和无机-有机杂化膜）自20世纪80年代诞生以来,已快速发展成为一个新的研究热点。该种膜在燃料电池、电化学分析和传感、电膜分离过程、扩散渗析等方面有广泛的应用前景。本文结合作者所在课题组相关方面的工作,综述了近5年来杂化离子膜制备和应用技术进展,重点包括溶胶-凝胶(sol-gel)法、共混法、原位渗入和沉积法等制备方法,以及杂化离子膜在燃料电池、电化学分析和传感器、电渗析膜、扩散渗析膜分离、以及超滤、纳滤、渗透汽化等其他方面的应用。最后对近年来的发展提出了看法和总结。     

油田清垢剂研究进展

油田清垢剂是使用化学方法清除油田生产过程中生成吸附于设备表面、地层的垢的药剂。本文总结了影响油田结垢的主要因素,综述了近十年油田清垢剂的主要清垢类型及各自的优缺点,对各种新型油田清垢剂的清垢类型、清垢效果及存在的主要问题进行了分析介绍,展望了油田清垢剂未来的研究方向和发展前景。     

ＴiB2纳米管的模板法制备及表征

ＴiO2纳米材料在太阳能的储存与利用、光电转换、光致变色及光催化降解大气和水中的污染物等方面具有广阔的应用前景,成为重点研究的课题之一^[1~5],目前,以ＴiＯ２纳米粉体和纳米膜的研究较为普遍,而Ｔi o２纳米管的报道不多,由于纳米比纳米膜具有更大的比表面积,因而具有较高的吸附能力,可望提高ＴiO2的光电转换效率,模板法（包括多孔阳极氧化铝膜（ＰＡＡ）、光刻蚀制备垢纳米模板、聚碳酸酯纳米滤膜等）在制备导电聚合物,金属,碳,无机半导体等纳米管或线型材料方面已得到广泛应用^[6~9],在这些模板中,ＰＡＡ模具有均匀分布的重直于表面的相互平行的密集纳米孔,且孔径,孔间距,膜厚可以通过电化学手段加以控制^[10~13]。     

高回收率膜法苦咸水淡化工艺的应用研究进展

膜法苦咸水淡化过程中,符合环境保护要求的浓排水处理方法成本高昂,所以只有当回收率达到较高值时,在实际运行中才具有经济可行性。目前,在不加剧膜污染的条件下进一步提高苦咸水淡化系统回收率的方法已成为该领域研究热点。本文详细综述了高回收率膜法苦咸水淡化工艺的应用研究进展,包括基于反渗透、纳滤、正渗透、膜蒸馏、电渗析和电容去离子化淡化工艺过程,以及这些过程面临的热点问题,并对此提出了建议。     

Molecular and Morphological Designs of High Performance Polymeric Membranes

Currently, membrane separation techniques, such as reverse osmosis and ultrafiltration, play an important role in industrial separation technology. To develop high performance polymeric membranes, it is essential to design the molecular and morphological structures of the membranes for their specific applications. In the reverse osmosis field, we have developed several kinds of composite membranes for specific uses. Applications include ultrapure water production, seawater desalination, softening and desalination of brackish water, and recovery of valuable substances. In the course of development, thin-film composite membrane materials and membrane morphology have been analyzed intensively and are becoming clearer. These results enable us to control membrane performance by an optimum combination of membrane materials and membrane morphology. The morphological structure and chemical structure of the composite membranes were designed to optimize the performance of both the ultrathin layer and the supporting substrate layer for each membrane's application. As ultrafiltration is expanding to various fields, requirements for membrane performance have become more severe, especially for 1) sharpness of molecular weight cutoff, 2) solvent and high temperature resistance, and 3) fouling resistance (low nonspecific protein adsorption). To satisfy these requirements, we have developed a new ultrafiltration membrane. Owing to the high resistivity and hydrophilicity of its chemical structure, the membrane shows excellent solvent and high temperature resistance as well as fouling resistance. In addition, sharp molecular cutoff was realized by controlling membrane morphology.     

A study of selected phytoestrogens retention by reverse osmosis and nanofiltration membranes - the role of fouling and scaling

Fouling and scaling are common phenomena that accompany membrane filtration and are caused by the presence of organic and inorganic matter in water, which may affect the removal of low-molecular mass organic micropollutants. Comparative filtration of deionized water containing selected phytoestrogens (biochanin A, daidzein, genistein, and coumestrol) was carried out using one new membrane and one contaminated with organic or inorganic matter. Two commercial Osmonics DS membranes were selected for the research, reverse osmosis DS3SE and nanofiltration DS5DK. Filtration was carried out in the dead-end mode. Higher removal of phytoestrogens was caused by reverse osmosis and retention depended on the molar mass of the compound. The decrease in membrane efficiency associated with fouling or scaling brings about an increase in the retention coefficient of phytoestrogens during both reverse osmosis and nanofiltration. The highest increase in phytoestrogen retention was found for the nanofiltraton membrane which was more susceptible to fouling than the osmotic one. This confirms the effect of membrane porosity on the phenomenon studied. The increase in micropollutants removal observed after fouling or scaling was caused by the modification of the membrane surface, hindered diffusion of the compound, and intensified or limited adsorption of micropollutants on the membrane surface.     

Aquaporin-Based Biomimetic and Bioinspired Membranes for New Frontiers in Sustainable Water Treatment Technology: Approaches and Challenges

Biomimetic and bioinspired membranes are the efficient membrane technology when it comes to multiple usage scenarios, including next generations of biomaterials within the commercial separation applications, as well as, water and wastewater treatment technologies. In recent years, aquaporin biomimetic membranes for water separation have raised considerable interest. These membranes have displayed distinguished properties and outstanding performances, as diverse interactions, varying selective transport mechanisms, superior stability, maximum resistance to membrane fouling, and distinct adaptability. The biomimetic membranes have made significant contributions when it comes to water stress, environmental threats and energy. It has the potential to produce clean water more efficiently than reverse osmosis membranes (RO), while saving up to 80% of the energy used for desalination processes. More than half of the 15000 desalination plants around the world utilize RO technologies, and the implementation of biomimetic membranes on a large scale could save hundreds of millions of dollars in energy cost annually (potential savings of $1.45 million/year for 100 ML/day desalination plant). This paper discusses the interplay of the main components of aquaporin biomimetic membranes: aquaporin proteins, block copolymers for aquaporin proteins reconstitution, and polymer-based supporting structures. We focus specifically on the challenges and review recent developments on the interplay between aquaporin proteins and block copolymers. The recent efforts in embedding reconstituted aquaporin proteins in membrane designs that are based on conventional thin film interfacial polymerization techniques are evaluated. In addition, emerging challenges and opportunities for biomimetic membranes are studied from the perspective of current and future applications.     

反渗透膜微结构的调控及海水脱硼性能的提升

通过引入聚乙烯亚胺(PEI)链与对叠氮苯甲酸(ABA)分子对薄层芳香聚酰胺复合反渗透膜(TFC)进行接枝改性, 采用傅里叶衰减全反射红外光谱(ATR-FTIR)和X射线光电子能谱(XPS)分析了反渗透膜活性分离层的化学组成和结构, 用静态水接触角仪与Zeta电位仪测试了反渗透膜表面的亲疏水性和电荷性质, 并利用扫描电子显微镜(SEM)及原子力显微镜(AFM)观察其表面形貌, 测试了反渗透膜在苦咸水与海水条件下的分离性能. 实验结果表明, 使用PEI与ABA对反渗透膜改性后, 提升了其分离层的致密度, 使硼渗透通过反渗透膜时的传质阻力变大, 从而将改性反渗透膜(TFC-PEI-ABA)对硼的截留率提升至90.45%, 达到了世界卫生组织对水质的要求.     

Zeolitic imidazolate framework-8 as a reverse osmosis membrane for water desalination: insight from molecular simulation

A molecular simulation study is reported for water desalination in zeolitic imidazolate framework-8 (ZIF-8) membrane. The simulation demonstrates that water desalination occurs under external pressure, and Na(+) and Cl(-) ions cannot transport across the membrane due to the sieving effect of small apertures in ZIF-8. The flux of water permeating the membrane scales linearly with the external pressure, and exhibits an Arrhenius-type relation with temperature (activation energy of 24.4 kJ∕mol). Compared with bulk phase, water molecules in ZIF-8 membrane are less hydrogen-bonded and the lifetime of hydrogen-bonding is considerably longer, as attributed to the surface interactions and geometrical confinement. This simulation study suggests that ZIF-8 might be potentially used as a reverse osmosis membrane for water purification.     

Photocatalytic Treatment of Desalination Concentrate Using Optical Fibers Coated With Nanostructured Thin Films: Impact of Water Chemistry and Seasonal Climate Variations

Treatment of desalination concentrate can reduce concentrate volume for disposal, increase water recovery and convert waste to resource. However, concentrate treatment is costly and energy intensive due to high concentrations of salt and recalcitrant organic matter in concentrate. Photocatalytic oxidation provides a novel energy neutral technology for concentrate treatment by degrading organic contaminants. Polymer‐assisted hydrothermal deposition method was used to synthesize innovative pure and Fe‐doped TiO₂ mixed‐phase nanocomposite thin films on side‐glowing optical fibers (SOFs). The properties of the photocatalysts‐coated SOF were characterized by surface morphology, nanostructure, crystallite size and phase and zeta potential. Photodegradation efficiency and durability of the photocatalysts treating different types of desalination concentrate was studied under natural sunlight. Synthetic solutions and reverse osmosis (RO) concentrates from brackish water and municipal wastewater desalination facilities were tested to elucidate the impact of water chemistry, operating conditions and seasonal climate variations (solar irradiation intensity and temperature) on photocatalytic efficiency. High ionic strength and divalent electrolyte ions in RO concentrate accelerated photocatalytic process, whereas the presence of carbonate species and organic matter hindered photodegradation. Outdoor testing of immobilized continuous‐flow photoreactors suggested that the catalyst‐coated SOFs can utilize a wide spectrum of natural sunlight and achieved durable photocatalytic performance.     

Generalization and prognostication of mass exchange characteristics of electrodialyzers operating in overlimiting current regimes with use made of similarity theory and compartmentation method

A semiempirical approach, which allows one to perform generalization, prognostication, and scaling of the mass exchange characteristics of electrodialyzers intended for the desalination of dilute solutions in the overlimiting current regimes, is proposed. The approach is based on modern theoretical notions concerning the dependence of mass transfer on conjugated effects of concentration polarization, such as electroconvection and the exaltation effect and makes use of the similarity theory principles. As a result, there are obtained sufficiently simple equations that describe to within a satisfactory accuracy characteristics of the process of electrodialysis (mass transfer coefficient, Sherwood number, solution desalination degree, and so on) as functions of four parameters, namely, the input concentration, the solution flow rate, the potential drop across the paired chamber of the membrane stack of an electrodialyzer, and the length of the desalination channel. For scaling the obtained dependences with respect to a channel length a compartmentation method is used. Results of experimental investigations and calculations of electrodialyzers with desalination channels without a filler, or containing an inert separator, a monolayer of an ion-exchange resin, a profiled membrane, are presented.     

静电纺丝复合反渗透膜的改性制备与脱盐性能

利用静电纺丝技术在无纺布上制备PET纳米纤维膜, 并用交联壳聚糖对其进行改性得到壳聚糖改性纳米纤维复合膜. 以间苯二胺(MPD)和均苯三甲酰氯(TMC)为单体, 采用界面聚合法在壳聚糖改性纳米纤维复合膜的表面制备聚酰胺分离层, 得到新型静电纺丝纳米纤维基复合反渗透膜. 新型复合反渗透膜具有典型的聚酰胺复合反渗透膜的表面脊-谷结构. 从膜的表面形貌、 亲水性、 分离性能等3个方面对水相MPD溶液中阴离子表面活性剂十二烷基苯磺酸钠(SDBS)的含量对膜结构和性能的影响进行了系统研究. 结果表明, SDBS的含量对膜形态结构的均匀性和亲水性有一定影响, 且随着SDBS含量的增加, 膜的脱盐率先增大后减小, 而通量小幅度上升后, 先减小后增大, 呈现规律性变化.