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。     

正渗透汲取液的研究进展

正渗透是以膜两侧汲取液和原料液之间的渗透压差为驱动力,使水从原料液(较低渗透压)一侧自发传递到汲取液(较高渗透压)一侧的膜分离技术。汲取液是影响正渗透分离性能的重要因素之一,然而目前使用的大多数汲取液面临反向溶质渗透严重和再生能耗高的问题,这导致了正渗透性能的显著下降。简要介绍了近几年国内外主要研究的新型汲取液,分析总结了不同汲取液的优点及其应用范围。     

Synthesis and application of ethylenediamine tetrapropionic salt as a novel draw solute for forward osmosis application

The development of suitable draw solutes for forward osmosis (FO) process is a big obstacle on the way of its real industrialization. In this work, a novel draw solute, ethylenediamine tetrapropionic (EDTP) acid (salt) is developed for FO application. The successful synthesis is confirmed by Fourier transform infrared spectroscopy, nuclear magnetic resonance spectroscopy, and high resolution mass spectrum. By optimizing the pH of EDTP solution, its composition is varied, and therefore, its water solubility and osmotic pressure are effectively improved. The effects of EDTP concentration on the osmotic pressure and FO performance are also investigated. Its outstanding osmotic pressure and big molecular size result in a high water flux of 22.69 LMH and a low salt flux of 0.32 gMH with 0.8 M EDTP draw solution (water as the feed solution, pressure retarded osmosis mode). The good stability and easy recovery by nanofiltration of EDTP solution also demonstrate its great potential as the draw solute for future FO applications. © 2015 American Institute of Chemical Engineers AIChE J, 61: 1309–1321, 2015     

正渗透水处理关键技术研究进展

正渗透是一种新型的膜分离技术,其分离的驱动力来源于原料液和汲取液之间自然存在的渗透压差,近年来正渗透技术已在国际上得到广泛关注。简述了基于此技术的正渗透水处理过程的基本原理,指出了这种新型水处理过程的关键技术——正渗透膜和汲取液,根据各自的技术特点对其进行分类概述,并从实验室基础研究和技术的商业化进程两方面介绍了这两项关键技术取得的最新研究进展。从水通量角度对不同体系进行了简单比较,分析了各材料和方法的优缺点,并对它们的应用前景进行了展望。     

Novel carboxyethyl amine sodium salts as draw solutes with superior forward osmosis performance

A series of carboxyethyl amine sodium salts (CASSs) with different carboxyl group numbers are synthesized as draw solutes for forward osmosis (FO) application. Their chemical structures are examined by ¹HNMR and HRMS. FO performances are investigated and compared in terms of different physicochemical properties. The effects of the CASS concentration on the osmotic pressure and viscosity of the draw solutions, as well as the resulted FO performance are also systematically investigated. A high water flux of 23.07 LMH and an acceptable reverse salt flux of 0.75 gMH can be achieved with 0.5 g mL^?1 triethylenetetramine hexapropionic acid sodium (TTHP‐Na) draw solution under PRO mode, which is superior to most other draw solutes reported in previous literatures. TTHP‐Na draw solution is further evaluated to recycle the Congo red solution via FO process to examine its applicability for waste water treatment. © 2015 American Institute of Chemical Engineers AIChE J, 62: 1226–1235, 2016     

正渗透技术研究综述及应用展望

正渗透技术是近年来新兴的水处理技术,其研发初始即指向各种高难度废水的处理回用及物料分离领域,是一项有广阔发展空间的水处理技术。目前对该技术的研究重点集中在膜材料和汲取液的选择上。从正渗透的原理出发,介绍了正渗透膜材质及汲取液的前沿科技成果,分析了未来正渗透膜材质和汲取液选择的方向。最后,总结了正渗透技术的优势,并对正渗透的未来应用做了展望。     

A review on the forward osmosis applications and fouling control strategies for wastewater treatment

During the last decades, the utilization of osmotic pressure-driven forward osmosis technology for wastewater treatment has drawn great interest, due to its high separation efficiency, low membrane fouling propensity, high water recovery and relatively low energy consumption. This review paper summarizes the implementation of forward osmosis technology for various wastewater treatment including municipal sewage, landfill leachate, oil/gas exploitation wastewater, textile wastewater, mine wastewater, and radioactive wastewater. However, membrane fouling is still a critical issue, which affects water flux stability, membrane life and operating cost. Different membrane fouling types and corresponding fouling mechanisms, including organic fouling, inorganic fouling, biofouling and combined fouling are therefore further discussed. The fouling control strategies including feed pre-treatment, operation condition optimization, membrane selection and modification, membrane cleaning and tailoring the chemistry of draw solution are also reviewed comprehensively. At the end of paper, some recommendations are proposed.     

Multi-functional forward osmosis draw solutes for seawater desalination

Forward osmosis (FO), as one of the emerging desalination technologies, has the potential to produce freshwater from a variety of water sources by utilizing the osmotic pressure gradient across a semi-permeable membrane. Drawsolution, as an essential component of any FO process, can extract watermolecules fromseawater orwastewater. An ideal draw solution should meet three essential requirements, namely high osmotic pressure, low reverse flux, and facile regeneration mechanism. The selection of proper draw solutes is especially critical for an energy-efficient FO process since the energy consumption mostly arises from the separation or regeneration of the draw solution. Recently, we developed a few multi-functional FO draw solutes, mainly aiming to enhance the FO water flux and to explore facile re-concentration methods. This review summarizes these draw solutes, including Na⁺-functionalized carbon quantum dots, thermoresponsive copolymers, hydrophilic magnetic nanoparticles, and thermoresponsive magnetic nanoparticles.     

双胺“可逆”溶剂强化正渗透脱盐及过程优化

正渗透作为非压力驱动膜脱盐技术,具有能耗低、膜污染轻、水回收率高等优点,其中汲取液的分离回收是整个正渗透技术的关键。本文提出采用双胺(TEPDA,N,N,N’,N’-四乙基-1,3-丙二胺)“可逆”溶剂经质子化-脱碳可逆循环作为正渗透汲取液进行脱盐的策略。首先,使用TEST软件预测发现,相比传统有机溶剂及单胺溶剂(如DMCHA,N,N-二甲基环己胺),TEPDA具有较低的挥发性、较高的安全性和低生育毒性。正渗透实验发现在两种模式下TEPDA的反向通量选择性均高于DMCHA,证明TEPDA具有更好的正渗透效果。同时发现TEPDA汲取液在PRO模式下效果要优于FO模式。通过对操作条件的优化得到TEPDA汲取液的最优操作温度为30℃,最佳流速为500mL/min。在最优条件下对1%(质量分数)的氯化钠溶液进行5h的连续运行发现,TEPDA汲取液在5h后仍能保持6.09L/(m²·h)的正向渗透通量,具有连续运行的稳定性。循环实验也证明了TEPDA具有较好的循环稳定性。上述结果为双胺(TEPDA)“可逆”溶剂应用于正渗透脱盐领域提供了基础的理论指导。     

Fast-responsive monolithic hydrogels as draw agent for forward osmosis membrane process

A monolithic copolymer hydrogel was synthesised by polymerising n-isopropylacrylamide and sodium acrylate in the presence of poly(sodium 4-styrenesulfonate) (PSSS) chains and studied as potential draw agent for forward osmosis (FO) process. The monolithic hydrogel synthesised from 19% NIPAM, 1% SA, and 15% PSSS at 60°C generated higher FO water flux and higher recovery rate than other hydrogels, due to improved membrane-hydrogel contact and water transport. In particular, the synthesised hydrogel draw agent achieved twice water flux compared with the particles. The monolithic hydrogel containing a smaller amount of water produced a higher water flux due to its high swelling pressure.     

The applications of porous FO membranes and polyelectrolyte draw solution in the high-salinity organic wastewater treatment with a hybrid forward osmosis-membrane distillation system

Hybrid forward osmosis-membrane distillation (FO-MD) system have been considered as a promising technology for wastewater treatment. In the current study, initial and modified porous FO membranes are fabricated, and the intrinsic membrane separation properties are also investigated. Polyacrylic acid sodium (PAAS), sodium polystyrene sulfonate (PSS) and polyethylene glycol (PEG) are used to evaluate the effects of draw solution (DS) in FO experiments. Particularly, alkali treated modified porous FO membrane and PAAS are utilized in the subsequent wastewater treatment owing to the high performance of permeation and rejection. Furthermore, the optimal values of operating parameters (flow velocity, DS concentration and DS temperature), which are selected according to the effects of water flux (J_V) in the FO and MD process, are evaluated and utilized to investigate the dynamic changes of J_V in the high-salinity organic wastewater treatment with hybrid FO-MD system. Results show that the hybrid FO-MD system with porous FO membranes and polyelectrolyte DS maintain the operation in a constant flux of 16.61 LMH, and the permeate solution can be effectively recovered with favorable quality. This study provides remarkable implications for the design of porous FO membranes and the application of hybrid FO-MD system in the wastewater treatment.     

正渗透过程中水与溶质的传递现象

正渗透是一种利用渗透原理的新兴膜技术,近年来在国内外受到了广泛的关注。解析该过程中溶剂水的传递和驱动溶质的反向传递对其发展和应用至为关键。首先开展了两种膜的取向下,正渗透过程中的水通量和溶质反向摩尔通量的实验研究。当驱动溶液在膜分离层侧时,水通量更高,而溶质反向摩尔通量更低,表明水的传递对溶质的反向传递有限制作用。而后分别考察了不同的单一溶质和二元混合溶质作为驱动溶质时,水和溶质的传递现象。当单一中性溶质或电解质作为驱动溶质时,水通量和溶质反向摩尔通量均随驱动溶液浓度的升高而增大;在相同操作条件下,驱动溶质的扩散系数越小,溶质反向摩尔通量越小;中性溶质与电解质混合溶液为驱动溶液时,溶质分子之间存在耦合传递效应。     

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。     

A trimethylamine–carbon dioxide draw solution for osmotic engines

This study evaluates the pressure retarded osmosis performance of TMA–CO₂ for potential use in osmotic heat engines. Power densities up to 18.6 W m^?2 were achievable at relatively low pressure (10 bar) using 5 M TMA–CO₂ draw solutions. Compared to NaCl control tests, the TMA–CO₂ exhibited 20% lower water flux due in large part to its larger molecular size and associated higher solution viscosity and lower diffusion coefficient. Compared to the ammonia‐carbon dioxide draw solution, water flux was comparable but reverse solute flux of TMA–CO₂ was nearly one order of magnitude lower. Larger solute size was found to create a performance tradeoff as reduced reverse solute flux improved water flux while higher viscosity and lower diffusion coefficient worsened water flux. © 2018 American Institute of Chemical Engineers AIChE J, 64: 3369–3375, 2018     

正向渗透膜分离技术及其应用综述

正向渗透是一项新型的利用半透膜两侧溶液渗透压差作为驱动力的膜分离技术。文章介绍了正向渗透膜分离技术的原理和影响因素,对其在各个领域(包括海水淡化、废水处理、橙汁浓缩、水袋)的研究进展进行了综述。现有的研究表明,可用于正向渗透工艺的膜不同于常规的反渗透膜,需要从膜结构开发适合的膜组件;采用NH3和CO2制备提取液是目前研究中具有应用前途的方式之一,具有产水率高且易于分离浓缩的优点。     

Selection of substrate manufacturing techniques of polyamine-based thin-film composite membranes for forward osmosis process

This paper is a comparative study on the preparation techniques used to make the support layer of polyamide-thin-film composite forward osmosis (TFC-FO) membranes. The role played by the support layer preparation technique in membrane performance is thoroughly investigated in this study. Electrospinning is shown to produce membranes of lower structural parameter compared to those obtained by conventional phase inversion techniques. The electrospun polyamide selective layer can also be tailored with the required properties. This makes electrospinning a promising process to design efficient FO membrane substrates. It is shown in this work that the FO water flux is more dependent on the internal structure of the support layer than the preparation materials. The main challenge remaining for substrates to operate in FO is to achieve simultaneously a low structural parameter, a high surface porosity, and the required mechanical properties. As most of today's approaches are not suitable, further materials development is essential in future investigations on TFC-FO membranes.     

正渗透-膜蒸馏耦合工艺在高难度废水处理中的应用研究进展

正渗透-膜蒸馏（FO-MD）耦合工艺作为一种新型膜分离工艺技术,具有工艺设备简单、处理效率高、无二次污染等特点,包含两个高截留率的膜过程,可实现废水的双阻隔处理,从而提高对有机物、油类物质、表面活性剂等污染物的去除率,在高难度废水处理方面具有良好的应用前景。本文综合分析了FO-MD耦合技术的工作原理及工艺特点,指出该工艺未来的研究方向是通过高性能膜材料的开发及处理过程的优化来提高工艺的处理效率并节约处理成本。重点介绍了FO-MD耦合工艺处理高浓度有机废水、高浓度氨氮废水和含油高盐废水等高难度废水的最新进展,探讨了FO-MD耦合工艺亟待研究和解决的问题,总结出FO-MD耦合工艺几个未来发展的方向,为该工艺技术的进一步发展提供参考。     

Fouling and cleaning of polymer-entwined graphene oxide nanocomposite membrane for forward osmosis process

In this study, we have characterized membrane fouling of polymer-entwined graphene oxide membranes with a simulated feed solution containing organic foulants for wastewater treatment applications, as well as with a simulated inorganic wastewater with high iron and silicon concentrations relevant to steel industry wastewater reclamation. Membrane cleaning processes by cross-flow surface flushing with water were then applied to demonstrate water flux recovery for long-term application. Salt rejection property was retained constant during fouling process, whereas water flux was found to be reduced continuously due to fouling but was readily recoverable following surface flushing.     

反渗透技术在碳酸钾生产废水处理中的应用

对碳酸钾生产中产生的废水进行了概述,针对目前生产情况和环保要求,经过多方面探讨,确定采用反渗透膜技术处理该废水,介绍了反渗透膜处理技术的工艺流程,详细说明了反渗透处理废水的应用经验及效果。分析了反渗透的优势与不足,提出了今后的改进设想。     

反渗透技术在TFT-LCD行业工艺废水回收中的应用

采用反渗透工艺对TFT-LCD行业的工艺废水的生化处理出水进行回用处理,重点介绍了该工艺的流程、设计参数及运行效果。运行结果表明,该工艺脱盐率为95.3%,TOC去除率为95.1%,清洗频率为4个月。该工艺运行稳定,出水达到超纯水制备系统水质要求。