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。     

Some transport characteristics of aromatic polyamide membranes in reverse osmosis

The effects of solute concentration in the range of 0.0013 to 1.051 molality in the feed solution and operating pressure in the range of 100 to 900 psig on solute transport parameter D_AM/Kδ in reverse osmosis have been studied for a class of laboratory-made aromatic polyamide membranes and aqueous sodium chloride feed solutions. The results showed that D_AM/Kδ for NaCl increased both with increase in operating pressure and solute concentration in the concentrated boundary solution on the high-pressure side of the membrane. A general expression for D_AM/Kδ for NaCl including the effects of both the above operating variables is given. These results are different from the corresponding results obtained for cellulose acetate membranes.     

Impact of osmotic agent on the transport of components using forward osmosis to separate ethanol from aqueous solutions

The separation of low molecular weight organic compounds such as the ethanol from aqueous solutions represents an important area to be investigated and increment the range of applications of forward osmosis. This investigation assesses the effects of using different draw solutes for ethanol separation from dilute aqueous solutions. The influence of glucose, sucrose, sodium chloride, and magnesium chloride was evaluated in terms of total permeate, reverse solute and ethanol fluxes. Inorganic solutes promoted higher total permeate and ethanol fluxes than the organic solutes (2.5 and 1.5 times higher in average, respectively) for the same molar concentration, while presenting only 1.1 times higher reverse solute fluxes. Despite the lower ethanol flux promoted by the organic draw solutes, these osmotic agents promoted higher concentration of ethanol in the total permeate flux, suggesting that they can also be alternatives for specific processes. © 2017 American Institute of Chemical Engineers AIChE J, 63: 4499–4507, 2017     

正渗透膜生物反应器膜过滤特性研究

以氯化钠为驱动溶质,采用正渗透膜生物反应器处理模拟生活污水,系统地考察了各因素对正渗透膜过滤性能的影响。结果表明,随着驱动液浓度增加,水通量和反向盐通量也随之增加;正渗透膜活性层朝向驱动液时(AL-DS)的水通量和反向盐通量较活性层朝向原料液(AL-FS)时大;水通量和反向盐通量与错流速率正相关,在错流速率较低时增加不明显;随着活性污泥浓度增加,水通量呈下降趋势,而反向盐通量呈上升趋势。     

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。     

Reverse osmosis separations of polyethylene glycols in dilute aqueous solutions using porous cellulose acetate membranes

Reverse osmosis separations of eight polyethylene glycol (PEG) solutes in the average molecular weight range of 200 to 6750 in single-solute dilute aqueous solutions have been studied using porous cellulose acetate membranes at the operating pressures of 50, 75, and 100 psig. Diffusivity data for the above PEG solutes have also been obtained from experimental data on intrinsic viscosities. From an analysis of all experimental data, numerical values for the parameters representing the polar (?ΔΔG/RT), steric (δ^*ΣE_s), and nonpolar (ω^*Σs^*) forces governing reverse osmosis separations of PEG solutes have been generated. These numerical values are useful for precise characterization of cellulose acetate membranes for whose specifications sodium chloride is not the appropriate reference solute because of its low or practically negligible separation under reverse osmosis operating conditions. This work also illustrates that solute separation in reverse osmosis can predictably increase or decrease with increase in operating pressure depending on experimental conditions.     

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.     

A physicochemical approach for the choice of polymeric membrane materials for water desalination by reverse osmosis

Interfacial properties such as the thickness of interfacial water layer, the distribution coefficient of solute between interfacial and bulk water phases, and the volume of interfacial water per unit mass of polymer material have been identified as relevant physicochemical quantities governing reverse osmosis transport and determined by gas and liquid chromatography methods with respect to different polymeric membrane materials. They are further split into the contribution from the structural component of polymer repeating unit. Force constants A and D for sodium chloride, representing the repulsive force working between membrane surface and solute, have been calculated on the basis of inter-facial properties obtained above. Using these force constants, the pore sizes required to achieve 99.9% of sodium chloride separation are obtained for different polymeric membrane materials. Furthermore, the prediction procedure for the effect of preferentially adsorbed organic molecules on the separation of sodium chloride and product rate is illustrated as a model for “fouling” in the desalination process by reverse osmosis.     

Reverse Osmosis Separation of Nickel from Dilute Solutions

Abstract

Cellulose acetate membranes were characterized in terms of the pure water permeability constant, the solute transport parameter, the mass transfer coefficient, and percent solute separation using a reference system of aqueous sodium chloride solution. The membranes were used in the determination of reverse osmosis characteristics such as product rates and solute separation of dilute nickel salt solutions. The effect of the chemical species present in aqueous nickel salt solution on the degree of separation of nickel has been determined. The results of this study can be used in predicting the general reverse osmosis separation behavior of metals such as Zn, Cu, Pb, Mg, and Mn encountered in acid mine-water samples     

Reverse osmosis separation of inorganic solutes in aqueous solutions using porous cellulose acetate membranes

Using a modified form of the Born expression for the free energy of ion-solvent interaction, to both the bulk solution phase and the membrane–solution interface, a parameter is obtained to express the repulsion of the ion at the interface. This parameter, called the free energy parameter for ions, is then related to solute transport parameter obtained from reverse osmosis experiments. Numerical values of this free energy parameter have been obtained for six monovalent and four divalent cations and for 12 monovalent anions. Using the experimental data for the reverse osmosis separation of sodium chloride as reference, the utility of the above parameter for predicting solute separation in reverse osmosis is illustrated for 32 other inorganic salts.     

THERMODYNAMIC MODELING OF SOLUTE TRANSPORT THROUGH REVERSE OSMOSIS MEMBRANE

A new thermodynamic model is developed for water and solute transports through reverse osmosis membranes. The model is featured with rigorous derivations in theoretical development and clearly defined parameters for membrane transport properties. The new model can correctly describe not only the dependence of salt rejection on pressure and salt concentration, but also the non-linearity between water flux and pressure. Comparisons of model simulations with the reported reverse osmosis experiments demonstrate that the parameters in the new model are concentration-independent. This study shows that water and salt transports through reverse osmosis membranes can be satisfactorily described with irreversible thermodynamics.     

Reverse Osmosis Separation of Metal Ions in Acid Mine-Water

Abstract

Cellulose acetate membranes obtained from Osmonics Inc. were characterized in terms of pure water permeability constant, solute transport parameter, and mass transfer coefficient with the reference system of aqueous sodium chloride solution. Reverse osmosis separation behavior of Ca, Mg, Zn, Mn, Cu, Al, and Fe as nitrate, chloride, and sulfate salts was studied. The effect of the addition of sodium sulfate to Mg(ClO₄)₂ and Mn(NO₃)₂ solutions on solute separation was also investigated. Acid mine-water obtained from New Brunswick was subjected to reverse osmosis, and separation of metal ions in the range of 95 to 99 % was obtained along with the recovery of product water of suitable quality for use in recycle operations.     

聚丙烯酸钠汲取液的正渗透性能

研究了聚丙烯酸钠溶液作为汲取液的渗透压特性,并考察了影响水通量和溶质反向渗透量的因素和机制. 结果表明,聚丙烯酸钠浓度与渗透压的关系符合维里方程,第二维里系数对渗透压有较大贡献,聚丙烯酸钠溶液浓度为0.2 g/mL时的渗透压达1.3 Osmol/kg以上,水通量为14.5 L/(m2×h),略高于相同渗透压的氯化钠汲取液[14.0 L/(m2×h)];聚丙烯酸钠汲取液的溶质反向渗透量为1.6 g/(m2×h),低于常规氯化钠汲取液的16.5 g/(m2×h). 升高温度能迅速提高水通量,反向溶质渗透量维持在较低水平,聚丙烯酸钠汲取液适合比常规小分子汲取液更高的操作温度. 聚丙烯酸钠汲取液较高的水通量和较低的溶质反向渗透量表明正渗透性能良好.     

Polar and steric effects in reverse osmosis

The effects of polar parameter Σσ^* and steric parameter ΣE_s on reverse osmosis separations of alcohols, aldehydes, ketones, and ethers (noncyclic) in aqueous solutions involving single solute systems and porous cellulose acetate membranes are discussed. The least-squares and multiple-regression analyses of solute transport parameter data show that the separation of aldehydes, just as that of alcohols, is predominantly a function of Σσ^*, and that of ethers is predominantly a function of ΣE_s, whereas that of ketones is best represented as a function of both Σσ^* and ΣE_s. The results also indicate that even where water is preferentially sorbed at the membrane solution interface, solute separation in reverse osmosis is affected by the nonpolar character of the solute molecule. A general expression for solute transport parameter in reverse osmosis is presented for further study.     

Reverse osmosis separation of phenols in aqueous solutions using porous cellulose acetate membranes

Reverse osmosis separations of phenol (9.4 to 108 ppm), p-cresol (108 ppm), and p-chlorophenol (129 ppm) were studied using Loeb-Sourirajan-type porous cellulose acetate membranes, and single-solute aqueous feed solutions at 500 psig and the indicated solute concentrations. It was found that, by dissociating the solute by changing the pH of the feed solution, all the above phenols could be separated by reverse osmosis. Solute separation increased with increase in the degree of dissociation of the solute in the feed solution; and, by the appropriate choice of pore size on the membrane surface, separations of phenol approaching the degree of dissociation of phenol in the feed solution could be obtained under the operating conditions used. Similar experiments using aniline (93 ppm) as the solute showed that dissociation of solute molecules in the feed solution could be a technique generally applicable for the reverse osmosis separation of nonionic solutes in aqueous solution. The effects of operating pressure in the range 250 to 1500 psig and pore size on the membrane surface on the separation of un-ionized phenol and p-chlorophenol showed that, with respect to single-solute aqueous feed solutions of phenols, the component whose relative acidity was greater was preferentially sorbed at the cellulose acetate membrane—aqueous solution interface, and the solute concentration in the membrane-permeated product solution was a function of the extent and mobility of each of the sorbed species.     

Cellulose triacetate membranes for seawater desalination

Experimental data on reverse osmosis using a sodium chloride solution by cellulose triacetate membranes are presented. The investigation involved studies on the composition of membrane casting solutions and their effects on the performance. A higher polymer concentration (11–13%) is found suitable for production of a uniform and highly salt rejecting membrane. Salt rejection of 99.0% and 4–5 GFD product water flux were obtained at 1000 psi operating pressure using 30,000 ppm TDS seawater in the initial experiments.     

Composite melamine-formaldehyde-furfuralcohol copolymerization membrane for reverse osmosis

The preparation and performance of the new composite reverse osmosis membrane were investigated. The ultrathin semipermeable barrier of the composite melamine-formaldehyde-furfuralcohol copolymerization membrane for reverse osmosis is formed on the porous surface of polysulfone support membrane by copolymerization between melamine-formaldehyde prepolymer and furfuralcohol under sulfuric acid catalyst. In the condition of operation pressure 20 kg/cm² and concentrated water flux 20 L/h, the membrane has 95% rejection and 0.3 m³/m².d flux for 1500 ppm aqueous sodium chloride. The factors affecting the reverse osmosis performance of the composite membrane, such as amount of the prepolymer and catalyst, the temperature of the polymerization and the properties of additives etc, were investigated.     

膜集成技术处理氯化法钛白后处理废水的研究

氯化法钛白无机包膜处理工序会产生大量中性废水,其中包含少量钛白粉和水溶性盐,现阶段企业多以外排为主。采用膜集成（陶瓷膜+反渗透膜+纳滤膜）技术对氯化法钛白后处理废水的处理进行研究。将氯化法钛白后处理废水用陶瓷膜过滤,分离回收二氧化钛;将陶瓷膜清液用反渗透膜浓缩,清水回收利用;将反渗透浓液用纳滤膜分离硫酸钠和氯化钠。结果表明：利用陶瓷膜处理氯化法钛白后处理废水,平均通量为650 L/（m ²·h）,浓液中钛白粉质量浓度达到90 g/L以上,清液中钛白粉质量浓度低于0.001 g/L;使用反渗透膜截留清液中的硫酸钠和氯化钠,硫酸钠和氯化钠的截留率为99.5%,浓水中的盐质量分数达到4%以上;浓水中的硫酸钠和氯化钠通过纳滤膜分离,纳滤膜对硫酸钠的截留率为97%,硫酸钠质量分数达到14%以上。     

Effect of Cyclic Changes in Temperature and Pressure on Permeation Properties of Composite Polyamide Seawater Reverse Osmosis Membranes

The effects of cyclic changes in feed water temperature and pressure on permeate flux, solute rejection, and compaction in spiral wound composite polyamide seawater reverse osmosis membranes were examined with pure water and 4% NaCl solutions. A membrane permeability hysteresis or memory effect due to the up and down temperature and pressure sequences was only seen with the saline water studies. However, the observed changes appeared to be reversible and were consistent with the Spiegler-Kedem/ Film Theory and the Kimura-Sourirajan Analysis/ Film Theory models. The overall results suggest that the net effect on permeance and solute rejection is the consequence of several interactions with feed/operating temperatures affecting membrane porosity and water/solute cluster size, and transmembrane pressure influencing membrane compaction.     

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