Membrane retention of herbicides from single and multi-solute media: The effect of ionic environment

Results are reported for a systematic study on retention of three selected herbicides, in single solute or multi-solute feed-waters, by three commercial NF/ULPRO membranes, using stirred cells in the dead-end filtration mode. The effect of ionic environment on the retention of herbicides is also examined by controlling sodium and calcium concentration. The results are interpreted on the basis of the characteristic properties of herbicides and membranes used. In general, size exclusion seems to be the dominant mechanism for retention by NF/ULPRO membranes, especially in the case of membranes with a pore size similar to that of herbicide molecules. Tight and thus high-desalting membranes exhibit the best retention performance. On the other hand, the retention efficiency of relatively loose nanofiltration membranes also appears to be significantly influenced by adsorption of herbicides on the membrane. Filtration of feed-waters with more than one herbicide present results in different retentions (usually reduced) compared to those determined in single compound solutions. This is attributed to the competition between the herbicides for adsorption sites, which is directly related to membrane surface properties. Filtration experiments with saline solutions, mimicking real conditions (e.g. surface water), reveal the significant effect of divalent cations on herbicide retention, which, depending on the membrane type, can be either positive or negative. However, the effect of ionic strength, due to monovalent ions (NaCl), on herbicides retention appears to be rather minor.     

Multilayer polyelectrolyte films as nanofiltration membranes for separating monovalent and divalent cations

Alternating adsorption of polyanions and polycations on porous supports provides a convenient way to prepare ion-selective nanofiltration membranes. This work examines optimization of ultrathin, multilayer polyelectrolyte films for monovalent/divalent cation separations relevant to water softening. Membranes composed of five bilayers of poly(styrene sulfonate)/poly(allylamine hydrochloride) (PSS/PAH) on porous alumina supports allow a solution flux of 0.85 m³/(m² day) at 4.8 bar, and exhibit 95% rejection of MgCl₂ along with a Na⁺/Mg²⁺ selectivity of 22. Similar results were obtained in Na⁺/Ca²⁺ separations. PSS/poly(diallyl-dimethylammonium chloride) (PDADMAC) films permit higher fluxes than PSS/PAH systems due to the higher swelling of films containing PDADMAC, but the Mg²⁺ rejection by PSS/PDADMAC membranes is less than 45%. However, capping PSS/PDADMAC films with a bilayer of PSS/PAH yields Mg²⁺ rejections and Na⁺/Mg²⁺ selectivities that are typical of pure PSS/PAH membranes. Separation performance can be optimized through control over deposition conditions (pH and supporting electrolyte concentration) and the charge of the outer layer since Donnan exclusion is a major factor in monovalent/divalent cation selectivity. Streaming potential measurements demonstrate that the magnitude of positive surface charge increases with increasing concentrations of Mg²⁺ in solution or when the outer polycation layer is deposited from a solution of high ionic strength.     

Nanoporous asymmetric polyaniline films for filtration of organic solvents

A new family of functional materials is reported for organic solvent nanofiltration, with excellent chemical stability and high retention of solute molecules. Integrally skinned asymmetric polyaniline (PANI) membranes were fabricated from concentrated solutions of doped PANI by phase inversion. Doped PANI solutions were prepared by adding organic acids directly to PANI dissolved in a mixture of NMP and 4-methyl piperidine before casting. Among the organic acids investigated, maleic acid, phthalic acid, sulfosalicylic acid and camphorsulfonic acid were able to dope PANI without causing gelation. These acids acted as soft templates, creating nanoporosity in the thin skin layer of the asymmetric PANI film. Their removal by alkaline extraction created membranes through which small solvent molecules can pass. After extracting the organic acids, the membranes were thermally crosslinked which conferred excellent solvent stability. These membranes had a molecular weight cut-off (MWCO) in the range of 150–250 g mol⁻¹ in methanol, making them the tightest OSN membranes reported to date. It was found that an increase in crosslinking temperature or time led to a decrease in solvent flux. PANI membranes were found to be resistant to a variety of organic solvents such as ethyl acetate, acetonitrile and acetone. These remarkable membranes have the potential to be used in OSN operations at high temperatures (up to 150 °C), and gave increasing fluxes with increasing temperature while maintaining a high solute rejection.     

静电位阻模型在纳滤膜跨膜电位解析中的应用

采用静电位阻模型对纳滤膜的跨膜电位进行了理论解析, 考察了溶液体积通量密度、原料液浓度、阴阳离子扩散系数比、膜孔半径和膜体积电荷密度对KCl(1-1型电解质)和MgCl2(2-1型电解质)中的纳滤膜跨膜电位的影响. 研究结果表明, 随着通量密度的增大, KCl和MgCl₂的跨膜电位线性程度增强; 两种电解质的跨膜电位均随着原料液浓度和膜孔半径的增大而下降; 在不同的考察范围内, 阴阳离子扩散系数比对1-1型和2-1型电解质的跨膜电位的影响差别较大; KCl的跨膜电位随着膜体积电荷密度的变化关于零点呈现出对称性, 而MgCl₂的跨膜电位零点则出现在膜体积电荷密度为负的条件下.     

Nano/subnano-tuning of porous ceramic membranes for molecular separation

In sol–gel processing, porous ceramic membranes can be prepared by sol-coating porous substrates and drying for gelling, followed by a firing process. Ceramic membranes prepared by sol–gel processing can be categorized into amorphous materials such as silica, and crystalline materials such as alumina and titania. Amorphous silica networks, which can be prepared by the polymeric sol route, have ultra-microporous pores that allow small molecules such as helium and hydrogen to permeate. On the other hand, crystalline materials, which are mostly prepared by the colloidal sol route, have nano-sized pores in the range of one to several nanometers. In this article, sol–gel derived SiO₂ and TiO₂ membranes with controlled pore sizes in the range of sub-nano to nanometers will be reviewed with respect to membrane preparation and to their application in the separation of the gas and liquid phases. Ceramic membranes with high performance can be obtained by precise control of membrane structures (pore size, pore size distribution, thickness, pore shape, etc.) and membrane materials (SiO₂, TiO₂, composite oxide, hybrid materials, etc.). Nano/subnano-tuning of porous ceramic membranes is quite important for the improvement of membrane permeability and selectivity.     

用流动电位法表征纳滤膜的结构及性能

利用测量流动电位的方法考察了纳滤膜的表面电学性能对纳滤膜的截留性能的影响.首先,采用不同功能层材料制备了复合纳滤(NF)膜,考察功能层的交联时间、单体结构等对表面电性能的影响,研究纳滤膜对不同无机盐的选择截留性能与表面电性能的关系.通过流动电位法测定纳滤膜的表面电学参数,如流动电位(ΔE)、zeta电位(ζ)和表面电荷密度(σd).实验表明,这些电学参数的变化与功能层交联时间和纳滤膜截留率的变化一致,在交联时间为45 s时,3种电学参数的绝对值均最大,而纳滤膜对无机盐的截留率也最大.复合纳滤膜zeta电位的绝对值(|ζ|)按照Na2SO4>MgSO4>MgCl2变化,同截留率的变化相同.带侧基单体交联后得到的纳滤膜的表面电性能参数的绝对值小于不带侧基单体的.因此,流动电位法可用于研究复合纳滤膜的截留机理和功能层结构.     

纳滤膜的制备技术及进展

介绍了纳滤膜的几种主要制备方法,概述了近年来国内外在纳滤膜材质、制备技术及制膜的性能等方面的进展情况。     

Effect of colloids on salt transport in crossflow nanofiltration

The role of colloid deposition on the performance of a salt-rejecting NF membrane was evaluated by modeling salt transport using a two-layer transport model, which quantified the relative contributions of advection and diffusion in the cake and the membrane layers, and the effects of flux on the membrane sieving coefficient. The model was able to accurately describe how the measured permeate concentration, rejection, osmotic pressure, and flux decline varied with time. The two-layer model confirmed that the Peclet number in the cake layer was about an order of magnitude higher than that in the membrane layer, leading to significant concentration polarization at the membrane surface, as shown by others. However, the cake layer also increased overall resistance, which resulted in flux decline during constant pressure operation. Flux decline caused an increase in the actual sieving coefficient, leading to higher solute flux, lower observed rejection, and thus lower the bulk concentration. These coupled phenomena tended to mitigate the increase in concentration polarization caused by the cake. Therefore, as predicted by the model and verified by experiment, the osmotic pressure does not increase monotonically as the cake grows, and in fact can decrease when the cake layer is thick and the flux decline is significant. In our experimental system, the pressure drop across the cake layer, which was proportional to the cake thickness, was significant under the conditions studied. The effects of cake-enhanced osmotic pressure analyzed here are lower than those observed in previous studies, possibly because the transport model employed explicitly accounts for the effect of flux decline due to cake growth on the membrane sieving coefficient, and possibly because we used a somewhat different methodology to estimate cake porosity.