脂肪族及杂环分子结构和纳滤膜特性对截留率的影响规律

选择20种脂肪族及杂环化合物作为模型污染物,分别测定了三种不同纳滤膜对脂肪族及杂环化合物的截留率.结果表明,脂肪族及杂环化合物的截留率受到分子的分枝结构、环状结构、酸性和膜特性的影响:对于同分异构体,分枝结构愈多,截留率愈高;环状有机物与分子量相近的直链有机物相比,截留率明显偏高;脂肪酸的截留率高于绝大多数醇类、醚类和酮类等不离解的化合物;孔径小、荷电量大的纳滤膜截留率更高.通过基于遗传算法结合偏最小二乘回归法(GA-PLS)建立了纳滤膜对脂肪族及杂环化合物截留率的定量构效关系模型,通过分析回归方程,可以看出膜与脂肪族及杂环化合物之间的电性作用并不是影响截留率的主要因素,而分子形状和大小对截留率的影响很显著.     

对位芳香族聚酰胺复合纳滤膜制备及高温纳滤性能

本文以对位芳香族聚酰胺(PPTA)超滤膜为基膜,无水哌嗪(PIP)与1,3,5-苯三甲酰氯(TMC)分别作为水相单体和油相单体,采用界面聚合法制得高通量耐热PPTA/PA复合纳滤膜.研究了反应条件对PPTA/PA复合纳滤膜高温纳滤性能影响,观察了复合纳滤膜表面形貌与致密层结构,考察了渗透通量、耐热性以及抗污染等性能.结果表明,当PIP浓度为15%wt,TMC浓度为2.5%wt,热处理温度和时间分别为60℃和8 min时,所得PPTA/PA复合纳滤膜对不同染料分子截留率可达95%以上,对二价盐截留率可达90%以上.在高温条件下,所得PPTA/PA复合纳滤膜表现出优良的染料脱盐性能,在刚果红染料与Na₂SO₄截留率保持在99%的同时,渗透通量可达50 L·m^-2·h^-1·MPa^-1以上.     

4-氨基安替比林比色法测定水中微量芳胺的研究

在六次甲基胺-盐酸缓冲体中,邻、对位未被全部取代的各种芳胺均可同4-氨基安替比林和过硫酸铵反应,生成紫红色化合物。用3cm比色糟在波长530nm测定吸光度,可测定0.15—1.5ppm的对位无取代基的芳胺。对位被取代,但邻位未全部被取代的芳胺的检测范围是10—100PPm。本方法的回收率为97％,变异系数为±1.6％。还原性物质、酚类化合物等对本方法有干扰。     

取代苯甲酸在江水中的生物降解性及QSBR研究

以松花江水作为微生物源，采用摇瓶法研究了取代苯甲酸的生物降解动力学。高效液相色谱测定了取代苯甲酸浓度随时间变化曲线，得到一级生物降解动力学常数K和降解半衰期t1/2。取代基对降解速度的影响依次为：硝基＞氯代＞氨基；对于同一种取代基，邻位＞对位≈间位。逐步回归分析表明，表征位阻效应的参数MW与表征电性效应的参数pKa相结合，能够较好地拟合取代苯甲酸的生物降解速率常数。同时考察了pH变化对苯甲酸生物降解的影响。     

聚醚砜超滤膜的研制

以聚醚砜为原料，二甲基乙酰胺为溶剂，研究了铸膜液组成和若干因素对膜性能的影响。选择适当的膜液组成和制备条件，可制得截留分子量分别为２０００，６０００，１００００的超滤膜，用该膜对α－干扰素进行分离。截留率均可达到９９％以上。     

聚砜—磺化聚砜共混超滤膜的研究

本文以聚砜和磺化聚砜为原料，制备了低截留分子量的共混超滤膜，此种膜具有适中透水量，对分子量３０００的ＰＥＧ截留率在９０％以上，对膜的制备参数，如聚合物浓度，不同溶剂，不同添加剂和凝胶介质对膜性能的影响进行了较详细的的研究。     

不同取代基对乙酰丙酮在水溶液中的光化学行为影响

乙酰丙酮(AA)作为光活化剂在水中可高效转化染料、硝酸盐、亚砷酸等污染物,但光反应发生的具体机理尚不清楚.本文选取AA及AA中心碳上的氢被不同基团取代的4种衍生物(AAs)为研究对象,初步探究AAs在水溶液中的光化学性质,包括:未经光照时和光照过程中的紫外吸收光谱,并选择3种不同类型的染料进行光反应实验,从取代基效应的角度出发比较不同取代基的存在对自身性质及其光化学活性的影响.实验结果表明,取代基的存在对物质在水中的稳定性、自身的紫外吸收光谱以及转化染料的光化学活性产生影响.吸电子基的存在对AA光化学转化染料的活性无明显的影响.推电子基的存在则会促进AAs的自身光降解,取代基的推电子能力越强,在水中越不稳定,转化染料的光活性越高.研究结果为选取合适的AAs用于光化学脱色提供了理论依据.     

聚吡咯/凯夫拉中空纤维复合纳滤膜的制备及其染料脱盐性能

以同质增强型凯夫拉(PPTA)中空纤维膜为基膜，吡咯(Py)和三氯化铁(FeCl₃)分别为反应单体和活化剂，采用化学气相沉积法制备了结构稳定、可控的聚吡咯(PPy)/PPTA中空纤维复合纳滤膜.采用FTIR、SEM、AFM、接触角测定仪以及固体表面Zeta电位仪对基膜和PPy/PPTA中空纤维复合纳滤膜的微观形貌、化学组成、亲水性、表面荷电性进行了表征.结果表明，经PPy气相沉积后，PPy/PPTA中空纤维复合纳滤膜表面形成具有图灵结构特征的分离层，并均匀覆盖膜表面.在0.6 MPa室温下，PPy/PPTA中空纤维复合纳滤膜具有较高的的脱盐性能，其顺序为R_Na2SO4 (93.59%)>RMgSO4(91.58%)>R_CaCl2(83.45%)> R_NaCl (54.04%)，同时对带负电染料表现出较高的截留率(?98.82%).当运行温度从25℃升高到90℃时，PPy/PPTA中空纤维复合纳滤膜的水通量较明显增加，而截留率几乎保持稳定，表现出优异的热稳定性，为纳滤膜在更高运行温度...     

VSMP预测两种不同电子受体对酚类化合物厌氧降解的影响

以原子类型电拓扑状态指数(ETSI)表征19个酚类化合物的分子结构,应用基于预测的变量选择与模型化(VSMP)方法,建立了酚类化合物在产甲烷和脱氮两种厌氧环境下的降解效果与分子结构的定量相关模型.结果表明:在产甲烷环境中,影响酚类化合物厌氧降解的主要结构因素是由4个ETSI描述子对应的子结构碎片,即aCHa,aaC-,-NH2和-OH,其中子结构aCHa和aaC-与酚环母体骨架密切相关,而-NH2和-OH反映取代基的变化.通过多元线性回归法建立的产甲烷条件下酚类化合物的结构-厌氧降解性相关模型(QSBR)发现,其模型估计相关系数,r=0.9173,LOO检验相关系数q=0.8461;反硝化条件下,影响酚类化合物厌氧降解的主要结构因素是=(C),aaC-,=O和-Cl,其中子结构aaC-与酚环母体骨架相关,而=(C),=O和-Cl反映支链或取代基的变化.其模型估计相关系数r=0.8953,LOO检验相关系数q=0.8488.以上结果均表明模型具有良好的估计能力与稳定性,进而从建模的角度证明了厌氧环境中,电子受体的选择影响酚类化合物的降解效果和机理.     

酚类化合物麻醉毒性的CoFMA研究

通过比较分子力场分析方法(CoMFA)建立酚类化合物对梨形四膜虫极性麻醉毒性(pT)的三维定量结构-活性相关(3D-QSAR)模型.基于训练集41个化合物建立了预测模型,10个化合物作为验证集(含模板分子).训练集的CoMFA模型显示立体场、静电场对麻醉毒性贡献依次为53.9％和46.1％.其交叉验证相关系数(R2cv)为0.735,非交叉验证相关系数(R2)为0.971.对训练集、测试集中的化合物麻醉毒性进行预测,显示出较强的稳定性和良好的预测能力.根据CoMFA模型的立体场和静电场三维等势线图可知,在羟基的间、对位上引入小体积基团,以及邻、对位有负电性基团,有利于提高酚类衍生物的麻醉毒性.基于此,设计了7种具有更高麻醉毒性的酚类化合物,有待生物医学实验验证.     

Role of membrane and compound properties in affecting the rejection of pharmaceuticals by different RO/NF membranes

This study was conducted to assess the merits and limitations of various high-pressure membranes, tight nanofiltration (NF) membranes in particular, for the removal of trace organic compounds (TrOCs). The performance of a low-pressure reverse osmosis (LPRO) membrane (ESPA1), a tight NF membrane (NF90) and two loose NF membranes (HL and NF270) was compared for the rejection of 23 different pharmaceuticals (PhACs). Efforts were also devoted to understand the effect of adsorption on the rejection performance of each membrane. Difference in hydrogen bond formation potential (HFP) was taken into consideration. Results showed that NF90 performed similarly to ESPA1 with mean rejection higher than 95%. NF270 outperformed HL in terms of both water permeability and PhAC rejection higher than 90%. Electrostatic effects were more significant in PhAC rejection by loose NF membranes than tight NF and LPRO membranes. The adverse effect of adsorption on rejection by HL and ESPA1 was more substantial than NF270 and NF90, which could not be simply explained by the difference in membrane surface hydrophobicity, selective layer thickness or pore size. The HL membrane had a lower rejection of PhACs of higher hydrophobicity (log D>0) and higher HFP (>0.02). Nevertheless, the effects of PhAC hydrophobicity and HFP on rejection by ESPA1 could not be discerned. Poor rejection of certain PhACs could generally be explained by aspects of steric hindrance, electrostatic interactions and adsorption. High-pressure membranes like NF90 and NF270 have a high promise in TrOC removal from contaminated water.

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Pilot study for the treatment of sodium and fluoride-contaminated groundwater by using high-pressure membrane systems

High-pressure membrane process is one of the cost-effective technologies for the treatment of groundwater containing excessive dissolved solids. This paper reports a pilot study in treating a typical groundwater in Huaibei Plain containing excessive sodium, sulfate and fluoride ions. Three membrane systems were set up and two brands of reverse osmosis (RO), four low-pressure RO (LPRO) and one tight nanofiltration (NF) membranes were tested under this pilot study. An apparent recovery rate at about 75% was adopted. Cartridge filtration, in combination with dosing antiscalent, was not sufficient to reduce the fouling potential of the raw water. All RO and LPRO systems (except for the two severely affected by membrane fouling) demonstrated similar rejection ratios of the conductivity (~98.5%), sodium (~98.5%) and fluoride (~99%). Membrane fouling substantially reduced the rejection performance of the fouled membranes. The tight NF membrane also had a good rejection on conductivity (95%), sodium (94%) and fluoride (95%). All membranes rejected sulfate ion almost completely (more than 99%). The electricity consumptions for the RO, LPRO and NF systems were 1.74, 1.10 and 0.72 kWh?m^-3 treated water, respectively. The estimated treatment costs by using typical RO, LPRO and tight NF membrane systems were 1.21, 0.98 and 0.96 CNY?m^-3 finished water, respectively. A treatment process consisting of either LPRO or tight NF facilities following multi-media filtration was suggested.     

Role of water chemistry on estrone removal by nanofiltration with the presence of hydrophobic acids

Hydrophobic acid organic matter (HpoA) extracted from treated effluent has been known to improve the rejection of steroid hormone estrone by reverse osmosis (RO) and nanofiltration (NF) membranes. In this study, the effects of solution chemistry (solution pH and ionic strength) on the estrone rejection by NF membrane with the presence of HpoA were systematically investigated. Crossflow nanofiltration experiments show that the presence of HpoA significantly improved estrone rejection at all pH and ionic strength levels investigated. It is consistently shown that the “enhancement effect” of HpoA on estrone rejection at neutral and alkaline pH is attributed to the binding of estrone by HpoA macromolecules via hydrogen bonding between phenolic functional groups in feed solutions, which leads to an increase in molecular weight and appearance of negative charge. The membrane exhibited the best performance in terms of estrone rejection at pH 10.4 (compared to pH 4 and pH 7) as a result of strengthening the electrostatic repulsion between estrone and membrane with the presence of HpoA. At neutral pH level, the ability of HpoA macromolecules to promote estrone rejection became stronger with increasing ionic strength due to their more extended conformation, which created more chances for the association between estrone and HpoA. The important conclusion of this study is that increasing solution pH and salinity can greatly intensify the “enhancement effect” of HpoA. These results can be important for NF application in direct/indirect potable water reuse.     

Influence of pore size and membrane surface properties on arsenic removal by nanofiltration membranes

Four NF membranes were compared regarding arsenate rejection and their properties. Rejection of arsenate had no relationship with membrane pore size. A more negative surface charge was favorable for arsenate rejection at neutral pH. A severe membrane fouling could lead to a great reduction of arsenic rejection. Nanofiltration (NF) has a great potential in removing arsenate from contaminated water. The performance including arsenate rejection, water permeability and resistance to fouling could however differ substantially among NF membranes. This study was conducted to investigate the influence of membrane pore size and surface properties on these aspects of membrane performance. Four fully-aromatic NF membranes with different physicochemical properties were adopted for this study. The results showed that surface charge, hydrophobicity, roughness and pore size could affect water permeability and/or arsenate rejection considerably. A more negative surface charge was desirable to enhance arsenate rejection rates. NF90 and a non-commercialized membrane (M#1) demonstrated the best performance in terms of arsenate rejection and water permeability. The M#1 membrane showed less membrane fouling than NF90 when used for filtration of real arsenic-containing groundwater. This was mainly due to its distinct chemical composition and surface properties. A severe membrane fouling could lead to a substantial reduction of arsenic rejection. The M#1 membrane showed the best performance, which indicated that membrane modification could indeed enhance the overall membrane performance for water treatment.     

Characterization and performance of nanofiltration membranes

The availability of clean water has become a critical problems facing the society due to pollution by human activities. Most regions in the world have high demands for clean water. Supplies for freshwater are under pressure. Water reuse is a potential solution for clean water scarcity. A pressure-driven membrane process such as nanofiltration has become the main component of advanced water reuse and desalination systems. High rejection and water permeability of solutes are the major characteristics that make nanofiltration membranes economically feasible for water purification. Recent advances include the prediction of membrane performances under different operating conditions. Here, we review the characterization of nanofiltration membranes by methods such as scanning electron microscopy, thermal gravimetric analysis, attenuated total reflection Fourier transform infrared spectroscopy, and atomic force microscopy. Advances show that the solute rejection and permeation performance of nanofiltration membranes are controlled by the composition of the casting solution of the active layer, cross-linking agent concentration, preparation method, and operating conditions. The solute rejection depends strongly on the solute type, which includes charge valency, diffusion coefficient, and hydration energy. We also review the analysis of the surface roughness, the nodule size, and the pore size of nanofiltration membranes. We also present a new concept for membrane characterization by quantitative analysis of phase images to elucidate the macro-molecular packing at the membrane surface.     

Using loose nanofiltration membrane for lake water treatment: A pilot study

• A pilot study was conducted for drinking water treatment using loose NF membranes. • The membranes had very high rejection of NOM and medium rejection of Ca²⁺/Mg²⁺. • Organic fouling was dominant and contribution of inorganic fouling was substantial. • Both organic and inorganic fouling had spatial non-uniformity on membrane surface. • Applying EDTA at basic conditions was effective in removing membrane fouling. Nanofiltration (NF) using loose membranes has a high application potential for advanced treatment of drinking water by selectively removing contaminants from the water, while membrane fouling remains one of the biggest problems of the process. This paper reported a seven-month pilot study of using a loose NF membrane to treat a sand filtration effluent which had a relatively high turbidity (~0.4 NTU) and high concentrations of organic matter (up to 5 mg/L as TOC), hardness and sulfate. Results showed that the membrane demonstrated a high rejection of TOC (by>90%) and a moderately high rejection of two pesticides (54%–82%) while a moderate rejection of both calcium and magnesium (~45%) and a low rejection of total dissolved solids (~27%). The membrane elements suffered from severe membrane fouling, with the membrane permeance decreased by 70% after 85 days operation. The membrane fouling was dominated by organic fouling, while biological fouling was moderate. Inorganic fouling was mainly caused by deposition of aluminum-bearing substances. Though inorganic foulants were minor contents on membrane, their contribution to overall membrane fouling was substantial. Membrane fouling was not uniform on membrane. While contents of organic and inorganic foulants were the highest at the inlet and outlet region, respectively, the severity of membrane fouling increased from the inlet to the outlet region of membrane element with a difference higher than 30%. While alkaline cleaning was not effective in removing the membrane foulants, the use of ethylenediamine tetraacetate (EDTA) at alkaline conditions could effectively restore the membrane permeance.     

Arsenic (V) removal from groundwater by GE-HL nanofiltration membrane: effects of arsenic concentration, pH, and co-existing ions

A laboratory-scale investigation was performed to study arsenic (As (V)) removal by negatively charged GE-HL nanofiltration (NF) membrane in simulated drinking water. Effects of As (V) concentration (0–200 μg·L^?1), pH, and co-ions and counter-ions were investigated. The NF membrane presented good stability, and the rejection rates exceeded 90%. The rejection rates of As (V) decreased with the increase of As (V) concentration, while it increased with the increase of pH (reached 96% at pH 6.75). Moreover, a negative relationship was observed between the co-existing ions of Cl^?, Na⁺, SO ₄ ^2? , and Ca²⁺ and the removal of As (V), in which bivalent ions presented more significant effects than monovalent ions.     

Tuning the primary selective nanochannels of MOF thin-film nanocomposite nanofiltration membranes for efficient removal of hydrophobic endocrine disrupting compounds

• PA layer properties tune the primary nanochannels in MIL-101(Cr) TFN NF membranes. • The dense PA layer induced transition of primary nanochannels of TFN NF membranes. • Nanochannels around MOF contributed to the improved flux with a loose PA structure. • Nanochannels in MOFs dominated the separation performance with a dense PA structure. Metal organic framework (MOF) incorporated thin-film nanocomposite (TFN) membranes have the potential to enhance the removal of endocrine disrupting compounds (EDCs). In MOF-TFN membranes, water transport nanochannels include (i) pores of polyamide layer, (ii) pores in MOFs and (iii) channels around MOFs (polyamide-MOF interface). However, information on how to tune the nanochannels to enhance EDCs rejection is scarce, impeding the refinement of TFN membranes toward efficient removal of EDCs. In this study, by changing the polyamide properties, the water transport nanochannels could be confined primarily in pores of MOFs when the polyamide layer became dense. Interestingly, the improved rejection of EDCs was dependent on the water transport channels of the TFN membrane. At low monomer concentration (i.e., loose polyamide structure), the hydrophilic nanochannels of MIL-101(Cr) in the polyamide layer could not dominate the membrane separation performance, and hence the extent of improvement in EDCs rejection was relatively low. In contrast, at high monomer concentration (i.e., dense polyamide structure), the hydrophilic nanochannels of MIL-101(Cr) were responsible for the selective removal of hydrophobic EDCs, demonstrating that the manipulation of water transport nanochannels in the TFN membrane could successfully overcome the permeability and EDCs rejection trade-off. Our results highlight the potential of tuning primary selective nanochannels of MOF-TFN membranes for the efficient removal of EDCs.     

Control strategies for disinfection byproducts by ion exchange resin,nanofiltration and their sequential combination

● Effects of AER adsorption and NF on DBP precursors, DBPs, and TOX were examined. ● A treatment approach of resin adsorption followed by nanofiltration was developed. ● Both DOC and Br⁻ could be effectively removed by the sequential approach. ● DBPs, TOX, and cytotoxicity were significantly reduced by the sequential approach. Disinfection byproducts (DBPs) are emerging pollutants in drinking water with high health risks. Precursor reduction before disinfection is an effective strategy to control the formation of DBPs. In this study, three types of anion exchange resins (AERs) and two types of nanofiltration (NF) membranes were tested for their control effects on DBP precursors, DBPs, and total organic halogen (TOX). The results showed that, for AER adsorption, the removal efficiencies of DBP precursors, DBPs, and TOX increased with the increase of resin dose, and the strong basic macroporous anion exchange resin (M500MB) had the highest removal efficiencies. For NF, the highest removal efficiencies were achieved at an operating pressure of 4 bar, and the membrane (NF90) with a smaller molecular weight cut-off, had a better control efficiency. However, AER adsorption was inefficient in removing dissolved organic carbon (DOC); NF was inefficient in removing Br⁻ resulting in insufficient control of Br-DBPs. Accordingly, a sequential approach of AER (M500MB) adsorption followed by NF (NF90) was developed to enhance the control efficiency of DBPs. Compared with single AER adsorption and single NF, the sequential approach further increased the removal efficiencies of DOC by 19.4%–101.9%, coupled with the high Br⁻ removal efficiency of 92%, and thus improved the reduction of cyclic DBPs and TOX by 3.5%–4.9%, and 2.4%–8.4%, respectively; the sequential approach also reduced the cytotoxicity of the water sample by 66.4%.