亲水化改性PVDF超滤膜的抗污染特性研究

以不同通量的自制亲水化纳米SiO2改性PVDF超滤膜(PS)和聚乙烯醇改性PVDF超滤膜(PA),对城市污水二级出水(EfOM)和牛血清蛋白(BSA)水溶液进行了过滤试验,通过对比未添加改性剂的PVDF超滤膜,考察通量衰减率、膜污染阻力构成、通量恢复率等指标,分析水质与膜材料间的相互关系对超滤膜抗污染能力的影响.结果表明,在BSA料液中,3种通量下,低通量的膜抗污染能力好于高通量膜.20 min内PA膜表现出最低的膜通量衰减,而P膜在过滤初期通量就急剧下降.在EfOM料液中,各通量下,P膜通量衰减严重且产生了不可逆的堵孔阻力,亲水化改性后膜通量衰减率降低,稳态通量高,膜污染阻力主要来自于浓差极化和滤饼层阻力,其中PS膜通量下降率最低,而PA膜清洗后通量易恢复.     

进水水质对纳滤膜苦咸水软化的分离性能

针对黄淮地区苦咸水,构建了小试级别的纳滤膜法软化系统,并开展了包括pH、总溶解固体含盐量(TDS)和总有机碳(TOC)等进水水质对DL、DK型纳滤膜的软化分离实验。结果表明,pH为3~10、TDS为1317~5926 mg·L~(-1)和TOC为2.72~12.24 mg·L~(-1)的进水条件下,DL和DK纳滤膜比通量随pH的增加分别呈先上升后下降和缓慢下降的趋势,随进水TDS和TOC的增加呈整体下降趋势,而纳滤膜对硬度离子(Mg~(2+)和Ca~(2+))的截留率均呈明显的上升趋势。DL膜运行至267 h时,膜比通量下降幅度超过10%,进行化学清洗,酸洗后膜比通量恢复率达到85.05%,酸洗加碱洗后该值高达97.2%,结合扫描电子显微镜和原子力显微镜表征结果,可知化学清洗对膜面污染有较好的去除效果。     

纳滤处理燃机电厂清洗废液及膜污染研究

采用NF 90、NF 270、NF 2001、NF 5001 4种纳滤膜对燃机电厂压气机清洗废液进行处理，考察操作压力、初始COD_Cr、温度和pH等因素对纳滤膜性能的影响。结果表明，操作压力为0.7 MPa时，4种纳滤膜对废液中低分子质量的难生物降解溶解性有机物截留效果均较好，产水水质满足纳管标准(COD_Cr≤500 mg/L)。操作压力在一定范围内增加，4种纳滤膜膜通量和COD_Cr截留率呈不同幅度的上升趋势，压力由0.6 MPa增加至1.0 MPa时，NF2001产水COD_Cr降幅最大(70.73%),NF 5001膜通量增幅最大(28.14%)。初始COD_Cr增加使膜通量下降而对COD_Cr的截留效果提高，且随着温度由20℃升高至40℃，及pH由3升至10，各膜通量均有一定程度的提高。此外，较低温度(20℃)下NF 270膜通量较大且不可逆污染值较小，因而在处理压气机清洗废液中具有良好的应用前景。     

羧基功能化石墨烯/聚偏氟乙烯混合基质超滤膜的制备及性能

以石墨烯/聚偏氟乙烯(PVDF)杂化超滤膜为研究对象,针对氧化石墨烯(GO)与PVDF相容性差且分散不均存在界面缺陷的问题。从GO表面官能团设计出发,采用羧基化方法对GO进行功能化处理得到羧基化氧化石墨烯(GO-COOH,GC)。通过浸没沉淀相转化技术制备了GO/PVDF和GC/PVDF混合基质超滤膜,对比探讨了两种超滤膜的性能(纯水通量、截留率、耐污染性能、机械性能及亲水性)。结果表明,当添加量为2.5wt%时,GC/PVDF超滤膜的纯水通量为GO/PVDF体系的1.5倍,接触角降低了13.9%,拉伸强度和断裂伸长率分别提高了1.3倍和1.1倍。GC/PVDF超滤膜的综合性能较好,膜的浓差极化阻力、可逆污染阻力、膜自身的阻力及过滤BSA溶液的阻力均较小,混合基质超滤膜的性能由GC的亲水性和相容性共同决定。     

一体式膜生物反应器膜污染现象及清洗试验研究

对新膜和在一体式膜生物反应器中运行而被污染的膜作扫描电镜对比,从微观角度解释膜污染现象。短期运行22d和长期运行210d的膜分别经冷水→热水→次氯酸钠→乙醇清洗,膜通量恢复到新膜的94.4%和70.3%;将另一长期运行210d的膜改变清洗程序为冷水→热水→次氯酸钠→硫酸,膜通量恢复到新膜的61.4%,说明不同的清洗程序清洗效果不同。将短期运行和长期运行的膜组件按Darcy定律过滤模型计算:二者运行后膜总阻力增大,短期运行22d和长期运行210d后,由于浓差极化和膜污染产生的阻力大约是膜自身阻力的4倍和11倍。     

多层羧甲基壳聚糖复合膜的制备及性能

以PES微滤膜为基膜,采用多层涂覆法制备了多层羧甲基壳聚糖(CMCS)复合膜,测定了复合膜对BSA溶液(1 g/L)的过滤性能及其因素的影响。实验结果表明,膜的浸涂层数显著影响膜的通量和对BSA的截留率,在压差为0.2 MPa、pH=5.5时,8层CMCS复合膜对BSA溶液的截留率达到90%,初始通量为54.8 L/(m~2·h)。与商业PS50超滤膜相比,制备的8层CMCS复合膜初始通量是PS50超滤膜的2.2倍,而PS50超滤膜对BSA的截留率为98%,大于8层CMCS复合膜的截留率。对比8层CMCS复合膜对BSA的初始和平均截留率表明,BSA在膜上的吸附能提高膜的截留率。     

进水水质对纳滤膜苦咸水软化的分离性能

针对黄淮地区苦咸水,构建了小试级别的纳滤膜法软化系统,并开展了包括pH、总溶解固体含盐量（TDS）和总有机碳（TOC）等进水水质对DL、DK型纳滤膜的软化分离实验。结果表明,pH为3~10、TDS为1317~5926 mg·L^-1和TOC为2.72~12.24 mg·L^-1的进水条件下,DL和DK纳滤膜比通量随pH的增加分别呈先上升后下降和缓慢下降的趋势,随进水TDS和TOC的增加呈整体下降趋势,而纳滤膜对硬度离子（Mg²⁺和Ca²⁺）的截留率均呈明显的上升趋势。DL膜运行至267 h时,膜比通量下降幅度超过10%,进行化学清洗,酸洗后膜比通量恢复率达到85.05%,酸洗加碱洗后该值高达97.2%,结合扫描电子显微镜和原子力显微镜表征结果,可知化学清洗对膜面污染有较好的去除效果。     

天然有机物和离子对纳滤膜过滤性能的影响研究

采用纳滤膜Desal 5 DK对天然有机物(NOM)和离子进行死端过滤实验,以考察进水组分对膜过滤性能的影响。结果表明,Desal 5 DK对NOM的截留率为60%~80%,由NOM引起的不可逆水通量降低占总水通量降低的70%。Desal 5 DK对水中Ca2+的截留率90%,而对Na+的截留率保持在20%~38%,离子与荷电纳滤膜之间的道南效应以及水合离子大小和扩散系数的不同引起二者截留率的差异,并导致了水通量衰减。     

天然有机质污染对纳滤膜去除水中邻苯二甲酸酯的影响

选用具有不同特性的2种纳滤膜NF90和NF270,采用错流试验研究了被天然有机质污染前后纳滤膜对水中邻苯二甲酸酯的去除效率和渗透通量。结果表明,NF90对邻苯二甲酸二甲酯(DMP)、邻苯二甲酸二乙酯(DEP)和邻苯二甲酸二丁酯(DBP)具有较高的截留率,分别为87.9%、95.3%和100%,且截留率随着有机物分子量的增大而增大;NF270对DMP、DEP和DBP的截留率分别为32.1%、50.4%和50%,较NF90的截留率低,且对分子量较大、较疏水的DBP未呈现较高的截留率。在进料液中添加海藻酸钠后,2种纳滤膜的渗透通量明显下降;污染后2种纳滤膜对DMP的截留率分别提高了5.9%和2.4%,对DEP的截留率略有下降,对DBP没有显著影响。改变离子强度(10 mmol/L到20 mmol/L)使NF270对DMP、DEP和DBP的截留率分别下降了2.4%、1.5%和1.5%,而NF90对3种邻苯二甲酸酯的截留率没有明显变化。     

纳滤膜在染料工业脱盐浓缩中的应用

对CA50(醋酸纤维素)纳滤膜的盐截留率和染料截留率进行了考察,并将CA50纳滤膜应用于染料工业脱盐浓缩,考察了膜污染现象,对综合效益进行了分析。结果表明,CA50纳滤膜的盐截留率较低,对染料则有很高的截留率：将CA50纳滤膜应用于黄染料工业生产中,使主体染料的纯度提高20％,对黑染料膜分离过程进行优化,当盐浓度保持在5％时能获得最佳的脱盐效果;膜分离蓝色染料一段时间后,会造成膜污染,引起膜污染的物质主要是油污、无机物、有机物和染料分子,通过适当的预处理和清洗可以保持膜通量和防止膜污染：采用膜分离工艺使染料工业在经济、环境和社会效益得到提高．     

淹没式加压MBR膜污染机理及治理措施

研究了加压MBR膜通量衰减规律,膜污染阻力的分布;尝试了空曝、水反冲洗、压缩空气反冲洗、物化清洗四种膜清洗方式的膜通量恢复．研究结果表明：加压MBR膜通量衰减迅速,运行17d后膜通量衰减83．5％;膜污染阻力主要由凝胶极化阻力Rp和内部污染阻力Rif构成。     

不同国产纳滤膜对饮用水中氟离子的去除影响研究

选用两种国产纳滤膜NF1和VNF2进行除氟的实验研究,考察了不同的原水pH、操作压力、进水F-浓度、温度以及腐殖酸的浓度对纳滤除氟截留率以及膜通量的影响。实验结果表明:VNF2膜的截留率高于NF1膜,而膜通量则低于NF1;同时两种膜的最佳操作条件为pH在6.5~7.0,温度在18~23℃,操作压力为0.4 MPa,进水氟离子浓度为4 mg/L;而腐殖酸主要通过静电斥力和氢键影响纳滤膜的截留率和膜通量,同时出水F-浓度满足生活饮用水卫生标准(GB5749-2006)。     

腐殖酸共存条件下NF90纳滤膜去除水中邻苯二甲酸二丁酯

水中共存有机物会对纳滤产生影响,以邻苯二甲酸二丁酯(DBP)为对象,研究了NF90膜对纯水、模拟水和河水中DBP的去除效果。DBP的初始质量浓度为100μg/L。结果表明,NF90膜能实现对微量DBP的有效去除,截留率高达90%以上;在模拟水中,腐殖酸共存时,会引起膜通量的下降和截留率的上升,pH为7时,截留率最高,其他无机离子(K+、Ca2+)的加入,会减小膜通量增大截留率,其中,Ca2+的影响尤为明显;河水中的无机物和有机物成分复杂,膜通量会进一步减小,截留率进一步提高;纳滤初期,吸附会影响截留率,6 h后吸附达到饱和,稳定运行96 h后,膜污染会引起膜通量和截留率的下降。     

Fouling effects of humic and alginic acids in nanofiltration and influence of solution composition

The objectives of this research were to investigate the combined and individual influence of hydrophobic and hydrophilic fractions of NOM on the fouling of thin-film composite nanofiltration (NF) membranes, and also the roles of solution chemistry on the permeate flux and fouling. Combined fouling is compared to the individual fouling behaviors (i.e., alginate or humic acid alone).Experiments were conducted using a “cross-flow” pilot-scale membrane unit with a full circulation mode. Fouling experiments were performed with individual and combined humic acid and alginate.The results demonstrated that increasing organic concentration increased greatly the rate and extent of flux reduction. Individual alginate fouling was more detrimental than individual humic acid fouling, and alginate exhibited greater flux decline than humic acid fouling alone at the same conditions. A higher flux decline was observed with increasing proportions of aliginate in combined fouling. In other word, there are antagonistic effects during combined fouling because the charge functional groups of two above foulants are negative and increase electrostatic repulsion between two foulants and also foulant-membrane. The flux reduction increased with increasing ionic strength, foulant concentrations, and with lower pH. This observation implies the importance of interaction between various foulants for deeper understanding of fouling phenomena. The membrane fouling was largely dependent on organic properties and fractions.     

天然有机物对纳滤水处理工艺的影响

天然有机物（NOM）广泛存在于天然水体中,对纳滤处理过程产生较大影响。该文在介绍NOM的组成和物化性质的基础上,讨论了NOM对截留率和膜通量的影响,阐述了纳滤过程中NOM的亲、疏水性,浓差极化效应,静电排斥作用,氢键作用,二价离子络合等对纳滤过程的影响机理,对提高纳滤膜过滤性能有重要意义。     

Advanced water treatment of high turbid source by hybrid module of ceramic microfiltration and activated carbon adsorption: Effect of organic/inorganic materials

We investigated the effect of organic or inorganic materials on membrane fouling in advanced drinking water treatment by hybrid module packed with granular activated carbon (GAC) outside a tubular ceramic microfiltration membrane. Instead of natural organic matters (NOM) and fine inorganic particles in the natural water source, synthetic water was prepared with humic acid and kaolin. Concentrations of kaolin or humic acid were changed to see effects of inorganic or organic matter. And periodic water-back-flushing using permeate water was performed during 10 sec per filtration of 10 min. As a result, both the resistance of membrane fouling (R _f ) and permeate flux (J) were influenced higher by concentration of humic acid rather than kaolin. It was proved that NOM like humic acid could be a more important factor on membrane fouling in drinking water treatment than fine inorganic particles. Treatment efficiencies of turbidity and UV₂₅₄ absorbance were very high above 97.4% and 92.0%, respectively. This article is dedicated to Professor Chang Kyun Choi for celebrating his retirement from the School of Chemical and Biological Engineering, Seoul National University.     

Membrane fouling and chemical cleaning in water recycling applications

Fouling and subsequent chemical cleaning are two important issues for sustainable operation of nanofiltration (NF) membranes in water treatment and reuse applications. Fouling strongly depends on the feed water quality, especially the nature of the foulants and ionic composition of the feed water. Consequently, appropriate selection of the chemical cleaning solutions can be seen as a critical factor for effective fouling control. In this study, membrane fouling and chemical cleaning under condition typical to that in water recycling applications were investigated. Fouling conditions were achieved over approximately 18 h with foulant cocktails containing five model foulants namely humic acids, bovine serum albumin, sodium alginate, and two silica colloids in a background electrolyte solution. These model foulants were selected to represent four distinctive modes of fouling: humic acid, protein, polysaccharide, and colloidal fouling. Three chemical cleaning solutions (alkaline solution at pH 11, sodium dodecyl sulphate (SDS), and a combination of both) were evaluated for permeate flux recovery efficiency. The results indicated that with the same mass of foulant, organic fouling was considerably more severe as compared to colloidal fouling. While organic fouling caused a considerable increase in the membrane surface hydrophobicity as indicated by contact angle measurement, hydrophobicity of silica colloidal fouled membrane remained almost the same. Furthermore, a mechanistic correlation amongst cleaning efficiency, characteristics of the model foulants, and the cleaning reagents could be established. Chemical cleaning of all organically fouled membranes by a 10 mM SDS solution particularly at pH 11 resulted in good flux recovery. However, notable flux decline after SDS cleaning of organically fouled membranes was observed indicating that SDS was effective at breaking the organic foulant—Ca²⁺ complex but was not able to effectively dissolve and completely remove these organic foulants. Although a lower permeate flux recovery was obtained with a caustic solution (pH 11) in the absence of SDS, the permeate flux after cleaning was stable. In contrast, the chemical cleaning solutions used in this study showed low effectiveness against colloidal fouling. It is also interesting to note that membrane fouling and chemical cleaning could permanently alter the hydrophobicity of the membrane surface.     

Self-doped sulfonated polyaniline ultrafiltration membranes with enhanced chlorine resistance and antifouling properties

Membranes heavily rely on chlorination to diminish (bio)fouling, but chlorination can also lead to membrane degradation. We developed sulfonated polyaniline (S-PANI) ultrafiltration (UF) membranes with improved chlorine resistance and intrinsic antifouling properties. The S-PANI membranes were synthesized through Non-solvent Induced Phase Separation (NIPS). Membrane performance was evaluated under harsh chlorine conditions (250 ppm sodium hypochlorite for 3 days under different pH conditions). The S-PANI membranes showed improved chlorine resistance including a stable performance without changes in model foulant BSA rejection. In contrast, PANI membranes suffered critical structural damage with complete leakage and commercial PES membranes showed a 76% increase in pure water flux and a noticeable change in BSA rejection. Small changes in S-PANI membrane performance could be linked to membrane structural changes with pH, as confirmed by SEM, IR spectroscopy, and contact angle measurements. Additionally, the S-PANI membranes showed better antifouling properties with a high flux recovery ratio in comparison to PANI membranes using alginic acid, humic acid, and BSA model foulants. Chemical cleaning by sodium hypochlorite re-instated the transport properties to its initial condition. Overall, the developed S-PANI membranes have a high chlorine tolerance and enhanced antifouling properties making them promising for a range of UF membrane applications.