超滤膜结构参数特性的分析研究

用电镜法和渗透率法对PVDF-300超滤膜表面的孔径分布、孔隙率以及膜孔密度等结构参数进行了测定.结果表明,用扫描电镜法和场发射扫描电镜法测定膜平均孔径及膜孔密度等结构参数是比较吻合的.从而可以根据膜结构参数在透水过程中的变化规律研究膜污染的机理,为以后建立以膜结构参数为参数的膜污染模型奠定了理论基础.     

Large pore size polyacrylonitrile membrane for ultrafiltration

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Effect of coagulation pretreatment on the fouling of ultrafiltration membrane

The purpose of this study is to understand the effect and mechanism of preventing membrane fouling, by coagulation pretreatment, in terms of fractional component and molecular weight of natural organic matter （NOM）. A relatively higher molecular weight （MW） of hydrophobic compounds was responsible for a rapid decline in the ultrafiltration flux. Coagulation could effectively remove the hydrophobic organics, resulting in the increase of flux. It was found that a lower MW of neutral hydrophilic compounds, which could remove inadequately by coagulation, was responsible for the slow declining flux. The fluxes in the filtration of coagulated water and supernatant water were compared and the results showed that a lower MW of neutral hydrophilic compounds remained in the supernatant water after coagulation could be rejected by a membrane, resulting in fouling. It was also found that the coagulated flocs could absorb neutral hydrophilic compounds effectively. Therefore, with the coagulated flocs formed on the membrane surface, the flux decline could be improved.     

Flux enhancement during ultrafiltration of produced water using turbulence promoter

IntroductionThe application of ultrafiltration for producedwater treatment is still costly in terms of energyconsumption and equipment cost compared withconventional water treatment processes. Thehigh-energy consumption comes from the highcirculation velocity, and it is necessary for controllingconcentration polarization and membrane fouling,which still remain a topical problem for an industrialdevelopment of ultrafiltration processes. Membranefouling in ultrafiltration is complex, accumulatio…     

Chemical cleaning of fouled PVC membrane during ultrafiltration of algal-rich water

Cleaning of hollow-fibre polyvinyl chloride (PVC) membrane with di erent chemical reagents after ultrafiltration of algal-rich water was investigated. Among the tested cleaning reagents (NaOH, HCl, EDTA, and NaClO), 100 mg/L NaClO exhibited the best performance (88.4% 1.1%) in removing the irreversible fouling resistance. This might be attributed to the fact that NaClO could eliminate almost all the major foulants such as carbohydrate-like and protein-like materials on the membrane surface, as confirmed by Fourier transform infrared spectroscopy analysis. However, negligible irreversible resistance (1.5% 1.0%) was obtained when the membrane was cleaning by 500 mg/L NaOH for 1.0 hr, although the NaOH solution could also desorb a portion of the major foulants from the fouled PVC membrane. Scanning electronic microscopy and atomic force microscopy analyses demonstrated that 500 mg/L NaOH could change the structure of the residual foulants on the membrane, making them more tightly attached to the membrane surface. This phenomenon might be responsible for the negligible membrane permeability restoration after NaOH cleaning. On the other hand, the microscopic analyses reflected that NaClO could e ectively remove the foulants accumulated on the membrane surface.     

无机陶瓷超滤膜处理乳化油的工程实例

清洗废水经过100nm陶瓷膜处理,浓缩倍数可达375倍。滤液含油量小于5mg/L,浓液经皂化沉降分离后,含油量约15%。60℃热水作为常规清洗和2%的Na OH溶液作为周期性的化学清洗,可使陶瓷膜的平均通量可以稳定在400LMH以上,废水的综合处理成本仅为30元/m~3。     

陶瓷膜处理油田采出水用于回注的试验研究

为满足低渗透油田的回注水质要求,采用非对称结构的陶瓷复合超滤膜对大庆油田采出水进行了处理.结果表明,该超滤膜的适宜操作条件为膜面流速5.0~5.5m/s,跨膜压差0.30 MPa,工作温度(37±0.5)℃.超滤对浊度、油和悬浮物的去除率分别达到97%,98%,94%以上,硫酸盐还原菌(SRB)、铁细菌(IB)、腐生菌(TGB)的去除率接近100%.渗透液浊度<1NTU,原油<1mg/L,悬浮物<1mg/L, IB<2CFU/mL,SRB、TGB和粒径中值未检出.挂片试验表明,渗透液对挂片只有轻微的点腐蚀,平均腐蚀率<0.065mm/a.除点腐蚀外,超滤出水达到了油田低渗透层的回注水质A1 级要求.     

污水深度处理中超滤工艺对有机物的截留模型

基于浓差极化现象和膜孔堵塞效应,建立了污水深度处理中超滤工艺对有机物的截留模型.利用中试试验数据率定模型参数并验证模型的模拟效果.模型验证结果表明,该模型能够较好地模拟超滤工艺出水UV254值随时间的变化特征,基于最优参数得到的模拟值与相应实测值相对误差的绝对值均低于10%.并且模型参数区域灵敏度分析和不确定性分析结果表明,该模型的结构具有较高的可靠性.应用该模型研究了过滤时间、通量和进水浓度变化对出水水质的影响.结果表明,在过滤初期膜孔堵塞效应占主导地位并增加超滤膜对有机物的截留效果,在过滤后期浓差极化现象占主导地位并降低超滤膜对有机物的截留效果;当进水UV254浓度恒为0.1cm-1时,通量从5×10-5m/s增至1×10-4m/s,导致UV254截留率降低13%;当通量恒为5×10-5m/s时,进水UV254浓度从0.2cm-1降至0.1cm-1,使得出水浓度降低50%.因此,模型可应用于模拟进水水质和操作条件对污水深度处理中超滤工艺出水水质的影响,为从预处理、过滤周期和通量等方面改进和优化超滤工艺提供基础.     

颗粒物对混凝过程及超滤膜污染的影响

以nm-SiO₂和μm-SiO₂体系为研究对象,使用3种不同Al形态的混凝剂（AlCl₃、Al₁₃和Al₃₀）进行混凝-超滤实验,考察不同pH值下SiO₂去除率、出水余Al及混凝预处理对膜通量的影响,借助马尔文激光粒度仪、SEM、BET和AFM表征絮体性质及在超滤膜表面的分布和作用力.结果表明,nm-SiO₂体系中SiO₂去除率均低于μm-SiO₂体系,在纳米颗粒物体系中投加混凝剂后膜通量从0.68分别提升至0.96（AlCl₃）、0.86（Al₁₃）和0.87（Al₃₀）,微米颗粒物体系中投加3种混凝剂后膜通量从0.79提升至0.80~0.84.微米级颗粒物是颗粒间的碰撞,纳米级颗粒物主要以团聚态的形式碰撞.低聚态铝（Al_a）和颗粒物形成絮体的粒径均大于150μm,体系zeta电位为负与膜表面产生斥力;在中性条件下Al₁₃与颗粒物形成絮体的强度因子远高于AlCl₃和Al₃₀,中聚态铝（Al_b）将膜孔内部较小颗粒物堵塞形成的不可逆膜污染转移成膜孔表面的可逆膜污染;高聚态铝（Al_c）具有较强吸附架桥和网捕卷扫能力,无定形、不规则的团聚态小颗粒在这一过程中形成较大絮体缓解膜污染.     

碳纳米管界面改性超滤膜的抗污机理解析

以碳纳米管(CNT)为核心改性材料,采用喷涂法对聚醚砜(PES)超滤膜进行界面改性,研究改性膜的抗污染性能.结果表明:改性膜经聚乙烯醇交联稳定后,呈现微弱的通透性降低和明显的亲水性提升,CNT交织网状层提高了界面粗糙度;在牛血清白蛋白(BSA)污染试验中,CNT-10改性膜的抗污性能最好,在20mg/L BSA试验后,其通量恢复率高达95.7%、膜界面可逆污染率接近60%;进一步分析界面电化学阻抗信息发现,污染实验后CNT-10膜的Nyquist曲线右移幅度(实部阻抗增加)明显小于原膜,且曲线半径未见明显扩大,这与改性膜呈现的较小幅度的电导降低和相对稳定的电容一致,表明改性膜具有更少的污染物粘附,与通量变化趋势相符.对频率-电导图进行分频讨论,表明BSA污染了PES-V整个膜表层与膜基层,而并未污染CNT-10整个表层和膜基层;CNT改性层与BSA的界面作用自由能(XDLVO)分析结果显示,改性膜与污染物相吸引作用仅为原膜的一半,从热力学上解释了其优异的抗污染性能.     

超滤去除水中内分泌干扰物（BPA）的效果和影响因素

采用终端超滤工艺去除饮用水中内分泌干扰物双酚A（BPA）,主要考察了BPA初始浓度、膜截留相对分子质量、pH、离子强度和有机物对BPA去除效果的影响.结果表明,超滤对饮用水中BPA具有良好的去除效果.当BPA的初始浓度在100～600μg/L范围内,截留相对分子质量2?000～10?000的超滤膜对BPA的去除率均在92.0%以上.溶液的pH值接近BPA的pK_a（9.6～11.3）时,BPA去除率明显降低.离子强度对去除率的影响较小.溶液中的腐殖酸对超滤去除BPA的影响较小.试验证实,吸附是超滤去除疏水性BPA分子的主要机理.     

Drinking water production by ultrafiltration of Songhuajiang River with PAC adsorption

In recent years, membrane ultrafiltration （UF） of surface water for drinking water treatment has become a more attractive technology worldwide as a possible alternative treatment to conventional clarification. To evaluate the performance of ultrafiltration membranes for treatment of surface water in North China, a 48-m^2 low pressure hollow fiber membrane ultrafiltration pilot plant was constructed. Ultrafiltration was operated in cross-flow and with powdered activated carbon （PAC） adsorption. Turbidity was almost completely removed to less than 0.2 NTU （below Chinese standard 1 NTU）. It was found that PAC addition enhanced organic matter removal. The combined process of PAC/UF allowed to 41% removal of CODMn, 46% removal of DOC and 57% decrease in UV254 absorbance. The elimination of particles, from average 12000/ml in the raw water to approximately 15/ml in the permeated, was observed. When PAC concentration was below 30 mg/L, backwashing could recovery the membrane flux with backwash interval/backwashing duration of 1/30.     

The role of extracellular organic matter on the cyanobacteria ultrafiltration process

The membrane fouling caused by extracellular organic matter (EOM) and algal cells and organic matter removal of two typical cyanobacteria (M. aeruginosa and Pseudoanabaena sp.) during ultrafiltration (UF) process were studied in this work. The results showed that EOM had a broad molecular weight (Mw) distribution and the irreversible membrane fouling was basically caused by EOM. Moreover, humic acid and microbial metabolites were major components of EOM of two typical cyanobacteria. Since EOM could fill the voids of cake layers formed by the algal cells, EOM and algal cells played synergistic roles in membrane fouling. Fourier transform infrared spectroscopy analysis indicated that the CH₂ and CH₃ chemical bonds may play an important role in membrane fouling caused by EOM. Interestingly, the cake layer formed by the algal cells could trap the organic matter produced by algae and alleviate some irreversible membrane fouling. The results also showed that although the cake layer formed by the algal cells cause severe permeate flux decline, it could play a double interception role with UF membrane and increase organic matter removal efficiency. Therefore, when using UF to treat algae-laden water, the balance of membrane fouling and organic matter removal should be considered to meet the needs of practical applications.     

纳米颗粒原位植入法制备改性超滤膜及其抗生物污染性能研究

选取氧化铝分散体(Al2O3)、Linde A型沸石(LTA)、Linde L型沸石(LTL)和X型八面沸石(FAU-X)4种纳米颗粒,采用原位植入的方法对超滤膜进行表面改性,以提高聚砜超滤膜的抗生物污染性能.通过扫描电子显微镜、接触角测定、抗生物污染性能测试等方法来表征改性前后膜结构和性能的变化.结果表明,纳米颗粒在膜表面的原位植入具有其可行性,该方法只改变超滤膜的表面形貌,对断面和底面的结构没有影响;纳米颗粒原位植入法改性后,超滤膜的亲水性有显著提高.就抗生物污染性能而言,纳米颗粒的植入提高了膜的抗粘附性能,在纳米颗粒覆盖的区域没有大肠杆菌粘附生长;在这4种膜中,UF-LTA和UF-LTL膜的抗粘附性能优于UF-Al2O3和UF-FAU-X膜.相较而言,LTA型沸石在膜表面分散效果良好,原位植入后显著改善了膜的亲水性并且表现出较好的抗粘附性能,可作为理想的材料用于下一步研究.但LTA型沸石的抗水流剪切的能力较弱,要想提高该种纳米颗粒在膜表面的结合牢固性,应考虑减小颗粒的粒径.     

加载絮体形态对短流程超滤膜污染影响效应

以聚硫酸铁（PFS）为混凝剂,微砂为载体颗粒,系统考察了采用加载絮凝-超滤联用工艺净化含高岭土、腐植酸和锑[Sb（Ⅲ）]的模拟原水过程中,不同PFS和微砂投加量条件下加载絮体形态特性以及其对超滤膜通量衰减、膜污染可逆性和宏观出水水质等的影响,并分析了膜污染机理.结果表明,PFS投加量对絮体形态及膜滤效能和膜污染影响显著,且投加量过少或过多均会产生不利影响,以30mg/L为宜;与不投加微砂的工况相比,加入微砂更易于形成大而结构较为松散的絮体,可有效削弱不可逆膜污染,并获得较为稳定的超滤出水水质;超滤末端膜比通量与絮体平均粒径呈良好的正相关性（R²=0.8774）,但因加载絮凝体系中引起分形维数变大的不同类型颗粒（包括小粒径范围絮体和未被加载絮体捕获的微砂）对超滤净水过程产生的影响各异,致使膜通量与分形维数的负相关性较差（R²=0.5760）.     

聚醚砜超滤膜接枝聚乙烯醇-氨基酸共聚物的亲水改性研究

基于聚合多巴胺的附着性及易与氨基(—NH2)等基团形成共价键的特性,本实验将聚合多巴胺作为对聚醚砜(PES)超滤膜进行表面改性的接枝中间物,将聚乙烯醇(PVA)-氨基酸共聚物接枝至PES膜表面,从而提高PES超滤膜的亲水性能.实验通过PVA与氨基酸的酯化反应形成PVA-氨基酸共聚物,将带有—NH2的共聚物与PES超滤膜表面的聚合多巴胺涂覆层形成共价键,从而将亲水的PVA-氨基酸共聚物接枝到疏水的超滤膜表面.实验利用通量的变化、红外光谱(FTIR)分析、表面接触角、场发射扫描电镜(FESEM)等手段来表征膜特征参数的变化,同时也考察了改性膜对油水乳化液的分离效率和抗污染能力.试验结果表明,经过PVA-氨基酸共聚物接枝改性的膜表面的亲水性有一定的提高,原膜接触角为91°,涂覆和接枝改性后的膜表面接触角分别为71°和53°,油水乳化液的分离实验显示,改性后的膜通量和清洗恢复率均有明显提高.     

亲水荷电超滤膜的制备及对腐殖酸的分离性能

为改善聚醚砜(PES)超滤膜的抗污染性能和提高对腐殖酸(HA)的截留率,以介孔二氧化硅(MS)为添加剂,采用相转化法制备了亲水性PES/MS复合超滤膜,并对膜表面进行荷电改性.研究了MS对膜的断面结构、表面化学性质和过滤性能的影响,考察了荷电改性PES/MS超滤膜对水中HA的分离性能以及溶液pH值、离子强度和钙离子浓度等因素对荷电膜超滤过程的影响.SEM表征结果显示,MS颗粒在PES/MS复合膜的表面分散均匀,膜孔的连通性改善.亲水荷电改性后,膜表面接触角由68°降至57°,zeta电位由-6.31mV降至-11.45mV,膜对HA的去除率由72%提高到95%,通量衰减率由29.8%减小到4.9%.结果表明,对PES超滤膜进行亲水荷电改性可有效提高对HA的截留率,同时减轻膜污染;另外,溶液的pH值、离子强度和钙离子浓度对荷电超滤膜的过滤性能有较大影响,调节合适的溶液环境可在提高截留率的同时,减轻膜污染.     

离子筛与醋酸纤维素混合超滤膜的制备及降氟性能

在超滤膜制备过程中，向铸膜液中引入亲氟物质———水合氧化镧，经熟化后制备的混合超滤膜具有分离大分子和降低水体中氟离子浓度两种功能．以含氟饮用水为研究对象，对其混合膜的降氟机理进行了探讨．     

Effects of protein properties on ultrafiltration membrane fouling performance in water treatment

Protein-like substances always induce severe ultrafiltration (UF) membrane fouling. To systematically understand the effect of proteins, regenerated cellulose UF membrane (commonly used for protein separation) performance was investigated in the presence of bovine serum albumin (BSA) under various water conditions. Results showed that although trypsin enhanced the membrane flux via proteolysis, catalysis took a long time. Membrane fouling was alleviated at high solution pH and low water temperature owing to the strong electrostatic repulsion force among BSA molecules. Both Na⁺ and Ca²⁺ could increase membrane flux. However, Ca²⁺ played a bridging role between adjacent BSA molecules, whereas membrane fouling was alleviated via a hydration repulsion force with Na⁺. The order of influence on membrane fouling was as follows: Ca²⁺ concentration > Na⁺ concentration > pH > temperature > trypsin concentration. Furthermore, a polyvinylidene fluoride UF membrane experiment showed that Ca²⁺ could reduce the fouling induced by BSA. Thus, the differences in UF membrane performance will have application potential for alleviating UF membrane fouling induced by proteins during water treatment.