混凝处理防止膜污染的作用与机理

通过膜过滤混凝上清液的方法 ,并比较膜进水和透过水中有机物相对分子质量分布的变化 ,探讨了混凝防止膜污染的作用和机理 .结果表明 ,相对分子质量大于 10 0 0的有机物是造成膜污染的主要因素 ,而相对分子质量小于 10 0 0的有机物对膜污染的影响较小 .尽管混凝能有效地去除相对分子质量较大的有机物 ,但混凝防止膜污染的效果与其投加量有密切的关系 .较低的混凝投加量 (2 5mg·L- 1 )防止膜污染的效果较差 ,较大的投加量 (>5 0mg·L- 1 )防止膜污染的效果较好 .UV2 54能更好地反映有机物对膜污染的影响程度 ,如何有效地去除这类有机物是防止膜污染的关键 .混凝防止膜污染的效果与去除相对分子质量大于 10 0 0的UV2 54的程度密切相关 .试验结果表明 ,混凝去除这类有机物的效果达到 5 0 %时 ,可有效地防止膜污染     

混凝对膜污染的防止作用

研究了混凝改善膜通量和防止膜污染的效果 .结果表明 :直接过滤原水的情况下 ,反冲洗后的膜通量恢复仅为初始通量的40% ;而投加了混凝剂 4mg/L和10mg/L(以Al计 )后 ,反冲洗后的通量得到了完全的恢复 .混凝防止膜污染取决于过滤过程在膜表面形成的滤饼层的性能 .在过滤混凝液的情况下 ,混凝能在膜表面形成滤饼层 ,从而有效地防止膜污染 ,而过滤上清液的情况下 ,无法为混凝去除的中性亲水性的有机物沉积在膜表面 ,造成膜污染 .     

超滤的预处理工艺对比研究:化学混凝与电絮凝

对比研究了化学混凝(chemical coagulation,CC)与电絮凝(electrocoagulation,EC)作为超滤膜分离的预处理工艺,在死端过滤条件下与超滤膜的作用机制以及对膜污染的减缓效果.主要研究了Al3+投加量对膜通量、絮体性质(粒径、强度系数、恢复系数、分形维数)、以及滤饼层性质的影响.结果表明,EC作为预处理时,生成的絮体强度大且结构紧实,在膜表面堆积形成的滤饼层具有疏松多孔、亲水性强的性质;而CC作为预处理时,生成的絮体强度低且比较松散,在膜过滤过程中容易被压力压碎压实,导致滤饼层比较密实、亲水性低.因此,EC作为预处理工艺对膜污染的减缓效果好,在运行过程中可以保持较高的膜通量,膜通量较CC高约5.57%.     

不同原水中膜污染物质的表征与确定

本文采用有机物的组分分析、相对分子质量分布及三维荧光等分析手段,研究了青草沙水库和滆湖原水的膜过滤通量的表现,探讨了膜污染的机理.试验结果表明,中亲组分有机物造成的微滤膜和超滤膜的通量下降最为严重,而疏水性有机物对通量的影响甚微.滆湖水对微滤膜的通量下降较青草沙水库水严重,而青草沙水库水对超滤膜的通量下降较滆湖水严重.膜污染机理的分析表明,微滤膜污染主要由膜孔堵塞造成,而超滤膜的通量主要受大分子有机物形成的滤饼层的影响.三维荧光分析表明,蛋白质类的有机物是造成膜污染的主要物质.     

Fouling of nanofiltration membrane by e uent organic matter: Characterization using di erent organic fractions in wastewater

The UF membrane with molecular weight cuto (MWCO) ranging from 2 to 100 kDa and XAD-8 resin were employed to identify the characteristic of molecular weight (MW) distribution of wastewater e uent organic matter (EfOM) in terms of TOC and UV254, as well as the amounts of the hydrophilic/hydrophobic organic fractions in di erent MW ranges. Then, the nanofiltration (NF) membrane fouling experiments were carried out using the above fractionated water to investigate the e ect of MW distribution and hydrophilic/hydrophobic characteristics of EfOM on the membrane flux decline using the fractionated water samples. The experimental results have shown that 45.61% of the total organics belongs to the low MW one, among which the percentage of the hydrophilic organics with low MW (less than 2 kDa) was up to 28.07%, while that of the hydrophobic organics was 17.54%. In particular, the hydrophilic fraction was found to be the most abundant fraction in the e uents. MW distribution has a significant e ect on the membrane fouling. When the MWwas less than 30 kDa, the lower the MW, the larger was the specific flux decline, while in the case of MW higher than 30 kDa, the higher the MW, the larger was the specific flux decline, and the decline degree of low MW organics was larger than the high MW one. With the same MW distribution range, specific flux decline of the hydrophilic organic was considerably slower than that of the hydrophobic organic, which indicated that the hydrophobic organic fractions dominantly contribute to the flux decline.     

粉末活性炭预处理对超滤膜通量的影响

研究了粉末活性炭预处理对改善超滤膜过滤通量的效果.试验采用了4种具有不同亲疏水性的水样,着重探讨粉末活性炭对有机物的疏水性和亲水性组分的去除效果以及所带来的通量改善.试验结果表明,对于4种水样,超滤膜直接过滤原水时,通量下降严重.虽然粉末活性炭预处理能在一定程度上提高通量,但通量下降的趋势仍未改善.对有机物各组分的分析表明,直接过滤原水时,膜主要截留疏水性有机物;粉末炭吸附主要去除亲水性有机物,而超滤膜过滤粉末炭处理水时,主要截留疏水性有机物.由此,超滤膜的通量下降主要是由疏水性有机物引起的,亲水性组分对通量的影响较小.     

Fouling of nanofiltration membrane by effluent organic matter： Characterization using different organic fractions in wastewater

The UF membrane with molecular weight cutoff (MWCO) ranging from 2 kDa to 100 kDa and XAD-8 resin were employed to identify the characteristic of molecular weight (MW) distribution of wastewater effluent organic matter (EfOM) in terms of TOC and UV254, as well as the amounts of the hydrophilic/hydrophobic organic fractions in different MW ranges. Then, the nanofiltration (NF) membrane fouling experiments were carried out using the above fractionated water to investigate the effect of MW distribution and hydrophilic/hydrophobic characteristics of EfOM on the membrane flux decline using the fractionated water samples above. The experimental results have shown that 45.61% of the total organics belongs to the low MW one, among which the percentage of the hydrophilic organics with low MW (less than 2 kDa) was up to 28.07%, while that of the hydrophobic organics was 17.54%. In particular, the hydrophilic fraction was found to be the most abundant fraction in the effluents. MW distribution has a significant effect on the membrane fouling. When the MW was less than 30 kDa, the lower the MW, the larger was the specific flux decline, while in the case of MW higher than 30 kDa, the higher the MW, the larger was the specific flux decline, and the decline degree of low MW organics was larger than the high MW one. With the same MW distribution range, specific flux decline of the hydrophilic organic was considerably slower than that of the hydrophobic organic, which indicated that the hydrophobic organic fractions dominantly contribute to the flux decline.     

Effects of ozonation and coagulation on effluent organic matter characteristics and ultrafiltration membrane fouling

Effluent organic matter （EfOM） is the major cause of fouling in the low pressure membranes process for wastewater reuse. Coagulation and oxidation of biological wastewater treatment effluent have been applied for the fouling control of microfiltration membranes. However, the change in EfOM structure by pre-treatments has not been clearly identified. The changes of EfOM characteristics induced by coagulation and ozonation were investigated through size exclusion chromatography, UV/Vis spectrophotometry, fluorescence spectrophotometry and titrimetric analysis to identify the mechanisms in the reduction of ultrafiltration （UF） membrane fouling. The results indicated that reduction of flux decline by coagulation was due to modified characteristics of dissolved organic carbon （DOC） content. Total concentration of DOC was not reduced by ozonation. However, the mass fraction of the molecules with molecular weight larger than 5 kDa, fluorescence intensity, aromaticity, highly condensed chromophores, average molecular weight and soluble microbial byproducts decreased greatly after ozonation. These results indicated that EfOM was partially oxidized by ozonation to low molecular weight, highly charged compounds with abundant electron- withdrawing functional groups, which are favourable for alleviating UF membrane flux decline.     

臭氧-粉末炭联用作为预处理缓解膜污染的效果与机制

研究臭氧、粉末炭以及它们的组合作为超滤膜的预处理,控制膜污染以及去除有机物的效果和机制.结果表明,臭氧主要氧化强疏组分的大分子有机物,将其转化为中分子和亲水性的小分子.臭氧可有效控制膜污染,表明大分子的疏水有机物是主要的污染因素.粉末炭可吸附小分子有机物,也可缓解膜污染,说明小分子有机物也对膜污染有所贡献.臭氧与粉末炭的组合不仅有效控制膜污染,还可强化有机物的去除,它们之间存在协同作用.     

荷电超滤膜对天然有机物去除及膜污染行为的影响

以Aldrich 腐殖酸溶液为水样,研究比较了溶液环境(pH值、离子强度和钙离子)对荷电改性再生纤维素超滤膜和传统中性未改性再生纤维素超滤膜过滤过程的影响.结果表明, ①pH值主要通过质子化作用影响荷电膜以及腐殖酸分子的荷电量,进而影响荷电超滤过程.溶液pH值从7.5下降到3.5时,荷电超滤膜对腐殖酸的截留率从92%减少到79%,超滤4 h时,膜通量下降从26%增加到36%.②离子强度的改变是通过影响腐殖酸分子的物化性质和静电屏蔽作用来影响超滤过程的.当溶液离子强度为0、 3和100 mmol/L时,初始截留率依次降低,分别为92%、 87%和48%,超滤4 h时,荷电超滤膜的通量下降依次增加,分别为26%、 35%和63%.③Ca2+浓度的影响,需要综合考虑静电屏蔽作用、Ca2+的架桥作用以及滤饼层的压实性等各方面的影响.④pH值、离子强度和钙离子对中性超滤膜过滤行为的影响趋势与荷电超滤膜相似,但其影响程度有着较大的差别.研究结果对荷电超滤膜技术在实际应用中选择合适环境条件提供了参考.     

海藻酸及腐殖酸共存对PVDF超滤膜的污染行为

为了揭示有机物对PVDF超滤膜的污染行为,选用典型亲/疏水性有机污染物海藻酸(SA)及腐殖酸(HA),采用原子力显微镜结合自制的PVDF膜材料探针和污染物探针定量测定了PVDF-污染物及污染物-污染物间的作用力,并进行PVDF膜污染试验和污染物去除效果分析.结果表明:亲水性SA-PVDF及SA-SA之间的作用力皆大于疏水性HA-PVDF及HA-HA间的作用力,且SA污染膜的通量衰减速率与衰减幅度明显大于HA污染膜,说明了亲水性有机物是引起PVDF超滤膜污染的优势污染物.HA/SA混合污染物试验表明,膜污染行为与混合污染物中优势污染物的含量密切相关;与单种污染物的膜污染行为相比,混合污染物间不存在明显的协同作用促进膜污染.此外,污染物的去除率与相应微观作用力大小及膜污染速率成正相关关系.     

太湖原水中膜污染物质的确定与表征

采用混凝沉淀和浸没式微滤膜联用技术处理太湖原水,考察组合工艺中的有机物亲疏水性和分子量分布变化,并分析化学清洗水的有机物组分,以期确定造成膜污染的主要物质成分.结果表明,混凝预处理可有效去除大分子的亲水性有机物,这类有机物仅能导致可逆污染,而中等和小分子的有机物会导致不可逆污染.此外,三维荧光光谱表明与膜污染关系最密切的2个区域为:λex=230nm/λem=330~350nm (区域Ⅰ)和λex=280nm/λem=300~350nm (区域Ⅳ),其对应的胞外蛋白质类有机物和溶解性微生物产物(SMP)是造成微滤膜不可逆污染的主要物质.     

DOM纳滤膜污染及对膜截留卡马西平性能的影响

研究了天然原水中溶解性有机物(DOM)对HL和ESNA1-K两种纳滤膜造成的膜污染及其对膜截留卡马西平(CBZ)性能的影响.结果表明,DOM的存在造成了严重的膜污染和通量衰减.膜污染对CBZ截留率的影响与膜本身的特性和污染物特性有关,DOM通过在膜表面形成污染滤饼层和进入膜孔内部造成的膜孔堵塞,影响弱疏水性的CBZ从水中的分离,青草沙水库原水中的DOM引起的膜污染提高了两种纳滤膜对CBZ的截留效果,而太湖DOM造成的膜污染会降低CBZ的截留效果.研究还发现,中等相对分子质量(1 500~10 000)有机物会紧密地黏附在膜表面形成滤饼层,从而改变膜表面的疏水性能,小分子主要通过进入膜孔导致膜孔径堵塞.滤饼层的疏水性和浓差极化作用以及膜孔径的堵塞造成膜通量衰减并影响CBZ去除率.应用XDLVO理论对DOM造成的膜污染的分析结果表明,太湖DOM的疏水性明显强于青草沙DOM,其分子间的聚合自由能更负,与膜的黏附自由能更负,因而造成的膜污染和通量衰减更严重.     

基于膜特征参数变化的蛋白质超滤过程膜污染研究

为进一步研究多种蛋白质体系超滤过程的膜污染机制,采用切割相对分子质量为50×103的聚醚砜(polyethersulfone,PES)超滤膜,对溶菌酶(lysozyme,LYS)、牛血清蛋白(bovine serum albumin,BSA)、LYS+BSA等3种不同蛋白质溶液的超滤过程进行了研究.运用接触角仪、场发射扫描电镜(field emission scanning electron microscope,FESEM)、原子力显微镜(atomic force microscope,AFM)测定了不同污染阶段膜特征参数的变化.结果表明,超滤膜通量变化明显呈现3个阶段:初期(约0~5min)衰减迅速、中期(约5~60 min)衰减缓慢、后期(约60~120 min)趋于稳定;整个超滤过程中,LYS污染膜的通量衰减幅度最大,LYS+BSA次之,BSA最小.膜特征参数变化表明:LYS对膜的初期污染主要以膜孔窄化为主,中期污染由膜孔堵塞和膜孔窄化共同控制;BSA初期膜污染以膜孔堵塞为主,中期污染以膜孔窄化为主;滤饼层过滤是BSA、LYS后期膜污染的主要机制.LYS+BSA二元混合溶液中的LYS对膜污染的产生起主导作用.     

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）.     

原水中有机物特性对纳滤膜污染的影响

通过XDLVO理论分析了赣江原水中亲疏水性有机污染物对纳滤(NF)膜的污染状况,对选取的不同分子量区间(<100 kDa、<50 kDa、<3 kDa)的6种亲、疏水性有机物及NF膜的界面自由能进行定量分析,分析了膜污染性能,并通过纳滤试验验证通量衰减与界面自由能的对应关系。结果表明：6种不同分子量的亲/疏水性有机污染物对膜造成污染严重程度与XDLVO理论分析结果相符。不同分子量的有机污染物对NF膜污染程度由大到小顺序为小于100 kDa(疏水性)>小于50 kDa(疏水性)>小于3 kDa(疏水性)>小于3 kDa(亲水性)>小于50 kDa(亲水性)>小于100 kDa(亲水性)。分子量<100 kDa的疏水性有机物与膜之间排斥作用最小,污染最为严重。膜表面的污染物主要是多糖、蛋白质和苯环烯烃类,且在过滤初期有机物堵塞膜孔,膜比通量下降速度较快,而在过滤后期滤饼层形成,膜比通量下降速度减缓。     

Membrane fouling reduction through electrochemically regulating flocs aggregation in an electro-coagulation membrane reactor

Coupling coagulation and applied electric field is an efficient method to regulate cake layer porosity and hydrophilicity for alleviating ultrafiltration membrane (UF) fouling. However, the Al/Fe flocs aggregation behavior are induced from electric field and determine the cake layer structure, which has not been studied comparatively yet. Herein, the anti-fouling performance in an efficient electro-coagulation membrane reactor (ECMR, in which UF membrane modules are placed between electrodes) was investigated with Al/Fe anode and various electrochemical parameters from the viewpoint of regulating flocs aggregation. Both the cake layers formed from Al and Fe flocs under an electric field were more porous and hydrophilic in comparison with that formed without electric fields, resulting in an enhanced water flux under higher electric field strength. Comparing with Fe flocs, Al flocs had a faster growth rate and larger size, facilitating membrane pore block resistant, which was more pronounced in a higher current density. Furthermore, the cake layer formed from Al flocs was more porous than that formed from Fe flocs. Therefore, the anti-fouling performance of ECMR with Al anode was superior to that of ECMR with Fe anode. When the electric field strength increased from 0 to 10?V/cm, the normalized specific flux was improved from 71.2% to 89.4% for ECMR (Al) and from 48.1% to 70.1% for ECMR (Fe) at 30?min.     

藻类有机物对纳滤膜去除萘普生效果影响研究

研究了2种藻类(鱼腥藻/小环藻)有机物(AOM)对纳滤膜去除萘普生(NPX)的影响效果.结果表明,在藻类AOM存在的情况下HL纳滤膜对NPX的去除率由63%增加至64.7%(小环藻)和72.7%(鱼腥藻);但同时造成了严重的膜污染,比通量由99.7%下降至89.6%(小环藻)和86.3%(鱼腥藻).研究发现,藻类AOM的中等分子量(1.5~5kDa)发挥了重要的作用,它们主要由疏水性有机物构成,紧密地黏附在膜表面形成滤饼层,使膜表面的疏水性增强.滤饼层的疏水性造成膜通量衰减并提高NPX去除率.研究还表明,鱼腥藻AOM在中等分子的疏水性明显比小环藻的强,造成的膜污染更严重以及更高的NPX去除效果.     

有机物对UF膜过滤通量的影响

采用截留分子量为30000的聚醚砜超滤膜进行膜过滤试验,研究有机物的特性,如亲疏水性以及相对分子质量对超滤膜通量的影响.试验结果表明,过滤亲水性组分时膜通量明显高于过滤疏水性组分.对2种不同水源的试验表明,尽管有机物含量相同,但由于亲疏水性的比例不同,造成的膜通量下降不同.疏水性越大的原水,其膜通量下降也越大.因此,疏水性组分是造成通量下降的主要因素.试验还表明,相对分子质量较大的有机物并非通量下降的主要因素,有机物的分散性可能是影响通量的主要因素.     

Ultrafiltration with in-line coagulation for the removal of natural humic acid and membrane fouling mechanism

Experimental and theoretical analysis were made on the natural humic acid removal and the membrane fouling of ultrafiltration （UF） with in-line coagulation. The results showed dissolved organic carbon （DOC） and UV254 removals by the UF with in-line coagulation at pH 7 were increased from 28% to 53% and 40% to 78% in comparison with direct UF treatment respectively. At the same time, the analysis of high performance liquid chromatography showed that UF with coagulation had significant improvement of removal of humic acid with molecular weights less than 6000 Da in particular. Compared to direct UF, the in-line coagulation UF also kept more constant permeate flux and very slight increase oftransmembrane pressure during a filtration circle. Two typical membrane fouling models were used by inducing two coefficients Kc and Kp corresponding to cake filtration model and pore narrowing model respectively. It was found that membrane fouling by pore-narrowing effect was effectively alleviated and that by cake-filtration was much decreased by in-line coagulation. Under the condition of coagulation prior to ultrafiltration at pH 7, the cake layer formed on the membrane surface became thicker, but the membrane filtration resistance was lower than that at pH 5 with the extension of operation time.