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.     

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.     

不同组分的有机物对膜过滤通量下降的影响

采用DAX-8、XAD-4、IRA-958型树脂将自来水中有机物分离成强疏水性、弱疏水性、极性亲水性、中性亲水性有机物,以聚偏氟乙烯、聚醚砜、醋酸纤维3种材质的膜对各组分水样进行膜过滤试验,研究不同组分的有机物对膜过滤通量的影响.结果表明,过滤原水时,PES膜、PVDF膜和CA膜的通量分别比初始通量下降了67%、 59%和19%,表明疏水性越强的膜,越容易造成污染.就各种组分对通量的影响而言,过滤中性亲水性组分的通量下降为初始通量的41%～75%,而弱疏水性组分为6%～33%,表明中性亲水性组分对膜过滤通量的影响最大.3种膜中,CA膜对中性亲水性组分的截留率最高,达14.69%,但通量下降程度却最小,说明膜通量下降的程度并不与有机物截留总量正相关.对膜污染机制进行探讨后发现,对于截留分子量较大的超滤或微滤膜,相对分子质量>3×10⁴的中性亲水性组分通过堵塞膜孔内部,从而造成严重的膜污染;而对于截留分子量较小的超滤膜,中性亲水性组分由于无法进入膜孔,主要在膜表面形成滤饼层,从而对膜通量的影响较小.     

混凝预处理对超滤膜通量的影响

为探讨混凝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,着重探讨混凝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,超滤膜直接过滤原水时,4种水样的有机物截留率在12%～20%,但其中的疏水性组分均超过了50%,说明膜倾向于截留疏水性有机物.投加25 mg/L的混凝剂,4种水样的有机物去除率在12%～28%,投加量增加至100 mg/L,去除率也相应增加至25%～38%,但其中的疏水性组分均占50%以上.混凝预处理均可有效提高通量.对有机物各组分的分析表明,膜处理混凝预处理水时,主要截留亲水性组分,这是由于混凝可有效去除疏水性组分的缘故.由此也可得出结论.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.     

厌氧膜生物反应器中亲疏水性有机物的膜污染特征

采用树脂吸附脱附的方法对厌氧膜生物反应器（AnMBR）中溶解性微生物代谢产物（SMP）的6种亲疏水性有机物进行了分离,其中,亲水中性物质是SMP的主要成分,占总有机物的74.84%.多糖、蛋白质和腐殖质类物质在亲疏水性有机物中均有分布.采用恒压死端过滤的方式对比分析了6种亲疏水性有机物的微滤特性,发现在TOC浓度相同的条件下,亲水性碱（HIB）是造成膜通量下降最快的物质,其次是亲水中性物（HIN）和疏水性酸（HOA）,膜通量下降速率与有机物平均粒径呈指数相关关系（R²=0.9965）.采用过滤模型对微滤过程进行拟合,HOA、HIN和HIB的过滤过程分别符合标准堵塞模型、中间过滤模型和滤饼过滤模型的特征,与其粒径分布特征相对应.试验进一步对比了亲疏水性有机物污染层的可逆性,结果表明HIN造成的膜污染不易通过物理反冲洗得到恢复.     

城市污水二级出水有机物分子量分布和亲疏水特性对纳滤膜污染的影响

分别采用分子量分级膜和XAD-8树脂,研究了污水厂二级出水中有机物分子量分布特征及不同分子量分布区间亲疏水有机物的相对含量,考察了分子量分布及亲疏水特性对纳滤膜透水性能的影响.结果表明,二级出水有机物中,小分子亲水性有机物含量最高,小于2k的有机物占总有机物含量的45.61%,其中亲水性物质占28.07%,疏水性物质占17.54%;不同特征的原水分别经纳滤膜过滤,分子量分布对膜污染影响较大,分子量小于30k时,分子量区间越小,比通量衰减越快,分子量大于30k时,分子量区间越大,比通量衰减越快,且分子量较小的有机物通量衰减程度大于分子量较大有机物;在分子量分布相同区间内,亲水性有机物的比通量衰减较慢,说明相同分子量时,膜对亲水性物质的截留率较低,而疏水性物质是引起膜通量衰减的主要原因.     

天然有机物的相对分子质量分布及亲疏水性对微滤膜组合工艺中膜污染的影响

研究采用混凝沉淀+粉末活性炭吸附+高锰酸钾+浸没式微滤膜的组合工艺对太湖水进行中试试验,通过高效凝胶色谱(HPSEC-UV-TOC)和三维荧光(3DEEM)的测定方法,着重考察有机物的相对分子质量(Mr)分布和亲疏水性对膜不可逆污染的影响.凝胶色谱分析表明:预处理可几乎完全去除大分子有机物(Mr>10×103),但仅能去除部分的中等分子(10×103>Mr>1×103)和小分子(Mr<1×103)有机物.研究发现化学清洗水中的有机物相对分子质量多为中等分子和小分子,说明导致膜不可逆污染的主要是中等分子和小分子有机物.此外,洗膜水中强疏和中性亲水组分含量远高于弱疏和极性亲水,说明强疏和中性亲水组分是不可逆污染的主要物质.三维荧光分析表明,芳香族蛋白质和溶解性微生物产物是造成膜不可逆污染的主要污染物.     

藻类有机物的特性以及对超滤膜的污染

采用凝胶色谱、亲疏水性、荧光色谱等方法研究铜绿微囊藻类有机物的特性.结果表明,铜绿微囊藻类有机物(AOM)主要由亲水性组分构成,占78%,比紫外吸光度仅为1.1 L/(mg.m).超滤膜法测定结果表明,藻类有机物中相对分子质量30 000的有机物占40%以上,并且主要由中性亲水性组分构成.荧光色谱分析表明,AOM中含有蛋白质类和腐殖质类物质.膜过滤试验表明,藻类有机物对超滤膜造成严重的通量下降,这可归结为大分子的中性亲水性组分堵塞膜孔的缘故.     

粉末活性炭预吸附改善超滤膜通量试验研究

研究了粉末活性炭(PAC)预处理长江原水对改善超滤膜通量的效果.试验采用截留相对分子质量分别为30000 Da和10 000 Da的2种超滤膜,着重探讨了PAC对长江水中不同分子量有机物的吸附去除效果以及其所带来的膜通量改善.试验结果表明,超滤膜直接过滤原水时,膜通量下降严重;采用PAC预吸附后,2种膜的通量在一定程度上均得到提高.对PAC预吸附和膜后水样进行不同相对分子质量有机物的测定,结果表明:PAC吸附小于1000Da相对分子质量有机物高于其他相对分子质量区间有机物总和;膜表观截留孔径越小,PAC预吸附改善膜通量效果越显著.     

不同相对分子质量的有机物对膜通量的影响

采用截留分子量分别为10、30kDa的聚醚砜膜和100kDa的聚偏氟乙烯膜对原水进行分级处理,并采用截留分子量分别为150kDa的聚偏氟乙烯膜和0.1μm的醋酸纤维素膜对出水进行膜过滤试验,研究不同相对分子质量的有机物对膜通量的影响.结果表明,虽然相对分子质量>30kDa的大分子有机物仅为总有机物的15%,但它分别引起微滤膜的通量下降86%和超滤膜通量下降54%.混凝处理可以去除相对分子质量>100kDa的有机物,这部分有机物导致通量下降40%以上.因此,尽管混凝处理仅去除10%的有机物,但改善通量的效果显著.粉末活性炭可以去除相对分子量<30kDa的小分子有机物,这部分有机物对通量下降的贡献程度甚低.因此,尽管粉末活性炭去除76%的有机物,但改善通量的效果甚微.预处理改善通量的效果并不取决于去除有机物的多少,而是取决于所去除的有机物对通量的影响大小.     

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.     

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.     

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.     

长江沿线城市水源氯(胺)化消毒副产物生成潜能研究

以长江上游重庆、中游武汉、下游上海等大城市的长江饮用水源为研究对象,在对溶解性有机物分子量和亲疏水性分离的基础上,分别采用氯和氯胺两种方式消毒,对比分析了相同时期沿江这些城市原水中氯(胺)化常规和新兴含氮消毒副产物生成潜能的分子组成规律.研究表明,重庆、武汉、上海三地的溶解性有机物均以小分子前体物为主,主要分布在<1kDa的区间内,且以强疏水性成分和亲水性成分为主,原水经氯(胺)化可产生三卤甲烷、卤乙酸、卤乙腈、三氯硝基甲烷等类型的消毒副产物;三地的氯(胺)化主要的含碳消毒副产物(C-DBPs)和含氮消毒副产物(N-DBPs)生成潜能均在<1kDa的区间内最大,从上游到下游,在<1kDa的区间内的生成潜能占各自总潜能比例逐渐增加.三地的氯(胺)化的C-DBPs和N-DBPs生成潜能均以强疏水性组分或亲水性组分为主,且氯胺化可导致亲水性组分C-DBPs和N-DBPs生成潜能所占总量比例增加.     

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.     

氯对饮用水中可同化有机碳的影响

通过分析太湖水的分子量分布变化以及亲疏组分,考察氯反应生成AOC的效果和机理.结果表明,弱疏组分的AOC生成量最大,其次为强疏,中亲和带负电亲水的生成量最少.氯主要与小分子的疏水性有机物反应,AOC的生成量最多.通过考察深度处理工艺的有机物分子量以及组分的变化,发现疏水性有机物呈逐渐下降而亲水性组分呈上升的趋势,表明氯化产生的AOC呈减少趋势.小分子的疏水性有机物是主要的氯化AOC的前体物.     

Characterization of dissolved organic matter as N-nitrosamine precursors based on hydrophobicity, molecular weight and fluorescence

It is very important to identify the dominant precursors for N-nitrosamine formation from bulk organic matter, to enhance the understanding of N-nitrosamine formation pathways in water treatment plants and allow the development of practical treatment technologies. In this study, dissolved organic matter (DOM) from two source waters was fractionated with XAD resins and ultra- filtration membranes. The N-nitrosamine formation potential (FP) (ng of N-nitrosamines formed per mg of dissolved organic carbon (DOC)) from raw water and each fraction were measured and correlated with the fluorescence excitation-emission matrix (EEM), molecular weight (MW) and other assays. The results showed that the hydrophilic fraction had N-nitrosamine FP 1.3 to 3.5 times higher than the hydrophobic fraction from both source waters. The DOM fraction with low MW was the dominant fraction in these two source waters and contributed more precursors for N-nitrosamine formation than the larger MW fraction. The EEM spectra indicated there were notable amounts of soluble microbial products (SMPs) and aromatic proteins in the two studied rivers, which probably originated from wastewater discharge. The SMPs tended to be more closely correlated with N-nitrosodimethylamine formation potential than the other DOM components. Higher N-nitrosamine FP were also related to fractions with lower DOC/DON ratios and lower SUVA 254 values.     

Effects of DOM characteristics from real wastewater on the degradation of pharmaceutically active compounds by the UV/H2O2 process

The characteristics of dissolved organic matter (DOM) can significantly affect the degradation of target compounds by the advanced oxidation processes. In this study, the effects of the different hydrophobicity/hydrophilicity fractions, molecular weight (MW) fractions, fluorescence components and molecular components of DOM extracted from municipal wastewater on the degradation of 4 pharmaceutically active compounds (PhACs), including carbamazepine, clofibric acid, atenolol and erythromycin by the UV/H₂O₂ process were investigated. The results showed that the degradation rate constants of 4 PhACs decreased dramatically in the presence of DOM. The linear regressions of 4 PhACs degradation as a function of specific fluorescence intensity (SFI) are exhibited during the degradation of 4 PhACs and the SFI may be used to evaluate effect of DOM on target compounds in wastewater. The hydrophobic acid (HPO-A) exhibited the strongest inhibitory effect on degradation of 4 PhACs during oxidation process. The small MW fractions of DOM significantly inhibited the degradation of 4 PhACs during oxidation process. Among three fluorescence components, hydrophobic humic-like substances may significantly inhibit the degradation of 4 PhACs during oxidation process. At the molecular level, the formulas may be derived from terrestrial sources. CHO compound may significantly inhibit the degradation of 4 PhACs during oxidation process on formula classes. The unsaturated hydrocarbons, carbohydrates and tannins compounds may significantly inhibit the effectiveness of the UV/H₂O₂ process on compound classes.     

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.