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.     

预臭氧化对二级出水微滤过程中膜有机物污染的影响

在二级出水溶解性有机物（secondary effluent organic matter,EfOM）的微滤过程中,多种因素均与膜的有机污染相关,比如总有机物的含量,溶解性有机物的亲疏水性组成等.本文主要研究了在二级出水微滤过程中溶解性有机物的膜污染,以及预臭氧化对二级出水溶解性有机物性质的影响进而对膜有机污染的影响....     

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.     

Tracking the reactivity of ozonation towards effluent organic matters from WWTP using two-dimensional correlation spectra

The characteristics of effluent organic matter (EfOM) from a wastewater treatment plant (WWTP) during ozonation were investigated using excitation and emission matrix (EEM) spectra, Fourier transform infrared spectroscopy (FT-IR) and high-performance size exclusion chromatography (HPSEC) at different ozone dosages. The selectivity of ozonation towards different constituents and functional groups was analysed using two-dimensional correlation spectra (2D-COS) probed by FT-IR, synchronous fluorescence spectra and HPSEC. The results indicated that ozonation can destroy aromatic structures of EfOM and change its molecular weight distribution (MWD). According to 2D-COS analysis, microbial humic-like substances were preferentially removed, and then the protein-like fractions. Terrestrial humic-like components exhibited inactivity towards ozonation compared with the above two fractions. Protein-like substances with small molecular weight were preferentially reacted during ozonation based on 2D-COS probed by HPSEC. In addition, the selectivity of ozone towards different functional groups of EfOM exhibited the following sequence: phenolic and alcoholic CO groups?>?aromatic structures containing CC double bonds?>?aliphatic CH. X-ray photoelectron spectroscopy (XPS) further elucidated the preferential reaction of aromatic structures in EfOM during ozonation.     

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.     

城市污水二级出水超滤膜污染与膜特性的研究

以城市污水二级出水为过滤介质,考察了PVA、PVP、PMMA等与PVDF的二元及三元共混超滤膜的过滤污染行为.结果表明,共混优化了PVDF超滤膜的结构参数,添加剂PVP、PVA可有效改善膜的亲水化程度,提高膜渗透通量.超滤膜的亲水性和结构特性对膜抗污染性能影响较大;堵孔阻力是二级出水过滤膜污染不可逆的主要原因.亲水性较强的超滤膜,二级出水过滤初期易因浓差极化而导致滤饼层污染,造成一定的通量衰减,但易清洗恢复,不可逆污染指数(rir)为0,抗污染性能好.致密的超滤膜表面有利于防止二级出水中的中低分子量污染物进入膜内部,而断面通透大孔和疏松海绵层结构的超滤膜,能减少二级出水中的污染物在膜中沉积形成堵孔阻力.膜表面多孔,内部大孔发育不充分,易形成堵孔污染,通量衰减大且不易清洗恢复,膜污染不可逆.     

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.     

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.     

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.     

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.     

混凝沉淀-UF工艺去除二级出水中ARGs效能研究

为了研究混凝沉淀-UF工艺对城市污水处理厂二级出水中ARGs（抗生素抗性基因）去除的影响,以PACl（聚合氯化铝）和PFS（聚合硫酸铁）作为混凝剂,采用qPCR（实时荧光定量聚合酶链式反应）和EEM（三维荧光光谱）等分析混凝沉淀-UF工艺对ARGs的削减及其影响因素.结果表明:① PACl、PFS投加量（分别以Al、Fe计,下同）分别为0.85、0.50 mmol/L时,与直接UF工艺相比,混凝沉淀-UF工艺对水中各类ARGs的去除量高2~3个数量级,其中PACl-UF工艺的效果更好,去除量为2.51~3.52个数量级;对水中DOC（溶解性有机碳）、富里酸类及溶解性微生物代谢产物的去除效果更好,DOC去除率由18%升至36%.②直接UF、PACl-UF、PFS-UF 3种工艺膜进、出水的线性拟合结果显示,ARGs浓度与ρ（DOC）、16S rDNA浓度均呈显著正相关.研究显示,混凝沉淀-UF工艺可以有效去除二级出水中的ARGs,且有机物、16S rDNA的去除有助于ARGs的削减.      

污水厂二级出水溶解性有机物臭氧化特性研究

采用液相色谱荧光检测器将三维荧光图谱与凝胶色谱分子量分布相结合,对污水处理厂二级出水溶解性有机物(EfOM)的臭氧化反应特性进行了研究.结果表明臭氧会使得二级出水溶解性有机物三维荧光强度明显降低.HPLC-SEC的结果表明臭氧不会改变腐殖质类物质的分子量分布,但臭氧会与小分子蛋白类物质发生反应.根据制备液相的分析结果,小分子蛋白类物质中含有大量苯环及其他共轭结果物质,因此臭氧会优先与小分子蛋白类物质发生反应.同时,XPS分析结果表明臭氧在低投加量下就会与苯环结构反应,提高脂肪类饱和有机物含量,随着投加量进一步升高,含氧官能团(羰基,羧基)数量有所升高.     

预涂动态膜强化超滤去除海水中有机物及其对膜污染的影响

以粉末活性炭和硅藻土为涂膜材料,在聚醚砜超滤膜表面形成预涂动态膜,考察了预涂动态膜对海水中有机物的去除效果和作用机制,通过比较分析直接超滤和预涂动态膜过滤海水前后膜表面亲疏水性、形貌结构、粗糙度及膜阻力分布的变化,探讨了活性炭和硅藻土预涂覆对超滤膜污染的影响.结果表明,预涂动态膜可提高超滤膜对海水中溶解有机碳(DOC)和UV_(254)的去除率,活性炭预涂动态膜对海水中DOC和UV_(254)的去除率较直接超滤分别提高11.2%和11.3%.硅藻土预涂膜主要利用超滤膜表面形成的硅藻土滤饼层强化海水中蛋白质类有机物的截留,活性炭对海水中小分子有机物的额外吸附导致海水过滤过程中活性炭预涂膜对有机物的去除效果优于硅藻土预涂膜.与直接超滤相比,预涂动态膜过滤海水后膜表面亲水性更好,膜表面粗糙度更低,膜过滤阻力也更小,活性炭预涂动态膜净化海水时膜过滤总阻力较直接超滤降低50.3%.利用涂膜材料在超滤膜表面形成的滤饼层将超滤膜与有机物进行了"隔离",避免了超滤膜与有机污染物直接接触,降低了小分子有机物在膜孔内的吸附堵塞,能够有效减缓超滤膜的不可逆污染.     

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.     

超滤及其组合工艺对污水的深度处理试验

超滤及其组合工艺 ,混凝 UF和粉末活性炭 (PAC) UF对污水深度处理的试验结果表明 ,超滤对水中浊度几乎可以完全去除 ,对细菌和大肠杆菌的去除效率大于 99% ,对水中有机物、氨氮、总铁和总锰也均有一定的去除。超滤前加混凝预处理或粉末活性炭吸附后 ,提高了水中有机物的去除率 ,同时减轻了膜污染 ,提高了膜通量和产水量。此外 ,三种工艺在等量冲洗用水的条件下 ,适当缩短过滤周期 ,增加反冲洗频率均提高了单位能耗产水量。     

污水再生处理反渗透系统进水膜污堵潜势评价方法及指标体系

由于污水中的有机物含量显著高于海水,因此污水再生处理反渗透（RO）系统面临比海水淡化RO系统更加严重的污堵问题。为了有效预测和控制RO膜的污堵,需要对RO系统进水污堵潜势进行全面评价。从颗粒物/胶体污堵、无机结垢、有机污堵和生物污堵4个方面,分析了目前RO系统理论研究和工程实践中常用的进水污堵潜势评价方法和指标体系的特点。针对颗粒物/胶体污堵和无机结垢,实际工程中的潜势评价与控制方法已经相对成熟。然而,目前污水再生处理RO系统的工程设计中尚无针对有机污堵和生物污堵的指标。现有研究表明,在污水再生处理RO系统中,当进水ρ（DOC）<4 mg/L时,RO膜的污堵速率显著降低,可将该数值作为RO系统进水水质设计的参考。除有机物总量外,还应综合考虑有机物分子量和亲疏水性-酸碱性等组分特性,大分子、疏水中性和酸性物质更容易沉积于RO膜面导致污堵。在生物污堵方面,现有的针对进水生物量和生物膜生长速率（BFR）的指标均不能有效反映进水的生物污堵潜势,因此,生物污堵的预防和控制,仍是未来RO系统污堵防控领域的研究重点。     

Membrane flux dynamics in the submerged ultrafiltration hybrid treatment process during particle and natural organic matter removal

Exponential relationship was developed to quantify the normalized membrane flux dynamics during the filtration period and fitted the results well.     

粉末活性炭预沉积去除藻类有机物及其对膜污染的影响

以东海原甲藻分泌的藻类有机物（AOM）为研究对象,研究粉末活性炭预沉积和预吸附两种膜前预处理手段对海水中AOM的去除作用,对比分析AOM直接超滤、预沉积和预吸附后再超滤时膜通量、膜阻力分布、膜表面亲疏水性和粗糙度的变化,探讨粉末活性炭孔隙结构、沉积量对AOM去除效果及超滤膜污染的影响.结果表明,活性炭预沉积和预吸附能够提高超滤膜对含AOM海水中DOC和UV₂₅₄的去除率,预沉积对AOM的去除作用优于预吸附,介孔活性炭较微孔活性炭的预沉积效果更好,当介孔活性炭PAC2的沉积量为0.4g/L时,DOC和UV₂₅₄的去除率较直接超滤分别提高了25.1%和33.6%.紫外吸收比指数（URI）分析表明,活性炭预沉积和预吸附对有机物的去除作用具有选择性,AOM中芳香族物质较脂肪族羧基类物质更易被除去.粉末活性炭预沉积下AOM超滤时的滤饼层污染阻力（R_c）和膜孔堵塞阻力（R_p）较直接超滤分别降低了39.6%和81.2%,活性炭在超滤膜表面形成的滤饼层结构将AOM与超滤膜进行了隔离,能够减缓膜污染速率,对于控制膜的不可逆污染亦具有重要作用.