二级出水微滤过程中对醋酸纤维素酯膜的有机污染特征

低压膜过滤技术(包括微滤和超滤)在再生水生产领域正引起越来越广泛的关注。然而如何解决低压膜过滤过程中的膜有机污染问题始终是膜技术所面临的技术挑战。本研究采用醋酸纤维素酯微孔滤膜对二级出水溶解性有机物(EfOM)及其不同亲疏水性组分、蛋白模拟溶液、腐殖酸(HA)等进行恒流过滤实验。对不同有机物污染后的膜表面使用全反射傅立叶红外光谱(ATR-FTIR)和X射线电子能谱(XPS)进行表征。结果表明,相对于蛋白质和EfOM等,HA所造成的膜污染最少。ATR-FTIR的结果同时显示,以官能团而言,更多的氨化物(1535cm-1)、脂肪族物质(2860～2970cm-1)和氢氧根(3400cm-1)存在于膜表面。TMP/V数据比较结果表明,在EfOM各亲疏水性组分、蛋白质和HA的对比中,EfOM中的疏水碱性物质(HPO-B)对膜污染的贡献最大,而HA的膜污染贡献最小。UVA和荧光激发-发射光谱(FEEM)结果表明,HPO-B和蛋白质对醋酸纤维素酯膜的污染贡献较大。综合不同分析手段可以对不同有机物造成膜污染的潜能大小得出如下排序:HPO-B>蛋白质>HPO-A、HPI>HA。     

城市污水二级出水中溶解性有机物特性分析

分别采用凝胶色谱、亲疏水性组分分离、荧光色谱等方法,研究了城市污水处理厂二级出水中溶解性有机物的分子量分布、亲疏水组分含量以及荧光光谱特性。结果表明,二级出水中疏水性组分较亲水性组分多,疏水性组分约占总有机物的64.3%,而亲水性组分占35.7%左右;二级出水及其不同亲/疏水组分中溶解性有机物分子量分布基本集中在4.5 kDa以下,其中弱疏水性组分和亲水性组分中主要为分子量小于1.5 kDa的有机物;二级出水溶解性有机物中含有腐殖酸类、富里酸类以及蛋白质类物质,其中含量以腐殖酸类为主。     

Differential pressure in membrane channel caused by foulant capture onto spacers.

Feed spacers in spiral-wound reverse osmosis membrane modules are highly susceptible to deposition or attachment of suspended particulates and organic matters in the feed stream. This type of fouling can cause a significant pressure drop along the membrane channel (differential pressure) without much effect on the average permeate flux. In practical applications, membrane cleaning is often triggered when the differential pressure in a membrane channel exceeds a threshold value. A mathematical model was developed to simulate the development of differential pressure in the feed channel resulting from foulant capture by the feed spacers. Simulations were carried out to investigate and demonstrate the effect of various parameters on differential pressures in the membrane channel. Differential pressures observed in a two-stage reverse osmosis water reclamation plant were simulated with the model, and the results showed that the model could adequately describe the increase of differential pressure with operating time in the reverse osmosis plant.     

Rejection of emerging organic micropollutants in nanofiltration-reverse osmosis membrane applications.

The rejection of emerging trace organics by a variety of commercial reverse osmosis (RO), nanofiltration (NF), and ultra-low-pressure RO (ULPRO) membranes was investigated using TFC-HR, NF-90, NF-200, TFC-SR2, and XLE spiral membrane elements (Koch Membrane Systems, Wilmington, Massachusetts) to simulate operational conditions for drinking-water treatment and wastewater reclamation. In general, the presence of effluent organic matter (EfOM) improved the rejection of ionic organics by tight NF and RO membranes, as compared to a type-II water matrix (adjusted by ionic strength and hardness), likely as a result of a decreased negatively charged membrane surface. Rejection of ionic pharmaceutical residues and pesticides exceeded 95% by NF-90, XLE, and TFC-HR membranes and was above 89% for the NF-200 membrane. Hydrophobic nonionic compounds, such as bromoform and chloroform, exhibited a high initial rejection, as a result of both hydrophobic-hydrophobic solute-membrane interactions and steric exclusion, but rejection decreased significantly after 10 hours of operation because of partitioning of solutes through the membranes. This resulted in a partial removal of disinfection byproducts by the RO membrane TFC-HR. In a type-II water matrix, the effect of increasing feed water recoveries on rejection of hydrophilic ionic and nonionic compounds was compound-dependent and not consistent for different membranes. The presence of EfOM, however, could neutralize the effect of hydrodynamic operating condition on rejection performance. The ULPRO and tight NF membranes were operated at lower feed pressure, as compared to the TFC-HR, and provided a product water quality similar to a conventional RO membrane, regarding trace organics of interest.     

Performance investigation of membrane bioreactor systems during municipal wastewater reclamation.

Four commercially available membrane bioreactor (MBR) systems were operated at the pilot scale, to investigate performance during the reclamation of municipal wastewater. The MBR performance was evaluated under a variety of operating conditions, including two types of feed wastewater (raw and advanced primary effluent), hydraulic retention times (HRTs) ranging from 2 to 6 hours, and permeate fluxes between 20 and 41 lmh. Test results showed that MBR systems were capable of operating on advanced primary effluent, despite the possible presence of coagulant and/or polymer residual, with minimal membrane fouling. Membrane performance data generated during this study was also used to quantify the relationship between permeate flux and membrane fouling. Cleaning intervals at various flux conditions were estimated as follows: 69 days at 20 lmh, 58 days at 25 lmh, and 30 days for operation between 31 and 41 lmh. It was also demonstrated that the MBR process could be optimized to operate with minimal fouling under high hydraulic (flux = 37 lmh) and organic loading (HRT = 2 hours and food-to-microorganism ratio = 0.33 g COD/g VSS x d) conditions. Water quality monitoring conducted throughout the study showed that each MBR system consistently produced an oxidized (5-day biochemical oxygen demand < 2 mg/L) and nitrified (ammonia < 1 mg-N/L) effluent low in particulate matter (turbidity < 0.1 NTU), under all conditions tested.     

印染生化尾水反渗透深度处理工艺膜污染成因分析简

为阐明印染生化尾水反渗透膜处理时膜污染的成因,使用小试装置进行40 h膜污染实验,研究膜污染速率、污染程度以及可逆性,同时应用扫描电子显微镜-EDS能谱仪、傅里叶变换红外光谱仪、电感耦合等离子发射光谱仪、总有机碳测定仪等仪器对进水水质、膜表面污染物的形态和组成等进行表征。结果表明,膜表面主要是碳酸钙无机污染和钙与有机物络合污染,无机污染占主导,且可逆性差,有机污染物主要含有—OH和—CC官能团;单一去除废水中有机物污染物（TOC去除率达88%）对膜污染缓解不明显,但钙离子的去除可显著缓解膜污染,膜通量可增加72.6%;同时去除有机物和钙离子,膜通量可增加80.4%。     

印染生化尾水反渗透深度处理工艺膜污染成因分析

为阐明印染生化尾水反渗透膜处理时膜污染的成因,使用小试装置进行40h膜污染实验,研究膜污染速率、污染程度以及可逆性,同时应用扫描电子显微镜一EDS能谱仪、傅里叶变换红外光谱仪、电感耦合等离子发射光谱仪、总有机碳测定仪等仪器对进水水质、膜表面污染物的形态和组成等进行表征。结果表明,膜表面主要是碳酸钙无机污染和钙与有机物络合污染,无机污染占主导,且可逆性差,有机污染物主要含有--OH和～c-c官能团;单一去除废水中有机物污染物（TOC去除率达88％）对膜污染缓解不明显,但钙离子的去除可显著缓解膜污染,膜通量可增加72．6％;同时去除有机物和钙离子,膜通量可增加80．4％。     

基于海水和盐田水的正渗透驱动液

采用海水和盐田水作为驱动液,研究正渗透过程中的通量变化和膜污染特征,探索其作为驱动液的可行性。结果表明,海水和盐田水含有大量的盐离子,具有高的渗透压,海水、2#、5#和9#盐田水与0.42、0.8、2.2和4.2 mol/L的氯化钠具有同样的通量行为。随海水和盐田水浓度增加,通量增加,同时污染也越严重。扫描电子显微镜观察和荧光光谱分析发现,盐田水中的硅酸盐和有机物会沉积在膜表面,引起比较严重的膜污染,尤其是高浓度的盐田水。海水和盐田水作为正渗透过程中的驱动液需要进行一定的预处理。     

一体式膜-生物反应器中膜污染过程的动态分析

膜污染过程的动态研究对于有效地控制膜污染意义重大。结合膜过滤压差的上升和污染膜表面微观形态的变化 ,对不同污泥浓度和膜通量条件下 ,一体式膜 生物反应器中膜污染过程进行了动态分析。结果表明 ,膜污染初期主要是水中溶解性物质在膜表面附着 ,随后污泥在膜表面沉积。溶解性有机物在膜面的附着 ,对膜过滤压差即膜过滤阻力的变化影响不大 ,而活性污泥在膜表面的大量沉积将导致膜过滤压差迅速上升。污泥浓度愈高 ,膜通量愈大时 ,活性污泥颗粒愈易在膜面沉积。通过停止进出水维持空曝气、降低反应器内污泥浓度或延长膜的停抽时间可以使沉积在膜表面的悬浮污泥脱离膜表面 ,从而使膜过滤能力得到很好的恢复。采用经典的膜污染模型对各运行阶段膜污染模式进行了分析 ,模型拟合结果与电镜观察结果基本吻合。     

Transformation of effluent organic matter during subsurface wetland treatment in the Sonoran Desert

The fate of dissolved organic matter (DOM) during subsurface wetland treatment of wastewater effluent in a hot, semi-arid environment was examined. The study objectives were to (1) discern changes in the character of dissolved organics as consequence of wetland treatment (2) establish the nature of wetland-derived organic matter, and (3) investigate the impact of wetland treatment on the formation potential of trihalomethanes (THMs). Subsurface wetland treatment produced little change in DOM polarity (hydrophobic-hydrophilic) distribution. Biodegradation of labile effluent organic matter (EfOM) and internal loading of wetland-derived natural organic matter (NOM) together produced only minor changes in the distribution of carbon moieties in hydrophobic acid (HPO-A) and transphilic acid (TPI-A) isolates of wetland effluent. Aliphatic carbon decreased as a percentage of total carbon during wetland treatment. The ratio of atomic C:N in wetland-derived NOM suggests that its character is determined by microbial activity. Formation of THMs upon chlorination of HPO-A and TPI-A isolates increased as a consequence of wetland treatment. Wetland-derived NOM was more reactive in forming THMs and less biodegradable than EfOM. For both HPO-A and TPI-A fractions, relationships between biodegradability and THM formation potential were similar among EfOM and NOM isolates; the less biodegradable isolates exhibited greater THM formation potential.     

Microbial fouling of a reverse osmosis municipal water treatment system

Microbial fouling of a municipal water treatment system using reverse osmosis was investigated. From a combination of growth and molecular assays, it was discovered that the prefilter unit concentrated and facilitated microbial growth, and such growth led to microbial fouling of the reverse osmosis unit. Few cells were observed in the prefilter influent, but substantial microbial contamination was observed in the prefilter effluent, and this correlated with increasing headloss across the prefilter. The effluent caused microbial fouling of the leading elements of the reverse osmosis unit, as determined by reduced permeate flow, analysis of the elements, and assays of the membrane foulant. Both the introduction of microorganisms to the reverse osmosis unit from the prefilter unit and headloss across the prefilter could be effectively controlled through cleansing of the prefilter housing unit with sulfuric acid. Such treatments must be performed at appropriate intervals to prevent subsequent microbial growth in the prefilter unit.     

不同工艺再生水补给对景观湖水质变化的影响

再生水回用于景观水体过程中,为了比较不同再生水工艺对景观水体富营养化的影响,以"二级出水+BAF+O3+GFH"和"二级出水+O3"作为再生水处理工艺,以岸滤(bank filtration,BF)作为水质维持工艺,进行再生水景观水体水质保障技术研究。结果表明,"二级出水+O3"出水流量较大,水力流动快,每天运行24 h,平均出水流量25.5 m3/d,氮磷含量偏高;"二级出水+BAF+O3+GFH"出水的氮磷指标控制在较低水平,GFH出水流量8～14 m3/d,水力流动较缓,湖中出现蓝藻。2套系统中BF对NH4+-N的去除率分别为30.5%和20.8%。"二级出水+O3+BF"系统中人工湖进水TN平均浓度24.309 mg/L,TP平均浓度0.583 mg/L,N/P=41,适宜水网藻生长,对湖中N(主要是NH4+-N)、P有较强的去除能力;"二级出水+BAF+O3+GFH+BF"系统中人工湖进水TP<0.05 mg/L,适宜蓝藻生长。     

Spectroscopic study of the degradation of antibiotics and the generation of representative EfOM oxidation products in ozonated wastewater

This study examined effects of ozonation on thirteen fluoroquinolone, macrolide and lincosamide antibiotics present in municipal wastewater. Transformations of effluent organic matter (EfOM) caused by ozonation were characterized using absorbance/fluorescence spectroscopy and high performance size exclusion chromatography (HPSEC). Concentrations of aldehydes and carboxylic acids generated via the oxidation of EfOM were also determined. The absorbance and fluorescence of ozonated wastewater decreased with increasing ozone dose or treatment time. HPSEC data showed that these phenomena corresponded to the oxidation of all EfOM fractions, with some preference towards the degradation of the EfOM molecules with high apparent molecular weight. The removal of antibiotics and production of aldehydes and carboxylic acids were strongly correlated with the changes in both EfOM absorbance and fluorescence. Applications of a model describing the concurrent degradation of trace level contaminants and relative changes of EfOM emission allowed achieving a good fitting between the experimental and modeled ΔC/C₀ vs. ΔA/A₀ and ΔC/C₀ vs. ΔF/F₀ data.     

不同超滤膜过滤天然有机物的膜污染特性研究

超滤膜的截留分子量、天然有机物的分子量分布以及两者之间的相对关系对于膜污染以及过滤阻力的组成有很大的影响。MWCO140kDa、70kDa、30kDa、10kDa、4kDa和1kDa的超滤膜过滤10mg/L腐殖酸溶液和未名湖湖水的试验结果表明,在过滤初始时刻就发生了膜污染,膜的截留分子量越大,膜污染越显著。在长期过滤的过程中,截留分子量>10kDa的超滤膜的过滤阻力受到膜污染的控制,膜孔堵塞和膜面形成凝胶层是造成膜污染的主要原因;当膜的截留分子量≤10kDa时,过滤阻力主要由膜本身固有的阻力决定,膜污染影响较小。不同浓度、类型的腐殖酸溶液和不同种类的超滤膜过滤试验数据分析表明,当膜对腐殖酸分子的截留率超过40%时,膜污染的程度会逐渐减小,过滤阻力将由膜本身固有的阻力控制。     

膜-生物反应器混合液性质对膜污染影响的研究进展

膜-生物反应器作为一种新型的污水处理和回用技术,近年来在基础研究和实际应用领域都得到广泛关注,但是影响其长期稳定运行的膜污染问题却一直没有得到深入研究和解决.混合液特性是影响膜污染控制的重要因素,从混合液理化性质(组成、功能、结构和环境因素)和生物学性质(微生物群落结构、微生物功能特征)2个方面进行介绍,综述了目前关于混合液性质与膜污染关系的研究现状.目前的研究虽然取得一定进展,但在相关性分析、群落特征与膜污染关系、污染层形成机理等方面仍存在许多不足.     

Irreversible fouling during multicycle microfiltration of wastewater effluent

This study focused on irreversible fouling during microfiltration of primary and secondary effluents from municipal wastewater treatment plants. Flow resistances were calculated from the sum of clean membrane resistances, resultant cake layer resistances, and consequent irreversible fouling resistances. Results from a dead-end cell experimental system showed that the accumulated cake resistance was dominating for microfiltration of primary/secondary effluents. Suspended solids in the primary and secondary effluents had a similar compressibility index, n, with a value of approximately 0.5, indicating that they were moderately compressible particles. The value of irreversible resistance is dependent on the intensity of membrane cleaning; however, for a given membrane cleaning strategy, this value steadily increased and reached a maximum after approximately 6 cycles of filtration and cleaning. This study provided an explanation for the significant drop of throughput flux in the early application of membrane processes, and a plateau flux approached correspondingly.     

Treatment of municipal wastewater by membrane bioreactor: a pilot study

The operational performance of a submerged hollow fibre Membrane Bio-Reactor (MBR) for treatment of municipal wastewater on pilot scale was investigated. The experimental results indicated that the removal efficiency for SS, COD, NH₄-N, turbidity, bacterium, iron (Fe²⁺) and Manganese (Mn²⁺) was 100%, 94.5%, 98.3%, 99.7%, lg6, 99%, 92.3%, respectively. The water quality of the effluent was quite good. The reclaimed water could be reused either directly or indirectly for municipal or industrial purposes. The MBR had a strong ability to resist loading shock and DO was a crucial factor to membrane fouling.     

Use of chemical coagulants to control fouling potential for wastewater membrane bioreactor processes.

Chemical coagulation with ferric chloride, alum, and an organic polymer were used to control the fouling potential of mixed liquors for submerged membrane bioreactor (MBR) processes in treating municipal wastewater. Their filterability was evaluated using a submerged hollow fiber ultrafiltration apparatus operated in constant permeate flux mode. The collected transmembrane pressures over filtration time were used to calculate the membrane fouling rates. The results showed that coagulation pretreatment can reduce fouling rates when MBRs were operated above the critical flux. Even though coagulation with the organic polymer formed larger mixed liquor suspended solids particles and had shorter time-to-filtration than those with ferric chloride and alum, the filterability for membrane filtration were similar, indicating that the membrane fouling in MBR systems was mainly controlled by the concentration of smaller colloidal particles.     

Dissolved organic matter from treated effluent of a major wastewater treatment plant: characterization and influence on copper toxicity

A combination of reverse osmosis (RO) concentration and DAX-8/XAD-4 resin adsorption techniques is used to isolate the various constituents of urban dissolved organic matter (DOM) from inorganic salts. Three fractions: hydrophobic (HPO), transphilic (TPI) and hydrophilic (HPI) accounting respectively for 35%, 20% and 45% of extracted carbon, are isolated from effluents of a major French wastewater treatment plant. This atypical DOC distribution, in comparison with natural water where the HPO fraction dominates, shows the significance of HPI fraction which often gets neglected because of extraction difficulties. A number of analytical techniques (elemental, spectroscopic: UV, FTIR) allow highlighting the weak aromaticity of wastewater effluent DOM (EfOM) due to fewer degradation and condensation processes and the strong presence of proteinaceous structures indicative of intense microbial activity. Copper toxicity in the presence of DOM is estimated using an acute toxicity test on Daphnia Magna (Strauss). Results reveal the similar protective role of each EfOM fraction compared to reference Suwannee river fulvic acid despite lower EfOM aromaticity (i.e. specific UV absorbance). The environmental implications of these results are discussed with respect to the development of site-specific water quality criteria.     

Removal of highly polar micropollutants from wastewater by powdered activated carbon

Due to concerns about ecotoxicological effects of pharmaceuticals and other micropollutants released from wastewater treatment plants, activated carbon adsorption is one of the few processes to effectively reduce the concentrations of micropollutants in wastewater. Although aimed mainly at apolar compounds, polar compounds are also simultaneously removed to a certain extent, which has rarely been studied before. In this study, adsorption isotherm and batch kinetic data were collected with two powdered activated carbons (PACs) to assess the removal of the polar pharmaceuticals 5-fluorouracil (5-Fu) and cytarabine (CytR) from ultrapure water and wastewater treatment plant effluent. At pH?7.8, single-solute adsorption isotherm data for the weak acid 5-Fu and the weak base CytR showed that their adsorption capacities were about 1 order of magnitude lower than those of the less polar endocrine disrupting chemicals bisphenol A (BPA) and 17-α-ethinylestradiol (EE2). To remove 90 % of the adsorbate from a single-solute solution 14, 18, 70, and 87 mg?L^?1 of HOK Super is required for EE2, BPA, CytR, and 5-Fu, respectively. Effects of solution pH, ionic strength, temperature, and effluent organic matter (EfOM) on 5-Fu and CytR adsorption were evaluated for one PAC. Among the studied factors, the presence of EfOM had the highest effect, due to a strong competition on 5-Fu and CytR adsorption. Adsorption isotherm and kinetic data and their modeling with a homogeneous surface diffusion model showed that removal percentage in the presence of EfOM was independent on the initial concentration of the ionizable compounds 5-Fu and CytR. These results are similar to neutral organic compounds in the presence of natural organic matter. Overall, results showed that PAC doses sufficient to remove >90 % of apolar adsorbates were able to remove no more than 50 % of the polar adsorbates 5-Fu and CytR and that the contact time is a critical parameter.