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。     

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.     

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 .     

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.     

Membrane fouling in ultrafiltration of natural water after pretreatment to different extents

The combined fouling during ultrafiltration(UF) of surface water pretreated to different extents was investigated to disclose the roles of polysaccharides, proteins, and inorganic particles in UF membrane fouling. Both reversible and irreversible fouling decreased with enhanced pretreatment(biologically active carbon(BAC) treatment and sand filtration). The sand filter effluent fouled the membrane very slowly. The UF membrane removed turbidity to less than 0.1 nephelometric turbidity unit(NTU), reduced polysaccharides by 25.4%–29.9%, but rejected few proteins. Both polysaccharides and inorganic particles were detected on the fouled membranes, but inorganic particles could be effectively removed by backwashing. The increase of turbidity in the sand filter effluent to 3.05 NTU did not significantly increase the fouling rate, but an increase in the turbidity in the BAC effluent to6.11 NTU increased the fouling rate by more than 100%. The results demonstrated that the polysaccharide, not the protein, constituents of biopolymers were responsible for membrane fouling. Membrane fouling was closely associated with a small fraction of polysaccharides in the feed water. Inorganic particles exacerbated membrane fouling only when the concentration of fouling–inducing polysaccharides in the feed water was relatively high. The combined fouling was largely reversible, and polysaccharides were the predominant substances responsible for irreversible fouling.     

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.     

Drinking water production by uitrafiltration 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-m2 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.     

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.     

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.     

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.     

Treatment of phosphate-containing oily wastewater by coagulation and microfiltration

The oily wastewater generated from pretreatment unit of electrocoating industry contains oils, phosphate, organic solvents, and surfactants. In order to improve the removal efficiencies of phosphate and oils, to mitigate the membrane fouling, coagulation for ceramic membrane microfiltration of oily wastewater was performed. The results of filtration tests show that the membrane fouling decreased and the permeate flux and quality increased with coagulation as pretreatment. At the coagulant Ca （OH）2 dosage of 900 mg/L, the removal efficiency of phosphate was increased from 46.4% without coagulation to 99.6%; the removal of COD and oils were 97.0% and 99.8%, respectively. And the permeate flux was about 70% greater than that when Ca（OH）2 was not used. The permeate obtained from coagulation and microfiltration can be reused as make-up water, and the recommended operation conditions for pilot and industrial application are transmembrane pressure of 0.10 MPa and cross-flow velocity of 5 m/s. The comparison results show that 0.2 μm ZrO2 microfilter with coagulation could be used to perform the filtration rather than conventional ultrafilter, with very substantial gain in flux and removal efficiency of phosphate.     

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%.     

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.     

预处理对短流程超滤工艺不可逆膜污染影响的中试试验

以东江水为处理对象,进行直接超滤、微絮凝-超滤和絮凝/活性炭-超滤中试研究,探讨预处理对短流程超滤工艺不可逆膜污染的影响.利用扫描电镜形貌观察、三维荧光光谱(EEM)和高效排阻色谱法等手段对不可逆膜污染物进行表征分析,比较预处理对不可逆膜污染物含量和组分的影响,阐述预处理对不可逆膜污染影响的机制.结果表明,在10 L·(m~2·h)~(-1)低通量运行下,微絮凝预处理使不可逆膜污染增长速率从直接超滤的0.32 k Pa·d~(-1)下降到0.16 k Pa·d~(-1),絮凝/活性炭预处理后超滤工艺几乎零污染运行,且当絮凝/活性炭-超滤运行通量增加至17 L·(m~2·h)~(-1)时,仍没有观察到明显的不可逆膜污染增长.东江水中不可逆膜污染的主要组分是蛋白质类和富里酸等腐殖质类物质.微絮凝通过改变膜表面滤饼层的结构(厚度和密实性),提高物理清洗效率,减轻不可逆膜污染的积累;絮凝/活性炭预处理提高对不可逆膜污染物的去除效果,减轻膜污染负荷,控制不可逆膜污染.因此,采用絮凝和絮凝/活性炭预处理工艺,均可有效降低短流程超滤工艺不可逆膜污染积累.     

UF膜与混凝粉末活性炭联用处理冬季黄河水

针对低温低浊水处理的难题,采用混凝和粉末活性炭预处理超滤系统对冬季黄河水进行了净化研究,通过投加混凝剂Al(2SO)4·318H2O以及粉末活性炭,比较了其对于原水的处理效果和对膜过滤性能的影响。试验结果表明,混凝超滤系统用于处理冬季黄河水在技术上是可行的,混凝剂与粉末活性炭对水中污染物质的去除和膜过滤性能有很大的影响;调整合适的操作参数,其对低温黄河水中的高锰酸盐指数、UV254、NH3-N、铁和浊度的平均去除率分别达到70%、60%、30%、80%和96%以上,出水水质达到《生活饮用水源水质标准》(CJ3020-93)的标准。对于已污染的膜,水反冲洗、水/酸洗、水/碱洗可使膜通量恢复至新膜的38%,82%,89%。     

混凝对微滤膜处理含磷废水的影响

采用直接微滤和混凝-微滤2种工艺对高浓度含磷废水进行了处理.结果表明,混凝预处理减轻了膜孔堵塞污染,改善了膜表面沉积层的存在形态,提高了膜的渗透通量;与原水直接微滤相比,混凝-微滤组合工艺改进了出水水质,磷酸盐的去除率从11.0%提高到99.7%,出水满足国家一级排放标准;经过相同方法清洗后,混凝-微滤工艺的膜通量能恢复到初始通量的90%以上,而直接微滤工艺的膜通量只能恢复到初始通量的72%.     

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.     

投加粉末活性炭对一体式膜-生物反应器膜污染的影响研究

通过试验考察了粉末活性炭（PAC）对一体式膜-生物反应器中膜污染的影响．在2种类型的污泥（膨胀污泥和非膨胀）中，投加适量PAC可以减轻膜污染，表现为临界膜通量的提高和连续运行中膜污染增长速率的降低．当污泥性质和浓度不同时，最佳PAC投加范围亦不同．PAC投量过大会引起临界通量下降．PAC的投加显著降低了混合液中溶解性物质的浓度，减轻了溶解性物质的吸附和膜孔堵塞污染，并改善了絮体结构．污泥比阻与污泥混合液膜过滤性能之间有很好的相关性，可作为污泥混合液膜过滤性能的快速评价指标．     

超滤处理洗涤污水循环利用的中试研究

采用不同材质国产超滤膜聚丙烯（PP）、聚丙烯腈（PAN）和聚砜（PS）,进行了洗涤污水处理循环利用的现场中试研究.结合超滤工艺出水水质和膜污染分析,3种膜材质中PAN膜较优,有效去除了水中浊度、悬浮物、油脂等污染物,一定程度保留了游离阴离子表面活性剂（LAS）,长期循环洗涤对衣物的白度无不良影响.根据相关性分析,超滤出水较高COD值很大程度上是由水中LAS引起的.超滤膜对细菌、大肠菌群的去除率较低,出水通过紫外消毒,当紫外线密度≥3?750 J/m²时,微生物水平能够达到国家饮用水水质标准.根据不同水力反冲洗条件下膜渗透通量和净产水量比较,PAN膜最佳水力反冲洗条件为0.5 h反冲洗2 min.长期运行时超滤膜化学清洗方法采用碱洗法方便有效.     

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.