微絮凝对腐殖酸超滤过程膜污染的减缓特性

以硫酸铝[Al_2(SO_4)_3·18H_2O]为絮凝剂,腐殖酸(humic acid,HA)和高岭土(Kaolin)水溶液为原水,研究微絮凝过程产生的不同絮体形态,对自制聚偏氟乙烯(PVDF)超滤膜过滤过程的影响.主要考察了微絮凝过程中絮体的特性(粒径大小及分布,分形维数)以及不同条件下形成的絮体形态对膜通量的影响,利用扫描电镜(SEM)和原子力显微镜(AFM)对污染膜的表面形貌进行表征,并测定了PVDF膜与有机污染物之间黏附力大小,来解析不同絮体形态对超滤膜的膜污染影响机制.结果表明,Al~(3+)以电性中和作用水解去除有机物,随着絮凝剂投加量的增加,絮体粒径不断增大,絮体的分形维数减小.膜通量衰减速率与絮体的粒径呈负相关,絮体粒径越大,膜通量衰减速率越小,超滤过程中形成的滤饼层越疏松,同时,较小分形维数的絮体引起的膜污染较轻,其膜通量恢复率也较高.PVDF-有机污染物之间的相互作用力大小与运行初期相应污染膜通量衰减速率呈正相关.当Al~(3+)投加量为5 mg·L~(-1),初始pH=7时,HA去除率为96.7%,膜通量衰减最小,通量恢复率达到88%.     

三种典型混凝剂处理带正电胶粒絮体性能的影响因素

采用光学散射絮凝度测定仪(IPDA2000型)研究3种典型混凝剂(PAC、PFS、FeCl_3)在不同pH值和混凝剂投加量下处理带正电胶粒时的絮体絮凝特性、絮体强度以及破碎后恢复性能。结果表明:过低和过高的pH值及投加量都不利于絮体形成;PAC投加量50 mg/L(pH=8.5),PFS投加量50 mg/L(pH=8),FeCl_3投加量30 mg/L(pH=7)条件下,絮凝速度最快,絮体尺寸最大,且FeCl_3絮体的稳定尺寸为PAC和PFS的1.5倍,絮体形成速度更快,达到最优条件需要碱度更低。投药量是影响絮体强度和恢复性能的重要因素,随着投加量增加,FeCl_3、PFS、PAC絮体强度增大,但恢复性能降低;同条件下FeCl_3的恢复因子为PFS和PAC的0.5倍。     

低温条件下絮体破碎再絮凝去除水中颗粒的研究

为了了解低温条件下絮体的形成/破碎/再絮凝过程在适当条件下对絮凝去除水中颗粒物的强化效果,采用PDA2000透光率脉动检测仪对絮凝破碎再絮凝过程进行了在线监测.研究结果表明,当电中和机理占主导作用时(混凝剂投加量小于0.1 mmol·L-1),絮体破碎后能重新絮凝,絮体大小能恢复到破碎之前;而当网捕卷扫机理占主导作用时(混凝剂投加量大于0.2 mmol·L-1),絮体的恢复情况不如电中和条件,再絮凝能力降低.投加适量的腐殖酸会增加絮体破碎前后的分形维数,但过量的腐殖酸则会降低破碎前后絮体的分形维数.絮体破碎再絮凝后其分形维数比破碎前高.腐殖酸的投加量并不会明显影响絮凝和破碎后再絮凝的FI指数.电中和絮体破碎前初始絮凝时间越长破碎后沉后水浊度越低,破碎后其浊度会比破碎前显著减小.较低投量的铝盐就能使得沉后水浊度降到很低,因此可以降低混凝剂投量而达到更好的水处理效果.     

调控絮体形态强化电絮凝减缓膜污染

本研究通过调节电絮凝工艺参数来实现对絮体形态的调控,进而达到减缓膜污染的目的.主要考察了电流密度、初始pH、初始电导率对絮体性质以及膜通量的影响,并解析了超滤膜对不同形貌结构絮体的膜污染响应机制.结果表明,电絮凝减缓膜污染的关键是在膜表面形成疏松多孔的滤饼层,电絮凝-超滤(electrocoagulation-ultrafiltration,EC-UF)工艺不但能够有效地减缓膜污染,而且还极大提升了出水水质.增加电流密度,以及在pH中性水质条件下,EC-UF工艺中膜通量保持更高.j=20 A·m~(-2)、初始pH=7、初始电导率=1 000μS·cm~(-1),EC-UF工艺对水中的腐殖酸(humic acid,HA)去除率为97%,平衡阶段归一化通量J/J0达到81%.     

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%.     

颗粒物对混凝过程及超滤膜污染的影响

以nm-SiO₂和μm-SiO₂体系为研究对象,使用3种不同Al形态的混凝剂（AlCl₃、Al₁₃和Al₃₀）进行混凝-超滤实验,考察不同pH值下SiO₂去除率、出水余Al及混凝预处理对膜通量的影响,借助马尔文激光粒度仪、SEM、BET和AFM表征絮体性质及在超滤膜表面的分布和作用力.结果表明,nm-SiO₂体系中SiO₂去除率均低于μm-SiO₂体系,在纳米颗粒物体系中投加混凝剂后膜通量从0.68分别提升至0.96（AlCl₃）、0.86（Al₁₃）和0.87（Al₃₀）,微米颗粒物体系中投加3种混凝剂后膜通量从0.79提升至0.80~0.84.微米级颗粒物是颗粒间的碰撞,纳米级颗粒物主要以团聚态的形式碰撞.低聚态铝（Al_a）和颗粒物形成絮体的粒径均大于150μm,体系zeta电位为负与膜表面产生斥力;在中性条件下Al₁₃与颗粒物形成絮体的强度因子远高于AlCl₃和Al₃₀,中聚态铝（Al_b）将膜孔内部较小颗粒物堵塞形成的不可逆膜污染转移成膜孔表面的可逆膜污染;高聚态铝（Al_c）具有较强吸附架桥和网捕卷扫能力,无定形、不规则的团聚态小颗粒在这一过程中形成较大絮体缓解膜污染.     

投加氢氧化铁对SMBR中活性污泥性能的影响

试验研究了在SMBR中投加不同量氢氧化铁对出水水质以及膜污染的影响。结果表明,生物铁-SMBR中随氢氧化铁投加量的增加,COD出水及去除率略有提高;氢氧化铁投加量为5%时,对活性污泥的活性促进作用最强;活性污泥SVI的降低主要是氢氧化铁絮体本身的化学絮凝作用所致;试验条件下氢氧化铁最佳投加量为混合液污泥浓度的5%时,半透膜压增长最慢,膜污染程度最轻。     

加载混凝-高梯度磁过滤工艺处理污染河水的试验研究

首先对污染河水通过搅拌烧杯试验比较了聚合硫酸铁(PFS)和自制的磁性絮凝剂(MF)加载磁粉混凝沉淀去除浊度和总磷的效果,结果表明,当PFS或MF投加量均为30 mg/L、PAM投加量为0.5 mg/L,磁粉投加量为0.5 g/L,加载混凝沉淀后浊度均1NTU,总磷0.2 mg/L。对河水加载磁粉混凝-高梯度磁过滤现场试验表明,MF混凝产生的絮体密实,加载混凝-磁过滤出水浊度、总磷和SS均比PFS和磁粉的复配投加要小,本工艺处理污染河水具有流程短、效率高和占地面积少的优势。     

颗粒计数仪在水处理絮凝过程中的应用研究

以水中高岭土颗粒和腐殖酸有机物为去除对象,首次采用颗粒计数仪对铝盐絮体的动态絮凝变化过程进行了在线监测和分析。通过改变水力条件和投药量,分析了硫酸铝和聚合氯化铝(PAC)絮凝剂絮凝过程中各阶段的絮体颗粒粒径分布情况,在此基础上分析并确定絮凝反应的最佳条件。通过实验表明:颗粒计数仪能够较好地表现出絮凝过程的粒径分布变化,同时得出颗粒总数变化与絮凝效果的相关性很好,可以灵敏地表征絮凝效果的好坏,因而可以用来优化絮凝剂的投加量,提高出水水质和降低出水成本。可以预期,颗粒计数器在未来水处理中一定会得到广泛的应用。     

藻形态及混凝剂组成对混凝-超滤过程的影响

为了保证藻类暴发阶段优质的饮用水供应,提高藻类的去除率,缓解藻类对水处理过程的影响,本研究以铜绿微囊藻(蓝藻)、小球藻(绿藻)和小环藻(硅藻)这3种不同形态藻细胞为研究对象,使用了3种具有不同铝形态分布的混凝剂[Al_2(SO_4)_3(AS)、Al_(13)、Al_(30)]进行混凝-超滤实验.在分离胞外有机物(EOM)的情况下,考察混凝过程中絮体的特性(粒径,强度因子,恢复因子)以及不同条件下形成的絮体对膜通量的影响.结果表明Al_(13)与Al_(30)的混凝作用以静电簇作用为主导,AS主要是以电中和作用为主导.对于铜绿微囊藻与小球藻体系,由于藻颗粒表面存在一定的凹陷,当Al_(13)与Al_(30)做混凝剂时,在投加量较低的情况下,吸附在颗粒表面凹陷处的混凝剂“失活”,其他部位由于仍带有一定的负电荷而造成絮体形成不明显,而AS做混凝剂时,混凝机制主要是电中和作用,可以明显降低颗粒之间的排斥力,在较低投加量下即可形成絮体.对于小环藻体系,由于其藻细胞呈现光滑的表面,Al_(13)与Al_(30)可有效发挥其静电簇作用机制,絮体在较低投加量下即可有效形成.膜通量与絮体粒径有明显的相关性,絮体粒径越大,超滤过程中形成的沉积层越疏松,膜比通量越大.     

Purification, characterization and application of dual coagulants containing chitosan and different Al species in coagulation and ultrafiltration process

The objective of this study was to investigate the effect of different Al species and chitosan (CS) dosages on coagulation performance, floc characteristics (floc sizes, strength and regrowth ability and fractal dimension) and membrane resistance in a coagulation–ultrafiltration hybrid process. Results showed that different Al species combined with humic acid in diverse ways. Al_a had better removal efficiency, as determined by UV₂₅₄ and dissolved organic carbon, which could be further improved by the addition of CS. In addition, the optimal dosage of different Al species was determined to be 4.0 mg/L with the CS concentration of 1.0 mg/L, by orthogonal coagulation experiments. Combining Al_a/Al_b/Al_c with CS resulted in larger flocs, higher recovery, and higher fractal dimension values corresponding to denser flocs; in particular, the floc size at the steady state stage was four times larger than that obtained with Al species coagulants alone. The results of ultrafiltration experiments indicated that the external fouling percentage was significantly higher than that of internal fouling, at around 85% and 15%, respectively. In addition, the total membrane resistance was significantly decreased due to CS addition.     

二氧化氯预氧化对藻类絮体形态的影响

针对高含藻高含盐杨埕水库原水藻类特征,采用聚合氯化铝(PAC)、硫酸铝(AS)、聚合硫酸铁(PFS)和氯化铁(FC)4种混凝剂进行混凝除藻试验,用图像法对藻类絮体的分形维数进行测定,分析混凝剂种类及投量、二氧化氯投加量等因素对混凝除藻效果及藻类絮体形态的影响。结果表明,杨埕水库夏季藻类种属相对较为单一,以小型色球藻、微小平裂藻、不整齐蓝纤维藻为优势藻类;4种混凝剂的除藻性能优劣依次为:AS>PAC>PFS>AC。在AS最佳投加量(以Al2SO4计)70 mg/L下,藻类的去除率为85.3%。此时,杨埕水库夏季藻类以藻类絮体分形维数值为1.54,形成的絮体密实且沉降性好。以AS为混凝剂,投加量为70 mg/L下,二氧化氯投加量为0.8 mg/L时助凝效果最好,藻类的去除率比单独投加AS时提高了6.3%,藻类絮体分形维数值为1.71,形成的藻类絮体更加密实。二氧化氯过量投加无益于藻类去除。     

Characterization of cake layer structure on the microfiltration membrane permeability by iron pre-coagulation

A cake layer is formed by coagulation aggregates under certain transmembrane pressure in the coagulation-microfiltration (MF) process. The characteristics of humic acid aggregates coagulated by different iron-based coagulants, such as charge, size, fractal dimension and compressibility, have an effect on the cake layer structure. At the optimum iron dose of 0.6 to 0.8 mmol/L for ferric chloride (FC) and polymer ferric sulfate (PFS) pre-coagulation, at the point of charge neutralization for near zero zeta potential, the aggregate particles produced possess the greatest size and highest fractal dimension, which contributes to the cake layer being most loose with high porosity and low compressibility. Thus the membrane filterability is better. At a low or high iron dose of FC and PFS, a high negative or positive zeta potential with high charge repulsion results in so many small aggregate particles and low fractal dimension that the cake layer is compact with low porosity and high compressibility. Therefore the membrane fouling is accelerated and MF permeability becomes worse. The variation of cake layer structure as measured by scanning electric microscopy corresponds with the fact that the smaller the coagulation flocs size and fractal dimension are, the lower the porosity and the tighter the cake layer conformation. This also explains the MF membrane flux variation visually and accurately.     

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.     

Influence of floc dynamic protection layer on alleviating ultrafiltration membrane fouling induced by humic substances

Cake layer formation is inevitable over time for ultrafiltration (UF) membrane-based drinking water treatment. Although the cake layer is always considered to cause membrane fouling, it can also act as a “dynamic protection layer”, as it further adsorbs pollutants and dramatically reduces their chance of getting to the membrane surface. Here, the UF membrane fouling performance was investigated with pre-deposited loose flocs in the presence of humic acid (HA). The results showed that the floc dynamic protection layer played an important role in removing HA. The higher the solution pH, the more negative the floc charge, resulting in lower HA removal efficiency due to the electrostatic repulsion and large pore size of the floc layer. With decreasing solution pH, a positively charged floc dynamic protection layer was formed, and more HA molecules were adsorbed. The potential reasons were ascribed to the smaller floc size, greater positive charge, and higher roughness of the floc layer. However, similar membrane fouling performance was also observed for the negative and positive floc dynamic protection layers due to their strong looseness characteristics. In addition, the molecular weight (MW) distribution of HA also played an important role in UF membrane fouling behavior. For the small MW HA molecules, the chance of forming a loose cake layer was high with a negatively charged floc dynamic protection layer, while for the large MW HA molecules it was high with a positively charged floc dynamic protection layer. As a result, slight UF membrane fouling was induced.     

地下水源膜法给水厂长期运行过程中膜性能演变

大庆油田水务公司西水源水厂以地下水作为主要水源,采用臭氧/活性炭+超滤膜（UF）处理工艺;自2014年投产至2019年底已经运行5年,水厂出水浊度、有机物（COD_Mn）和菌落总数等水质指标均稳定达标,但超滤膜污染导致膜性能变化。为了探究5年运行过程中超滤膜处理性能演变情况,对膜出水水质、膜通量、跨膜压差和膜污染层等进行分析。结果表明:超滤膜对浊度和微生物的去除率保持在90%以上,对COD_Mn平均去除率维持在9%。运行5年过程中,超滤膜的比通量每年下降2.1%~4.6%,恢复性化学清洗（CIP）对超滤膜的通量与比通量恢复率分别维持在73%~91%和85%~92%。污染层分析结果表明,超滤膜的有机污染物主要是腐植酸和蛋白质等;无机污染物包括锰、铁、硅、钙和铝等。高价金属元素与有机物形成络合污染物,在污染层中起到支配作用;另外,钙和硅的无机盐垢也不可忽视。     

Removal characteristics of microplastics by Fe-based coagulants during drinking water treatment

Microplastics have caused great concern worldwide recently due to their ubiquitous presence within the marine environment. Up to now, most attention has been paid to their sources, distributions, measurement methods, and especially their eco-toxicological effects. With microplastics being increasingly detected in freshwater, it is urgently necessary to evaluate their behaviors during coagulation and ultrafiltration (UF) processes. Herein, the removal behavior of polyethylene (PE), which is easily suspended in water and is the main component of microplastics, was investigated with commonly used Fe-based salts. Results showed that although higher removal efficiency was induced for smaller PE particles, low PE removal efficiency (below 15%) was observed using the traditional coagulation process, and was little influenced by water characteristics. In comparison to solution pH, PAM addition played a more important role in increasing the removal efficiency, especially anionic PAM at high dosage (with efficiency up to 90.9%). The main reason was ascribed to the dense floc formation and high adsorption ability because of the positively charged Fe-based flocs under neutral conditions. For ultrafiltration, although PE particles could be completely rejected, slight membrane fouling was caused owing to their large particle size. The membrane flux decreased after coagulation; however, the membrane fouling was less severe than that induced by flocs alone due to the heterogeneous nature of the cake layer caused by PE, even at high dosages of Fe-based salts. Based on the behavior exhibited during coagulation and ultrafiltration, we believe these findings will have potential application in drinking water treatment.