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.     

Effects of different Ca2+ behavior patterns in the electric field on membrane fouling formation and removal of trace organic compounds

The effects of Ca²⁺ on membrane fouling and trace organic compounds (TrOCs) removal in an electric field-assisted microfiltration system were investigated in the presence of Na⁺ alone for comparison. In the electric field, negatively charged bovine serum albumin (BSA) migrated towards the anode far away from the membrane surface, resulting in a 42.9% transmembrane pressure (TMP) reduction in the presence of Na⁺ at 1.5 V. In contrast, because of the stronger charge shielding of Ca²⁺, the electrophoretic migration of BSA was limited and led to a neglectable effect of the electric field (1.5 V) on membrane fouling. However, under 3 V applied voltage, the synergistic effects of electrochemical oxidation and bridging interaction between Ca²⁺ and BSA promoted the formation of denser settleable flocs and a thinner porous cake layer, which alleviated membrane fouling with a 64.5% decrease in TMP and nearly 100% BSA removal. The TrOCs elimination increased with voltage and reached 29.4%–80.4% at 3 V. The electric field could prolong the contact between TrOCs and strong oxidants generated on the anode, which enhanced the TrOCs removal. However, a stronger charge shielding ability of Ca²⁺ weakened the electric field force and thus lowered the TrOCs removal.     

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.     

Floc structure and membrane fouling affected by sodium alginate interaction with Al species as model organic pollutants

Membrane filtration combined with pre-coagulation has advantages in advanced wastewater treatment. As a model of a microbial polysaccharide, research on the effect of sodium alginate(SA) on alum hydrolysis has been rare; therefore, it is necessary to gain insight into the interface interaction between SA molecules and Al species, and the role SA plays during floc formation. In this study, the interaction mechanism between SA and Al species has been investigated, by evaluating the effect of SA on floc characteristics and membrane fouling during coagulation–ultrafiltration with different Al species coagulants(AlCl3 and preformed Al13). Al 2 p X-ray photoelectron spectroscopy(XPS) confirmed that the complexation of ligands and Al species strongly affects the reaction pathways for Al hydrolysis and the final nature of the flocs, as Al13 can be decomposed into octahedral precipitates when SA is added. The presence of SA can affect floc properties, which have important impacts on the characteristics of the cake layer and membrane fouling. Due to the bridging ability of SA, the floc strength increased by about 50% using Ala, which was much better than preformed Al13, with a percentage increase of only about 6%. Moreover,the recovery factor of HA-flocs was decreased from 96% to 43% with SA addition of 0.5 mg/L.It was concluded that SA can affect the characteristics of the cake layer and membrane fouling through participating in the formation of primary flocs and altering the Al hydrolysis pathway.     

Optimized coagulation pretreatment alleviates ultrafiltration membrane fouling: The role of floc properties and slow-mixing speed on mechanisms of chitosan-assisted coagulation

To alleviate ultrafiltration(UF) membrane fouling, the pre-coagulation of poly-aluminum chloride(PACl) with the aid of chitosan(CTS) was conducted for synthetic humic acid–kaolin water treatment. Pre-coagulation of three molecular weights(MW) CTSs(50–190 kDa(CTSL), 190–310 kDa(CTSM) and 310–375 kDa(CTSH)) was optimized with slow-mixing speeds of 30, 60 and 90 r/min, respectively. The removal efficiency and floc properties as well as membrane fouling were analyzed, and were compared to results obtained by conventional coagulation with PACl. Results showed that variations in floc properties could be ascribed to the coagulation mechanisms of CTS_L/CTS_M/CTS_H at different slow-mixing speeds, resulting in reduced UF membrane fouling. Specifically, at the low speed of 30 r/min, all three CTS types produced flocs with similar properties, while CTSLresulted in the lowest removal efficiency and aggravated irreversible fouling. At the appropriate speed of 60 r/min, CTSMgenerated the most compact flocs with the combined effects of bridging and path mechanisms. The compact cake layer formed could alleviate irreversible fouling,which was beneficial for prolonging the operation of the UF membrane. At the high speed of90 r/min, CTSHformed fragile flocs and aggravated irreversible membrane fouling. We considered membrane fouling to be affected by floc properties and the resultant removal efficiency, which was governed by the MW of the CTS used and the slow-mixing speed applied as well.     

Structure and flow calculation of cake layer on microfiltration membranes

Submerged membrane bioreactors(SMBR) are widely used in wastewater treatment. The permeability of a membrane declines rapidly because of the formation of a cake layer on the membrane surface. In this paper, a multiple staining protocol was conducted to probe the four major foulants in the cake layer formed on a filtration membrane. Fluorescent images of the foulants were obtained using a confocal laser scanning microscope(CLSM). The three dimensional structure of the cake layer was reconstructed, and the internal flow was calculated using computational fluid dynamics(CFD). Simulation results agreed well with the experimental data on the permeability of the cake layer during filtration and showed better accuracy than the calculation by Kozeny–Carman method. β-D-Glucopyranose polysaccharides and proteins are the two main foulants with relatively large volume fractions, while α-D-glucopyranose polysaccharides and nucleic acids have relatively large specific surface areas. The fast growth of β-D-glucopyranose polysaccharides in the volume fraction is mainly responsible for the increase in cake volume fraction and the decrease in permeability. The specific area, or the aggregation/dispersion of foulants, is less important to its permeability compared to its volume fraction.     

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.     

The effects of hydrogen peroxide pre-oxidation on ultrafiltration membrane biofouling alleviation in drinking water treatment

Pre-oxidation is widely used to reduce ultrafiltration membrane fouling.However,the variation in the composition of microbial communities and extracellular polymeric substances(EPSs) accompanying pre-oxidation in drinking water treatment has received little attention.In this study,hydrogen peroxide(H_2O_2) was used in a coagulationultrafiltration process with Al_2(SO_4)_3·18H_2O.A long-term reactor experiment(60 d) showed that pre-oxidation alleviated membrane fouling,mainly due to its inhibition of microbial growth,as observed by flow cytometry measurements of the membrane tank water.Further analysis of the formed cake layer demonstrated that the corresponding levels of EPS released from the microbes were lower with than without H_2O_2 treatment.In comparison to polysaccharides,proteins dominated the EPS.2 D-electrophoresis showed little difference(p 0.05,Student's t-test) in the composition of proteins in the cake layer between the treatments with and without H_2O_2.The molecular weights of proteins ranged from approximately 30–50 kDa and the majority of isoelectric points ranged from 6 to 8.Highthroughput sequencing showed that the predominant bacteria were Proteobacteria,Bacteroidetes,and Verrucomicrobia in both cake layers.However,the relative abundance of Planctomycetes was higher in the cake layer with H_2O_2 pre-oxidation,which was likely probably due to the strong oxidative resistance of its cell wall.Overall,our findings clarify the fundamental molecular mechanism in H_2O_2 pre-oxidation for ultrafiltration membrane bio-fouling alleviation in drinking water treatment.     

Characterization of dissolved organic matter and membrane fouling in coagulation-ultrafiltration process treating micro-polluted surface water

Coagulation–ultrafiltration(C–UF) is widely used for surface water treatment. With the removal of pollutants, the characteristics of organic matter change and affect the final treatment efficiency and the development of membrane fouling. In this study, we built a dynamic C–UF set-up to carry out the treatment of micro-polluted surface water, to investigate the characteristics of dissolved organic matter from different units. The influences of poly aluminum chloride and poly dimethyldiallylammonium chloride(PDMDAAC) on removal efficiency and membrane fouling were also investigated. Results showed that the dosage of PDMDAAC evidently increased the UV254 and dissolved organic carbon removal efficiencies,and thereby alleviated membrane fouling in the C–UF process. Most hydrophobic bases(HoB)and hydrophobic neutral fractions could be removed by coagulation. Similarly, UF was good at removing HoB compared to hydrophilic substances(HiS) and hydrophobic acid(HoA)fractions. HiS and HoA fractions with low molecule weight accumulated on the surface of the membrane, causing the increase of transmembrane pressure(TMP). Membrane fouling was mainly caused by a removable cake layer, and mechanical cleaning was an efficient way to decrease the TMP.     

A fouling suppression system in submerged membrane bioreactors using dielectrophoretic forces

A novel method was developed to suppress membrane fouling in submerged membrane bioreactors. The method is based on the dielectrophoretic (DEP) motion of particles in an inhomogeneous electrical field. Using a real sample of biomass as feed, the fouling-suppression performance using DEP with different electrical field intensities (60-160 V) and different frequencies (50-1000 Hz) was investigated. The fouling-suppression performance was found to relate closely with the intensity and frequency of the electrical field. A stronger electrical field was found to better recover the filtrate flux. This is because of a stronger DEP force acting on the biomass particles close to themembrane's surface. Above an intensity and frequency value of 130 V and 1 kHz, respectively the permeate flux was reduced due to an electrothermal effect.     

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.     

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%.     

一体式絮体-超滤工艺去除腐殖酸效能与机制

近年来,一体式吸附剂-超滤膜组合工艺以其效率高、膜污染程度低且占地面积小等优势逐渐在水处理中广泛应用.然而,目前所用吸附剂多为颗粒型,如粉末活性炭、碳纳米管、纳米铁等.不仅长期运行极易引起膜表面损伤,且多数吸附剂成本较高.为有效克服上述问题,以水处理中广泛应用的铝盐混凝剂水解絮体为吸附剂,以天然水体中普遍存在的腐殖酸为目标污染物,考察了松散且密度低的絮体直接注入膜池后腐殖酸的去除效率及膜污染行为.结果表明,曝气方式、絮体注入频率及注入量均能不同程度地影响该组合工艺效能.与间歇曝气和一次性注入相比,采用连续曝气且分批次注入时,絮体在膜表面形成松散"保护膜",充分发挥了絮体作用,腐殖酸去除效率较高,膜污染程度显著降低.单独HA污染超滤膜时,5d内跨膜压差急剧增至74.8 k Pa,而连续曝气且每次2 d注入5.4 mmol·L-1絮体运行8 d后跨膜压差仅增至6.3 k Pa.此时HA去除率为73.3%(8 d),远高于无絮体注入时(5 d,32.1%).此外,分批次注入絮体时仅有少量腐殖酸吸附于膜孔,松散滤饼层为主要污染方式,且单次注入量越大,运行结束经水洗后膜表面平均孔径也越大.本研究表明一体式松散絮体-超滤膜组合工艺在水处理中具有潜在应用前景.     

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 .     

电辅助膜生物反应器体系中Co纳米催化膜处理焦化废水研究

为探究电辅助膜生物反应器（electrical membrane bioreactor,EMBR）处理难降解有机废水的效果、产电性能及抗膜污染性能,以金属有机骨架化合物（metal-organic frameworks,MOFs）为前驱体,通过碳化制备具有高催化氧还原（oxygen reduction reaction,ORR）活性的负载Co纳米颗粒的氮掺杂碳催化剂（Co-NPs）,以碳纤维布作为基体组装Co-NPs/PVDF碳纤维基催化膜,并构建催化膜耦合EMBR体系处理实际焦化废水.考察碳化温度、Co/N协同作用、N掺杂含量及形态对ORR活性的影响,探究了催化膜在EMBR体系中处理实际焦化废水的污染物去除效率、抗污染特性和产能效果.结果表明:①Co-NPs的ORR反应为4电子转移还原途径,还原产物为水.②Co-NPs/PVDF碳纤维基催化膜在微电场下保持稳定的高膜通量.催化膜污染在运行初期符合膜孔堵塞模型,后期表现为滤饼层污染模型控制,膜污染以滤饼层污染为主.微电场可以降低滤饼层比阻,能有效解决膜污染问题.③EMBR体系处理实际焦化废水,COD、TN、NH₄+-N和挥发酚的去除率分别为97.2%、43.8%、82.9%和99.8%.④系统最大产电功率密度为823.8 mW/m3,库仑效率为8.3%.研究显示,以MOFs为前驱体制备的Co-NPs纳米催化剂,以碳纤维布作为基体制备Co-NPs/PVDF碳纤维基催化膜,耦合EMBR体系在焦化废水处理过程中表现出了高效的污染物降解效率、能源转化效率,并且微电场环境可达到抗膜污染效果.      

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.