不同价态铁离子对膜生物反应器影响研究进展

膜生物反应器(Membrane bioreactor,MBR)作为一种新型的污水处理技术,近些年来备受关注。然而,膜污染问题成为了该工艺广泛应用的最大障碍。现已证明,向MBR中投加铁系混凝剂能够减缓膜污染。本文首先综述了不同价态铁离子对MBR污染物去除的影响,然后对铁离子在污泥混合液中分布及迁移转化进行了分析,接着阐明了铁离子对膜污染的影响,最后对该领域的研究进行了展望。     

铁系混凝剂的投加对膜生物反应器运行效能的影响

膜生物反应器(MBR)作为一种高效的污水处理及回用工艺,与传统活性污泥法相比具有众多优势。然而,膜污染问题限制了该工艺的进一步大规模应用。众多研究者已证实,投加铁系混凝剂能有效改善MBR中混合液的可滤性,从而减缓膜污染。本文首先介绍了胞外聚合物对膜污染的影响机制,然后总结了铁系混凝剂投加对MBR污染物去除、膜污染速率及Fe3+在污泥混合液中的分布的影响;最后,对铁系混凝剂在MBR中应用进行了展望。     

大蒜素包埋球对MBR混合液可滤性影响解析

本研究采用大蒜素为原料,将其包埋在海藻酸钠中,制成大蒜素包埋球(allicin entrapping beads, AEBs)并投加至膜生物反应器(membrane bioreactor, MBR)中,以探讨大蒜素的群体淬灭(quorum quenching, QQ)效应对MBR污泥混合液可滤性的影响。实验结果表明：QQ作用对污泥混合液性质影响显著,对MBR污染物去除影响较小;混合液中胞外聚合物(extracellular polymeric substances, EPS)和溶解性微生物代谢产物(soluble microbial products, SMP)含量降低;通过对修正污染指数(modified fouling index, MFI)检测表明,QQ可提高污泥混合液可滤性,该指标与胞外多糖浓度紧密相关。     

八羧基铜酞菁修饰海藻酸钠阳膜层制备CuPc(COOH)8-SA/mCS双极膜及其表征

在海藻酸钠(SA)中添加八羧基铜酞菁(CuPc(COOH)₈),并分别用Fe³⁺离子和戊二醛作为交联剂对海藻酸钠-八羧基铜酞菁阳膜层和壳聚糖(CS)阴膜层进行改性,制备了八羧基铜酞菁-海藻酸钠/改性壳聚糖双极膜(CuPc(COOH)₈-SA/mCS BPM)。在海藻酸钠中添加八羧基铜酞菁以促进中间层中水的解离。用FTIR、SEM等对制备的CuPc(COOH)₈-SA/mCS双极膜进行了表征。作为比对,制备了Fe³⁺离子改性的Fe-SA/mCS双极膜和二茂铁(Fc)离子改性的Fc-SA/mCS双极膜。实验结果表明,CuPc(COOH)₈-SA阳离子交换膜的离子交换容量、H⁺离子透过率均获得提高。与Fe³⁺离子改性或二茂铁离子改性的mSA/mCS双极膜相比,CuPc(COOH)₈-SA/mCS双极膜的阻抗、电阻压降(IR降)和溶胀度降低,在H+离子浓度低于8 mol·L^-1的酸溶液中具有稳定的工作性能。     

大蒜素包埋球对膜生物反应器混合液可滤性影响解析

将由大蒜素包埋在海藻酸钠中制成的大蒜素包埋球(AEBs)投加至膜生物反应器(MBR)中,以探讨大蒜素的群体猝灭(QQ)效应对MBR污泥混合液可滤性的影响。结果表明,QQ作用对污泥混合液性质影响显著,对MBR污染物去除影响较小;混合液中胞外聚合物(EPS)和溶解性微生物代谢产物(SMP)含量降低;通过对修正污染指数(MFI)检测表明,QQ可提高污泥混合液可滤性,该指标与胞外多糖浓度紧密相关。     

可回收Fe3O4@SiO2-Ag磁性纳米微球对染料污染物的快速脱色处理

介绍了一种采用无毒廉价的前驱物制备Fe₃O₄@SiO₂-Ag磁性纳米微球的快捷方法,制备的Fe₃O₄@SiO₂-Ag纳米微球在NaBH₄存在下可以催化还原染料污染物.实验结果表明,Fe₃O₄@SiO₂-Ag磁性纳米粒子保持了Ag纳米粒子和Fe₃O₄纳米粒子的双重优点,不仅对染料罗丹明B和曙红Y具有良好的催化还原效率,而且可以在外加磁场作用下从溶液中快速有效的分离.催化还原反应速率与反应温度及Fe₃O₄@SiO₂-Ag催化剂用量有关,反应体系中表面活性剂和无机盐(Na₂SO₄)的存在也会影响催化剂的催化活性.该Fe₃O₄@SiO₂-Ag磁性纳米粒子在工业染料污染物处理方面具有应用前景.     

纳米Fe3O4及Ni2 掺杂Fe3O4的制备、表征及吸附Pb(Ⅱ)的特性

采用一种改进的共沉淀法制备了纳米磁铁矿(Fe₃O₄)及Ni²⁺掺杂磁铁矿(Ni_xFe_3-xO₄,x=0.1,0.3,0.6),用X-射线衍射(XRD)、扫描电镜(SEM)、氮气物理性吸附、酸碱滴定等手段对产物进行了表征,用平衡吸附法研究了4种样品对Pb(Ⅱ)离子的吸附容量及吸附模型。结果表明,Fe₃O₄和3种Ni_xFe_3-xO₄均为近似球形的单相晶质纳米颗粒;与Fe₃O₄比较,Ni_xFe_3-xO₄的颗粒尺寸变小、表面电荷零点和pH＝5.0时的表面正电荷量降低;样品的孔体积、比表面积和表面分形度以及表面羟基含量都随产物中Ni²⁺掺杂量的增加而升高。4种样品对Pb(Ⅱ)的等温吸附数据均适合用Langmuir模型拟合(R²=0.9942~0.9858),其相关系数的大小表现为：Fe₃O₄>Ni_0.1Fe_2.9O₄>Ni_0.3Fe_2.7O₄=Ni_0.6Fe_2.4O₄;Freundlich模型对样品等温吸附Pb(Ⅱ)的实验数据拟合度较低(R²=0.981 3~0.947 7),4种样品的Freundlich相关系数的大小关系与Langmuir相关系数相反。初始pH=5.0时,Fe₃O₄,Ni_0.1Fe_2.9O₄,Ni_0.3Fe_2.7O₄和Ni_0.6Fe_2.4O₄对Pb(Ⅱ)的最大吸附容量分别为6.02,6.68,7.29和8.34 mg·g^-1。可见,Ni_xFe_3-xO₄(尤其是Ni²⁺掺杂量较高的产物)对水环境中重金属Pb(Ⅱ)的去除能力明显高于Fe₃O₄。     

纳米Fe3O4及Ni2+掺杂Fe3O4的制备、表征及吸附Pb(Ⅱ)的特性

采用一种改进的共沉淀法制备了纳米磁铁矿(Fe₃O₄)及Ni²⁺掺杂磁铁矿(Ni_xFe_3-xO₄,x=0.1,0.3,0.6),用X-射线衍射(XRD)、扫描电镜(SEM)、氮气物理性吸附、酸碱滴定等手段对产物进行了表征,用平衡吸附法研究了4种样品对Pb(Ⅱ)离子的吸附容量及吸附模型。结果表明,Fe₃O₄和3种Ni_xFe_3-xO₄均为近似球形的单相晶质纳米颗粒;与Fe₃O₄比较,Ni_xFe_3-xO₄的颗粒尺寸变小、表面电荷零点和pH＝5.0时的表面正电荷量降低;样品的孔体积、比表面积和表面分形度以及表面羟基含量都随产物中Ni²⁺掺杂量的增加而升高。4种样品对Pb(Ⅱ)的等温吸附数据均适合用Langmuir模型拟合(R₂=0.9942~0.9858),其相关系数的大小表现为:Fe₃O₄>Ni_0.1Fe_2.9O₄>Ni_0.3Fe_2.7O₄=Ni_0.6Fe_2.4O₄;Freundlich模型对样品等温吸附Pb(Ⅱ)的实验数据拟合度较低(R²=0.9813~0.9477),4种样品的Freundlich相关系数的大小关系与Langmuir相关系数相反。初始pH=5.0时,Fe₃O₄,Ni_0.1Fe_2.9O₄,Ni_0.3Fe_2.7O₄和Ni_0.6Fe_2.4O₄对Pb(Ⅱ)的最大吸附容量分别为6.02,6.68,7.29和8.34mg·g^-1。可见,Ni_xFe_3-xO₄(尤其是Ni²⁺掺杂量较高的产物)对水环境中重金属Pb(Ⅱ)的去除能力明显高于Fe₃O₄。     

一锅法制备S型异质结光催化剂Fe2O3/Fe2TiO5及其高效降解有机污染物性能

首次采用简单的一锅法制备了Fe₂O₃/Fe₂TiO₅异质结纳米材料。构建S型异质结后,与纯的Fe₂O₃和Fe₂TiO₅相比,Fe₂O₃/Fe₂TiO₅复合材料表现出更高的光催化降解速率和效率。经过2.5 h的光照后,Fe₂O₃/Fe₂TiO₅可以降解接近100%的亚甲基蓝（MB）。在Fe₂O₃/Fe₂TiO₅复合材料中,Fe₂O₃和Fe₂TiO₅之间形成了内建电场,可以促进光生电子-空穴对的分离。因此,具有更高能量的Fe₂TiO₅导带中的电子和具有更高能量的Fe₂O₃价带中的空穴可以得到有效的保留,从而使它们更加有效地扩散到催化剂表面,并参加降解反应。此外,Fe₂O₃/Fe₂TiO₅复合材料具有很好的光催化稳定性。     

聚乙二醇-四氧化三铁纳米粒子复合材料的结构、物理性质及应用

在β-环糊精作保护剂条件下, 制备了高对称的十八面体四氧化三铁(Fe₃O₄)纳米材料. 通过胶体化学方法, 合成了一系列不同起始计量比的聚乙二醇(PEG)和Fe₃O₄纳米粒子复合物(CM-1-CM-4). 这些PEG复合材料展示出重要特性: 首先, 它们的表面形貌依赖于Fe₃O₄的计量; 其次, PEG的熔化过程受Fe₃O₄的影响, 并且直接与Fe₃O₄的含量相关; 进一步研究表明, 除CM-4外, Fe₃O₄的引入导致PEG结晶度下降, 而且Fe₃O₄纳米粒子量越少, 降低幅度越大; 更为有趣的是, PEG的降解过程受制于Fe₃O₄纳米粒子的影响, 导致不同降解产物的出现; 而且, 与纯Fe₃O₄纳米粒子一样, 复合材料中的Fe₃O₄也显示典型的软铁磁性行为, 但饱和磁化强度相对较小; 此外, X射线光电子能谱(XPS)实验揭示在这些PEG复合材料中, 有从Fe到O的电子转移, Fe电子密度的降低可用来解释复合材料饱和磁化强度的减小; 最后, 这些PEG复合材料呈现出对有机染料的表面增强拉曼效应, 并且这种效应随Fe₃O₄纳米粒子含量的增加而增加. 这些结果将会对聚合物/无机纳米粒子复合材料的发展起到推进作用.     

Membrane fouling in a submerged membrane bioreactor (MBR) under sub-critical flux operation: Membrane foulant and gel layer characterization

Membrane foulants and gel layer formed on membrane surfaces were systematically characterized in a submerged membrane bioreactor (MBR) under sub-critical flux operation. The evaluation of mean oxidation state (MOS) of organic carbons and Fourier transform infrared (FT-IR) spectroscopy demonstrated that membrane foulants in gel layer were comprised of not only extracellular polymeric substances (EPS) (proteins, polysaccharides, etc.) but also other kinds of organic substances. It was also found that fine particles in mixed liquor had a strong deposit tendency on the membrane surfaces, and membrane foulants had much smaller size than mixed liquor in the MBR by particle size distribution (PSD) analysis. Gel filtration chromatography (GFC) analysis showed that membrane foulants and soluble microbial products (SMP) had much broader distributions of molecular weight (MW) and a larger weight-average molecular weight (M_w) compared with the influent wastewater and the membrane effluent. Scanning electron microscopy (SEM) and energy-diffusive X-ray (EDX) analysis indicated that membrane surfaces were covered with compact gel layer which was formed by organic substances and inorganic elements such as Mg, Al, Fe, Ca, Si, etc. The organic foulants coupled the inorganic precipitation enhanced the formation of gel layer and thus caused membrane fouling in the MBR.     

Membrane adsorption bioreactor (MABR) for treating slightly polluted surface water supplies: As compared to membrane bioreactor (MBR)

In this paper, a submerged membrane adsorption bioreactor (MABR) was evaluated for drinking water treatment at a hydraulic retention time (HRT) as short as 0.5 h. As powdered activated carbon (PAC) was added to the bioreactor at 8 mg/L raw water, the MABR achieved much higher removal efficiency for organic matter in the raw water than the parallel-operated membrane bioreactor (MBR). Moreover, the trans-membrane pressure (TMP) of MABR developed much lower than that of MBR, demonstrating PAC in MABR could mitigate membrane fouling. It was also identified here that the removal of dissolved organic matter (DOM) in MABR was accomplished through the combination of three unit effects: rejection by ultrafiltration (UF) membrane, biodegradation by microorganism, and adsorption by PAC; the last was of great importance. A sludge layer was observed on the membranes surface in both MABR and MBR and PAC particles themselves constituted a part of the cake layer and helped to intercept DOM in the mixed liquor by adsorption in MABR, especially for organic molecules of 5000–500 Da. The UF membrane together with the sludge layer and PAC layer in the MABR was able to reject hydrophobic bases (HoBs), hydrophobic neutrals, hydrophobic acids (HoAs), weakly hydrophobic acids (WHoAs) and hydrophilic matter (HiM) in the mixed liquor by 40.0%, 43.9%, 71.8%, 56.6% and 35.9%, respectively.     

Effects of Sludge Concentrations and Different Sponge Configurations on the Performance of a Sponge-Submerged Membrane Bioreactor

The performance of a novel sponge-submerged membrane bioreactor (SSMBR) was evaluated to treat primary treated sewage effluent at three different activated sludge concentrations. Polyurethane sponge cubes with size of 1?×?1?×?1?cm were used as attached growth media in the bioreactor. The results indicated the successful removal of organic carbon and phosphorous with the efficiency higher than 98% at all conditions. Acclimatised sponge MBR showed about 5% better ammonia nitrogen removal at 5 and 10?g/L sludge concentration as compared to the new sponge system. The respiration test revealed that the specific oxygen uptake rate was around 1.0?C3.5?mgO₂/gVSS.h and likely more stable at 10?g/L sludge concentration. The sludge volume index of less than 100?mL/g during the operation indicated the good settling property of the sludge. The low mixed liquor suspended solid increase indicated that SSMBR could control the sludge production. This SSMBR was also successful in reducing membrane fouling with significant lower transmembrane pressure (e.g. only 0.5?kPa/day) compared to the conventional MBR system. Further study will be conducted to optimise other operating conditions.     

Influence of macromolecule adsorption during filtration of a membrane bioreactor mixed liquor suspension

The aim of this study was to quantify the specific effect of adsorption on membrane fouling during filtration of a membrane bioreactor (MBR) mixed liquor suspension. Adsorption experiments were performed on well-defined protein solutions (β-lactoglobulin solutions) to provide reference results and compare them to those obtained during the filtration of MBR suspensions (raw suspension and settled suspension). Two different methods were used to quantify the role of adsorption in membrane fouling: a “static” method in which membranes were immersed in the biological suspension and a “dynamic” method supposing that the resistance due to adsorption is an irreversible phenomenon that remains after filtration and back-washing. It was shown for the two types of suspensions that (i) due to limited diffusion, the dynamic method appears to be more adapted than the static method; (ii) adsorption is a rapid fouling phenomenon that induces irreversible resistance and that, in frontal mode takes place at the beginning of the operation; (iii) the adsorption phenomenon shows specific hydraulic resistance of the same order of magnitude as the clean membrane resistance; (iv) other phenomena, i.e. progressive pore clogging, can also take place though subcritical hydrodynamic conditions.     

Improving the Performance of Membrane Bioreactors by Adding a Metabolic Uncoupler, 4-Nitrophenol

Effects of 4-nitrophenol (4NP) on the overall performance of membrane bioreactors (MBRs) were investigated in two bench-scale submerged MBRs. Positive impacts of 4NP on activated sludge production and membrane fouling were demonstrated over 45 days of stable operational period. After addition of 4-nitrophenol, the sludge production could be reduced effectively, but only a slight reduction in chemical oxygen demand removal was obtained. The effluent NH₄ ⁺-N concentrations were almost the same in two MBRs. The transmembrane pressures (TMPs) and resistance R increased with increasing mixed liquor suspended solid concentration at each MBR. The average daily TMP increase rates in the control MBR reactor remained at about 0.23 kPa day^?1 and dropped to about 0.12 kPa day^?1 in the 4NP-MBR. Compared with the control MBR, a wider dispersion and lower peak of floc size, a lower zeta potential, and a lower extracellular polymeric substance concentration were observed in the 4NP-MBR.     

进水盐度对膜生物反应器运行效能的影响研究

进水盐度对膜生物反应器(MBR)的运行效能影响显著,尤其是进水含盐量为5 g/L时,明显恶化了污泥可滤性,膜污染速率加快;MBR混合液中溶解性微生物产物(SMP)和胞外聚合物(EPS)含量随钠离子浓度变化而变化,其中SMP中蛋白质含量与钠离子浓度密切相关;与紧密结合态EPS(TB)相比,钠离子含量对松散结合态EPS(LB)浓度的影响更大;不同盐度对COD及NH4+-N影响不明显,系统对COD及NH4+-N的去除效果稳定,分别保持在92%及94%以上,高盐度对MBR总磷去除率降低明显。     

Mitigated membrane fouling in a vertical submerged membrane bioreactor (VSMBR)

In a laboratory-scale study, characteristics of membrane fouling in an A/O (anoxic/oxic) series membrane bioreactor (MBR) and in a vertical submerged membrane bioreactor (VSMBR) treating synthetic wastewater were compared under the same operating conditions. Accordingly, fouling characteristics of a pilot-scale VSMBR treating municipal wastewater were studied under various operating conditions. Various physical, chemical, and biological factors were used to describe membrane resistances. As a result, it was concluded that high concentrations of extracellular polymeric substances (EPS), high viscosity and a high sludge volume index (SVI) corresponded to high membrane resistance indicating severe membrane fouling in both the laboratory-scale MBRs and the pilot-scale VSMBR. In addition, high fouling potential was observed in the pilot-scale VSMBR at 60-day sludge retention time (SRT). In this case, as hydraulic retention time (HRT) decreased from 10 to 4 h, EPS concentrations increased and the average particle size increased, leading to reduced settling of the sludge and increased membrane fouling. To mitigate fouling, two different methods using air bubble jets were adopted in the pilot-scale VSMBR. As a result, it was found that air backwashing was more efficient for fouling mitigation than was air scouring.     

Impact of cation concentrations on fouling in membrane bioreactors

In this study, the interaction of calcium, magnesium, and sodium as well as impact of monovalent to divalent (M/D) cation ratio and magnesium to calcium (Mg/Ca) ratio in the feed wastewater on membrane fouling in submerged membrane bioreactor (MBR) was investigated. The protein and carbohydrate content of soluble microbial products (SMP) and extracellular polymeric substances (EPS) as well as their relative hydrophobicities was examined. The mixed liquor and its components (soluble and suspended solids) were analyzed for their filtration resistance, as reflected by the modified fouling index (MFI). Based on the findings of this study, the optimum conditions with respect to fouling rate were calcium and sodium concentrations of 36 and 140 mg/L, respectively, M/D of 1:1 and Mg/Ca of 5:1, with all parameters on an equivalent basis. High sodium concentration at high M/D ratio was found to decrease the floc size and increase the fouling rate. At the low M/D ratio of 1:1, introduction of magnesium was beneficial in reducing the fouling rate by increasing the EPS concentration and floc size and decreasing the SMP concentration and relative hydrophobicity in the supernatant. The fouling rate was found to be statistically correlated with the concentrations of Ca, Mg, and Na, with both Ca and Na adversely impacting fouling and Mg alleviating fouling propensity.