Changes in characteristics of soluble microbial products in membrane bioreactors associated with different solid retention times: Relation to membrane fouling

A membrane bioreactor (MBR) is a promising wastewater treatment technology, but there is a need for efficient control of membrane fouling, which increases operational and maintenance costs. Soluble microbial products (SMP) have been reported to act as major foulants in the operation of MBRs used for wastewater treatment. In this study, SMP in MBRs operated with different sludge retention times (SRTs) were investigated by means of various analytical techniques and their relations to the evolution of membrane fouling were considered. Bench-scale filtration experiments were carried out in a laboratory with synthetic wastewater to eliminate fluctuations that would occur with the use of real wastewater and that would lead to fluctuations in compositions of SMP. Three identical submerged MBRs were operated for about 50 days under the same conditions except for SRT (17, 51 and 102 days). Accumulation of SMP in the MBRs estimated by conventional analytical methods (i.e., the phenol-sulfuric acid method and the Lowry method) was significant in the cases of short SRTs. However, the degrees of membrane fouling in the MBRs were not directly related to the concentrations of SMP in the reactors estimated by the conventional analytical methods. Non-conventional analytical methods such as excitation-emission matrix (EEM) fluorescence spectroscopy revealed that characteristics of SMP in the three reactors considerably differed depending on SRT. Foulants were extracted from the fouled membranes at the end of the operation and were compared with SMP in each MBR. It was clearly shown that characteristics of the foulants were different depending on SRT, and similarities between SMP and the extracted foulants were recognized in each MBR on the basis of results of EEM measurements. However, such similarities were not found on the basis of results obtained by using the conventional methods for analysis of SMP. The results of this study suggest that the use of conventional methods for analysis of SMP is not appropriate for investigation of membrane fouling in MBRs.     

Novel electrokinetic approach reduces membrane fouling

An innovative submerged membrane electro-bioreactor (SMEBR) was built to reduce membrane fouling through a combination of various electrokinetic processes. The objective of this research was to assess the capability of SMEBR to reduce fouling under different process conditions. At the bench scale level, using synthetic wastewater, membrane fouling of the SMEBR was compared to the fouling of a membrane bioreactor (MBR) in five runs. Different protein concentrations in the influent synthetic wastewater were selected to develop different membrane fouling potentials: high (240 mg/l), low (80 mg/l) and zero protein addition. The MBR and SMEBR were operated at a flux equal to the membrane critical flux in order to create high fouling rate conditions. Membrane fouling rate, expressed as the change in the trans-membrane pressure per day (kPa/d), decreased in the SMEBR 5.8 times (standard deviation (SD) = 2.4) for high protein wastewater, 5.1 times (SD = 2.4) for low protein content, and 1.3 times (SD = 0.7) for zero protein, when compared to the MBR. The supernatant concentrations of the soluble microbial products (SMP) were 195–210, 65–135 and less than 65 mg/l in respective experimental series. Following the bench scale study, membrane fouling was assessed in a pilot scale SMEBR, fed with raw un-clarified municipal wastewater, and operated under real-sewage variable quality conditions. The pilot SMEBR exhibited three times smaller membrane fouling rate than the MBR. It was concluded that electrokinetic processes generated by SMEBR led to a reduction of membrane fouling through: i) removal of soluble microbial products (mainly protein and polysaccharides) and colloidal organic materials; ii) change of the structure and morphology of the suspended solids due their conditioning by DC field.     

Novel filtration mode for fouling limitation in membrane bioreactors

A novel filtration mode is presented to reduce fouling propensity in membrane bioreactors (MBR). During this mode, an elevated high instantaneous flux (60Lm(-2)h(-1)) is initially applied for a short time (120s), followed by a longer filtration (290s) at lower flux (10.3Lm(-2)h(-1)) and a backwash in each filtration cycle. The mixed mode is expected to limit irreversible fouling as the reversible fouling created during the initial stage appears to protect the membrane. Hydraulic performance and the components of foulants were analyzed and compared with conventional continuous and backwash modes. It was found that the mixed mode featured lower trans-membrane pressure (TMP) after 24h of filtration when compared to other modes. The mixed mode was effective in preventing soluble microbial products (SMP) attaching directly onto the membrane surface, keeping the cake layer weakly compressed, and reducing the mixed liquor suspended solids (MLSS) accumulation on the membrane. This strategy reduced the resistances of both the cake layer and the gel layer. A factorial experimental design was carried out for eight runs with different conditions to identify the major operational parameters affecting the hydraulic performances. The results showed that the value of the flux in the initial high-flux period had the most effect on the performance of the mixed mode: high initial flux (60Lm(-2)h(-1)) led to improved performance.     

Biopolymer fouling in dead-end ultrafiltration of treated domestic wastewater

Ultrafiltration (UF) is considered as a suitable treatment process after conventional wastewater treatment to produce reuse water. Nevertheless, fouling affects the performance of UF to a large extent. As biopolymers (mostly macro polysaccharide-like and protein-like molecules) have been identified as major foulants affecting the filterability of water in dead-end UF, the present study focuses on investigating the reversibility of biopolymer fouling occurring at different biopolymer mass loads to the membrane and under different compression conditions. UF-membrane stirred cell tests using five cycles show that filtering treated domestic wastewater leads to a significant permeability reduction due to the accumulation of biopolymers on the membrane surface and/or in the membrane pores. Although they can be removed by hydraulic backwashing, an increased mass load of biopolymers reduces the removal efficiency. This correlation was verified using a UF pilot plant filtering treated wastewater (secondary effluent or slow sand filtrate). The effect of biopolymer fouling layer deformation on its reversibility was studied using multi-cycle membrane filtration tests under different filtration pressures. The results showed that higher filtration pressures result in more compact biopolymer fouling which is more difficult to be hydraulically backwashed. This phenomenon was also confirmed by pilot-scale UF experiments.     

Cleaning strategies for flux recovery of an ultrafiltration membrane fouled by natural organic matter

One of the most common problems encountered in water treatment applications of membranes is fouling. Natural organic matter (NOM) represents a particularly problematic foulant. Membranes may be fouled by relatively hydrophilic and/or hydrophobic NOM components, depending on NOM characteristics, membrane properties, and operating conditions. To maximize flux recovery for an NOM-fouled ultrafiltration membrane (NTR 7410), chemical cleaning and hydraulic rinsing with a relatively high cross-flow velocity were investigated as cleaning strategies. The modification of the membrane surface with either an anionic or a cationic surfactant was also evaluated to minimize membrane fouling and to enhance NOM rejection. Foulants from a hydrophobic NOM source (Orange County ground water (OC-GW)) were cleaned more effectively in terms of permeate flux by acid and caustic cleanings than foulants from a relatively hydrophilic NOM source (Horsetooth surface water (HT-SW)). An anionic surfactant (sodium dodecyl sulfate (SDS)) was not effective as a cleaning agent for foulants from either hydrophobic or hydrophilic NOM sources. High ionic strength cleaning with 0.1 M NaCl was comparatively effective in providing flux recovery for NOM-fouled membranes compared to other chemical cleaning agents. Increased cross-flow velocity and longer cleaning time influenced the efficiency of caustic cleaning, but not high ionic strength cleaning. The membrane was successfully modified only with the cationic surfactant; however, enhanced NOM rejection was accompanied by a significant flux reduction.     

Combined coagulation-disk filtration process as a pretreatment of ultrafiltration and reverse osmosis membrane for wastewater reclamation: an autopsy study of a pilot plant

The effects of the combined coagulation-disk filtration (CC-DF) process on the fouling characteristics and behavior caused by interactions between effluent organic matter (EfOM) and the membrane surfaces of the ultrafiltration (UF) and reverse osmosis (RO) membranes in a pilot plant for municipal wastewater reclamation (MWR) were investigated. The feed water from secondary effluents was treated by the CC-DF process used as a pretreatment for the UF membrane to mitigate fouling formation and the permeate from the CC-DF process was further filtered by two UF membrane units in parallel arrangement and fed into four RO modules in a series connection. The CC-DF process was not sufficient to mitigate biofouling but the UF membrane was effective in mitigating biofouling on the RO membrane surfaces. Fouling of the UF and RO membranes was dominated by hydrophilic fractions of EfOM (e.g., polysaccharide-like and protein-like substances) and inorganic scaling (e.g., aluminum, calcium and silica). The desorbed UF membrane foulants included more aluminum species and hydrophobic fractions than the desorbed RO membrane foulants, which was presumably due to the residual coagulants and aluminum-humic substance complexes. The significant change in the surface chemistry of the RO membrane (a decrease in surface charge and an increase in contact angle of the fouled RO membranes) induced by the accumulation of hydrophilic EfOM onto the negatively charged RO membrane surface intensified the fouling formation of the fouled RO membrane by hydrophobic interaction between the humic substances of EfOM with relatively high hydrophobicity and the fouled RO membranes with decreased surface charge and increased contract angle.     

Identification and quantification of major organic foulants in treated domestic wastewater affecting filterability in dead-end ultrafiltration

Ultrafiltration (UF) membranes can be used after conventional wastewater treatment to produce particle free and hygienically safe water for reuse. However, membrane fouling affects the performance of UF to a large extent. Stirred cell tests with UF membrane show high flux decline filtering treated domestic wastewater. Investigation on the impact of size fractioned substances indicates that dissolved substances are major foulants affecting water filterability. Dissolved organic substances in feed and permeate samples of the stirred cell tests are analyzed by liquid chromatography with online organic carbon detection (LC-OCD). The resulting chromatograms displayed a significant difference of feed and permeate samples in the range of large molecules identified as biopolymer peak. The substances detected in this peak (mostly macro polysaccharide-like and protein-like molecules) are almost completely retained by UF membranes. Quantified investigation shows that biopolymer concentration influences filterability of corresponding water sample proportionally. The apparent magnitude of delivered biopolymer to membrane has a striking correlation with fouling resistance. The relationship was verified to be reproducible using different water samples. Mechanism analysis demonstrates that based on the delivered biopolymer load to membrane pore blocking or cake/gel fouling is the main fouling mechanism in the present experiment conditions.     

MBR、MCR处理微污染水的膜污染比较

膜污染是影响膜反应器稳定运行的重要原因之一，为此考察了膜生物反应器(MBR)和膜混凝反应器(MCR)处理微污染地表水时的运行状况，并对膜比通量的变化进行了比较，发现MBR的膜污染情况比MCR的严重。MCR和MBR的膜组件经物理、化学清洗后膜比通量分别恢复至新膜比通量的99．7％和76．9％，物理清洗对此的贡献较大。经分析发现，MCR中无机污染占优势，主要污染元素是Fe；MBR中微生物和有机物是膜污染的主要组成，而无机污染物则主要是铁盐和磷酸盐。     

Fouling characteristics of NF and RO operated for removal of dissolved matter from groundwater

A pilot study had been performed for about 6 months in order to investigate the removal efficiency of dissolved matter and its fouling potential during nanofiltration (NF) and reverse osmosis (RO) of local groundwater that was pretreated with an ultrafiltration (UF) membrane system. After pilot plant operation, autopsy tests were performed to identify the characteristics of foulants that were attached to the membrane surface. In the autopsy tests, the flux recovery for each specific cleaning scheme (hydraulic washing, acid cleaning, and alkaline cleaning) was also measured using a dead-end filtration cell unit. The washing solution used in each chemical cleaning was analyzed to identify major components of the foulants, and the membrane surface was observed using the scanning electron microscopy (SEM).Among three kinds of membranes tested, one NF and two RO membranes, the NF and RO1 membranes showed a rapid flux decline after 100 days of operation. Especially, the RO1 membrane showed the more serious flux decline than the NF membrane. The RO2 membrane, with the lowest recovery rate, demonstrated a gradual flux decline. The removal efficiency of dissolved inorganic matter (as conductivity) for each NF, RO1 and RO2 membrane was 76.3%, 88.2% and 95.3%, respectively. The removal of dissolved organic matter (as total organic carbon) was found to be about 80% for both NF and RO membranes used in this study. During the membrane autopsy tests, five sections of the fouled membrane were cut along each NF and RO membrane module from the feed inlet side to the concentrate outlet side, the specific flux for each membrane section was measured before and after each cleaning step. As expected, the degree of fouling was intensified along the membrane surface as the feed flow approached the outlet. Based on the analysis results of wash water used in each cleaning step, the major foulants attached to the membrane surface appeared to be Ca bound with inorganic matter and Si bound with organic matter. Fe seemed to be a great contributor to irreversible fouling. The SEM analysis indicated that the organic matter was forming the first fouling layer close to the membrane and that the inorganic matter was layered top of the organic fouling layer in a tetragonal shape. Any evidence of biofouling was not observed in this study because most of microorganisms had been already removed by the UF pretreatment.     

混凝沉淀/MBR组合工艺中膜污染清洗方法的研究

针对混凝沉淀预处理/膜生物反应器组合工艺,采用能谱分析和傅里叶红外光谱对膜表面的污染物进行分析,并对不同清洗剂的清洗效果进行了探讨。结果表明,酸性清洗剂对膜的清洗效果较好,膜表面的无机污染物基本被去除,但不能完全有效地去除膜表面的有机污染物;NaOH和NaClO的清洗效果不佳。从酸碱交替清洗效果来看,先酸洗后碱洗过程的膜恢复率比先碱洗后酸洗过程的高8%。对膜污染过程进行推测,胞外聚合物(EPS)和残留的絮凝颗粒一并沉积并吸附在膜表面,形成以有机物为主体、粘结性很强的凝胶层(内层);在混凝沉淀预处理长期运行条件下,凝胶层由内向外又不断吸附了无机盐类物质,凝胶层(外层)逐渐过渡为以无机污染为主,期间还存在无机物和有机物的络合,导致单纯采用碱和氧化剂的清洗效果不佳。     

Effect of NOM characteristics and membrane type on microfiltration performance

Efforts to understand and predict the role of different organic fractions in the fouling of low-pressure membranes are presented. Preliminary experiments with an experimental apparatus that incorporates automatic backwashing and filtration over several days has shown that microfiltration (MF) of the hydrophilic fractions leads to rapid flux decline and the formation of a cake or gel layer, while the hydrophobic fractions show a steady flux decline and no obvious formation of a gel or cake layer. The addition of calcium to the weakly hydrophobic acid (WHA) fraction led to the formation of a gel layer from associations between components of the WHA. The dominant foulants were found to be neutral and charged hydrophilic compounds, with hydrophobic and small pore size membranes being the most readily fouled. The findings suggest that surface analyses such as FTIR will preferentially identify hydrophilic compounds as the main foulants, as these components form a gel layer on the surface while the hydrophobic compounds adsorb within the membrane pores. Furthermore, coagulation pre-treatment is also likely to reduce fouling by reducing pore constriction rather than the formation of a gel layer, as coagulants remove the hydrophobic compounds to a large extent and very little of the hydrophilic neutral components.     

预处理对东江原水超滤过程中膜污染的控制作用

以珠江流域东江水作为原水,研究不同预处理(混凝、吸附、氧化)及其组合对水体中有机污染物的去除效果及对超滤膜污染的控制作用。试验结果表明,针对东江原水中天然有机物的去除,聚合氯化铝(PACl)、粉末活性炭(PAC)和高锰酸钾(KMnO4)的最佳投加量分别为20、30、0. 1 mg/L;三种单一预处理方法能够在一定程度上缓解膜通量衰减,而两两组合预处理则能够进一步提高膜运行通量;对于聚偏氟乙烯膜,PACl+PAC组合预处理对膜污染的控制作用最好。对于UV254和蛋白质,PACl和KMn O4对其去除效果优于PAC;对于多糖,三种预处理方法对其去除效果均不佳(<40%),其中PAC略好于PACl和KMn O4。此外,三种单一预处理方法对腐殖酸类荧光物质的去除效果高于蛋白质类荧光物质,而组合预处理能够更加显著地降低这两类荧光物质的响应强度,其中PACl+PAC组合预处理对有机物各荧光组分的去除效果最佳。通过对膜污染物成分的识别分析可知,东江原水中造成超滤膜污染的物质有腐殖酸类、多糖类和蛋白质类物质,而化学不可逆污染物主要为多糖类物质及少量的腐殖酸类物质,化学可逆污染物主要为蛋白质类物质及部分腐殖酸类物质。     

Investigation of the effect of coagulation bath composition on PVDF/CA membrane by evaluating critical flux and antifouling properties in lab‐scale submerged MBR

Ultrafiltration membranes were prepared from blends of poly(vinylidene fluoride) (PVDF)/cellulose acetate (CA) via phase inversion method. The effect of different coagulation bath compositions on the morphology and performance of the blend membrane prepared from casting solution of PVDF/CA with ratio of 80/20 was investigated using sewage wastewater. NaCl and ethanol were used as additives of coagulation bath. Fouling analysis was conducted with Bovine Serum Albumin solution and critical flux evaluation was performed using a lab‐scale membrane bioreactor. In terms of morphological structure, the macrovoids decreased and changed to finger‐like structure. The irreversible fouling reduced and the flux recovery ratio (FRR) of the modified membranes increased remarkably while the reversible fouling caused by deposition of foulants on the surface of the membranes increased. The maximum values of FRR and critical flux of irreversibility were reached by the membrane which was prepared in the coagulation bath containing the highest concentration of NaCl.     

The role of hydrodynamic conditions and pH on algal-rich water fouling of ultrafiltration

The aim of this paper was to study the membrane fouling phenomena by eutrophic water using Microcystis aeruginosa under various operational conditions (flux and air flow rate) and solution chemistry (pH). All the experiments were performed in a lab scale employing the polyvinyl chloride ultrafiltration membrane with nominal cut-off of 10 kDa. A slight fouling appeared at the flux not more than 10 L/m²/h, and the trend of trans-membrane pressure (TMP) development varied as a function of flux from linear to exponential with the increase of cell concentration. This paper also studied an important consideration of aeration in algal fouling: shear force. Besides alleviating membrane fouling, the shear produced by the bubbling should take responsible for the breakup of cells and the release of intracellular organic matters which caused the rate of the TMP increase closed to that without aeration. The optimum aeration intensity was observed to be 2.5 m³/m²/h in this experimental condition. As another important parameter considered in the study, the pH value of the raw water changed the physical and chemical reaction between the membrane and foulants or themselves. The results showed that the final TMP reduced with the pH increase due to the electro-static repulsion strengthening between the macromolecules which developed a looser gel. The most severe fouling was obtained at pH 5.0 near to the iso-electric point of algal solution, where electrostatic repulsion between algal cells was weakest. Furthermore, low pH value had a negative impact on cell integrity which gave rise to much more dissolved algogenic organic matter in the solution. It also played a part role on the membrane fouling.     

Performing a microfiltration integrated with photocatalysis using an Ag-TiO2/HAP/Al2O3 composite membrane for water treatment: Evaluating effectiveness for humic acid removal and anti-fouling properties

Membrane filtration has been increasingly used for water treatment and wastewater reclamation in recent years. To further improve the effectiveness of membrane process and reduce membrane fouling, a highly reactive photocatalytic membrane, Ag-TiO₂/hydroxiapiate (HAP, Ca₁₀(PO₄)₆(OH)₂)/Al₂O₃, was employed to realize microfiltration (MF) coupling photocatalysis for surface water treatment. The effectiveness on the potential of membrane was investigated by removing humic acid (HA) test under different feed total organic carbon (TOC), light intensity and transmembrane pressure (TMP). The HA removal and anti-fouling property of as-prepared membrane was improved under UV irradiation, likely due to photocatalytic degradation of foulants along with filtration simultaneously. Under given feed water composition, increasing the light intensity resulted in increased removal of HA from aqueous solution. However, a limiting TMP seems to exist beyond which the increased HA removal cannot be sustained. Fouling behavior analysis indicated that the transition in fouling mode from initial pore blocking to cake filtration occurred much slower as UV irradiated. Furthermore, a superior efficiency on removal of trace organic contaminants, as well as milder flux reduction, was presented from surface water treatment, which demonstrated that the integrated system with enhanced performance is foreseen as an emerging technique for water treatment.     

Carbon nanotube blended polyethersulfone membranes for fouling control in water treatment

Multi-walled carbon nanotube/polyethersulfone (C/P) blend membranes were synthesized via the phase inversion method. The resultant membranes were then characterized by scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FTIR), and contact angle. The C/P blend membranes appeared to be more hydrophilic, with a higher pure water flux than the polyethersulfone (PES) membranes. It was also found that the amount of multi-walled carbon nanotubes (MWCNTs) in the blend membranes was an important factor affecting the morphology and permeation properties of the membranes. After 24 h of surface water filtration with 7 mgC/L TOC content, the C/P blend membranes displayed a higher flux and slower fouling rate than the PES membranes. Subsequent analyses of the desorbed foulants showed that the amount of foulant on bare PES membranes was 63% higher than the C/P blend membrane for 2% MWCNTs content. Thus, the carbon nanotube content of the C/P membranes was shown to alleviate the membrane fouling caused by natural water.     

Characterization of dissolved organic matter in a submerged membrane bioreactor by using three-dimensional excitation and emission matrix fluorescence spectroscopy

Three-dimensional excitation-emission matrix (EEM) fluorescence spectroscopy was employed to characterize dissolved organic matter (DOM) in a submerged membrane bioreactor (MBR). Three fluorescence peaks could be identified from the EEM fluorescence spectra of the DOM samples in the MBR. Two peaks were associated with the protein-like fluorophores, and the third was related to the visible humic acid-like fluorophores. Only two main peaks were observed in the EEM fluorescence spectra of the extracellular polymeric substance (EPS) samples, which were due to the fluorescence of protein-like and humic acid-like matters, respectively. However, the EEM fluorescence spectra of membrane foulants were observed to have three peaks. It was also found that the dominant fluorescence substances in membrane foulants were protein-like substances, which might be due to the retention of proteins in the DOM and/or EPS in the MBR by the fine pores of the membrane. Quantitative analysis of the fluorescence spectra including peak locations, fluorescence intensity, and different peak intensity ratios and the fluorescence regional integration (FRI) analysis were also carried out in order to better understand the similarities and differences among the EEM spectra of the DOM, EPS, and membrane foulant samples and to further provide an insight into membrane fouling caused by the fluorescence substances in the DOM in submerged MBRs.     

超滤膜的零污染通量及其在城市水处理工艺中的应用

对于超滤膜在城市水处理工艺中的应用,选择合适的膜通量和控制膜污染是其成功的关键所在。围绕上述关键点,结合城市超滤水厂的运行要求,系统论述了超滤膜零污染通量和经济通量的关系,并以东营超滤水厂为例,开展了超滤膜的零污染通量生产性试验,确定了该水厂在不同条件下的超滤膜零污染通量。超滤膜零污染通量相关内容的研究将可能成为膜技术发展的一个新方向。     

Effects of ozonation on the permeate flux of nanocrystalline ceramic membranes

Titania membranes, with a molecular weight cut-off of 15 kD were used in an ozonation/membrane system that was fed with water from Lake Lansing, which had been pre-filtered through a 0.45 microm glass fiber filter. The application of ozone gas prior to filtration resulted in significant decreases in membrane fouling. The effects of ozonation could not be explained by physical scouring of the filter cake. Decrease in the pH resulted in a concomitant increase in the dissolved ozone concentration in the feed water and in an improvement in permeate flux recovery. Increasing the ozone concentration beyond a threshold value had no beneficial effect on permeate flux recovery. Ozone decomposition, resulting in the formation of OH or other radicals at the membrane surface, is thought to result in the decomposition of organic foulants at the membrane surface and reduce the extent of membrane fouling.     

Post-treatment of upflow anaerobic sludge blanket effluent by combining the membrane filtration process: fouling control by intermittent permeation and air sparging

In this study, the membrane filtration process was proposed as a post-treatment process to treat the upflow anaerobic sludge blanket (UASB) effluent. The flat-sheet membrane modules were submerged into the UASB reactor to retain the suspended solids in the UASB effluent under intermittent permeation and air sparging conditions. The results indicated that intermittent permeation enhanced the sustainability of the submerged membrane and an idle time of 4 min with a 10-min filtration was optimal for reducing membrane fouling under the experimental conditions. Air sparging could also alleviate membrane fouling, and the lowest transmembrane pressure (TMP) change rate (dTMP/d t ) was achieved at the moderate aeration rate of 2 L/min. It appears to be effective to alleviate membrane fouling and achieve high effluent production at a flux of 25 L/m² h and an idle time of 4 min with a 10-min filtration considering the energy consumption.