Alginate block fractions and their effects on membrane fouling

Alginate has been commonly used as a model foulant in studies of membrane organic fouling. As a complex polymer, alginate is composed of two different monomers, namely M ((1 → 4) linked β-D-mannopyranuronic acid) and G ((1 → 4) linked α-L-gulopyranuronic acid) which are randomly arranged into MG-, MM- and GG-blocks. So far, little information is available about fouling propensity of each block in microfiltration. In this study, microfiltration experiments were conducted respectively with MG-, MM- and GG-blocks separated from alginate under defined conditions. Results showed the severest fouling in the filtration of MG-block, and the least flux decline in the filtration of MM-block. The initial pore blocking was found to be responsible for the fouling observed in MG-block filtration, while the cake layer formed on membrane surface during the MM-block filtration could serve as a pre-filter that prevented membrane from further pore blocking. In order to look into fouling mechanisms, the effects of transparent exopolymeric particles (TEP) on membrane fouling were also studied. TEP were found to form through aggregation or cross-link of alginate blocks. As TEP were bigger than original alginate blocks, they could facilitate the formation of cake layer on membrane surface. It was observed that more TEP were produced from MM-blocks than from MG-blocks in solutions. This in turn explained why cake resistance was dominant in the filtration of MM-blocks as compared to MG-blocks. The analysis by the extended Derjaguin-Landau-Verwey-Overbeek (XDLVO) theory further revealed that MM-blocks had lowest cohesive interaction energy among all three alginate blocks, which favoured aggregation of MM-blocks, and ultimately leading to the formation of more TEP. This study provided insights into the roles of different alginate blocks in development of membrane fouling, and suggested that the membrane fouling would be related to molecular structure of alginate.     

Critical flux and chemical cleaning-in-place during the long-term operation of a pilot-scale submerged membrane bioreactor for municipal wastewater treatment

The critical flux and chemical cleaning-in-place (CIP) in a long-term operation of a pilot-scale submerged membrane bioreactor for municipal wastewater treatment were investigated. Steady filtration under high flux (30 L/(m² h)) was successfully achieved due to effective membrane fouling control by sub-critical flux operation and chemical CIP with sodium hypochlorite (NaClO) in both trans-membrane pressure (TMP) controlling mode (cleaning with high concentration NaClO of 2000-3000 mg/L in terms of effective chorine was performed when TMP rose to 15 kPa) and time controlling mode (cleanings were performed weekly and monthly respectively with low concentration NaClO (500-1000 mg/L) and high concentration NaClO (3000 mg/L)). Microscopic analysis on membrane fibers before and after high concentration NaClO was also conducted. Images of scanning electron microscopy (SEM) and atomic force microscopy (AFM) showed that NaClO CIP could effectively remove gel layer, the dominant fouling under sub-critical flux operation. Porosity measurements indicated that NaClO CIP could partially remove pore blockage fouling. The analyses from fourier transform infrared spectrometry (FTIR) with attenuated total reflectance accessory (ATR) and energy dispersive spectrometer (EDS) demonstrated that protein-like macromolecular organics and inorganics were the important components of the fouling layer. The analysis of effluent quality before and after NaClO CIP showed no obvious effect on effluent quality.     

Enhancement of filterability in MBR achieved by improvement of supernatant and floc characteristics via filter aids addition

Reduction of membrane fouling in membrane bioreactors (MBR) by addition of three typical filter aids (aluminum sulfate (Al(2)(SO(4))(3)), polymeric ferric sulfate (PFS) and Chitosan) was investigated. The effects of filter aids on membrane pore blocking, gel layer and cake layer resistance were analyzed respectively. Significant improvement of the sustainable filtration was demonstrated in the filter aids added MBRs. The membrane fouling rate of the MBRs operated under 20L/m(2)h flux was in the order of Control MBR (no filter aid added)>Al(2)(SO(4))(3) added MBR>Chitosan added MBR>PFS added MBR. Membrane inner fouling due to pore blocking was analyzed by means of Fourier-transform infrared microscope (FTIR). Compared to the control MBR, significantly low protein and carbohydrate concentrations were measured in the membranes of the filter aids added MBRs, indicating that filter aids could effectively alleviate membrane pore blocking. Gel Permeation Chromatography (GPC) analysis suggested that both the concentration and molecular weight distribution of the macromolecules in supernatant play an important role in gel layer formation and loss of membrane porosity. The reduction of fouling rate in the filter aids added MBRs could be attributed to lower concentration and reduction in molecular weight of macromolecules in supernatant. The specific cake resistance (alpha(c)), mean floc size (d(p)) and fractal dimension of the flocs (df) in the filter aids added MBRs were also investigated. It was demonstrated that alpha(c) decreased with the increase of d(p) and with the decrease of df, which is in consistent with the model prediction.     

Comparison of fouling characteristics of two different poly-vinylidene fluoride microfiltration membranes in a pilot-scale drinking water treatment system using pre-coagulation/sedimentation, sand filtration, and chlorination

Two pilot-scale hybrid water treatment systems using two different poly-vinylidene fluoride (PVDF) microfiltration (MF) membranes (i.e. symmetric and composite) were operated at a constant permeate flux of 104.2l m(-2)h(-1) (=2.5 md(-1)) with a pre-coagulation/sedimentation, sand filtration (SF), and chlorination to produce potable water from surface water. Turbidity was removed completely. And humic substances, Al, and Fe were removed very well by the pilot-scale membrane system. To control microbial growth and mitigate membrane fouling, a NaOCl solution was injected into the effluent from SF before reaching the two membranes (pre-chlorination). However, it adversely affected membrane fouling due to the oxidization and adsorption of inorganic substances such as Al, Fe, and Mn. In the next run, the NaOCl was introduced during backwash (post-chlorination). As compared with the result of pre-chlorination, this change increased the operating period of the symmetric and the composite membranes from about 10 and 50 days to about 60 and 200 days, respectively.     

SMBR在次临界通量下的运行特性

利用“通量阶式递增法”测定了两种膜组件的临界通量,在此基础上考察了次临界通量下的运行特性。试验发现,次临界通量操作下的膜污染过程具有明显的两阶段特征,与第一阶段跨膜压差(TMP)平缓直线上升相对应的膜污染机制主要是膜孔堵塞和凝胶层污染,与第二阶段TMP剧烈直线上升相对应的膜污染机制则是颗粒沉积层污染;先清水冲洗再化学清洗的方式能有效恢复膜的过滤能力,其中清水冲洗能有效去除颗粒沉积层污染,而化学清洗则能有效去除膜孔堵塞和凝胶层污染。     

Analysis of filtration characteristics in submerged microfiltration for drinking water treatment

Hollow fiber membranes have been widely employed for water and wastewater treatments. Nevertheless, understanding the filtration characteristics of hollow fiber membranes is complicated by the axial distributions of transmembrane pressure (TMP) and flux, which are key factors for both fouling control and module design. In this study, model equations to account for different fouling mechanisms were derived to analyze the performance of submerged hollow fiber systems with different conditions in terms of feed water characteristics and membrane material. A series of experiments with synthetic feed and raw water were carried out using hydrophilic and hydrophobic membrane modules. The model successfully fits the experimental results for synthetic feed as well as raw water. The major fouling mechanisms for filtration of raw water using hydrophilic and hydrophobic membranes are identified as cake formation and standard blocking, respectively. The model calculations indicate that the distributions of flux and cake (fouling) resistance are sensitive to the fiber length of the membrane.     

Engineering of an MBR supernatant fouling layer by fine particles addition: a possible way to control cake compressibility

For membrane bioreactors (MBR) applied to wastewater treatment membrane fouling is still the prevalent issue. The main limiting phenomena related to fouling is a sudden jump of the transmembrane pressure (TMP) often attributed to the collapse of the fouling layer. Among existing techniques to avoid or to delay this collapse, the addition of active particles membrane fouling reducers (polymer, resins, powdered activated carbon (PAC), zeolithe…) showed promising results.Thus the main objective of this work is to determine if fouling can be reduced by inclusion of inert particles (500 nm and inert compared to other fouling reducers) and which is the impact on filtration performances of the structuring of the fouling. Those particles were chosen for their different surface properties and their capability to form well structured layer.Results, obtained at constant pressure in dead end mode, show that the presence of particles changes foulant deposition and induces non-compressible fouling (in the range of 0.5-1 bar) and higher rejection values compared to filtration done on supernatant alone. Indeed dead end filtration tests show that whatever interactions between biofluid and particles, the addition of particles leads to better filtration performances (in terms of rejection, and fouling layer compressibility). Moreover results confirm the important role played by macromolecular compounds, during supernatant filtration, creating highly compressible and reversible fouling.In conclusion, this study done at lab-scale suggests the potential benefit to engineer fouling structure to control or to delay the collapse of the fouling layer. Finally this study offers the opportunities to enlarge the choice of membrane fouling reducers by taking into consideration their ability to form more consistent fouling (i.e. rigid, structured fouling).     

Analysis of microfiltration performance with constant flux processing of secondary effluent

This study involves the microfiltration (MF) of secondary effluent from a sequencing batch reactor processing industrial waste. The MF unit was a hollow fibre module with gas backwash capability, and operated with pumped permeate (controlled flux) and dead-end, crossflow or intermittent feed. The results showed that crossflow had no effect on flux and that intermittent dead-end filtration was less productive than non-intermittent operation. For dead-end filtration the cycle-time between gas backwashes depends very significantly on the imposed flux (varying from about 100 min at 30 L/m² h to about 5 min at 90 L/m² h) and the feed solids content. Optimal operation has to balance operating (energy for backwash) costs and the capital (membrane area) costs. Cost analysis based on capital and energy costs indicates that for lower energy cost the unit needs to be operated at lower imposed flux but to minimise total cost it is necessary to operate the unit above 60 L/m² h imposed flux depending on the maximum transmembrane pressure (TMP) allowed before back washing. Further analysis of TMP profiles showed that membrane resistance increased over time towards a maximum, which tended to increase with imposed flux. This implies more frequent chemical cleaning for high flux operation. Specific cake resistances were deduced from the profiles and indicated cake compression at higher flux and larger maximum TMP. Results of long-term trials are also reported. Water quality analysis shows consistent quality of permeate regardless of operating conditions.     

High-performance thin-layer hydrogel composite membranes for ultrafiltration of natural organic matter

Thin-layer hydrogel composite (TLHC) ultrafiltration (UF) membranes were synthesized by photo-grafting of either poly(ethylene glycol) methacrylate (PEGMA) or N,N-dimethyl-N-(2-methacryloyloxyethyl-N-(3-sulfopropyl) ammonium betaine (SPE) onto commercial polyethersulfone (PES) UF membranes. The performance of TLHC UF membranes was evaluated for natural organic matter (NOM) filtration and compared to commercial PES UF membranes. The fouling evaluation was done by investigation of membrane-solute interactions (adsorptive fouling) and membrane-solute-solute interactions (UF). The results suggest that the TLHC membranes convincingly displayed a higher adsorptive fouling resistance than unmodified PES UF membranes. In long-term stirred dead-end UF, a much lower fouling was observed for TLHC membranes than for commercial membranes with the same flux and rejection. Further, water flux recovery was also much higher. An analysis using an existing blocking model was performed in order to elucidate the effect of a polymer hydrogel layer on fouling mechanism as well as cake layer characteristics. The TLHC membranes synthesized by photo-grafting of PEGMA (40 g/L) and PEGMA with a low concentration of cross-linker monomer in the reaction mixture (ratio: 40/0.4 (g/L)/(g/L)) showed a much better performance than the other composite membranes. Those membranes could reduce the cake resistance on the membrane surface. This work has relevance for the design of high-performance UF membranes for applications in water treatment.     

SMSBR处理焦化废水的膜污染机理研究

在采用SMSBR处理焦化废水的过程中，通过对污泥进行终端过滤来反映膜污染机理，着重考察了过滤过程中的阻力分布，并通过标准堵塞过滤定律和沉积过滤定律来拟合膜过滤过程，从而确定了膜污染的控制因素。污泥的阻力分布试验表明，沉积阻力占总阻力的90％以上，并随压力的升高而增大，而内部污染阻力所占比例最小；污泥的终端过滤过程严格符合沉积过滤定律，即使在过滤初期也不受堵塞过滤的控制，这与阻力分布的结果相对应；污泥在严格符合沉积过滤定律，即使在过滤初期也不受堵塞过滤的控制，这与阻力布的结果相对应；污泥在终端过滤过程中膜的相对通量随过滤时间呈指数衰减趋势，并在几分钟内就达到相对稳定值，且低压对应较高的相对通量，但通量衰减指数和压力之间没有相关性；污泥的压密指数为0．7015。     

Sub-critical fouling in a membrane bioreactor for municipal wastewater treatment: experimental investigation and mathematical modelling

Fouling is a major limitation for the application of membrane bioreactors (MBRs) in municipal wastewater treatment; the critical flux concept represents a valid tool for process optimisation in planning fouling control strategies. The paper presents the results obtained on a large pilot MBR equipped with a plate-and-frame ultrafiltration membrane. The experimental assessment of flux criticality was carried out by flux-stepping tests showing the positive impact of liquid temperature on the value of the critical threshold. The reliability of short-term tests was then verified over a long period by determining the time of sustainability, t(sust), of six different sub-critical fluxes ranging between 17 and 30Lm(-2)h(-1). An exponential fitting was observed in terms of fouling rate both before and after t(sust), though fouling after t(sust) is likely to be ascribed not only to cake formation. Finally, a new mathematical formulation was proposed according to the local flux approach to model the sub-critical TMP transients. The model involves both bound and free forms of EPS and, once experimentally calibrated, it provided a fair prediction of the TMP jump.     

Effects of operational parameters on cake formation of CaSO4 in nanofiltration

Inorganic fouling is one of the major limitations of nanofiltration (NF) application in drinking water treatment. In this study, we report the effect of operating parameters on the fouling of NF membranes by CaSO4 in terms of cake growth at membrane surface under various operating conditions. Increasing operating pressure and decreasing crossflow velocity promote CaSO4 nucleation and crystallization, thus enhance membrane fouling. The flux decline and its dynamics due to the change of operating parameters are assessed quantitatively based on a resistance model. Applied filtration pressure is found to have the most dominant impact on the inorganic fouling. It is shown that the filtration resistance caused by the formation and growth of CaSO4 cake on membrane surface is dependent on operating parameters.     

Modeling cake buildup under TMP-step filtration in a membrane bioreactor: cake compressibility is significant

Fouling is inevitable in membrane bioreactors (MBRs) due to the complex nature of activated sludge, which contains a broad variety of potential foulants. Filter cakes that build up from sludge particles are traditionally highly compressible due to both the deformation of the individual sludge particles and the rearrangement of these particles in the cake. However, this phenomenon has been little examined in studies of fouling mechanisms in MBR systems. This study examines the properties of the cake layer, modeling the cake buildup and specific cake resistance (α), including compressibility, in terms of pressure-dependent α.The changes in fouling resistance during transmembrane pressure (TMP)-step filtration in an MBR setup were simulated using an empirical pressure dependence of the specific cake resistance and a simple mass balance model. The total change in fouling resistance in each TMP step could be divided into an initial rapid change in specific cake resistance due to filter cake compression followed by simple cake buildup. By including cake compression in this simple model, the model fitted the data with high precision. We demonstrated that compressibility should be considered when describing cake fouling in MBRs.     

浸入式膜系统的操作条件对膜污染的影响研究

采用浸入式膜处理滦河水,考察了膜系统的操作条件对膜污染的影响。结果表明:适当降低膜通量对膜处理系统的稳定运行起关键作用,试验条件下,膜通量为53.3L/(m2.h)、过滤周期为30min较适宜。提高曝气强度和水反冲洗强度可有效提高反冲洗效果,改善膜污染。浸入式膜对原水水质有较强的适应能力,可适当减少反冲洗排放次数,试验条件下,采用四轮一排较为可行。相比三氯化铁,聚合铝更适合作为PVDF膜的混凝预处理药剂。     

Novel magnetically induced membrane vibration (MMV) for fouling control in membrane bioreactors

Conventional submerged membrane bioreactors (MBRs) rely on the coarse bubbles aeration to generate shear at the liquid-membrane interface to limit membrane fouling. Unfortunately, it is a very energy consuming method, still often resulting in a rapid decrease of membrane permeability and consequently in higher expenses. In this paper, the feasibility of a novel magnetically induced membrane vibration (MMV) system was studied in a lab-scale MBR treating synthetic wastewater. The effects on membrane fouling of applied electrical power of different operation strategies, of membrane flux and of the presence of multiple membranes on one vibrating engine on membrane fouling were investigated. The filtration performance was evaluated by determining the filtration resistance profiles and critical flux. The results showed clear advantages of the vibrating system over conventional MBR processes by ensuring higher fluxes at lower fouling rates. Intermittent vibration was found a promising strategy for both efficient fouling control and significant energy saving. The optimised MMV system is presumed to lead to significant energy and cost reduction in up-scaled MBR operations.     

Effect of two-stage coagulant addition on coagulation-ultrafiltration process for treatment of humic-rich water

A novel two-stage coagulant addition strategy applied in a coagulation-ultrafiltration (UF) process for treatment of humic-rich water at neutral pH was investigated in this study. When aluminum sulfate (alum) doses were set at a ratio of 3:1 added during rapid mix stage and half way through flocculation stage, the integrated process of two-stage alum addition achieved almost the same organic matter removal as that of conventional one-stage alum addition at the same overall dose. Whereas membrane fouling could be effectively mitigated by the two-stage addition exhibited by trans-membrane pressure (TMP) developments. The TMP developments were found to be primarily attributed to external fouling on membrane surface, which was closely associated with floc characteristics. The results of jar tests indicated that the average size of flocs formed in two-stage addition mode roughly reached one half larger than that in one-stage addition mode, which implied a beneficial effect on membrane fouling reduction. Moreover, the flocs with more irregular structure and lower effective density resulted from the two-stage alum addition, which caused higher porosity of cake layer formed by such flocs on membrane surface. Microscopic observations of membrane surface demonstrated that internal fouling in membrane pores could be also remarkably limited by two-stage alum addition. It is likely that the freshly formed hydroxide precipitates were distinct in surface characteristics from the aged precipitates due to formation of more active groups or adsorption of more labile aluminum species. Consequently, the flocs could further connect and aggregate to contribute to preferable properties for filtration performance of the coagulation-UF process. As a simple and efficient approach, two-stage coagulant addition strategy could have great practical significance in coagulation-membrane processes.     

Transition in fouling mechanism in microfiltration of a surface water

The main disadvantage of membrane filtration is membrane fouling, which remains as the major obstacle for more efficient use of this technology. Information about the constituents that cause fouling is indispensable for more efficient operation. We examined the changes in both foulant characteristics and membrane morphology by performing the pilot-scale filtration test using one microfiltration membrane. During the operation, we cut the membrane fibers three times, and the components that caused irreversible fouling were extracted by acid or alkaline solution. We found that the characteristic of inorganic matter extracted by acid solution completely differed depending on the filtration period. A large amount of iron was extracted in the second chemical cleaning, while manganese was the dominant component of the extracted inorganic matter in the third chemical cleaning. The analysis of Fourier transform infrared (FTIR) and cross polarization magic angle spinning carbon-13 (CPMAS (13)C) nuclear magnetic resonance (NMR) demonstrated that the contribution of humic substances and carbohydrate in the organic foulant had increased as fouling developed. The changes in the major foulant have no relation with the fluctuation in feed water. The analysis of membrane morphology illustrated that the cake layer started to build up after the blockage of membrane pores. Based on the above results, we hypothesized the following fouling mechanism: the pores were covered or narrowed with relatively large particles such as iron, carbohydrate or protein; small particles such as manganese or humic substances blocked the narrowed pores; and finally an irreversible cake layer started to build up on the membrane surface.     

High-concentration food wastewater treatment by an anaerobic membrane bioreactor

The viability of treating high-concentration food wastewater by an anaerobic membrane bioreactor (AMBR) was studied using polyethersulfone (PES) ultrafiltration membranes PES200, PES300, PES500 and PES700 with norminal molecular weight cutoff (MWCO) ranging from 20,000 to 70,000 Da. Hydraulic and solid retention time significantly affected the treatment performance of the AMBR kept at 60 h and 50 days in the study. The four membranes exhibited a similar efficiency in removal of suspended solids, color, chemical oxygen demand (COD) and bacteria. When the volumetric loading rate was below 4.5 kg/m3d, COD removal rate was in the range of 81-94% and the gas yield stabilized at 0.136 m3/kg COD. The effect of membrane properties including MWCO, hydrophobicity and surface morphology on membrane fouling and cleaning was evaluated. The PES200 membranes with the smallest MWCO and smoothest surface exhibited a serious initial flux decline, whereas the PES700 membranes with the largest MWCO and roughest surface were observed related to the highest flux decline and the lowest recoverable flux rate during long-term operation. Membrane autopsy revealed that the significant flux decline was caused by the formation of a thick biofouling layer onto the membrane surfaces.     

Comparison of the filtration characteristics of organic and inorganic membranes in a membrane-coupled anaerobic bioreactor

Comparison of filtration characteristics of organic and inorganic membranes was made in terms of physicochemical properties of the membrane materials, cake layer formation, backflushing and backfeeding effects in a membrane-coupled anaerobic bioreactor. For the inorganic membrane, struvite (MgNH4PO4 x 6H2O) was found to have accumulated inside the membrane pore and plays a key role in flux decline. For the organic, however, a thick cake layer composed of biomass and struvite formed on the membrane surface, thus causing a major hydraulic resistance. In order to mitigate flux decline for both membranes, backflushing and backfeeding modes were examined. With acidic (pH 2.0) backflushing, the flux was approximately doubled for the organic membrane. However, unexpectedly a negative effect was observed for the inorganic membrane. An alkaline backflushing instead of acidic backflushing gave rise to a flux improvement by a factor of two without any negative effect, even for the inorganic membrane. The backfeeding mode gave rise to a much higher flux compared with the normal mode in both types of membrane, although the flux returned to the same level as that with the normal mode after 6 days for the inorganic membrane. The differences between the two types of membranes were explained by membrane morphology, a ligand exchange reaction as well as a surface charge effect.     

Effects of mass retention of dissolved organic matter and membrane pore size on membrane fouling and flux decline

Ultrafiltration (UF) fouling has been attributed to concentration polarization, gel layer formation as well as outer and inner membrane pore clogging. It is believed that mass of humic materials either retained on membrane surface or associated with membrane inner pore surface is the primary cause for permeate flux decline and filtration resistance build-up in water supply industries. While biofilm/biofouling and inorganic matter could also be contributing factors for permeability decline in wastewater treatment practices. The present study relates UF fouling to mass of dissolved organic matter (DOM) retained on membrane and quantifies the effect of retained DOM mass on filtration flux decline. The results demonstrate that larger pore membranes exhibit significant flux decline in comparison with the smaller ones. During a 24-h period, dissolved organic carbon mass retained in 10 kDa membranes was about 1.0 g m⁻² and that in 100 kDa membranes was more than 3 times higher (3.6 g m⁻²). The accumulation of retained DOM mass significantly affects permeate flux. It is highly likely that some DOMs bind or aggregate together to form surface gel layer in the smaller 10 kDa UF system; those DOMs largely present in inner pore and serving as pore blockage on a loose membrane (100 kDa) are responsible for severe flux decline.