Fouling indices for low pressure hollow fiber membrane performance assessment

This study evaluated the use of fouling indices to describe low pressure membrane fouling. One critical aspect of this study was the use of a bench-scale hollow fiber membrane system that imitated full-scale operation (constant flux with automatic hydraulic backwash and chemical cleaning). Fouling indices were based on a resistance-in-series model. Two different hollow fiber membrane types (membrane A and B) were tested with water from two water utilities (A and B) and three other natural sources (oligotrophic, algal bloom impacted, and wastewater impaired). The bench-scale testing included use of the same membrane as utilized at Utility B. Most fouling was reversible by hydraulic backwash and chemical cleaning. Specific flux and fouling indices for the bench-scale system were higher than those determined from full-scale data but fouling index ratios were comparable, suggesting a similar fouling nature. At similar organic loading, fouling was specific to water source and membrane type, i.e., no generalization on the impact of water source was possible. Full-scale data were compared with bench-scale data to validate the use of fouling indices. Fouling indices based on a resistance-in-series are useful tools to describe membrane performance data for both raw and pretreated water, for different water sources, and different membrane types.     

改性PVDF中空纤维膜处理压裂返排液研究

针对中空纤维膜应用于水力压裂返排液处理时存在的膜污染严重、通量衰减快、影响处理效率等问题,研究了PVDF固含量、凝固浴温度等因素对PVDF膜性能的影响,通过非溶剂致相分离法制备了PVDF中空纤维膜,并采用表面接枝技术,对PVDF中空纤维膜进行了表面亲水化改性。压裂返排液吸附实验结果表明,表面接枝降低了PVDF的接触角,提高了膜的亲水性。与未接枝改性的PVDF膜相比,亲水改性后的PVDF膜表面吸附的压裂返排液更少。将亲水性中空纤维膜用于页岩气水力压裂返排液的过滤处理,应用结果表明其对压裂返排液中的总铁、SS、浊度、细菌去除率达到90%以上,长时间运行后的通量保持率高,有较好的抗膜污染性。     

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.     

Reversible and irreversible low-pressure membrane foulants in drinking water treatment: Identification by principal component analysis of fluorescence EEM and mitigation by biofiltration pretreatment

With the increased use of membranes in drinking water treatment, fouling - particularly the hydraulically irreversible type - remains the main operating issue that hinders performance and increases operational costs. The main challenge in assessing fouling potential of feed water is to accurately detect and quantify feed water constituents responsible for membrane fouling. Utilizing fluorescence excitation-emission matrices (EEM), protein-like substances, humic and fulvic acids, and particulate/colloidal matter can be detected with high sensitivity in surface waters. The application of principal component analysis to fluorescence EEMs allowed estimation of the impact of surface water constituents on reversible and irreversible membrane fouling. This technique was applied to experimental data from a two year bench-scale study that included thirteen experiments investigating the fouling potential of Grand River water (Ontario, Canada) and the effect of biofiltration pre-treatment on the level of foulants during ultrafiltration (UF). Results showed that, although the content of protein-like substances in this membrane feed water (= biofiltered natural water) was much lower than commonly found in wastewater applications, the content of protein-like substances was still highly correlated with irreversible fouling of the UF membrane. In addition, there is evidence that protein-like substances and particulate/colloidal matter formed a combined fouling layer, which contributed to both reversible and irreversible fouling. It is suggested that fouling transitions from a reversible to an irreversible regime depending on feed composition and operating time. Direct biofiltration without prior coagulant addition reduced the protein-like content of the membrane feed water which in turn reduced the irreversible fouling potential for UF membranes. Biofilters also decreased reversible fouling, and for both types of fouling higher biofilter contact times were beneficial.     

Impact of polymer flocculants on coagulation-microfiltration of surface water

Organic polymers are widely used as flocculants in pretreatment for microfiltration. However, their impact on microfiltration system performance was not well understood. In this study, the effects of three types of polymer flocculants on microfiltration permeate water quality and membrane fouling were evaluated using a hollow fiber membrane under two different operation modes, coagulation/flocculation-sedimentation-microfiltration (CFSM) and coagulation/flocculation-microfiltration (CFM). Interestingly, the effect of polymers on membrane fouling did not appear to reflect their impact on dissolved organic matter content or floc particle properties in the membrane feed water. The addition of polymer flocculants resulted in floc particles of larger size and smaller fractal dimension and slightly enhanced the removal of dissolved organic matter, both of which were expected to reduce membrane fouling. However, it significantly aggravated membrane fouling in all cases except when the positively charged poly(diallyldimethylammonium) chloride was used in the CFSM process. In particular, all polymers greatly increased hydraulically irreversible fouling in the CFM mode. The increased fouling in the CFSM mode is attributed to the residual polymer, while that in the CFM mode is attributed to the enhanced irreversible floc particle attachment on the membrane surface. Considering the potential severe membrane fouling and the small improvement in treated water quality when polymers are used, the application of polymers in microfiltration pretreatment needs to be carefully evaluated.     

Application of ceramic membranes with pre-ozonation for treatment of secondary wastewater effluent

Membrane fouling is an inevitable problem when microfiltration (MF) and ultrafiltraion (UF) are used to treat wastewater treatment plant (WWTP) effluent. While historically the use of MF/UF for water and wastewater treatment has been almost exclusively focused on polymeric membranes, new generation ceramic membranes were recently introduced in the market and they possess unique advantages over currently available polymeric membranes. Ceramic membranes are mechanically superior and are more resistant to severe chemical and thermal environments. Due to the robustness of ceramic membranes, strong oxidants such as ozone can be used as pretreatment to reduce the membrane fouling. This paper presents results of a pilot study designed to investigate the application of new generation ceramic membranes for WWTP effluent treatment. Ozonation and coagulation pretreatment were evaluated to optimize the membrane operation. The ceramic membrane demonstrated stable performance at a filtration flux of 100 gfd (170 LMH) at 20 °C with pretreatment using PACl (1 mg/L as Al) and ozone (4 mg/L). To understand the effects of ozone and coagulation pretreatment on organic foulants, natural organic matter (NOM) in four waters - raw, ozone treated, coagulation treated, and ozone followed by coagulation treated wastewaters - were characterized using high performance size exclusion chromatography (HPSEC). The HPSEC analysis demonstrated that ozone treatment is effective at degrading colloidal NOMs which are likely responsible for the majority of membrane fouling.     

Correlation of EPS content in activated sludge at different sludge retention times with membrane fouling phenomena

In this study, activated sludge characteristics were studied with regard to membrane fouling in membrane bioreactors (MBRs) for two pilot plants and one full-scale plant treating municipal wastewater. For the full-scale MBR, concentrations of extracellular polymeric substances (EPS) bound to sludge flocs were shown to have seasonal variations from as low as 17mgg(-1) dry matter (DM) in summer up to 51mg(gDM)(-1) in winter, which correlated with an increased occurrence of filamentous bacteria in the colder season. Therefore, it was investigated at pilot-scale MBRs with different sludge retention times (SRTs) whether different EPS contents and corresponding sludge properties influence membrane fouling. Activated sludge from the pilot MBR with low SRT (23d) was found to have worse filterability, settleability and dewaterability. Photometric analysis of EPS extracts as well as LC-OCD measurements showed that it contained significantly higher concentrations of floc-bound EPS than sludge at higher SRT (40d) The formation of fouling layers on the membranes, characterised by SEM-EDX as well as photometric analysis of EPS extracts, was more distinct at lower SRT where concentrations of deposited EPS were 40-fold higher for proteins and 5-fold higher for carbohydrates compared with the membrane at higher SRT. Floc-bound EPS and metals were suggested to play a role in the fouling process at the full-scale MBR and this was confirmed by the pilot-scale study. However, despite the different sludge properties, the permeability of membranes was found to be similar.     

Effect of membrane character and solution chemistry on microfiltration performance

To help understand and predict the role of natural organic matter (NOM) in the fouling of low-pressure membranes, experiments were carried out with an apparatus that incorporates automatic backwashing and long filtration runs. Three hollow fibre membranes of varying character were included in the study, and the filtration of two different surface waters was compared. The hydrophilic membrane had greater flux recovery after backwashing than the hydrophobic membranes, but the efficiency of backwashing decreased at extended filtration times. NOM concentration of these waters (7.9 and 9.1mg/L) had little effect on the flux of the membranes at extended filtration times, as backwashing of the membrane restored the flux to similar values regardless of the NOM concentration. The solution pH also had little effect at extended filtration times. The backwashing efficiency of the hydrophilic membrane was dramatically different for the two waters, and the presence of colloid NOM alone could not explain these differences. It is proposed that colloidal NOM forms a filter cake on the surface of the membranes and that small molecular weight organics that have an adsorption peak at 220nm but not 254nm were responsible for "gluing" the colloids to the membrane surface. Alum coagulation improved membrane performance in all instances, and this was suggested to be because coagulation reduced the concentration of "glue" that holds the organic colloids to the membrane surface.     

中空纤维超滤膜处理滦河水中试研究

采用混凝-超滤工艺对滦河原水进行了中试研究,重点考察了PVC中空纤维超滤膜对不同水质期的滦河水中污染物的去除情况。结果表明：水温降低使膜性能下降。膜污染较严重;在高藻期进行预氯化有助于减缓膜污染;针对不同的水质期要采用不同的预处理方法。在低温期适当增加铁盐投量,高藻期进行预氯化都有助于系统稳定运行;膜出水在3个水质期（低温、常温、高藻期）均很稳定,与常规工艺相比,膜工艺具有一定的优越性,在去除浊度和颗粒物方面尤为突出。     

Natural organic matter fouling of low-pressure, hollow-fiber membranes: Effects of NOM source and hydrodynamic conditions

Effects of natural organic matter (NOM) source and hydrodynamic conditions on both hydraulically reversible and irreversible fouling of low-pressure, hollow-fiber (LPHF) membranes were systematically investigated using representative sources of natural waters and wastewater effluents. It was found that NOM source plays a primary role in determining the fouling of these membranes. Increase in permeate flux promoted membrane fouling, but to a lesser extent than NOM source. Permeate backwash flux appeared to restore permeability more effectively for the polyether sulfone (PES) membranes than to the polyvinylidene fluoride (PVDF) membranes used. NOM characterization revealed that organic colloids contributed predominantly to the hydraulically reversible fouling, and potentially to the irreversible fouling. Overall, this study demonstrated the importance of NOM source and the presence of organic colloids in the fouling of LPHF membranes, as well as the relevance of hydrodynamic operating conditions on the hydraulic reversibility of the fouling.     

Water hammer reduces fouling during natural water ultrafiltration

Today’s ultrafiltration processes use permeate flow reversal to remove fouling deposits on the feed side of ultrafiltration membranes. We report an as effective method: the opening and rapid closing of a valve on the permeate side of an ultrafiltration module. The sudden valve closure generates pressure fluctuations due to fluid inertia and is commonly known as “water hammer”. Surface water was filtrated in hollow fiber ultrafiltration membranes with a small (5%) crossflow. Filtration experiments above sustainable flux levels (>125 l (m²h)⁻¹) show that a periodic closure of a valve on the permeate side improves filtration performance as a consequence of reduced fouling. It was shown that this effect depends on flux and actuation frequency of the valve. The time period that the valve was closed proved to have no effect on filtration performance. The pressure fluctuations generated by the sudden stop in fluid motion due to the valve closure are responsible for the effect of fouling reduction. High frequency recording of the dynamic pressure evolution shows water hammer related pressure fluctuations to occur in the order of 0.1 bar. The pressure fluctuations were higher at higher fluxes (higher velocities) which is in agreement with the theory. They were also more effective at higher fluxes with respect to fouling mitigation.     

Full-scale simulation of seawater reverse osmosis desalination processes for boron removal: Effect of membrane fouling

The objective of this study is to further develop previously reported mechanistic predictive model that simulates boron removal in full-scale seawater reverse osmosis (RO) desalination processes to take into account the effect of membrane fouling. Decrease of boron removal and reduction in water production rate by membrane fouling due to enhanced concentration polarization were simulated as a decrease in solute mass transfer coefficient in boundary layer on membrane surface. Various design and operating options under fouling condition were examined including single- versus double-pass configurations, different number of RO elements per vessel, use of RO membranes with enhanced boron rejection, and pH adjustment. These options were quantitatively compared by normalizing the performance of the system in terms of E_min, the minimum energy costs per product water. Simulation results suggested that most viable options to enhance boron rejection among those tested in this study include: i) minimizing fouling, ii) exchanging the existing SWRO elements to boron-specific ones, and iii) increasing pH in the second pass. The model developed in this study is expected to help design and optimization of the RO processes to achieve the target boron removal at target water recovery under realistic conditions where membrane fouling occurs during operation.     

Autopsy of high-pressure membranes to compare effectiveness of MF and UF pretreatment in water reclamation

A pilot-plant study was designed to compare the effectiveness of microfiltration (MF) and ultrafiltration (UF) as pretreatment for high-pressure membranes in reclamation of biologically treated wastewater effluent. Granular media, filtered secondary effluent from a full-scale wastewater treatment plant, was fed to MF and UF units that operated in parallel. Each of these filtrates served as the feedwater to two reverse osmosis (RO) units and one nanofiltration (NF) unit that operated in parallel. The decline in specific flux was substantially lower for high-pressure membranes receiving UF than MF pretreatment over the course of each of four pilot plant runs that lasted from 1 to 7 weeks. The removal of organic matter as measured by dissolved organic carbon (DOC) was somewhat higher by UF than MF pretreatment (about 15% by UF compared with 11% by MF). Addition of ferric chloride ahead of the UF unit, but not ahead of the MF unit, may account for this additional removal of organic matter. However, the additional DOC removal appeared insufficient to explain the differential in foulant accumulation between high-pressure membranes receiving UF and MF pretreatment. Extensive autopsy analyses of these high-pressure membranes showed from 35% to 56% less organic carbon on those receiving UF rather than MF pretreatment. A more specific indicator of a differential in organic fouling was the accumulation of polysaccharides and this showed from 27% to 38% less on UF- than on MF-pretreated membranes. Yet another possible source of foulants is inorganic material given that the inorganic and organic weight percentages were nearly equal (56% vs. 44%) on the membrane surface. One specific source was aluminum added for phosphorus removal. Less fouling of high-pressure membranes pretreated by UF than MF could be due to the following: (1) a small, but very important, colloidal fouling fraction may have passed through MF but was rejected by UF pretreatment; (2) organic fouling was not related to organics in either the MF or UF filtrates but rather to organics that are generated in situ by microbial activity on the membrane surface; and/or (3) less passage of colloidal Al-P that carried over from secondary wastewater treatment.     

Power induced by bubbles of different sizes and frequencies on to hollow fibers in submerged membrane systems

To shed light onto the relationship between sparging conditions and fouling control in submerged hollow fiber membranes, the effects of bubble size and frequency on the hydrodynamic conditions induced in membrane system were studied. Two general classes of bubbles were considered: coarse (0.75–2.5 mL) and pulse (100–500 mL). The power transferred (P_trans) onto membranes could be used to characterise the multiple effects induced under different sparging conditions. P_trans is proportional to root mean square of shear stress (τ_rms), the area of zone of influence (i.e. the fraction in the system where high velocity and high vorticity (turbulence) are induced by the bubble) and their rise velocity. At a given sparging rate, the power transferred onto membranes was less with coarse bubble sparging than pulse bubble sparging and increased with the size of pulse bubbles. For all cases, the power transfer efficiency was consistently higher for pulse bubble sparging than for coarse bubble sparging. The power transfer efficiency to the system was greatest for the small pulse bubbles considered when a small amount of power is required for fouling control. However, when fouling is extensive, large pulse bubbles may be required to generate the required amount of power for fouling control.     

Fouling behavior of microstructured hollow fiber membranes in submerged and aerated filtrations

The performance of microstructured hollow fiber membranes in submerged and aerated systems was investigated using colloidal silica as a model foulant. The microstructured fibers were compared to round fibers and to twisted microstructured fibers in flux-stepping experiments. The fouling resistances in the structured fibers were found to be higher than those of round fibers. This was attributed to stagnant zones in the grooves of the structured fibers. As the bubble sizes were larger than the size of the grooves of the structured fibers, it is possible that neither the bubbles nor the secondary flow caused by the bubbles can reach the bottom parts of the grooves. Twisting the structured fibers around their axes resulted in decreased fouling resistances. Large, cap-shaped bubbles and slugs were found to be the most effective in fouling removal, while small bubbles of sizes similar to the convolutions in the structured fiber did not cause an improvement in these fibers. Modules in a vertical orientation performed better than horizontal modules when coarse bubbling was used. For small bubbles, the difference between vertical and horizontal modules was not significant. When the structured and twisted fibers were compared to round fibers with respect to the permeate flowrate produced per fiber length instead of the actual flux through the convoluted membrane area, they showed lower fouling resistance than round fibers. This is because the enhancement in surface area is more than the increase in resistance caused by stagnant zones in the grooves of the structured fibers. From a practical point of view, although the microstructure does not promote further turbulence in submerged and aerated systems, it can still be possible to enhance productivity per module with the microstructured fibers due to their high surface area-to-volume ratio.     

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.     

Surface modification of polypropylene microporous membrane to improve its antifouling characteristics in an SMBR: N2 plasma treatment

Fouling is the major obstacle in membrane processes applied in water and wastewater treatment. The polypropylene hollow fiber microporous membranes (PPHFMMs) were surface modified by N₂ low-temperature plasma treatment to improve the antifouling characteristics. Morphological changes on the membrane surface were characterized by field emission scanning electron microscopy (FE-SEM). The change of surface wettability was monitored by contact angle measurements. The static water contact angle of the modified membrane reduced obviously; the relative pure water flux of the modified membranes increased with the increase of plasma treatment time. To assess the relation between plasma treatment and membrane fouling in a submerged membrane bioreactor (SMBR), filtration of activated sludge was carried out by using synthetic wastewater. After continuous operation in the SMBR for about 90 h, flux recoveries for the N₂ plasma-treated PPHFMM for 8 min were 62.9% and 67.8% higher than those of the virgin membrane after water and NaOH cleaning. The irreversible fouling resistance decreased after plasma treatment.     

混凝—微滤工艺去除膜反洗水中有机物的试验研究

采用混凝-微滤工艺处理混凝-超滤中试装置的膜反洗水(MBW),将试验原水和出水经不同截留分子质量的超滤膜过滤,分析了不同分子质量区间的有机物分布.此外通过改变混凝剂(FeCl3)投量、采取投加粉末活性炭(PAC)等措施,考察了MBW中有机物的去除率与FeCl3投量、处理工艺(混凝-微滤、混凝-PAc吸附-微滤工艺)的关系.研究结果表明,MBW中DOC主要分布在分子质量>30 ku和分子质量<1 ku的区间内,THMFP、UV254主要集中在分子质量<1ku的区间内;混凝过程能有效去除分子质量>30 ku的大分子有机物,PAC能有效去除小分子有机物;随混凝剂投量的增加,对DOC、UV254、THMFP的去除率均有不同程度的提高.     

Efficacy of relaxation, backflushing, chemical cleaning and clogging removal for an immersed hollow fibre membrane bioreactor

A pilot-scale hollow fibre immersed MBR, challenged with real municipal wastewater, was studied and operated under conditions identical to those prevailing at full-scale to assess the relative influence of backflushing, relaxation, chemical enhanced backflushing (CEB) and declogging on permeability decline and recovery. The influence of relaxation and backflushing was initially assessed using the conventional flux step method; results indicated reversible fouling to be similar for each method, whilst the irreversible fouling rate was significantly reduced by backflushing. For a given total backflush volume, fouling mitigation was found to be marginally better through employing higher backflush fluxes than longer backflush durations.The impact of the CEB on permeability recovery assessed at low and high fluxes indicated operation at more conservative fluxes to yield more sustained permeability. Under more aggressive operating conditions - fluxes of up to 35 L m⁻² h⁻¹ at specific aeration demand values of 0.25 Nm³/(m² h) - long-term permeability decline took place which was not significantly ameliorated by chemical cleaning. On declogging the membrane through gentle agitation permeability recovery was significant, but was followed by a rapid permeability decline over the course of a few hours. Results suggested control of clogging to be of greater importance than that of fouling in sustaining permeability.     

Fouling of microfiltration membranes by organic polymer coagulants and flocculants: Controlling factors and mechanisms

Organic polymers are commonly used as coagulants or flocculants in pretreatment for microfiltration (MF). These high molecular weight compounds are potential membrane foulants when carried over to the MF filters. This study examined fouling of three MF membranes of different materials by three commonly used water treatment polymers: poly(diallyldimethylammonium) chloride (pDADMAC), polyacrylamide (PAM), and poly(acrylic acid-co-acrylamide (PACA) with a wide range of molecular weights. The effects of polymer molecular characteristics, membrane surface properties, solution condition and polymer concentration on membrane fouling were investigated. Results showed severe fouling of microfiltration membranes at very low polymer concentrations, suggesting that residual polymers carried over from the coagulation/flocculation basin can contribute significantly to membrane fouling. The interactions between polymers and membranes depended strongly on the molecular size and charge of the polymer. High molecular weight, positively charged polymers caused the greatest fouling. Blockage of membrane pore openings was identified as the main fouling mechanism with no detectable internal fouling in spite of the small molecular size of the polymers relative to the membrane pore size. Solution conditions (e.g., pH and calcium concentration) that led to larger polymer molecular or aggregate sizes resulted in greater fouling.