Permeability of low molecular weight organics through nanofiltration membranes

The removal of natural organic matter (NOM) using nanofiltration (NF) is increasingly becoming an option for drinking water treatment. Low molecular weight (LMW) organic compounds are nevertheless only partially retained by such membranes. Bacterial regrowth and biofilm formation in the drinking water distribution system is favoured by the presence of such compounds, which in this context are considered as the assimilable organic carbon (AOC). In this study, the question of whether NF produces microbiologically stable water was addressed. Two NF membranes (cut-off of about 300 Da) were tested with different natural and synthetic water samples in a cross-flow filtration unit. NOM was characterised by liquid chromatography with organic carbon detection (LC-OCD) using a size-exclusion column in addition to specific organic acid measurements, while AOC was measured in a batch growth bioassay.Similarly to high molecular weight organic compounds like polysaccharides or humic substances that have a permeability lower than 1%, charged LMW organic compounds were efficiently retained by the NF membranes tested and showed a permeability lower than 3%. However, LMW neutrals and hydrophobic organic compounds permeate to a higher extent through the membranes and have a permeability of up to 6% and 12%, respectively. Furthermore, AOC was poorly retained by NF and the apparent AOC concentration measured in the permeated water was above the proposed limit for microbiologically stable water. This indicates that the drinking water produced by NF might be biologically unstable in the distribution system. Nevertheless, in comparison with the raw water, NF significantly reduced the AOC concentration.     

New PVDF membranes: The effect of plasma surface modification on retention in nanofiltration of aqueous solution containing organic compounds

New nanofiltration membranes were prepared by non-solvent-induced phase inversion from a PVDF/DMF/water system. The effect of exposure time before coagulation on the membrane characteristics (morphology, thickness, overall porosity, tensile strength) was investigated. PVDF membrane prepared at a fixed exposure time of 45s (PF45) was further plasma surface modified (RF 13.56 MHz) (PF45psm), introducing amino groups on the membrane. The performances of PF45, PF45psm and of a commercial nanofiltration membrane (N30F) were tested in the removal of two dyes from aqueous solution, characterized by different charge and molecular weight (congo red and methylene blue). The observed rejections depended more on the charge of the compound than on their molecular weights and results were optimized for the plasma modified membrane (PF45psm) with respect to unmodified (PF45) and commercial N30F membranes. In particular, methylene blue was retained for 100% by PF45psm with a relative flux of 65% compared to 38% of rejection and 59% of relative flux observed for N30F.     

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.     

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.     

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.     

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.     

Cost factors and chemical pretreatment effects in the membrane filtration of waters containing natural organic matter

This paper compares the membrane processes available for water treatment. Membranes have the advantage of currently decreasing capital cost, a relatively small footprint compared to conventional treatment, generally a reduction in chemicals usage and comparably low maintenance requirements. Three membrane processes applicable to water treatment, micro- (MF), ultra- (UF), and nanofiltration (NF), are compared in terms of intrinsic rejection, variation of rejection due to membrane fouling and increase in rejection by ferric chloride pretreatment. Twelve different membranes are compared on the basis of their membrane pore size which was calculated from their molecular weight cut-off. A pore size of < 6 nm is required to achieve substantial (> 50%) organics removal. For a fouled membrane this pore size is about 11 nm. UV rejection is higher than DOC rejection. Coagulation pretreatment allows a higher rejection of organics by MF and UF and the cut-off criterion due to initial membrane pore size is no longer valid. A water quality parameter (WQP) is introduced which describes the product water quality achieved as a function of colloid, DOC and cation rejection. The relationship between log (pore size) and WQP is linear. Estimation of membrane costs as a function of WQP suggests that open UF is superior to MF (similar cost at higher WQP) and NF is superior to tight UF. Chemical pretreatment could compensate for the difference between MF and UF. However, when considering chemicals and energy costs, it appears that a process operated at a higher energy is cheaper at a guaranteed product quality (less dependent on organic type). This argument is further supported by environmental issues of chemicals usage, as energy may be provided from renewable sources.     

A membrane biological filter device for reducing waterborne biodegradable pollutants

A device having potential applications to water pollution control problems is modeled by a laboratory system in which a phenylcarbamate-degrading population of micro-organisms reduces the concentration of the herbicide Isopropylphenylcarbamate (IPC) in a continuously flowing stream. The micro-organisms are kept separate from the feed stream by an ultrafilter membrane which retains the micro-organisms but allows passage of all smaller materials. As the feed stream passes through the device, IPC is transferred to the bath of micro-organisms and metabolized. The percentage reduction of IPC in the feed stream depends primarily on the efficiency of transfer across the membrane, the velocity of the feed stream, the quantity of microbes retained in the bath and the factors affecting their activity. An equation is derived relating these variables under the assumption of complete transfer of IPC to the bath and a constant rate of IPC degradation per unit of microbes. Problems and improvements are discussed.     

Combined influence of membrane surface properties and feed water qualities on RO/NF mass transfer, a pilot study

The impact of membrane surface characteristics and NOM on membrane performance has been investigated for varying pretreatment and membranes in a field study. Surface charge, hydrophobicity and roughness varied significantly among the four membranes used in the study. The membranes were tested in parallel following two different pretreatment processes, an enhanced Zenon ultrafiltration process (ZN) and a compact CSF process (Superpulsator (SP)) prior to RO membrane treatment for a total of eight integrated membrane systems. All membrane systems were exposed to the similar temperature, recovery and flux as well as chemical dosage. The membrane feed water qualities were statistically equivalent following ZN pretreatment and SP pretreatment except for NOM and SUVA. Membrane surface characteristics, NOM and SUVA measurements were used to describe mass transfer in a low-pressure RO integrated membrane system. Solute and water mass transfer coefficients (MTCs) were investigated for dependence on membrane surface properties and NOM mass loading. Inorganic MTCs were accurately described by a Gaussian distribution curve. Water productivity decreased with NOM loading and increased with contact angle and roughness. The negative effects of NOM loading on productivity were reduced as the negative charge on the membrane surface increased. Inorganic MTCs were also correlated to surface hydrophobicity and surface roughness. The permeability change of identical membranes was related to NOM loading, hydrophobicity and roughness. Organic fouling as measured by water, organic and inorganic mass transfer was less for membranes with higher hydrophilicity and roughness.     

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.     

Removal of anionic reactive dyes from water using anion exchange membranes as adsorbers

Two commercial anion exchange membranes, strong basic (SB6407) and weak basic (DE81), were evaluated for the removal of anionic reactive dyes, Cibacron blue 3GA (three sulfonic acid groups per dye molecule) and Cibacron red 3BA (four sulfonic acid groups per dye molecule), from water in this study. The adsorption isotherm results show that the Langmuir maximum adsorption capacities of Cibacron blue 3GA (31.5mg/cm(3) for SB6407 and 25.5mg/cm(3) for DE81) were greater than those of Cibacron red 3BA (24.5mg/cm(3) for SB6407 and 18.5mg/cm(3) for DE81). For each reactive dye, the capacity for SB6407 was higher than DE81 based on the same membrane volume. However, consideration of the number of ion exchange sites interacting with a dye molecule indicates that the DE81 results are close to the theoretical values while the SB6407 membrane had some unused binding sites. In addition, Cibacron red 3BA demonstrated faster and stronger binding with both anion exchange membranes than Cibacron blue 3GA. Both dyes could bind with strong basic SB6407 more quickly and stronger. In the batch desorption process, different desorption solutions were tested and the mixtures of salt, acid, or base in methanol solution (e.g. 1N KSCN in 60% methanol or 1N HCl in 60% methanol) achieved better performance. Finally, in the flow process with one piece of anion exchange membrane (initial dye concentration of 0.05g/L), SB6407 was found superior to DE81 in dye recovery and both membranes retained their original uptake capacities over three cycles of adsorption, washing, and desorption.     

Selection of NF membrane to improve quality of chemically treated surface water

The requirement for higher quality drinking water necessitates the application of more efficient water treatment techniques. Nanofiltration is one promising option for enhanced water treatment, for example, in enhanced organic matter removal. The characteristics of different nanofiltration membranes vary remarkably, and the selection of a membrane has to be made according to the requirements of an application. In this study six nanofiltration membranes (NF70, NF255, NTR-7450, NTR-7410, Desal-5 and TFC-S) were evaluated in improving the quality of chemically pre-treated surface water in a pilot-scale process. The results indicate that the membrane with high organics removal and slightly reduced ion removal characteristics (NF255) performed best in terms of product water quality as well as membrane productivity and fouling. The most permeable membrane (NTR-7410) suffered intensive fouling and insufficient product water quality. An interesting finding was that the permeates of all the tested membranes possessed a significant potential for microbial growth, despite the low nutrient contents.     

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.     

大型超滤水厂PVC和PVDF膜运行特性差异与优化

超滤技术已广泛应用于城镇给水处理厂,使得饮用水水质得到显著改善。不同材质超滤膜的运行周期、膜通量、跨膜压差(TMP)等的变化规律会有显著的差异,需要根据各自的特点对超滤系统进行运行参数调控与优化,以保证超滤系统的长期稳定运行。分析了山东某大型超滤水厂超滤系统长期运行的特点,对比了PVC膜和PVDF膜孔结构特征、膜通量、跨膜压差变化趋势及膜过滤阻力特性,调控和优化超滤系统运行参数,并进行了长时间的运行验证。结果表明,膜孔径和膜孔结构不同造成的膜污染是PVC膜与PVDF膜过滤特性差异的主要因素,恒定过滤周期运行模式下PVC膜通量加速衰减时段为82~220 min,造成PVC膜通量衰减了9. 14%,并形成了约5%的永久衰减膜通量,而PVDF膜的通量衰减并不明显,使得水厂超滤系统在恒定过滤周期(180min)运行模式下,出现了PVC膜的污染速率明显高于PVDF膜、系统的运行工况出现显著差异的现象。按照恒定过滤阻力模式运行时,PVC膜和PVDF膜的最佳过滤周期范围分别为82~108 min和96~155 min。水厂超滤系统在恒定过滤阻力运行模式下将PVC膜与PVDF膜在高温期和低温期的过滤周期分别调整为110、90 min和150、120 min,TMP的增长速率和化学维护清洗周期均基本一致,超滤系统实现了长期稳定运行。研究成果为我国超滤水厂中不同材质超滤膜的运行参数优化及协同稳定运行提供了参考。     

A synopsis of membrane technologies in UK municipal potable water treatment: history, status and prospects

The current status of membrane filtration for potable water and wastewater applications is assessed with reference to recent history and key legislative drivers. The current installed capacity for potable water membrane treatment is around 1100 ML/day provided by over 100 plants, with the majority being conventional pumped systems using hollow fibre ultrafiltration (UF) or microfiltration (MF) membranes. An examination of the distribution of membrane plants reveals that capacity is provided predominantly by two commercial UF/MF membrane suppliers, but that a large number of smaller nanofiltration plants have been installed in one UK region. Future prospects for desalination are considered.     

Combination of coagulation and ion exchange for the reduction of UF fouling properties of a high DOC content surface water

The treatment of a high DOC content surface water (about 6mg DOC/L) using anion exchange resins (MIEX resin from Orica or IRA958 resin from Rohm and Haas) can remove up to 80% of DOC in less than 45min. The combination of coagulation prior to or after resin treatment only slightly improves the removal of DOC (0.2-0.3mg/L) but eliminates the high MW organic compounds (MW >20kDa) attributed to biopolymers (proteins and polysaccharides) that were not removed using anion exchange resins alone and that were found to be responsible for reversible fouling of UF membranes (YM 100 UF membrane from Millipore with MW cut-off of 100kDa). The combination of treatments then significantly improves the permeability of the UF membrane. Also, the combination of both treatments allows a reduction of the coagulant doses by a factor of 6 with no impact on the DOC removal and the filterability of produced waters.     

堆石体灌水法密度试验薄膜探讨

目前,我国堆石坝技术已较为成熟,堆石体是筑坝和围堰结构的重要组成部分,而碾压方式下堆石体的干密度是影响坝体变形的主要因素,也是大坝填筑质量的主要控制指标之一。现场常采用挖坑灌水法来测定其填筑的密实度,挖坑灌水法原理简单,操作简便,但要测定准确却非常困难,且薄膜厚度对测定结果也存在一定影响,现介绍某工程采用挖坑灌水法测定堆石体填筑密度过程中,采用两种厚度薄膜进行试验比对的工程经验。     

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.     

Comparison of the performance of UF membranes in olive mill wastewaters treatment

Olives are known to contain an appreciate amount of phenols with good antioxidant properties which are lost in large part in olive mill wastewaters (OMWs) during olive oil production.Membrane technology offers several advantages (low energy consumption, no additive requirements, no phase change) over traditional techniques to recover phenolic compounds from OMWs.The aim of this work was to evaluate the performance of different UF membranes in the treatment of OMWs finalized to the recovery of polyphenols. For this purpose, OMWs were processed, in selected operating conditions, with four flat-sheet UF membranes characterized by different molecular weight cut-off (MWCO) (4, 5 and 10 kDa) and polymeric material (regenerated cellulose and polyethersulphone). Permeate fluxes, fouling index and retention coefficients towards phenolic compounds, total antioxidant activity (TAA) and total organic carbon (TOC) were evaluated.Regenerated cellulose membranes exhibited lower rejections towards phenolic compounds, higher permeate fluxes and lower fouling index if compared with PES membranes.     

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.