Humic substances fouling in ultrafiltration processes

Membrane fouling by humic substances (HS) is a major problem in UF water treatment. The complex phenomena involved have been the subject of numerous investigations. HS fouling is attributed to accumulation of particles in the feed water on the membrane surface forming a cake layer and adsorption of small particles in the inner pores thus constricting or blocking the pore mouth. The exact contribution of each of these mechanisms to membrane fouling and to flux reduction is not sufficiently clear. While there is a substantial qualitative agreement on various fouling aspects in studies focusing on commercial humic acid solutions, the extensive literature on fouling by natural organic matter (NOM) is less coherent. The major deficiency in the available information is the lack of reliable predictive models. This paper presents a systematic review of scattered literate information and outlines HS fouling aspects that await elucidation.     

天然有机物对国产纳滤膜的污染及清洗效果研究

为考察水体中天然有机物(NOM)对纳滤膜性能产生的影响,以腐殖酸(HA)、牛血清蛋白(BSA)和海藻酸钠(SA)分别模拟水中常见NOM,腐殖质、蛋白质和多糖,对国产NF-1812纳滤膜进行单组分及其混合物定性定量有机污染及清洗实验。结果表明,有机污染造成膜通量下降,膜污染程度为SA>HA>BSA;NOM截留率可稳定在99.2%~99.6%;膜污染阻力主要为浓差极化阻力,其次是凝胶层阻力和内部污染阻力,有机污染液综合黏度和综合含量越大,浓差极化阻力的比例越高;对多组分有机污染膜进行错流速度9 cm/s的物理水力清洗和pH=10.0的质量分数分别为0.1%的NaOH+0.025%Na-SDS化学药剂清洗,膜通量、NOM截留率、苦咸水截留率、SEM成像均恢复至原膜状态,纳滤膜清洗效果良好,适用于中国西北苦咸水地区。     

Natural organic matter fouling due to foulant–membrane physicochemical interactions

An extended DLVO (XDLVO) force analysis was introduced to predict natural organic matter (NOM) fouling in ultrafiltration (UF) membrane processes. Ultrafiltration membrane fouling experiments were performed using two NOM extracts from real waters and two commercial polymeric UF membranes. The hydrodynamic force by permeation drag and three interfacial forces of XDLVO (van der Waals, electrostatic, acid–base energy) were used for the force analysis. Acid–base interaction forces between NOM and UF membranes were dominant in short range (separation distances < 5 nm) and appear to determine the potential of NOM deposition. Relative extents of flux decline were successfully predicted using the short-range force analyses.     

Colloidal organic matter fouling of UF membranes: role of NOM composition & size

The aim of this study was to fractionate pre-filtered surface water using a 3.5 and a 10 kDa dialysis membrane, and to compare the rate of fouling and the fouling reversibility/irreversibility of the NOM fractions. Trial dialyses (3.5 and 10 kDa) were carried out for 6 and 21 days with pre-filtered surface water using synthetic surface water as dialysate. The aim of the trials was to optimize the dialysis process for NOM fractionation. DOC, Ca²⁺, Mg²⁺, soluble silica and bacteria were monitored at intervals during the dialysis process. Thereafter, the various NOM fractions (with low and high Ca²⁺) were fed to a miniature UF system operated at a constant flux of 138.5 L/m2 h, filtration cycle times of 31.5 min and backwash duration of 1.75 min. A PES/PSV hollow fiber UF membrane (MWCO 100 kDa) with a surface area of 0.0125 m² was employed for the filtration tests (X-Flow). Transmembrane pressure (TMP) and UF feed and permeate (LC-OCD) were monitored at regular intervals. For a dialysate recirculation of 95 L/h, sample to dialysate ratio of 5.2:80 L and a dialysate change frequency of 3 times per 24 h, the shortest duration of dialysis was about 6–7 days for both 3.5 and 10 kDa dialyses membranes. The removal of organic carbon (OC) increased with dialysis duration and MWCO of the bags. The biopolymer fraction increased from 120% to 240% when the duration of dialysis was increased from 6 days (1.1 mg DOC/L, 151 mg Ca/L) to 21 days (0.82 mg DOC/L, 133 mg Ca/L) with the 10 kDa dialysis membrane. The increased biopolymer fraction in the NOM sample that was dialyzed for 21 days resulted in a doubling of the fouling rate from 3.5 to 6.6 mbar/min per mg DOC/L. The other NOM fractions (humics and building blocks) and the Ca/DOC ratio was more or less the same in both NOM samples suggesting that biopolymers were the major cause of UF fouling.     

Grey water treatment and simultaneous surfactant recovery using UF and RO process

The membrane-based grey water treatment for grey water reuse and surfactant recovery is presented in this research paper. Grey water from washing machine discharges having turbidity and used surfactant was processed through the polymeric ultrafiltration (UF) membrane to remove the turbidity. The UF treated grey water is further purified by reverse osmosis (RO) membrane for surfactant recovery and water reuse. The surfactant trapped inside the RO spiral wound membrane module is recovered through various membrane physical regeneration techniques such as backwashing, simultaneous backwash–back-flush and ozone back-flush. Among this, backwash–back-flush is found to be effective process for surfactant recovery. The methodology for optimising surfactant recovery is captured by studying effect of various operating parameters such as feed detergent concentration, backwash pressure, backwash temperature and back-flush flow rate. By implementing optimal process conditions, the integrated UF and RO membrane process is able to produce 300 L of reusable pure water and 80 L of concentrated detergent solution and 20 L of turbid water while treating 400 L of grey water discharges. Maximum surfactant recovery of 82% is obtained while treating grey water which consists of 720 ppm of total dissolved solids (detergent) and 45 ppm of surfactant. The extent of UF and RO membrane fouling is determined by measuring the pure water flux before and after the grey water treatment. The membrane performance is found to be stable when membrane is regenerated by backwash–back-flush technique for RO and gravity backwash for UF membrane.     

Application of combined coagulation-ultrafiltration membrane process for water treatment

The objectives of this research are to identify the membrane fouling potential due to different fractions of NOM and correlate the physicochemical properties of NOM and membranes with the adsorption of humic substances on membrane and investigate the mechanism of coagulation affecting UF, and find the optimum conditions of the combined of coagulation with UF membrane filtration for NOM removal. For Nakdong river water, the humic acid fraction was the most reactive precursor fraction for the formation of the ratio of THMFP/DOC (STHMFP) and TOXFP/DOC (STOXFP). The result of adsorption kinetics tests showed that hydrophobic organics adsorbed much more quickly than hydrophilic organics on both membranes. Thus, hydrophobic compounds exhibited a preferential adsorption onto membrane. In case of the effect of membrane properties on the adsorption of organic fractions, the adsorption ratio (C₁/C_e) was greater for the hydrophobic membrane than for the hydrophilic membrane regardless of the kind of organic fractions. For combined coagulation with membrane process, flux reduction rate showed lower than the UF process alone. Also, the rate of flux decline for the hydrophobic membrane was considerably greater than for the hydrophilic membrane. Applying the coagulation process before membrane filtration showed not only reduced membrane fouling, but also improved removal of dissolved organic materials that might otherwise not be removed by the membrane. That is, during the mixing period, substantial changes in particle size distribution occurred under rapid and slow mixing conditions due to the simultaneous formation of microflocs and NOM precipitates. Therefore, combined pretreatment using coagulation (both rapid mixing and slow mixing) improved not only dissolved organic removal efficiency but also DBP (Disinfection By-Product) precursor's removal efficiency.     

不同预处理方式对超滤膜深度处理印染废水效能影响的研究

以印染废水处理站的二级出水为原水,考察了不同预处理方式(砂滤、微絮凝、微絮凝直接过滤)对超滤膜性能及其去除印染废水中污染物的影响。结果表明,砂滤随着运行时间的延长造成膜的不可逆污染,微絮凝可缓解膜污染,微絮凝直接过滤对膜污染在微絮凝基础上有所改善;不同预处理方式均能保证出水浊度小于0.1NTU;微絮凝直接过滤预处理工艺对CODCr去除率接近70%,微絮凝直接过滤处理方法能有效缓解膜污染,对浊度和有机物的去除效果较好,是较有优势的预处理工艺。     

Natural organic matter (NOM) fouling in low pressure membrane filtration — effect of membranes and operation modes

The objective of this study was to evaluate the effects of operating modes, membrane materials and pore size on natural organic matter (NOM) fouling. A range of flat sheet microfiltration (MF) and ultrafiltration (UF) membranes were tested under conditions of various constant pressure and constant flux filtration modes. Based on experimental filtration profiles, molecular weight (MW) distributions of NOM obtained using high performance size exclusion chromatography (HPSEC) and autopsies of fouled membranes using force emission scanning electron microscopy (FESEM), it was concluded that medium to low MW component of NOM (300–1,000 Da) is responsible for the initiation of fouling, where bulk of the fouling observed is due to very high MW ‘colloidal’ NOM (>50,000 Da). This two stage fouling phenomenon was in good agreement with classical blocking laws. As a general observation hydrophilic membranes were less prone to NOM fouling. A comparison of constant pressure and constant flux tests confirmed that modest constant flux, as used in industry, provided the most beneficial conditions.     

A new combination of a membrane and a photocatalytic reactor for the depollution of turbid water

This paper describes the combination of a dialysis membrane and a photocatalytic reactor into an original membrane photoreactor (MPR) to mineralize organic compounds contained in artificial turbid waters which are obtained by using natural clay named bentonite. Various systems have been described in the literature, combining photocatalysis with pressure-driven membrane techniques, such as nanofiltration (NF) and ultrafiltration (UF), but these systems can lead to membrane fouling. Only the combination of photocatalysis and membrane distillation avoids this problem, but it needs energy to reach pervaporation phenomena. The MPR system presented here works at ambient temperature, with the membrane used as a barrier for particles and to extract the organic compounds from the turbid water without transmembrane pressure. Thus, we were able to separate the polluted turbid water from the photoreactor compartment and to separate TiO₂ continuously from the treated water. The photocatalytic reaction and dialysis were studied separately before the MPR process was developed. A model pollutant, 2,4-dihydroxybenzoic acid (2,4-DHBA), was mineralized from turbid waters by photocatalysis. By means of the membrane, the TiO₂ remained in the photoreactor compartment without filtration and bentonite was kept away from the photoreactor.A mathematical model, based on diffusion through the membrane, with zero-order reaction in the reactor, is in good agreement with the experimental data.     

Preparation of poly(ether sulfone) hollow fiber UF membrane for removal of NOM

In this study, a high performance poly(ether sulfone) (PES) hollow fiber ultrafiltration (UF) membrane has been prepared for removal of natural organic matter (NOM). The membrane was spun from a dope solution containing PES/poly (vinyl pyrrolidone) (PVP 40K)/N‐methyl‐2‐pyrrolidone (NMP) by using a wet‐spinning process. Characterization of the membrane in terms of pure water flux, molecule weight cut‐off (MWCO), and retention for a model humic acid (HA) were conducted, and the fouling resistance was analyzed. The experimental results showed that the membrane had a pure water permeability of 20 × 10^?5 L m^?2 h^?1 Pa^?1 and a nominal MWCO of 6000 Da. The results also showed that the membrane retention for humic acid was over 97% and both productivity and selectivity for HA increased with increasing feed velocity. The PES membrane in this study exhibited a much lower fouling tendency than the commercial polysulfone membrane. SEM images revealed that the membrane had an outer dense skin and a porous inner surface. © 2005 Wiley Periodicals, Inc. J Appl Polym Sci 99: 430–435, 2006     

Advanced water treatment of high turbid source by hybrid module of ceramic microfiltration and activated carbon adsorption: Effect of organic/inorganic materials

We investigated the effect of organic or inorganic materials on membrane fouling in advanced drinking water treatment by hybrid module packed with granular activated carbon (GAC) outside a tubular ceramic microfiltration membrane. Instead of natural organic matters (NOM) and fine inorganic particles in the natural water source, synthetic water was prepared with humic acid and kaolin. Concentrations of kaolin or humic acid were changed to see effects of inorganic or organic matter. And periodic water-back-flushing using permeate water was performed during 10 sec per filtration of 10 min. As a result, both the resistance of membrane fouling (R _f ) and permeate flux (J) were influenced higher by concentration of humic acid rather than kaolin. It was proved that NOM like humic acid could be a more important factor on membrane fouling in drinking water treatment than fine inorganic particles. Treatment efficiencies of turbidity and UV₂₅₄ absorbance were very high above 97.4% and 92.0%, respectively. This article is dedicated to Professor Chang Kyun Choi for celebrating his retirement from the School of Chemical and Biological Engineering, Seoul National University.     

超滤集成工艺对西北村镇窖水处理的应用研究

研究了以超滤为核心,流程为颗粒活性炭-纳米金属簇-超滤-紫外线的集成净水工艺对原水中浊度、CODMn、氨氮的去除,进行了不同原水浊度下超滤的膜污染成因分析和化学清洗试验。结果表明,集成工艺出水浊度稳定在1 NTU以下,对CODMn和氨氮的平均去除率为29.86%和50.95%。出水水质达到了现行GB 5749-2006的要求。在短时间内较高浊度的进水对超滤膜不会造成不可逆的膜污染,但在持续较高浊度进水条件下膜阻力会快速提高并最终造成膜污染。对原水中的有机物和浊度进行更有效的预处理能减缓膜污染的进程,膜污染发生后进行有针对性的化学清洗能有效的恢复膜通量。     

Performance of RC and PES ultrafiltration membranes in filtration of pulp mill process waters

Issues of fouling and effective cleaning limit the adoption of UF in pulp and paper mill applications. The choice of an optimal membrane for a specific filtration application is a challenging task due to the fact that fouling is a complex phenomenon. This study compares regenerated cellulose (RC) and polyethersulphone (PES) membranes in UF of two chemithermomechanical pulp mill process waters. The process waters originated from hardwood and softwood pulping. Based on their flux recovery, PES membranes sustained greater fouling than RC membranes even though the hydrophobicity of RC membranes was increased remarkably by adsorptive fouling. The process water affected the performance of the membranes. The membrane characteristics were more important in determining fouling when softwood process water was used than when hardwood process water was used. Hydrophilicity and morphology of the membranes were seen to have a clear influence on fouling.     

超滤膜处理乳化油废水的研究进展

综述了近年来国内外超滤膜分离技术应用于乳化油废水处理的研究进展,着重介绍了超滤处理工业乳化油废水的分离性能,以及超滤过程存在的问题和解决途径.针对实际运行过程中产生的膜污染现象,在新膜材料、膜组件改进和耦合工艺3方面进行了阐述.最后对今后的研究方向提出了建议.     

Ozone Cleaning of Fouled Poly(Vinylidene) Fluoride/Carbon Nanotube Membranes

This research demonstrates for the first time that ozone is an effective cleaning agent for polyvinylidene fluoride (PVDF) membranes fouled by natural organic matter (NOM). Bare PVDF membranes as well as PVDF impregnated with CNTs (pristine (CNTs–P) and oxidized (CNTs–O)) at 0.3% mass membranes were used. Three different methods were investigated for cleaning the fouled membranes including; A: 10-min cleaning by pure water, B: 5-min water followed by 5-min ozonated water, and C: 10-min fully ozonated water. It was found that the application of fully ozonated water for 10 min was very effective to reinstate the flux to almost its original value of unfouled membrane. The CNTs–P/PVDF membrane exhibited the highest fouling with a total fouling ratio of 81%, while for the bare PVDF and the CNTs–O/PVDF membranes, the fouling ratios were 76% and 74%, respectively. The full ozonated water cleaning method gave the highest removal of fouling leaving the lowest irreversible fouling on the membrane as compared to the other cleaning methods. On the other hand, the highest removal of NOM fouling was obtained for CNTs–O/PVDF membranes indicating that fouling on CNTs–O/PVDF membrane was less bound than the other membranes. Contact angle measurements of the fouled membranes showed that all membranes exhibited increased contact angles due to the NOM deposition but after cleaning, particularly with ozonated water, the membrane contact angles returned to almost their original values. FTIR analysis of the membranes corroborated the results obtained.     

水处理工业中超滤膜应用的问题探讨

简单介绍了超滤膜和超滤过程,总结了在水处理工业上的应用。比较了各种膜材料的性能,并着重论述了水处理工业应用中应注意和考虑的问题:超滤膜的选择、超滤操作条件的选择、超滤膜的浓差极化和污染与处理对策。     

内外压式超滤组件在反渗透预处理中的应用比较

分别选取一种内压式和一种外压式中空纤维膜超滤组件,从超滤膜材质、运行参数和出水水质等方面对这2种组件在海水淡化反渗透预处理中的应用做了比较。结果表明:由于超滤膜的材料不同,使得2种组件运行工艺有较大差异:内压式组件在跨膜压差和膜通量方面要好于外压式组件,而2种组件出水水质在同一水平上。在进水浊度小于20NTU时,内压式膜组件更适合作为反渗透的预处理工艺。     

Comparison of ceramic and polymeric membranes for natural organic matter (NOM) removal

Ceramic membranes were compared with polymeric membranes with respect to natural organic matter (NOM) removal using two removal mechanisms (i.e., size exclusion and charge repulsion). NOM properties including molecular weight and molecular structure, at different charge densities, were examined, along with membrane characteristics, including molecular weight cut-off (MWCO) and surface charge. Integrated analyses of both NOM and membrane characteristics provided information for membrane evaluation of different membrane materials and configurations (i.e., tubular vs. flat sheet type). A ceramic tight-ultrafiltration (UF) membrane showed the same potential as a similar nanofiltration (NF) polymeric membrane, in terms of the minimization of haloacetic acid (HAA) formation. Moreover, a ceramic OF membrane with a MWCO of 8000 Daltons showed almost the same behavior as an equitable polymeric UF membrane with a MW CO of 8000 Daltons in terms of NOM removal.     

Determination of the Apparent Charge of Natural Organic Matter

The charge of natural organic matter (NOM) is an important parameter for understanding the membrane fouling and NOM removal mechanism with charged membrane. However, there is a lack of technology to make direct measurement of the NOM charge. In this study, we report a novel concept of measuring an apparent charge of the NOM using selectivity coefficient. The apparent charges of three different NOM containing different structures were evaluated to validate this proposed method. The apparent charge of the NOM exhibited a good correlation with specific UV absorbance of the NOM. This apparent charge is therefore a useful indicator for predicting the membrane fouling and NOM removal in membrane filtration technology.     

Effect of slow sand filtration of treated wastewater as pre-treatment to UF

Ultrafiltration (UF) of treated municipal wastewater has been used to produce high-quality reuse water for different applications. However, without pre-treatment, secondary treated wastewater effluent shows high fouling potential and reduces the performance of UF membrane filtration significantly. To remove foulants prior to UF, slow sand filtration (SSF) was investigated in the present work. Two pilot-scale slow sand filters were operated in tandem with UF. The performance of the UF plant was improved to a large extent by delivering slow sand filtrate compared to direct secondary effluent filtration. Removal of common organic fouling indicators (i.e., proteins, carbohydrates, and biopolymers) by SSF was significantly higher at 0.25 m/h versus 0.5 m/h filter loading rate. Results of a comparative analysis of SSF effluent characteristics and UF performance showed that the biopolymer content detected by size exclusion chromatography displayed a good correlation with the filterability of corresponding water sample by UF, while photo-metrically detected proteins and polysaccharides did not present any relationship with UF performance.