Removal of natural organic matter by ultrafiltration and nanofiltration for drinking water production

Water from Lake Butoniga near the town of Buzet, Croatia, was used as a source for drinking water production. Since lake water has a high concentration of trihalomethane precursors, a treatment was necessary. A process including ozonation, flocculation and filtration was chosen on the basis of preliminary work in a trial pilot plant with a capacity of 10 m³ h⁻¹. Although the chosen process succeeded in producing water that met the demands for drinking water, the efficiency of the removal of natural organic matter was relatively low. Ultrafiltration (UF) and nanofiltration (NF) processes were investigated as alternatives and possible upgrades of the process. Experiments were conducted at pilot plants with the Mavibran SP 006A and Romicon PM 10, PM 50, GM 80 and PM 500 OF membranes as well as with the Filmtec NF 45 NF membrane. Since most of the organic matter in the lake water was smaller than 6-8 kD, the use of the NF process was proposed. To avoid fouling of the NF membrane, we used flocculated and filtrated water from the trial plant as NF feed water. This combination produced water of high quality while process parameters remained stable over the entire period of investigation.     

Evaluation of the performance of tight-UF membranes with respect to NOM removal using effective MWCO, molecular weight, and apparent diffusivity of NOM

Concepts for the effective MWCO of tight-UF membranes, and apparent diffusion coefficients for NOM, were introduced to determine the mechanisms influencing NOM removal and to explain the various behaviors of NOM removal by UF membranes with different hydrophobicities, permeability, and surface charges. Colloidal NOM (COM) and non-colloidal hydrophobic NOM (NCD HP) constituents were chosen for the evaluation of two different UF membranes. For a relatively hydrophobic, relatively high permeability, and less negatively charged UF membrane, the hydrophobic fractions of COM were preferentially removed and were also removed by a size exclusion mechanism (i.e., both hydrophobic interaction and size exclusion mechanisms). The NCD HP exhibited no such preferential removal of the hydrophobic fractions, but could be removed by a size exclusion mechanism (i.e., only size exclusion mechanism). With a relatively hydrophilic, relatively low permeability, and more negatively charged UF membrane, COM exhibited no preferential removal of the hydrophobic fractions, but could be removed by a size exclusion mechanism (i.e., only size exclusion mechanism). Whereas the hydrophobic fractions of the NCD HP were preferentially removed, these could not be removed by a size exclusion mechanism (i.e., only hydrophobic interaction mechanism). The apparent diffusion coefficients of NOM, as determined from NOM diffusion experiments using a diffusion cell equipped with a regenerated cellulose membrane, were much lower than those calculated by the Stokes-Einstein relation. The diffusion coefficient of NOM is expected to be used to predict and explain NOM transport behaviors in tight-UF membranes.     

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.     

Integration of immersed membrane ultrafiltration with coagulation and activated carbon adsorption for advanced treatment of municipal wastewater

A pilot-scale hollow-fiber ultrafiltration unit was installed in the wastewater treatment plant of Rethymno, Crete, Greece. The system was fed with treated unchlorinated effluent. Three sets of experiments were conducted. At first, the UF pilot unit was operated as a direct filtration unit. During the second phase, ultrafiltration was combined with the addition of a coagulant (alum). The last phase of the experiments involved the addition of activated carbon (either powdered or granular) into the system. During direct filtration, the average COD removal was 19%, while the average DOC was removed to a similar extent (25%). Effluent turbidity was practically independent of the influent turbidity with an overall average removal of 90%. Faecal and total coliform were also removed efficiently reaching average removals of 99.94% and 99.96%, respectively. Removal of heavy metals in particulate form also took place. When ultrafiltration was combined with in-line coagulation, the results were similar to those exhibited without coagulation. Combining ultrafiltration with powdered activated carbon resulted in DOC removal as high as 60%. However, after the addition of the PAC, the transmembrane pressure increased rapidly due to the formation of PAC cake on the membrane surface. Application of granular activated carbon resulted in 36% reduction of DOC without causing an increase to the trans-membrane pressure. Heavy metals present in the secondary effluent were also removed very efficiently by the GAC in the UF tank.     

Effect of potassium permanganate dosing position on the performance of coagulation/ultrafiltration combined process

The effects of potassium permanganate(KMnO_4)dosing position on the natural organic matter(NOM)removal as well as membrane fouling were investigated in the coagulation/ultrafiltration combined process.KMnO_4 oxidation altered the NOM characteristics in terms of hydrophobicity and molecular weight,and destroyed humic substances originated from terraneous organisms in raw water.The optimal KMnO_4 dosage was 0.5 mg·L~(-1) in the peroxidation enhanced coagulation process with respect to the dissolved organic carbon(DOC)removal.When KMnO_4 was dosed into both upstream and downstream of coagulation,namely in the proposed twoposition dosing mode,coagulation and KMnO_4 oxidation worked individually on the apparent DOC removal.However,compared to the KMnO_4 addition prior to or after coagulation,the two-position dosing mode dramatically alleviated membrane fouling and reduced fouling irreversibility.This was attributed to the change of NOM characteristics as a result of KMnO_4 addition prior to coagulation and the presence of MnO_2 on membrane surface as a result of KMnO_4 addition prior to ultrafiltration.This work may provide useful information for the application of KMnO_4 oxidation in the coagulation/ultrafiltration combined system.     

Characterization of anion exchange membranes with natural organic matter (NOM) during electrodialysis

Natural organic matter (NOM) is thought to be a major source of fouling during membrane filtration of natural waters. The organic matter present in surface waters was characterized in terms of its molecular weight distribution, acidity and electrokinetic properties. The fouling potentials of anion exchange membranes were predicted by the characterization. Changes in the physicochemical properties of anion exchange membranes were also examined during electrodialysis (ED) process of solutions containing NOM. The ED performances were evaluated for the three anion exchange membranes (AMX, AM-1 and ACM) in the presence of NOM. Fouling phenomena in terms of current efficiency and NaCl flux were in good agreement with the fouling potentials predicted by the characterization results. Observations of the molecular weight distribution and the constituents of NOM revealed that the hydrophobic NOM fraction with high molecular weights deposited mainly on the membrane surface, providing fouling effects on the anion exchange membrane.     

Optimizing the coagulant dose to control membrane fouling in combined coagulation/ultrafiltration systems for textile wastewater reclamation

Optimal coagulation conditions need to be re-examined when coagulation is coupled to membrane filtration for wastewater treatment. This work focused on the optimization of coagulant dosing in order to control membrane fouling in ultrafiltration (UF), following coagulation for the reclamation of textile wastewater. The effects of pore size and coagulant types and dosages on flux decline were investigated using a stirred-cell UF unit. The flux was greatly enhanced for the UF membrane when a coagulant was added, whereas for the microfiltration (MF) membrane the flux decreased. This could be attributed to changes in the size of coagulated particles and their interaction with membrane pores. At a low dosage (e.g., 0.0371 mM as Al), the polyaluminum chloride (PACl) coagulant was found to control the flux decline most effectively for low ionic-strength wastewater. The optimal dose minimized the fouling and cake layer resistances, although it was sharp and dependent on influent composition. The cake layer protected the membrane from fouling, but it provided additional resistance to permeation. Analyses of turbidity, particle size, and membrane surface exhibited the characteristics of coagulated particles and their cake structures that are closely associated with flux behavior.     

Application of hybrid coagulation–microfiltration process for treatment of membrane backwash water from waterworks

A coagulation–microfiltration (MF) system was studied to treat the discharged membrane backwash water (MBW) to meet the drinking water quality requirements. The values of dissolved organic carbon (DOC) and trihalomethanes formation potential (THMFP) in MBW were higher than those in Luan River water (LRW, the raw water for a pilot-scale membrane plant, which produced MBW used in this study), and organic matter enriched in MBW distributed mainly in molecular weight (MW) > 10k Da. When 15 mg FeCl₃/L and 15 mg/L powdered activated carbon (PAC) were added into the system, the average concentration of DOC was reduced from 5.731 mg/L in MBW to 3.377 mg/L in the treated water, and the average UV₂₅₄ was reduced from 0.047 to 0.030 cm⁻¹. The removal of organic matter was main in the range of MW > 30k Da. Efficient organic removal by the hybrid coagulation–MF system resulted in significant reduction of THMFP in the treated water. Concentrations of trihalomethanes, turbidity, bacteria and coliforms in the treated water were below the limit value of the drinking water standards. The results show that the treated water from MBW is with satisfactory organic and microbiological quality.     

Fabrication of low-cost ceramic ultrafiltration membrane made from bentonite clay and its application for soluble dyes removal

This work reports the preparation and the characterization of low-cost ultrafiltration bentonite membrane deposited on ceramic perlite support. The bentonite layer was obtained by spin-coating process of colloidal solution with different bentonite contents ranging from 0.25 to 1.50 wt.%, followed by sintering at 500 °C. It was confirmed that optimized membrane prepared with 0.75 wt.% of bentonite is homogeneous and exhibits a good adhesion on perlite support. Furthermore, the membrane has a thickness of 6 μm, a pore size of 13 nm and a permeability of 30 L/h.m².bar. In addition, the filtration performance of bentonite membrane was evaluated by tangential filtration of Direct Red 80 and Rhodamine B solutions under pressure of 4 bar. The effect of filtration time and initial feed concentration on flux and rejection was studied and showed that the rejection of Direct Red 80 and Rhodamine B could achieve value of 97.0 and 80.1 % respectively.     

Integrating a membrane and a fluidized pellet reactor for removing hardness: effects of NOM and phosphate

A novel treatment process combining a membrane with outside-in flow configuration and a fluidized pellet rector for removing hardness was studied. The effects of influent water quality, e.g., concentrations of natural organic matter (NOM) and phosphate along with the hydrophobicity of NOM, on the hardness removal efficiency of the novel process were investigated. The hardness removal efficiency decreases with increasing NOM concentration. However, the NOM removal efficiency is independent of NOM concentration and is related to the hydrophobicity of NOM samples. Raw water containing phosphate has adverse impact on the hardness removal efficiency, which decreases from 85% for treating water containing no phosphate to only 38% and 14% for water containing 0.33 mg/L and 1.63 mg/L of phosphate, respectively.     

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     

Stoichiometric relationship in the coagulation of melanoidins-dominated molasses wastewater

Batch experiments of coagulation/flocculation of biologically treated molasses wastewater were conducted to investigate the stoichiometric relationship between the concentration of melanoidins-dominated organics and the dosage of hydrolyzing metal salts (ferric chloride and aluminum sulfate). Wastewater samples were first fractionated by ultrafiltration. Jar tests were conducted to evaluate coagulation efficiency by measuring zeta potential, removal rates of color and chemical oxygen demand (COD). Experimental results indicate that the dissolved organic fraction accounts for predominant portion of the organic compounds present in biologically treated molasses effluent. A stoichiometric relationship exists between the concentration of melanoidins-based organic compounds and coagulant demand. When the change in solution conditions is proportional to that in organic concentration, such stoichiometric relationship still exists. On the other hand, no stoichiometry was observed between the concentration of melanoidins-dominated organics and the metal dosage when substantial changes in the nature of organics or solution conditions occur. The optimal dosage of ferric chloride expressed in terms of the ratio of metal to organic carbon removed was calculated as 0.73-0.81 g Fe³⁺/g COD.     

Role of coagulation in membrane filtration of wastewater for reuse

This study explains the role of coagulation in membrane filtration of wastewater for reuse. For this purpose, a coagulation-ultrafiltration (UF) membrane system was used to treat secondary effluent from a nearby wastewater treatment plant using a rotating biological contactor. The study proceeded with the hypothesis that coagulation could affect membrane filtration through two phenomena: change in particle characteristics and contaminant loading reduction. If fouling reduction were observed at a low alum dosage, coagulation would affect membrane performance by changing particle characteristics because contaminant reduction could not be possible at low dosage. If fouling reduction were observed only at a high alum dosage, the role of coagulation would be contaminant loading reduction. Results showed that both phenomena were important. Coagulation improved the membrane performance by changing particle characteristics at a low alum dosage. The improvement was achieved through both a change in particle characteristics and contaminant loading reduction at a high alum dosage. Particle size among various characteristics was found the most important for membrane fouling. Coagulation increased particle size, which led to a reduction of fouling. The beneficial effect from coagulation was observed at both fouling steps of pore blocking/adsorption and cake formation. Coagulation pretreatment was also beneficial for the improvement of the permeate quality in terms of organic matter.     

Dissolved organic matter and arsenic removal with coupled chitosan/UF operation

Long time uptake arsenic will cause cancers and blackfoot disease. There are still several million people suffering from drinking arsenic contaminated water. This work studied the performance of coupled chitosan/UF for arsenic removal and the influence of dissolved organic matter on arsenic removal with UF operation. Humic acid representing dissolved organic matter was fractionated into five groups of molecular sizes by gel filtration chromatography. Arsenic rejection by UF under the experimental condition is only 10%. In the presence of humic compounds, the arsenic removal of 22% is obtained. DOM with apparent molecular weight > 35,000 Da is the principle component responsible for chelating arsenic and thereafter being rejected by UF membrane. The combined interactions of humic compounds, chitosan, and arsenic enable a 65% arsenic rejection by UF. The results presented here enable our understanding of the complicated mechanisms involved in chitosan/UF/DOM/arsenic system.     

Coagulation pretreatment for a large-scale ultrafiltration process treating water from the Taihu River

A large-scale ultrafiltration (UF) system integrated with coagulation was applied to produce drinking water from the highly turbid Taihu River. This UF installation could produce 10,000 m³ drinking water per day. In this study, the effect of FeCl₃ coagulant on the performance of the UF system was evaluated. Results showed that with the integration of coagulation, not only qualified drinking water was obtained from the high turbidity raw water, but also high UF specific flux was maintained, ca.190 200 L/m²·hr·bar, and the chemical cleaning period was largely prolonged. The natural organic matter removal mechanism by coagulation was also discussed.     

Integration of immersed membrane ultrafiltration with the reuse of PAC and alum sludge (RPAS) process for drinking water treatment

Effects of PAC and alum sludge generated from water treatment process on the effluent quality and fouling of immersed UF membrane were systematically investigated with representative source of natural water and the efficiency of coagulation, PAC adsorption and RPAS to treat natural surface water prior to UF were compared. It was found that the average turbidity removal by RPAS could reach up to 80.2%, and the turbidity removal of immersed membrane UF was independent of the influent, which could be kept at 99%. Particulates were reduced after being pre-treated by different processes, and particles with sizes ranging from 0.5 to 3.5 μm and larger than 13.5 μm were effectively removed by RPAS. UF coupled with RPAS pre-treatment got the best removal for DOM compared to other processes with average DOC and UV₂₅₄ removal 54.1% and 47.2% due to the high removal in the influent of UF. The residual alum content in the effluent of RPAS with UF was less than coagulation and bacteria were almost all removed by membrane. The membrane-fouling was mitigated by pre-treatment processes at different degrees, TMP of UF coupled with RPAS process was relatively stable in 15 d of run, the adsorption of PAC and large number of Al(OH)₃ complexes and precipitates for the foulant molecules might be an important mechanism.     

Lab and pilot scale investigations on membrane fouling during the ultrafiltration of surface water

In the combined laboratory and pilot plant investigation powder activated carbon dosing and inline coagulation were investigated for surface water from river Spree. The aim was to understand the fouling behaviour of this raw water and to understand and to identify strategies to minimize the irreversible fouling in this application. Trials with activated carbon showed significant differences in the adsorption of biopolymers on different types of carbon. Whereas the TOC removal was in the same range for both types the coarse carbon type showed very small removal of biopolymers. The effect of different types of coagulants, dosage and pH was investigated in a laboratory filtration set up. Samples were investigated by LC-OCD measurements for fractionation of DOC for raw water, flocculated water and permeate. The removal of biopolymers was possible with iron and alumina salts, however the alumina salts tend to remove humic acids as well and this results in a higher overall DOC removal. In the pilot plant the inline coagulation was investigated under actual site conditions. Whereas the results for the effect of coagulation and DOC removal were confirmed it turned out that aluminium coagulants give a significantly higher increase in differential pressure. The use of ferric coagulants at slightly acidic pH was thus identified as a robust method to achieve a stable performance of the ultrafiltration system at this site.     

Effect of hydrophilic/hydrophobic fractions of natural organic matter on irreversible fouling of membranes

Natural organic matter (NOM) has been identified as a major factor affecting membrane processes performances, but its impact is difficult to quantify from global parameters such as organic carbon content. The extent of fouling due to the different fractions of NOM from surface water has been examined in dead-end ultrafiltration using criteria such as flux decline and irreversibility in regard with organic matter rejection. The most important flux decline was observed during the filtration of the hydrophilic acids fraction whereas fulvic acids led to the most irreversible fouling. Furthermore, the hydrophilic fraction lost its fouling character when mixed with other fractions underlining that interactions between numerous components are possibly more important than the composition itself.     

自然有机物对地下水混凝除铁的影响试验研究

通过模拟试验,考察了自然有机物的浓度、分子质量以及溶液的pH、温度对地下水混凝除铁的影响,并研究了预氧化在混凝除铁中的作用.结果表明,有机物的浓度越高、分子质量越大,有机铁的去除率越高.当Fe2 与分子质量＞10 ku的有机物络合时,用混凝除铁能取得良好的效果;当Fe2 与分子质量＜4 ku的有机物络合时,采用预氧化混凝工艺能达到较好的除铁效果.在pH6.0～7.5的范围内,降低pH有利于混凝除铁.温度升高对混凝除铁有利.