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.     

投加粉末活性炭对超滤膜去除海水中有机物的影响

超滤膜的有机污染问题是膜法海水预处理技术在海水淡化工程应用面临的重要挑战,粉末活性炭吸附是目前常用的膜前预处理手段之一。本文对比分析了直接超滤和投加粉末活性炭后对海水中有机物的截留能力,利用三维荧光光谱分析了投加粉末活性炭对超滤膜截留有机物的影响机制,并考察了海水超滤过程中通量变化及膜污染情况。研究结果表明,投加粉末活性炭能够强化超滤膜对海水浊度和有机物的去除,当粉末活性炭投量为200mg/L时,整个系统对海水中DOC去除率从直接超滤时的55.1%提高到77.6%。利用粉末活性炭的吸附作用及其在超滤膜表面形成的疏松滤饼层能够显著提高超滤系统对海水中腐植酸类有机物的去除能力。与直接超滤相比,粉末活性炭-超滤系统对改善膜通量的作用有限,但粉末活性炭形成的滤饼层能够避免超滤膜与有机物直接接触,可显著减缓超滤膜的不可逆污染。     

A Comparative Approach to the Application of a Physico‐Chemical and Advanced Oxidation Combined System to Natural Water Samples

Abstract

Natural organic matter removal (NOM) efficiencies of samples from three major drinking water sources (Elmali, Omerli, and Buyukcekmece) of Istanbul were compared using different treatment systems. Enhanced coagulation as a physico‐chemical method was applied using ferric chloride and aluminum sulphate as the coagulating agents. Moreover, the application of enhanced coagulation in combination with photocatalytic oxidation using TiO₂ was investigated. The efficiency of NOM removal relevant to each treatment step was assessed through DOC removal, UV₂₅₄ removal, and fluorescence measurements.

Irrespective of the treatment applied as enhanced coagulation, photocatalytic oxidation or their combinations, the highest removal efficiency was determined for Elmali followed by Omerli and Buyukcekmece samples both in terms of DOC and UV₂₅₄. Enhanced alum coagulation leads to significant variation in DOC removals as 44%, 28% and 26% for Elmali, Omerli, and Buyukcekmece water samples, respectively. Upon application of ferric chloride as the coagulant, the DOC removals achieved were found to be slightly higher as compared to alum. Moreover, the combined treatment incorporating photocatalytic oxidation subsequent to alum coagulation leads to 36%, 37%, and 50% of DOC removal for Omerli, Buyukcekmece, and Elmali respectively. The improvement of removal efficiencies in combined treatment systems were scrutinized with an emphasis on induced water properties as supported by the specific fluorescence intensities of the samples.     

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.     

循环絮凝对水中SUVA及膜污染的影响

将循环接触絮凝与膜过滤相结合组成循环接触絮凝-膜过滤（CF-MF）工艺,以传统混凝-膜过滤（C-MF）工艺为对照,考察两种工艺在延缓膜污染方面的差异。采用比紫外吸光度（SUVA）作为有机物亲/疏水特性的评价指标,分析工艺变化对SUVA的影响以及SUVA和综合膜污染指数（UMFI）之间的内在联系。结果发现,膜出水SUVA与膜污染呈很好的相关性,出水SUVA越高,膜污染越严重;在最佳工艺条件下,CF-MF出水和混凝上清液SUVA分别达到了1.74 L·mg^-1·m^-1和1.18 L·mg^-1·m^-1,去除率与C-MF工艺相比分别提高17%和29%,说明CF-MF工艺对水中疏水性物质的去除效果比C-MF更好,能够有效控制疏水性物质对膜形成的污染;与C-MF相比,CF-MF能够更有效地去除水中的有机物,当混凝剂氯化铁投加量为6 mg·L^-1、回流絮体浓度为10 mg·L^-1时,UV₂₅₄和DOC的去除率分别达到了58.75%和49.7%。     

氧化预处理延缓超滤膜污染试验研究

分析了膜前氧化对超滤膜污染规律和水中有机组分构成的影响,并对延缓膜污染的机理与方法进行探讨。结果表明,试验所用3种氧化剂KMnO4、高锰酸钾复合盐(PPC)、H2O2均能延缓膜污染进程,在投加量为1 mg.L-1条件下,预处理效果PPC>KMnO4>H2O2;KMnO4和PPC对UV254的去除效果优于溶解性有机物,表明2种氧化剂优先去除含有双键的疏水性有机物;通过研究氧化剂投加量对比紫外吸光度变化的影响,说明氧化作用使水中腐殖质类成分向非腐殖质类成分转化。     

Comparative analysis for fouling characteristics of river water,secondary effluent,and humic acid solution in ceramic membrane ultrafiltration

Ceramic membrane ultrafiltration experiments were performed with 7-channel tubular membrane (molecular weight cutoff = 300 kD) at a constant transmembrane pressure and crossflow rate under recirculation mode. In the experiments, the fouling characteristics of river water (RW, dissolved organic carbon (DOC) = 3.4 mg/L) were compared with humic acid solution (HA1, DOC = 3.7 mg/L). Also, the fouling behaviors of secondary effluent (SE, DOC = 7.9 mg/L) were compared with HA2 (DOC = 8.5 mg/L). Fluorescence excitation-emission matrix, modified Hermia’s model, and resistance-in-series model were used to analyze the fouling characteristics. Results demonstrated that RW and SE could cause ceramic membrane fouling more rapidly due to their hydrophilic organic compositions in comparison with hydrophobic HA.     

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.     

Comparative Studies on Coagulation and Adsorption as a Pretreatment Method for the Performance Improvement of Submerged MF Membrane for Secondary Domestic Wastewater Treatment

Abstract

Membrane fouling is the main limitation of water and wastewater treatment. Coagulation and adsorption can remove organic materials which play an important role in fouling phenomena. Thus, this study focused on the comparison of the hybrid process of coagulation and adsorption coupled with microfiltration (MF) membrane for the secondary domestic wastewater from an apartment complex in Gwangju city, South Korea. Coagulation and adsorption were adopted as a pretreatment method prior to MF treatment. Three different powdered activated carbon (PAC) and ferric chloride were used as an adsorbent and as a coagulant. MF was operated in a submerged mode using hollow fiber polyethylene membrane with pore size of 0.4 µm for the separation of suspended organic solids resulted from coagulation or PAC particles, which are used for adsorbing organics dissolved in wastewater. Prior to study on the hybrid system, the performance of coagulation and adsorption processes were optimized individually for the removal of organics. Then, the overall performance for the hybrid system of coagulation/MF and PAC/MF was evaluated based on TOC removal, turbidity removal, and flux decline. It was found that the combined coagulation/MF and PAC/MF showed similar performance for TOC removal while coagulation/MF resulted in a significant decrease of the flux decline.     

铝系混凝剂减缓膜污染的红外光谱-多变量曲线分辨分析

超滤是一种高效的水处理技术,近年来被广泛应用于工业废水处理、生活污水回用、海水淡化预处理等领域。然而,超滤长期运行会造成膜污染。本文采用了在线混凝结合超滤工艺,使用不同形态的铝系混凝剂（硫酸铝、氯化铝或聚合氯化铝）,处理含有不同溶解性有机质组分（腐殖酸、牛血清白蛋白和高岭土）的模拟原水,研究不同铝形态、不同组分及其相互作用对超滤膜污染过程的影响。本研究建立了流量衰减模型模拟膜污染过程,结合衰减全反射红外光谱（IR-ATR）和多变量曲线分辨-交替最小二乘法（MCR-ALS）的数据处理方法对膜上的多种污染物进行定性和定量分析。结果表明硫酸铝和氯化铝混凝剂均可明显提高膜比通量,减缓膜污染。该工艺混凝剂投加量低于常规处理工艺即可明显减缓膜污染。混凝剂投加量为0.4mg/L时,氯化铝混凝效果较好,混凝剂投加量为2.4mg/L时,硫酸铝混凝效果较好。低投加量（0.2mg/L、0.4mg/L）下,PAC对缓解膜污染程度不明显,反而加重膜污染。牛血清白蛋白对超滤膜的污染比腐殖酸严重。因为牛血清白蛋白的存在大大降低了混凝的效果,阻碍疏松滤饼层的形成。向原水中投加硫酸铝混凝剂,膜污染主要发生在过滤前期,即...     

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.     

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.     

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.     

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。     

Huangpu River water treatment by microfiltration with ozone pretreatment

With the promulgation of more stringent regulations to guarantee the quality of drinking water, low pressure membrane processes are nowadays considered for surface water treatment. But these membranes are sensitive to fouling. In this study ozone is introduced to pretreatment for membrane filtration to get a high quality permeate and improve membrane performance. The organic matter characteristics, such as AMWD of organic matter, hydrophilic/hydrophobic fractions were studied with ozone oxidation. Results show that for Huangpu River water, ozone oxidation offers high percentage of UV absorbance removal than DOC removal. Highest removal of DOC and UV₂₅₄ of 10% and 71% respectively were observed. The dominant organic matter oxidized by ozone was 2-7.0 kDa in terms of molecule distribution investigation. Ozone oxidizes more hydrophobic fraction to hydrophilic one. Changes of organic matter composition improved membrane flux. There is the optimal dosage with ozone of 1.5 mgO₃/L made membrane flux maximum during 0.5-3.0 mgO₃/L ozone dosage. Ozone oxidization provided degradation of macromolecule organic matter, which is responsible to membrane fouling, to small molecule organic substance. Study about the chemical cleaning of the fouled membrane also supports the point that membrane fouling is produced by the organic substance with high molecule weight.     

饮用水安全保障关键技术集成及工程示范

以北江水为原水,通过中试试验分别考察了以强化混凝、两相催化氧化助凝、活性炭吸附、膜分离和紫外消毒为核心的多种饮用水安全保障关键技术。结果表明以强化混凝为核心的工艺在重金属去除方面有优异的表现,两相催化氧化助凝技术在节能减排方面表现突出,超滤膜技术在浊度去除方面有优势,臭氧一生物活性炭工艺对有机物的去除效果较好,紫外消毒技术能有效减少消毒过程中有毒有害副产物的生成。     

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.     

Effects of O3, O3/H2O2 and Coagulation on Natural Organic Matter and Arsenic Removal from Typical Northern Serbia Source Water

The objectives of this study were to investigate the effects of ozone and the O₃/H₂O₂ process on FeCl₃ coagulation efficiency for the removal of the high content of natural organic matter (NOM) and arsenic (As) from groundwater (DOC = 9.27 ± 0.92 mg/L; 51.7 ± 16.4 µg As/L). Arsenic and NOM removal mechanisms during coagulation/flocculation are well investigated. However, data concerning arsenic removal in the presence of NOM, which is the subject of this article, are still insufficient. Laboratory and pilot plant test results have shown that the competition of NOM and As for adsorption sites on the coagulant surface have great influence on coagulation/flocculation efficiency for their removal. With both oxidation pre-treatments, arsenic content after the coagulation process was less than 2.0 µg/L in treated water. Application of ozone has a lower influence on coagulation efficacy in terms of DOC reduction, compared to the O₃/H₂O₂ process with the same ozone dose.     

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.     

高锰酸钾预氧化耦合混凝工艺对藻类及类蛋白物质的控制效果

为降低水中藻类及有机物含量,利用三维荧光和藻类分析仪,研究KMnO4强化混凝对藻类和类蛋白物质的去除,探索KMnO4投加量和反应时间的影响。研究表明:KMnO4对藻类和藻蓝蛋白的去除率仅为38.46%和15%,KMnO4耦合混凝对两者的去除率分别为86%和75%。铜绿微囊藻中主要荧光组分为可溶性微生物产物和小分子类蛋白,KMnO4耦合混凝对其的去除率为32.77%。结果表明,1 mg/L KMnO4预氧化30 min后投加混凝剂,能最大程度地去除藻类及藻蓝蛋白,但并不能较好地去除类蛋白物质。