二氧化钛光催化降解腐殖酸的试验研究

研究了不同pH条件下二氧化钛(TiO2)对腐殖酸的吸附和光催化降解过程,重点考察了腐殖酸降解过程中UV254、A436、TOC、SUVA254、AOC的变化.结果表明:随着pH值的升高,Ti02对腐殖酸的吸附率下降;当腐殖酸初始浓度为10 mg/L、初始pH=7、二氧化钛投量为2g/L时,反应2 h后,对UV254、A436、TOC的去除率分别可达98.21%、99.11%、71.02%,SUVA254值由初始的7.58 L/(mg·m)持续降低至0.467 L/(mg·m),AOC浓度则先升高后降低.     

Identification and understanding of fouling in low-pressure membrane (MF/UF) filtration by natural organic matter (NOM)

An understanding of natural organic matter (NOM) as a membrane foulant and the behavior of NOM components in low-pressure membrane fouling are needed to provide a basis for appropriate selection and operation of membrane technology for drinking water treatment. Fouling by NOM was investigated by employing several innovative chemical and morphological analyses.

Source (feed) waters with a high hydrophilic (HPI) fraction content of NOM resulted in significant flux decline. Macromolecules of a relatively hydrophilic character (e.g. polysaccharides) were effectively rejected by low-pressure membranes, suggesting that macromolecular compounds and/or colloidal organic matter in the hydrophilic NOM fraction may be a problematic foulant of low-pressure membranes. Moreover, the significant organic fouling that is contributed by polysaccharides and/or proteins in macromolecular and/or colloidal forms depends on molecular shape (structure) as well as size (i.e. molecular weight). More significant flux decline was observed in microfiltration (MF) compared to ultrafiltration (UF) membrane filtration. MF membrane fouling may be caused by pore blockage associated with large (macromolecular) hydrophilic molecules and/or organic colloids. In the case of UF membranes, the flux decline may be caused by sequential or simultaneous processes of surface (gel layer) coverage during filtration. Morphological analyses support the notion that membrane roughness may be considered as a more important factor in membrane fouling by controlling interaction between molecules and the membrane surface, compared to the hydrophobic/hydrophilic character of membranes. Membrane fouling mechanisms are not only a function of membrane type (MF versus UF) but also depend on source (feed) water characteristics.     

Photocatalytic oxidation and ozonation of catechol over carbon-black-modified nano-TiO2 thin films supported on Al sheet

The photocatalytic activity of the carbon-black-modified nano-TiO2) (CB-TiO2) thin films was 1.5 times higher than that of TiO2 thin films in degrading Reactive Brilliant Red X-3B. Photocatalytic oxidation and ozonation of catechol over CB-TiO2 thin films supported on Al sheet was investigated. The experiments showed that ozone concentrations had an important effect on TOC removal. The combined photocatalysis with UV irradiation and ozonation (TiO2/UV/O3) process considerably increased TOC removal rate compared to combined photocatalysis with UV irradiation and oxygen oxidation (TiO2/UV/O2) process, ozonation alone (O3) process, combined ozonation and UV irradiation (UV/O3) process. The complete mineralization of catechol followed pseudo-zero-order kinetics dependent upon ozone (oxygen) concentration and indicated catechol concentration did not affect the kinetics during UV/O3 and TiO2/UV/O3 (O2) processes. The kinetic study showed that the rate constants in the complete mineralization of catechol with TiO2/UV/O3 are 1.32-1.80 times higher than that of UV/O3 with the same concentration of ozone. The rate constants are 2.56-5.36 times higher than the maximal rate constants of TiO2/UV/O2 and 4.68-9.8 times higher than the maximal rate constants of TiO2/UV.     

混凝/PAC/超滤工艺去除水中天然有机物的研究

在饮用水处理过程中如何去除天然有机物是一个亟待解决的问题。混凝能降低水中污染物的浓度,避免这些物质进入膜孔内部,改善沉积在膜表面滤饼层的过滤性能和水中颗粒、胶体的迁移性能,提高膜通量。投加粉末活性炭(PAC)吸附溶解性有机物,利用超滤(UF)膜截留粉末炭,可达到提高出水水质的目的,还能防止膜污染。试验结果表明,混凝/PAC/UF组合工艺对水中UV254、UV410、TOC有较好的去除效果,平均去除率分别为92%、95%、84%,同时能改善膜透水通量、降低膜的吸附阻力、延长过滤周期、有效减少膜污染。     

Removal of natural organic matter and THM formation potential by ultra- and nanofiltration of surface water

Natural organic matter (NOM) and trihalomethane formation potential (THMFP) removal were evaluated by ultrafiltration (UF) and nanofiltration (NF). Ten different raw water sources in Alicante province (SE Spain) were analysed. Five types of membranes of different materials were tested with a dead-end-type stirred UF cell. Additional measurements, such as dissolved organic carbon, ultraviolet absorbance (254nm), THMFP, ion concentration, pH, conductivity, etc. were made on raw water, permeates and concentrates. The SUVA value was used to determine the hydrophobicity of the water analysed. The elimination of NOM and THMFP is correlated with the molecular weight (MW) of NOM determined by size exclusion chromatography (SEC). The flux decline trends were correlated with cation concentration. NOM removal by UF is low, which correlates with the average MW determined by SEC with an average value of 922g/mol (between 833 and 1031g/mol). However, the NOM removal obtained with the NF90 and NF270 NF membranes for all water sources is almost complete (90%). THMFP removal is related to hydrophobicity and permeability of membrane. The NFT50 membrane removes almost 100% of the THMFP of more hydrophobic waters.     

Identification of effluent organic matter fractions responsible for low-pressure membrane fouling

Anion exchange resin (AER), powder activated carbon (PAC) adsorption and ozonation treatments were applied on biologically treated wastewater effluent with the objective to modify the effluent organic matter (EfOM) matrix. Both AER and PAC led to significant total organic carbon (TOC) removal, while the TOC remained nearly constant after ozonation. Liquid Chromatography-Organic Carbon Detection (LC-OCD) analysis showed that the AER treatment preferentially removed high and intermediate molecular weight (MW) humic-like structures while PAC removed low MW compounds. Only a small reduction of the high MW colloids (i.e. biopolymers) was observed for AER and PAC treatments. Ozonation induced a large reduction of the biopolymers and an important increase of the low MW humic substances (i.e. building blocks).Single-cycle microfiltration (MF) and ultrafiltration (UF) tests were conducted using commercially available hollow fibres at a constant flux. After reconcentration to their original organic carbon content, the EfOM matrix modified by AER and PAC treatments exhibited higher UF membrane fouling compared to untreated effluent; result that correlated with the higher concentration of biopolymers. On the contrary, ozonation which induced a significant degradation of the biopolymers led to a minor flux reduction for both UF and MF filtration tests. Based on a single filtration, results indicate that biopolymers play a major role in low pressure membrane fouling and that intermediate and low MW compounds have minor impact. Thus, this approach has shown to be a valid methodology to identify the foulant fractions of EfOM.     

Characterizing algogenic organic matter (AOM) and evaluating associated NF membrane fouling

Occasional algal blooms, comprised of blue-green algae and/or green algae, cause significant challenges in drinking water treatment due to the release of algogenic organic matter (AOM) into water extracellularly and, upon cell lysis, intracellularly. AOM has been extracted from blue-green algae (cyanobacteria) by various means and analyzed by UV absorbance scanning, HPSEC-UV-fluorescence-DOC, UV absorbance ratio index (URI), FTIR, and fluorescence excitation emission matrix (EEM). AOM extracted in water as a solvent exhibited a high hydrophilic fraction (57.3%) with a low SUVA (1.0 L/m-mg). The molecular weight (MW) distribution showed a significant heterogeneity (high value of polydispersivity) and high protein content (as indicated by specific fluorescence). Significant amounts of proteinaceous components such as mycosporine-like amino acids (MAAs, UV-screening components) and phycobilins (light-harvesting pigment) were detected by UV/visible absorption. The presence of proteins was confirmed by FTIR (at 1661 and 1552 cm(-1)), EEM spectra (EX:278-282 nm and EM:304-353 nm), and high URI values (3.1-6.0). A bench-scale cross-flow unit, employing a flat-sheet membrane specimen, was used to examine nanofiltration (NF) membrane fouling and removal of natural organic matter (NOM) derived from different blends of Suwannee River humic acid (SRHA) and AOM: SRHA 10 mgC/L, AOM 3mg C/L + SRHA 7 mgC/L, AOM 7 mgC/L + SRHA 3 mgC/L, and AOM 10 mgC/L. The study focused mainly on the effects of two different sources of organic matter on NF (NF 200) membrane fouling under otherwise similar conditions. Flux decline and organic matter rejection as a function of delivered DOC (cumulative mass of feed DOC per unit area) showed significantly different results depending on the organic matter composition of samples even though the test conditions were the same (organic matter concentration, pH, temperature, inorganic salt composition and concentration, and recovery). A higher flux decline was observed with increasing proportions of AOM. Organic matter rejections also decreased with higher AOM contributions to the samples, indicating that lower molecular weight (MW) AOM components were not well rejected by the NF 200 membrane having a 360 Da MWCO. However, SRHA that exhibited a relatively high MW (1000-5000 Da range) and high SUVA (7.4 L/m-mg) was preferentially rejected through electrostatic repulsion/size exclusion by the NF 200 membrane, having a high negative charge, low MWCO, and relatively low hydrophobicity. Even though the DOC concentration of feed water is a decisive factor for membrane fouling along with membrane properties and operating conditions, the characteristics of organic matter are more influential in fouling potential. Protein-like and polysaccharide-like substances were found as major foulants by FTIR.     

Hybrid photocatalysis/membrane treatment for surface waters containing low concentrations of natural organic matters

Since the mid-1990s, numerous studies on the treatment of drinking water by photocatalysis have been reported. Once optimised, the photocatalytic process can completely degrade numerous natural and artificial organic compounds. In this study, a hybrid photocatalysis/membrane process was used as a polishing treatment of surface water containing a small concentration of natural organic matters (i.e. total organic carbon (TOC) concentration of around 3mg/L) which may be difficult to remove using conventional filtration or coagulation. An optimum pH of 4.5 and a TiO(2) concentration of 0.1g/L were found to lead to the highest removal efficiencies. The relative effect of the individual processes featuring in the hybrid system (UV radiation, TiO(2) adsorption and membrane filtration) was also assessed for different pH values. The membrane separation process was accounted to remove around 18% of the initial TOC concentration, while TiO(2) adsorption alone was generally responsible for less than 5% of TOC removal during the 120 min of the experiments. However, when the natural water was only radiated by UV light, up to 70% of TOC was removed. A synergetic effect was observed when the three processes (TiO(2), UV and membrane) were used together. Comparison of removal efficiencies obtained during real and model (International Humic Substance Society) waters treatment by photocatalysis is also presented, revealing the importance of the nature of the feed in this type of treatment.     

TiO_2光催化降解TCAA及其动力学研究

三氯乙酸(TCAA)是饮用水中普遍存在,且难以去除的高致癌风险物.考察了通气种类、TiO2用量、溶液初始pH及共存的Fe2+浓度等因素对TiO2光催化降解TCAA效率的影响,分析了pH对TiO2光催化降解TCAA效率的影响机理,探讨了TiO2光催化降解TCAA反应动力学及Fe2+促进TiO2光催化降解TCAA反应的机理.结果表明,当通入气体为O2、TCAA初始浓度为2.0mg/L、TiO2用量为1.0g/L、溶液初始pH为5.80,共存Fe2+浓度为0.10mmol/L时,反应120min,TiO2光催化降解TCAA效率为96.18%;用Langmuir-Hinshelwood模型模拟TiO2光催化降解TCAA反应动力学,UV/TiO2、Fe2+/UV/TiO2反应体系对TCAA的降解速率常数分别为0.0131、0.0237min-1,半衰期分别为52.92和29.25min.     

光氧化降解饮用水中微量有机物研究

针对饮用水进行深度处理提出紫外光激发催化化工艺,研究表明：（１）ＵＶ／ＴｉＯ２／Ｈ２Ｏ２工艺能有效去除水中的ＣＨＣｌ３;（２）ＣＨＣｌ３的光氧化降遵循一级动力学反应规律,反应速率常与Ｈ２Ｏ２投加量及紫外线辐射强度相关。     

A hybridized photocatalysis-microfiltration system with iron oxide-coated membranes for the removal of natural organic matter in water treatment: Effects of iron oxide layers and colloids

A photocatalysis/microfiltration (MF) hybrid system, with the coating of a membrane using iron oxide particles (IOPs), was investigated with respect to natural organic matter (NOM) removal and membrane permeability during the treatment of various surface waters. A comparison of the performance between bare (uncoated) and IOP-coated membranes employed for the photocatalytic hybrid system was made. Due to the additional adsorption of NOM onto IOPs on the membrane surface, the IOP-coated membrane system always achieved greater DOC removal efficiencies during photocatalysis/MF. Particularly, the influence of colloidal particles that were present in different water sources with respect to membrane fouling was explored. Colloidal fouling occurred to both bare and IOP-coated membranes, but the interaction of colloids with IOP coating layers was in close association with the characteristics of colloids, such as size distribution, resulting in opposing fouling behaviors with varying water sources. The IOP-coated membrane was able to control fouling properly when a relatively large size of colloidal particles existed in raw water, but not for the case of small colloids. The IOP coat layer may become denser as small colloids penetrate into it, therefore leading to further fouling. The analysis of the hydraulic filtration resistances revealed that such fouling was virtually reversible in being removed by backwashing processes. Scanning electron microscopic observations, however, visualized the existence of several foulants remaining at the membrane surface after backwashing when feed water, containing a relatively large portion of small-sized colloids, was supplied.     

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.     

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.     

Impact of recycling filter backwash water on organic removal in coagulation-sedimentation processes

The overall purpose of this research was to examine the impacts of filter backwash water (FBWW) and membrane backwash water (MBWW) recycles on water quality in coagulation-sedimentation processes. Specifically, the impact of recycling 5 or 10% by volume of FBWW and MBWW with surface water on the removal of natural organic matter (NOM) was evaluated at bench-scale using a standard jar-test apparatus and measurement of specific water quality parameters including total organic carbon (TOC), dissolved organic carbon (DOC), UV254, turbidity, total aluminum and zeta potential. The results of jar test conducted on a source water with a specific UV absorbance (SUVA) value within the range of 2-4 mg/L m showed a significantly higher removal of DOC from the raw water that was blended with 5 and 10% by volume of FBWW as compared to control trials where backwash water was not added. Increasing rates of MBWW that did not contain destabilized hydroxide precipitates did not significantly change DOC concentrations in the settled water samples as compared to the control trials. For source waters that are characterized as having low turbidity with medium SUVA values, these results could hold particular significance for plants that have reached treatment ceilings in terms of dissolved NOM removal using conventional coagulation designs.     

微滤/反渗透净化污水厂二级处理出水

以微絮凝和微滤作为反渗透的预处理工艺,采用连续流微滤-反渗透集成膜工艺深度处理城市污水厂二级生物处理出水,比较了投加聚合氯化铝和氯化铁进行微絮凝控制微滤膜污染的效果.结果表明,投加氯化铁对微滤膜污染具有更好的控制效果;微滤出水浊度＜0.5 NTU,对TOC的去除率为50%左右,对UV260的去除率＜30%.     

Assessing PAC contribution to the NOM fouling control in PAC/UF systems

This paper investigates the powdered activated carbon (PAC) contribution to the fouling control by natural organic matter (NOM) in PAC/UF hybrid process, as well as the foulant behaviour of the PAC itself. Solutions of NOM surrogates (humic acids, AHA, and tannic acid, TA) and AOM/EOM (algogenic organic matter/extracellular organic matter) fractions from a Microcystis aeruginosa culture were permeated through an ultrafiltration (UF) hollow-fibre cellulose acetate membrane (100 kDa cut-off). The greatest impairment on flux and the poorest rejection were associated with polysaccharide-like EOM substances combined with mono and multivalent ions. PAC, either in the absence or in the presence of NOM, did not affect the permeate flux nor the reversible membrane fouling, regardless of the NOM characteristics (hydrophobicity and protein content) and water inorganics. However, PAC controlled the irreversible membrane fouling, minimising the chemical cleaning frequency. Furthermore, PAC enhanced AHA and TA rejections and the overall removal of AOM, although it was apparently ineffective for the highly hydrophilic EOM compounds.     

High-performance thin-layer hydrogel composite membranes for ultrafiltration of natural organic matter

Thin-layer hydrogel composite (TLHC) ultrafiltration (UF) membranes were synthesized by photo-grafting of either poly(ethylene glycol) methacrylate (PEGMA) or N,N-dimethyl-N-(2-methacryloyloxyethyl-N-(3-sulfopropyl) ammonium betaine (SPE) onto commercial polyethersulfone (PES) UF membranes. The performance of TLHC UF membranes was evaluated for natural organic matter (NOM) filtration and compared to commercial PES UF membranes. The fouling evaluation was done by investigation of membrane-solute interactions (adsorptive fouling) and membrane-solute-solute interactions (UF). The results suggest that the TLHC membranes convincingly displayed a higher adsorptive fouling resistance than unmodified PES UF membranes. In long-term stirred dead-end UF, a much lower fouling was observed for TLHC membranes than for commercial membranes with the same flux and rejection. Further, water flux recovery was also much higher. An analysis using an existing blocking model was performed in order to elucidate the effect of a polymer hydrogel layer on fouling mechanism as well as cake layer characteristics. The TLHC membranes synthesized by photo-grafting of PEGMA (40 g/L) and PEGMA with a low concentration of cross-linker monomer in the reaction mixture (ratio: 40/0.4 (g/L)/(g/L)) showed a much better performance than the other composite membranes. Those membranes could reduce the cake resistance on the membrane surface. This work has relevance for the design of high-performance UF membranes for applications in water treatment.     

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.     

Low-pressure membrane (MF/UF) fouling associated with allochthonous versus autochthonous natural organic matter

Natural organic matter (NOM) isolates/fractions; organic colloids, and hydrophobic (HPO), transphilic (TPI), and hydrophilic (HPI) fractions; isolated from a natural surface water as an allochthonous source, and in the form of algal organic matter (AOM) derived from blue green algae as an autochthonous source, were investigated in low-pressure membrane filtration. The most significant flux decline was caused by organic colloids, with an intermediate flux decline caused by AOM derived (isolated) from ground and sonicated blue green algae. 3D fluorescence excitation-emission matrix (EEM) analyses revealed that colloids and AOM contain protein-like substances, and FTIR analyses showed overlapping peaks associated with the peptide bonds in proteins and alcohols in polysaccharides originating from extra- and/or intra-cellular materials. HP-SEC results also support a high content of apparently macromolecular compounds in the colloid fraction. The presence of a divalent cation (Ca(2+)), hypothesized to enhance fouling by NOM acids by a reduction in molecular charge, showed little effect. Morphological analyses indicated that the surface topography of fouled UF membranes was elevated, presumably due to deposition of NOM on the membrane surface. The pores of MF membranes were reduced, suggesting pore blockage and/or constriction by NOM aggregates.     

Photocatalysis of p-chlorobenzoic acid in aqueous solution under irradiation of 254 nm and 185 nm UV light

The photolytic and photocatalytic degradation of p-chlorobenzoic acid (p-CBA) in aqueous solution were investigated using two kinds of low-pressure mercury lamps: one emitted at 254 nm and the other emitted at 254 nm and 185 nm. Both the photolytic and photocatalytic degradations of p-CBA followed pseudo first-order reaction rate form. The rate constants decreased with increase of initial concentration in VUV and TiO2/VUV. The TiO2/VUV was the most efficient process, in which rate constants was 3.0-6.5 times as that in TiO2/UV depending on the initial concentration. The gas bubbling efficiently improved the mass transfer and the kind of bubbling gas had evident influence on the reaction rate except in UV photolysis. TOC reduction rate was greatly reduced in VUV and TiO2/VUV processes when bubbled with nitrogen gas, it was no more than one third of that when bubbled with oxygen, however, the degradation rate of p-CBA was not affected by bubbled nitrogen so greatly.