纳滤、反渗透工艺深度处理饮用水研究

利用纳滤和反渗透膜深度处理工艺进行长江原水水质净化中试研究,工艺流程为长江原水→混凝沉淀→沙滤→颗粒活性炭→纳滤/反渗透,比较纳滤、反渗透膜工艺对污染物特别是微量有机物苯系物、三氯乙烯及消毒副产物等的去除效果。结果表明膜工艺预处理能够有效地去除原水的浊度和部分污染物,有利于纳滤、反渗透的稳定运行。纳滤膜工艺的最佳操作压力是0.4 MPa,此压力下产水量为250 L/h,回收率为24%,SO₄^2-,Cl^-,NO₃^-和总硬度的去除率分别为91.7%,85.4%,85.2%,89.3%;采用浓缩水回流能兼顾较高的回收率和良好的去除率。2种膜工艺对苯系物与三氯乙烯的去除率均在95.7%以上;对消毒副产物也有较好的控制效果,其中大部分的削减率在63.7%以上。与反渗透膜工艺比较,纳滤膜工艺具有较低的生产成本。纳滤膜工艺净化出水中可部分保留对人体有益的矿物质,使得净化后的出水成为优质健康饮用水。     

Natural Organic Matter and Disinfection By-products Formation Potential in Water Treatment

The performance of a conventional sequence (pre-ozonation, coagulation/ flocculation/ sedimentation, filtration, disinfection) and two non-conventional sequences (pre-ozonation, nanofiltration; and pre-ozonation, coagulation/ flocculation/ sedimentation, nanofiltration) on the removal of natural organic matter (NOM) and disinfection by-products (DBPs) formation potential was evaluated. Raw and treated waters were characterized in terms of molecular weight, which includes the amount of NOM removed and the qualitative changes in the NOM characteristics (molecular weight and hydrophobicity) since they could be directly related with the DBPs formation. The results demonstrate that, for the type of raw water analysed (hydrophilic with low dissolved organic carbon content, 0.99 L/(mg.m) and 1.31 mg DOC/L), both treatment sequences remove larger molecular weight compounds (>1,900 g/mol). Treated waters have the dominant fractions in the smaller molecular size fractions (<750 g/mol). However, the sequences with nanofiltration have a higher percentage of low molecular weight compounds removed (between 430 and 250 g/mol), when compared with conventional sequence, thus the water from nanofiltration sequences will have lower DBPs formation potential. The removal of the smallest molecular size fractions can be enhanced by optimising the water treatment process and the quality of water will improve relating with DBPs formation.     

The effect of colloid stability of wastewater treatment plants effluent on nanofiltration performance.

Laboratory-scale filtration tests utilizing wastewater treatment plants (WWTP) effluent were conducted to investigate fouling and filtration behaviour, especially the influence of colloidal stability on nanofiltration performance. Acidification and coagulant dosage were used to create unstable colloidal conditions. Colloidal stability of the effluent was analysed on by zeta potential measurements. A statistical design method, full factorial design with blocking, has been used to account for effluent composition variations and to account for interaction between experimental parameters. The results show a high correlation between unstable colloidal natural organic matter and the formation of dense fouling layers. The reversibility of the fouling process was shown to be independent from colloidal stability. Irreversible fouling was show to be promoted by mild acidic (pH 5) effluent conditions, whereas coagulant addition showed an increase in the reversibility of the fouling.     

Integrated biological treatment of recalcitrant effluents from pulp mills.

This work aimed at determining the degree of depuration of a recalcitrant effluent (weak black liquor, WBL) achieved in a series treatment consisting of a first stage methanogenic fluidised bed reactor followed by a second stage aerobic, upflow reactor packed with "biocubes" of Trametes versicolor immobilised onto small cubes of holm oak wood. The mesophilic, lab scale methanogenic fluidised bed reactor contained a microbial consortium immobilised onto granular activated carbon 500 microm average size. The process removed decreasing amounts of organic matter at decreasing hydraulic retention times (HRT), eventually reaching an average of 50% at 0.5 day HRT. Colour and ligninoid removals also decreased with decreasing HRT. Although the methanogenic fluidised bed reactor provided an effective treatment for the degradable organic matter, important concentrations of recalcitrant organic matter and colour still remained in the anaerobic effluent. This anaerobic effluent was fed to the aerobic packed bed reactor. Two HRT were tested in this unit, namely 5 and 2.5 days. The reactor averaged an organic matter removal in the range of 32% COD basis, during an experimental run of 95 days. Colour and ligninoid contents were removed in high percentages (69% and 54%, respectively). There was no significant difference in reactor performance at 5- and 2.5-day HRT. There was a positive correlation between pollutant removal efficiencies and Laccase activity in crude extracts of the reactor liquor. No supplemental soluble carbohydrate was required to sustain the fungus activity and the consistent reactor performance. Overall, the two-stage treatment achieved approximately a 78% removal of the original organic matter of the WBL (COD basis) and ca. 75% of colour and ligninoid contents.     

Fate of effluent organic matter (EfOM) and natural organic matter (NOM) through riverbank filtration.

Understanding the fate of effluent organic matter (EfOM) and natural organic matter (NOM) through riverbank filtration is essential to assess the impact of wastewater effluent on the post treatment requirements of riverbank filtrates. Furthermore, their fate during drinking water treatment can significantly determine the process design. The objective of this study was to characterise bulk organic matter which consists of EfOM and NOM during riverbank filtration using a suite of innovative analytical tools. Wastewater effluent-derived surface water and surface water were used as source waters in experiments with soil columns. Results showed the preferential removal of non-humic substances (i.e. biopolymers) from wastewater effluent-derived surface water. The bulk organic matter characteristics of wastewater effluent-derived surface water and surface water were similar after 5 m soil passage in laboratory column experiment. Humic-like organic matter in surface water and wastewater effluent-derived surface water persisted through the soil passage. More than 50% of total dissolved organic carbon (DOC) removal with significant reduction of dissolved oxygen (DO) was observed in the top 50 cm of the soil columns for both surface water and wastewater effluent-derived surface water. This was due to biodegradation by soil biomass which was determined by adenosine triphosphate (ATP) concentrations and heterotrophic plate counts. High concentrations of ATP in the first few centimeters of infiltration surface reflect the highest microbial activity which correlates with the extent of DOC reduction. Good correlation of DOC removal with DO and biomass development was observed in the soil columns.     

Foulant characterization of the NF membranes with and without pretreatment of biologically treated wastewater.

In this study, different pretreatment methods such as ferric chloride (FeCl3) flocculation and powdered activated carbon (PAC) adsorption were evaluated in terms of their capability in removing effluent organic matter (EfOM) and the characteristics of the foulants on the NF membranes. A detailed experiment was conducted with two NF membranes (NTR 729HF with MWCO 700 daltons and LF 10 with MWCO 200 daltons). With pretreatment, the concentration of organic matter on the membranes decreased to 5.671 x 10(-3) (NTR 729HF) and 4.940 x 10(-3) (LF 10) mg EfOM/cm2 of membrane from 6.372 x 10(-3) (NTR 729HF) and 4.979 x 10(-3) (LF 10) mg EfOM/cm2 of membrane. The MW of the solute fraction of biologically treated sewage effluent (BTSE) ranged from 250 daltons to about 3573 (the most important being 250-520 daltons). The weight-averaged MW values of the foulants on the NTR 729HF membrane reduced from 304 daltons without pre-treatment to 208 daltons with pretreatment. In the case of EfOM, the small molecules (MW 300 to 500 daltons) are mainly responsible for the membrane fouling. Thus, the MW distribution of organic matter in the effluent and in the foulant can be used as a representative tool to evaluate the efficiency of pretreatment and NF and in the selection of their operating conditions.     

Evaluation of bipolar electrocoagulation applied to biofiltration for phosphorus removal.

To reduce the residual organic matter and phosphorus contained in secondary effluent, a biofiltration system combined with electrocoagulation using bipolar iron electrodes was evaluated as a supplementary treatment to existing small-community sewage treatment. Based on the results of batch tests, bipolar electrocoagulation (BEC) was found to be more effective on phosphorus removal than monopolar electrocoagulation (MEC) but energy consumption was less in monopolar electrocoagulation. Optimum conditions of BEC to treat the secondary effluent were current density 15 A/m2, electrode spacing 1 cm and pH < 8. The removals of COD(Cr) and phosphorus by biofiltration system without BEC were 69.1% and 9.6%, respectively. However, biofiltration system combined with BEC showed 76.6-83.7% and 70.7-93.0% removal for COD(Cr) and phosphorus respectively. Extraordinary increase in phosphorus could be achieved by introducing electrocoagulation to biofiltration, and BEC/biofiltration system was evaluated to be applicable to existing small-community sewage treatment plants as a supplementary process.     

Importance of the order in enhancing EfOM removal by combination of BAC and MIEX(?)

Biological activated carbon (BAC) is operationally a simple treatment which can be employed to remove effluent organic matter (EfOM) from secondary wastewater effluent (SWWE). Unfortunately, BAC removes only a limited amount of dissolved organic carbon (DOC). Thus, maximizing DOC removal from SWWE using BAC is a major concern in wastewater reuse. This study has investigated a hybrid system of BAC and Magnetic Ion Exchange Resin (MIEX(?)) for the enhanced removal of DOC. Performance of both BAC prior to MIEX(?) (BAC/MIEX(?)) and reverse (MIEX(?)/BAC) combination was evaluated in terms of DOC removal. The BAC/MIEX(?) showed much better DOC removal. This is because microbial activity in the BAC bed converted MIEX(?) non-amenable DOC to MIEX(?) amenable DOC. As a result, BAC/MIEX(?) combination synergised DOC removal. In addition, BAC was also found to be highly effective in reducing MIEX(?) dose for a given DOC removal from SWWE.     

组合工艺控制有机物及消毒副产物前体物的特性研究

通过XAD-8树脂将水中有机物分成疏水性、亲水性两部分,对传统常规处理工艺(混凝气浮、过滤)和深度处理工艺(臭氧氧化、生物活性炭)出水的DOC,UV254THMFP,HAAFP指标以及疏水、亲水有机物去除率进行了检测分析。结果表明,生物活性炭(BAC)单元工艺能同时去除疏水性和亲水性两种有机物,且两者去除率均为最高。其次去除效果较好的是传统的常规工艺。臭氧工艺具有将天然的疏水性有机物氧化成可生化降解的亲水性小分子有机物的特点,在预臭氧+常规以及O3-BAC组合工艺中,起到了强化去除有机物和消毒副产物前体物的效果。     

Combined chemical biological treatment of bleached eucalypt kraft pulp mill effluent.

Effectiveness of ozonation before and after biological treatment for removal of recalcitrant organic matter in bleached kraft pulp effluents was compared. Two industrial ECF bleached eucalypt kraft pulp effluents (E1 and E2) were pretreated with 100 mg O3/L. Raw and pretreated effluents were treated biologically in bench-scale sequencing batch reactors, under constant conditions. Following biological treatment, effluents were post-treated with 100 and 200 mg O3/L. Effluent pretreatment increased effluent biodegradability by 10% in E1 and 24% in E2. Combined O3-biological treated led to small but significant increases in COD, BOD and lignin removal over biological treatment alone, but pretreatment had no significant effect on effluent colour and carbohydrate removal. Ozone pretreatment did not affect biological activity during treatment of effluent E1 but resulted in a 38% lower specific oxygen uptake rate in effluent E2. At an equivalent dose of 100 mg/L, pre-ozonation produced better quality effluent than post-ozonation, especially with regard to COD and colour. Likewise, when an equivalent dose of 200 mg/L was applied, splitting the dose equally between pre- and post-treatments was more efficient than applying the entire dose in the post-treatment. The potential for combined chemical-biological treatment to improve effluent quality has been confirmed in this study.     

Effect of recirculation on organic matter removal in a hybrid constructed wetland system

This research project aimed to determine the technologically feasible and applicable wastewater treatment systems which will be constructed to solve environmental problems caused by small communities in Turkey. Pilot-scale treatment of a small community's wastewater was performed over a period of more than 2 years in order to show applicability of these systems. The present study involves removal of organic matter and suspended solids in serially operated horizontal (HFCW) and vertical (VFCW) sub-surface flow constructed wetlands. The pilot-scale wetland was constructed downstream of anaerobic reactors at the campus of TUBITAK-MRC. Anaerobically pretreated wastewater was introduced into this hybrid two-stage sub-surface flow wetland system (TSCW). Wastewater was first introduced into the horizontal sub-surface flow system and then the vertical flow system before being discharged. Recirculation of the effluent was tested in the system. When the recirculation ratio was 100%, average removal efficiencies for TSCW were 91 +/- 4% for COD, 83 +/- 10% for BOD and 96 +/- 3% for suspended solids with average effluent concentrations of 9 +/- 5 mg/L COD, 6 +/- 3 mg/L BOD and 1 mg/L for suspended solids. Comparing non-recirculation and recirculation periods, the lowest effluent concentrations were obtained with a 100% recirculation ratio. The effluent concentrations met the Turkish regulations for discharge limits of COD, BOD and TSS in each case. The study showed that a hybrid constructed wetland system with recirculation is a very effective method of obtaining very low effluent organic matter and suspended solids concentrations downstream of anaerobic pretreatment of domestic wastewaters in small communities.     

Assessing the removal potential of soil-aquifer treatment systems for bulk organic matter.

The fate of effluent organic matter (EfOM) during groundwater recharge was investigated by studying the removal behavior of four bulk organic carbon fractions isolated from a secondary effluent: Hydrophilic organic matter (HPI), hydrophobic acids (HPO-A), colloidal organic matter (OM), and soluble microbial products (SMPs). Short-term removal of the bulk organic fractions during soil infiltration was simulated in biologically active soil columns. Results revealed that the four organic fractions showed a significantly different behavior with respect to biological removal. HPI and colloidal OM were prone to biological removal during initial soil infiltration (0-30 cm) and supported soil microbial biomass growth in the infiltrative surface. Additionally, colloidal OM was partly removed by physical adsorption or filtration. HPO-A and SMPs reacted recalcitrant towards biological degradation as indicated by low soil biomass activity responses. Adsorbability assessment of the biologically refractory portions of the fractions onto powered activated carbon (PAC) indicated that physical removal is not likely to play a significantly role in further diminishing recalcitrant HPO-A, HPI and SMPs during longer travel times in the subsurface.     

Use of nanofiltration for potable water from an aquifer recharged with wastewater.

This paper presents the comparison of nine nanofiltration membranes to treat water coming from an aquifer recharged with wastewater and used as municipal supply in the Tula Valley, Mexico. The comparison was made based on (a) the amount of water produced; (c) the capability to produce a <1 mg TOC/L effluent without entirely eliminating salts, (b) the removal of specific organic and microbiological pollutants, and (c) the reduction of toxicity and mutagenicity from water. From the tested membranes, only four produce an effluent with <1 TOC mg/L, and three totally retained dibutyl phthalate, diethyl phthalate and hydroxytoluene butylate. Influent mutagenicity (Ames test) was negative but these was a certain degree of toxicity when Tetrahymena pyriformis was used as indicator. Toxicity was partially reduced by some of the NF membranes. The best membrane had a flux of 95 L m(-2)h(-1) and removal efficiencies of 98% for TOC, 92% for AUV(254), and 92% for TDS. The permeate had a final hardness of 76 mg/L and an alkalinity of 124 mg/L. Additionally, this membrane removed totally specific organic compounds, total and fecal coliforms and almost all the somatic coliphages.     

UV/H2O2联用工艺去除水中微量有机污染物的中试研究

为了考察UV/H2O2工艺对微量有机物的去除效果,在砂滤池出水后接UV/H2O2高级氧化中试设备,并投加了特征污染物(阿特拉津、臭味物质2-MIB与Geosmine)。结果表明,UV/H2O2工艺对Geosmine去除效果最好,去除率能达到90%以上,对MIB和阿特拉津的去除效果比较接近,去除率均在50%以上,对UV254的去除率为20%～38%。在UV/H2O2工艺中无溴酸盐生成。     

组合膜分离技术资源化处理印染废水工艺的研究

为解决印染废水的资源化处理问题,针对实际印染废水研究了以超滤和纳滤膜分离技术为核心的印染废水处理及回用工艺在工程上的可行性。实验结果表明:还原染料废水采用超滤系统处理,膜出水水质即能够满足印染厂内回用水质要求;活性染料废水通过纳滤浓缩能够获得较好的染料回收效果。采用双膜膜分离系统(UF+NF)能够使两种染料废水的污染物均得到明显去除,还原性染料废水的总悬浮物、COD、浊度和色度的去除率达到了100%、95.21%、92.86%和100%;活性染料废水上述各项指标去除率达到100%、82.85%、98.46%和99.43%。双膜膜分离系统适用于工业印染废水处理及染料回收,是资源化处理印染废水的发展方向。     

RO brine treatment and recovery by biological activated carbon and capacitive deionization process

The generation of brine solutions from dense membrane (reverse osmosis, RO or nanofiltration, NF) water reclamation systems has been increasing worldwide, and the lack of cost effective disposal options is becoming a critical water resources management issue. In Singapore, NEWater is the product of a multiple barrier water reclamation process from secondary treated domestic effluent using MF/UF-RO and UV technologies. The RO brine (concentrates) accounts for more than 20% of the total flow treated. To increase the water recovery and treat the RO brine, a CDI based process with BAC as pretreatment was tested. The results show that ion concentrations in CDI product were low except SiO2 when compared with RO feed water. CDI product was passed through a RO and the RO permeate was of better quality including low SiO2 as compared to NEWater quality. It could be beneficial to use a dedicated RO operated at optimum conditions with better performance to recover the water. BAC was able to achieve 15-27% TOC removal of RO brine. CDI had been tested at a water recovery ranging from 71.6 to 92.3%. CDI based RO brine treatment could improve overall water recovery of NEWater production over 90%. It was found that calcium phosphate scaling and organic fouling was the major cause of CDI pressure increase. Ozone disinfection and sodium bisulfite dosing were able to reduce CDI fouling rate. For sustainable operation of CDI organic fouling control and effective organic fouling cleaning should be further studied.     

Equalization characteristics of an upflow sludge blanket-aerated biofilter (USB-AF) system.

Equalization characteristics of the upflow sludge blanket-aerated bio-filter (USB-AF) were investigated with the fluctuated raw domestic sewage. Recycle of nitrified effluent from AF to USB triggered the equalization characteristics of the sludge blanket on both soluble and particulate organic matter. Increment of EPS in sludge blanket by nitrate recycle was detected and removal of turbidity and particulates increased at higher recycle ratios by bio-flocculation. Increased TCOD removal in the USB was due to both denitrification of recycled nitrate and entrapment of the particulate organic matter in sludge blanket. Capture of both soluble and particulate organic matter increased sludge blanket layer in the USB, which improved the reactor performances and reduced the organic load on the subsequent AF. Overall TCOD and SS removal efficiencies were about 98% and 96%, respectively in the USB-AF system. Turbidity in the USB effluent was about 44, 20 and 5.5 NTU, at recycle ratios of 0, 100 and 200%, respectively. Particle counts in the range 2-4 microm in the USB effluent were higher than those in influent without nitrate recycle, while particle counts in the range of 0.5-15 microm in the USB effluent decreased 70% at recycle ratio of 200%. The major constituent of EPS extracted from anaerobic sludge was protein and total EPS increased from 109.1 to 165.7 mg/g-VSS with nitrate recycle of 100%. Removal efficiency and concentration of T-N in the UBS-AF effluent was over 70% and below 16 mg/L, respectively.     

H_2O_2与沸石联用处理污水厂二级出水的研究

为探寻污水厂二级出水深度处理方法,以阜新市某污水处理公司二级出水为研究对象,进行H2O2与沸石联用去除水中COD、氨氮的研究。结果表明：在二氧化锰的催化作用下,pH值为7时,H2O2和沸石的投加量分别为1.5mL和2g,二级出水的COD从138.24mg/L降到52.76mg/L,去除率达到75.36%,NH3-N从20mg/L降到5mg/L,去除率为74.59%,出水有机物和氨氮含量达到国家相关出水标准。     

Increasing the capacity for treatment of chemical plant wastewater by replacing existing suspended carrier media with Kaldnes Moving Bed media at a plant in Singapore.

The Kaldnes biomedia K1, which is used in the patented Kaldnes Moving Bed biofilm process, has been tested along with other types of biofilm carriers for biological pretreatment of a complex chemical industry wastewater. The main objective of the test was to find a biofilm carrier that could replace the existing suspended carrier media and at the same time increase the capacity of the existing roughing filter-activated sludge plant by 20% or more. At volumetric organic loads of 7.1 kg COD/m3/d the Kaldnes Moving Bed process achieved much higher removal rates and much lower effluent concentrations than roughing filters using other carriers. The Kaldnes roughing stage achieved more than 85% removal of organic carbon and more than 90% removal of BOD5 at the tested organic load, which was equivalent to a specific biofilm surface area load of 24 g COD/m2/d. Even for the combined roughing filter-activated sludge process, the Kaldnes carriers outperformed the other carriers, with 98% removal of organic carbon and 99.6% removal of BOD5. The Kaldnes train final effluent concentrations were only 22 mg FOC/L and 7 mg BOD5/L. Based on the successful pilot testing, the full-scale plant was upgraded with Kaldnes Moving Bed roughing filters. During normal operation the upgraded plant has easily met the discharge limits of 100 mg COD/L and 50 mg SS/L. For the month of September 2002, with organic loads between 100 and 115% of the design load for the second half of the month, average effluent concentrations were as low as 9 mg FOC/L, 51 mg COD/L and 12 mg SS/L.     

Performance of constructed wetland treating wastewater from seafood industry.

Wastewater from seafood industry contains high concentrations of organic matter, nitrogen compounds, and solid matter. Constructed wetland can be used as tertiary treatment and for nutrient recycling. This research studied the performance of nitrogen and suspended solids removal efficiency of a constructed wetland treating wastewater from a seafood-processing factory located at Songkhla, southern Thailand. The existing constructed wetland has dimensions of 85 m, 352 m and 1.5 m in width, length and depth respectively, with an area of about 29,920 m2. The water depth of 0.30 m is maintained in operation with plantation of cattails (Typha augustifolia). Flow rate of influent ranged between 500-4,660 m3/d. Average hydraulic retention time in the constructed wetland was about 4.8 days. Influent and effluent from the constructed wetland were collected once a week and analyzed for pH, temperature, dissolved oxygen (DO), biochemical oxygen demand (BOD5), Suspended solid (SS), total Kjeldahl nitrogen (TKN), ammonia nitrogen (NH3-N), organic nitrogen (Org-N), nitrate (NO3-N), and nitrite (NO2-N). The average removal efficiencies of BOD5, SS, TKN, NH3-N, and Org-N were 84%, 94%, 49%, 52% and 82%, respectively. It was found that the constructed wetland acting as a tertiary treatment process provided additional removal of BOD5, SS and TKN from wastewater from the seafood industry.