臭氧-曝气生物滤池组合工艺处理石化二级出水的试验研究

采用臭氧-曝气生物滤池组合工艺对石化废水厂二级出水进行深度处理,系统探讨了pH值对臭氧氧化单元的影响,组合工艺对废水中COD、UV254的去除效果,对废水中有机物相对分子质量分布以及荧光物质含量的影响.结果表明,在臭氧投加量为10 mg·L-1,接触时间为4 min,pH值偏碱性时,臭氧预氧化石化二级出水效果较好.臭氧氧化能将大分子有机物转化为小分子物质,使得相对分子质量小于1 000的有机物比例增加约15%,有效提高了废水的可生化性,有利于后续曝气生物滤池的运行.在曝气生物滤池的停留时间为3 h,气水比为3∶1时,组合工艺对COD、UV254的去除率分别达到40.8%和45.8%.在最佳运行条件下,进水平均COD为86.5 mg·L-1时,组合工艺出水平均COD为49.4 mg·L-1.     

Toxicity-based assessment of the treatment performance of wastewater treatment and reclamation processes

The reclamation and reuse of wastewater is one of the possible ways to relieve the serious fresh water resource crisis in China. Efficient reclamation treatment technologies ensure the safe reuse of reclaimed water. In order to screen out and evaluate technologies appropriate for reclamation treatment, a great deal of efforts have been brought to bear. In the present study, a toxicity-based method including a Photobacterium phosphoreum test for acute toxicity and SOS/umu test for genotoxicity, accompanied by the traditional physicochemical parameters DOC (dissolved organic carbon) and UV₂₅₄ (absorbance at 254 nm), was used to measure the treatment performance of different reclamation processes, including the anaerobic-anoxic-oxic biological process (A²O) and subsequent physical/chemical reclamation processes (ultrafiltration, ozonation, chlorination). It was found that for the secondary effluent after the A²O process, both the toxicity and physicochemical indices had greatly decreased compared with those of the influent. However, chemical reclamation processes such as ozonation and chlorination could possibly raise toxicity levels again. Fortunately, the toxicity elevation could be avoided by optimizing the ozone dosage and using activated carbon after ozonation. It was noted that by increasing the ozone dosage to 10 mg/L and employing activated carbon with more than 10 min hydraulic retention time, toxicity elevation was controlled. Furthermore, it was shown that pre-ozonation before activated carbon and chlorination played an important role in removing organic compounds and reducing the toxicity formation potential. The toxicity test could serve as a valuable tool to evaluate the performance of reclamation processes.     

污水厂二级出水中难凝聚有机物的臭氧化特性

以城市污水处理厂二级出水为原水,研究臭氧化处理对水中难凝聚有机物的去除效果.结果表明单独混凝对水中有机物的去除率较低,混凝过程中未被去除的有机物属于难凝聚有机物,加入臭氧进行氧化,随着臭氧投加量的增加,二级出水色度和UV254去除率逐渐增大,而DOC去除率变化较小.当臭氧投加量(以O3/DOC计)增加至1.5 mg·mg-1时,色度、UV254和DOC的去除率分别为45%、34%和20%,说明臭氧易于与不饱和结构有机物反应,而直接氧化的矿化能力较弱.为进一步明确二级出水有机物种类和含量的变化,测定了混凝和不同臭氧投加量下有机物的相对分子质量和三维荧光光谱.结果表明混凝对有机物含量的影响很小,而臭氧能够优先氧化分解难凝聚有机物中的大分子物质,明显减弱腐殖质类物质的荧光峰强度,但不改变荧光峰位置.同时采用光电子能谱分析有机物结构的变化规律,结果表明混凝能够去除含羧基类官能团有机物,而臭氧则易于与含苯环类难凝聚有机物反应,随着臭氧投加量的增大,脂肪类饱和有机物含量有所升高.     

臭氧-生物活性炭组合工艺中最佳臭氧投加剂量的确定

在水处理过程中投加臭氧,可提高饮用水的可生物降解性.臭氧氧化后继的生物过滤,可以减少水中可生物降解有机物数量,提高饮用水的生物稳定性.试验表明,臭氧投加量2～8mg/L可使AOC-P17,AOC-NOX和BDOC分别增加20.9%～85.5%,42.1%～158.2%和21.4%～84.4%.臭氧投加量为3mg/L时,AOC和BDOC增加得最多,即3mg/L的臭氧投量为最佳投加剂量.生物活性炭滤柱(BAC)出水AOC浓度(乙酸碳)均低于50μg/L,在35.9～46.6μg/L之间,属于生物稳定性水质.     

饮用水中内分泌干扰物双酚A的臭氧氧化降解研究

采用臭氧氧化工艺对饮用水中内分泌干扰物双酚A特性进行了研究.研究表明:在原水浓度为1.0mg/L左右,臭氧总投加量为1.0、1.5和2.0mg/L条件下,30min BPA去除率可达70%、82%和90%.通过考察不同臭氧投加量、不同本底条件、不同BPA初始浓度和不同臭氧投加时间对BPA臭氧氧化的影响,分析得出臭氧投加量对BPA的降解占主导地位,而臭氧接触时间对去除效果的影响很小;采用紫外波长扫描确定在臭氧降解BPA的同时生成了在UV₂₅₄上有吸收的产物.通过考察臭氧氧化双酚A过程中UV₂₅₄的变化,提出低臭氧投加量下BPA不能完全被氧化,而采用缩短臭氧投加时间、加大臭氧投加量以及提高水中余臭氧浓度等方法,有利于水中BPA的完全降解.     

Dissolved organic matter removal using magnetic anion exchange resin treatment on biological effluent of textile dyeing wastewater

This study investigated the removal of dissolved organic matter（DOM） from real dyeing bio-treatment effluents（DBEs） with the use of a novel magnetic anion exchange resin（NDMP）.DOMs in two typical DBEs were fractionized using DAX-8/XAD-4 resin and ultrafiltration membranes. The hydrophilic fractions and the low molecular weight（MW）（〈3 kDa） DOM fractions constituted a major portion（〉50%） of DOMs for the two effluents. The hydrophilic and low MW fractions of both effluents were the greatest contributors of specific UV254absorbance（SUVA254）,and the SUVA254 of DOM fractions decreased with hydrophobicity and MW. Two DBEs exhibited acute and chronic biotoxicities. Both acute and chronic toxicities of DOM fractions increased linearly with the increase of SUVA254 value. Kinetics of dissolved organic carbon（DOC） removal via NDMP treatment was performed by comparing it with that of particle active carbon（PAC）. Results indicated that the removal of DOC from DBEs via NDMP was 60%,whereas DOC removals by PAC were lower than 15%. Acidic organics could be significantly removed with the use of NDMP. DOM with large MW in DBE could be removed significantly by using the same means. Removal efficiency of NDMP for DOM decreased with the decrease of MW. Compared with PAC,NDMP could significantly reduce the acute and chronic bio-toxicities of DBEs. NaCl/NaOH mixture regenerants,with selected concentrations of 10% NaCl（m/m）/1%NaOH（m/m）,could improve desorption efficiency.     

高藻水臭氧预氧化过程有机物转化及消毒副产物生成势

研究了高藻水预氧化处理过程中,不同臭氧氧化程度及不同pH值条件下,藻类有机物释放与转化规律以及氯化消毒副产物(DBPs)的生成特性.结果表明,臭氧投加量为28.92 mg·L-1时藻去除率达36%.随着臭氧投加量的增加,藻的去除率进一步增加,类腐殖酸先增加后持续减少,溶解性微生物代谢产物、类富里酸和类芳香蛋白物质持续减少;低投加量的臭氧对二氯乙腈(DCAN)、三氯乙腈(TCAN)生成势有明显的控制作用,但会增加三氯硝基甲烷(TCNM)以及1,1,1-三氯丙酮(1,1,1-TCP)前体物,随臭氧投加量增大,DBPs生成势显著增大.酸性条件下臭氧对藻的去除效果最好,UV254以及总有机碳(DOC)均随pH的增大有所上升,但变化较小;臭氧氧化可降解溶解性微生物代谢产物,降解效果受pH影响较小,类腐殖酸有机物随pH值增大而减少;DCAN、TCAN生成势随pH增大有所降低,TCNM生成势在pH=10条件下最高,1,1,1-TCP生成势在pH=7条件下最高.     

微气泡臭氧化预处理实际制药废水去除SS和有机物性能

采用臭氧微气泡预处理实际制药废水,并与氮气微气泡、臭氧普通气泡和氮气普通气泡处理过程比较,考察悬浮固体（SS）和有机物去除过程和性能.结果表明,臭氧微气泡存在强吸附-气浮-氧化作用,显著增强SS去除能力,60 min时SS去除率可达到81.67%,同时SS粒径减小,SS表面负电荷转变为正电荷.微气泡臭氧化具有强·OH氧化作用,显著增强有机物降解去除能力,60 min时溶解性COD （SCOD）去除率可达到36.60%,且SS去除可加速SCOD去除,UV₂₅₄去除率可达到36.91%,同时可生化性改善和生物毒性消除作用明显.三维荧光和GC-MS分析表明,微气泡臭氧化可有效氧化破坏废水中复杂结构大分子有机物,显著降低废水中有机物芳香性.微气泡臭氧化可为高浓度难降解实际制药废水提供高效可行的预处理手段.     

Effect of ozone on the performance of a hybrid ceramic membrane-biological activated carbon process

Two hybrid processes including ozonation-ceramic membrane-biological activated carbon （BAC） （Process A） and ceramic membrane-BAC （Process B） were compared to treat polluted raw water. The performance of hybrid processes was evaluated with the removal efficiencies of turbidity, ammonia and organic matter. The results indicated that more than 99% of particle count was removed by both hybrid processes and ozonation had no significant effect on its removal. BAC filtration greatly improved the removal of ammonia. Increasing the dissolved oxygen to 30.0 mg/L could lead to a removal of ammonia with concentrations as high as 7.80 mg/L and 8.69 mg/L for Processes A and B, respectively. The average removal efficiencies of total organic carbon and ultraviolet absorbance at 254 nm （UV254, a parameter indicating organic matter with aromatic structure） were 49% and 52% for Process A, 51% and 48% for Process B, respectively. Some organic matter was oxidized by ozone and this resulted in reduced membrane fouling and increased membrane flux by 25%-30%. However, pre-ozonation altered the components of the raw water and affected the microorganisms in the BAC, which may impact the removals of organic matter and nitrite negatively.     

预氯化对铝盐混凝铜绿微囊藻过程中溶解性有机物和残余铝的影响

以铜绿微囊藻为对象,研究了预氯化过程中藻胞内代谢物释放及铝盐混凝除藻过程中残留铝的变化规律.结果表明,氯投量对胞内物质释放量和释放有机物特征有重要影响.与未投加氯的对照体系相比,在较低氯投量时(1~2 mg·L-1),水中有机物浓度升高26%~31%,UV254值升高46%~49%,且有机物主要为中等分子量(2191、2830和3168 Da)和高芳香度的有机物.增大氯投量至3~4 mg·L-1,水中有机物浓度和UV254值有所下降;就不同分子量有机物而言,大分子量有机物(16304 Da)浓度升高而中等分子量有机物(2830、3168和6163 Da)浓度下降,且出现少量小分子量有机物(180 Da).分子量较大或芳香度较高的溶解性有机物在铝盐混凝中可被优先去除.释放到水中的蛋白质能与铝盐形成可溶性蛋白质-混凝剂复合物,从而导致出水铝浓度升高,但增大铝投量可在一定程度上降低残留铝浓度.     

O3/TiO2催化氧化工艺对饮用水中AOC的影响

以陶粒、硅胶和沸石为载体,分别负载二氧化钛（TiO₂）进行臭氧催化氧化去除硝基苯的实验,并对饮用水中生物可同化有机碳（AOC）所代表的小分子有机物(酮、醛、醇和羧酸类物质)的生成情况进行了研究.发现臭氧催化氧化比单纯的臭氧氧化能更彻底地将部分大分子有机物氧化成小分子中间产物,陶粒、硅胶和沸石负载TiO₂ 3种催化剂分别将AOC从大约300　μg·L^-1增加到 674.1　μg·L^-1、847.2　μg·L^-1和882.1　μg·L^-1,并且分别使AOC/TOC从原水的4.68%升高到30.5%、33.21%和46.04%,大大地提高了水中有机物的可生物降解性.如果增加臭氧投量,催化氧化可使小分子有机物部分被氧化,致使水样AOC又略有回降.在这一过程中,AOC-NOX所代表的羧酸类物质急剧增加,达到总AOC的90％以上,取代AOC-P17成为了AOC的主体组成部分.     

用于地下水回灌的再生水预处理工艺研究

将再生水回灌到地下含水层前,需对再生水进行预处理,以防止污染地下水.本研究比较了5种不同的再生水深度处理技术(超滤、臭氧、磁性离子交换树脂(MIEX)及超滤和臭氧、MIEX和臭氧两套组合工艺)对城镇二级出水的净化效果,并通过分析5种工艺对含水层净化效果的影响,评价其作为回灌预处理的可行性.针对再生水中的有机污染物溶解性有机碳(dissolved organic carbon,DOC)及比吸光度(specific ultraviolet absorbance,SUVA),MIEX(投加量为5 mL.L-1)能够去除20%的DOC和10%的SUVA;UF对DOC的去除率低于10%,对SUVA无显著去除效果,单独UF和MIEX预处理对后续含水层对再生水DOC的去除无促进作用;与此不同,臭氧[投加量(O3/DOC)为0.6 mg.mg-1]及其组合工艺对二级出水SUVA的去除率达60%～79%,能显著提高再生水的可生化性,强化土壤对回灌水中有机物的去除效果,使最终出水的DOC降低至1～2mg.L-1.针对再生水中的N素,MIEX(5 mL.L-1)能去除再生水中25%的NO3--N,臭氧能去除再生水中72%的NH4+-N.土壤处理能有效地去除NH4+-N,使出水浓度均在0.5 mg.L-1以下,但对NO3--N无显著去除效果.综合对比分析,在再生水回灌的预处理工艺中,需重点考察预处理对再生水中有机物和NO3--N的去除效果.臭氧和MIEX的组合工艺,能显著提高二级出水的可生化性,并去除部分溶解性有机物及NO3--N,与后续土壤处理具有较好的互补性,较适合用作地下回灌前处理工艺.     

臭氧氧化饮用水过程中可同化有机碳生成的影响因素

研究臭氧化过程中,臭氧投加量、p H值和离子强度对可同化有机碳(assimilable organic carbon,AOC)生成量的影响.结果表明,臭氧投加量在1~5 mg·L~(-1)范围,AOC的生成量随着投加量的增加而增加,但过高的臭氧投加量(9 mg·L~(-1))反而导致AOC生成量下降.p H越高(6~9),AOC的生成量也越高.AOC的生成量随着离子强度的升高而下降.臭氧氧化强疏组分AOC的生成量最高,其次为弱疏,而极亲和中亲最低.研究发现,AOC的生成量与小分子有机物的SUVA有密切的关系,较低的SUVA产生较多的AOC.     

臭氧氧化深度处理二级处理出水的研究

以某城市污水处理厂二级处理出水为原水,研究了臭氧氧化深度处理对水中残留有机物以及病原微生物的降解和去除效果.结果表明,臭氧投加量达到6mg/L时,DOC、UV254、色度的去除率分别为15.49%、36.36%、73.61%,环境激素类痕量有机物邻苯二甲酸二丁酯(DBP)和邻苯二甲酸二(2-乙基己基)酯(DEHP)的去除率分别为37.29%和14.6%,三维荧光光谱荧光峰的各区域有机物质平均去除率在80%以上,DBP出水浓度为2.64mg/L,DEHP出水浓度为1.4mg/L,满足《城市污水再生利用地下水回灌水质》(GB/T 19772-2005)的标准.臭氧投加量达到10mg/L时,出水中指示性微生物粪大肠菌群仍接近103CFU/L,5mg/L有效氯消毒后出水粪大肠菌群仍接近10CFU/L,6mg/L臭氧与5mg/L有效氯组合消毒出水的粪大肠菌群下降至3CFU/L,满足《城市污水再生利用景观环境用水水质》(GB/T 18921-2002)的标准.三卤甲烷(THMs)的生成量随着有效氯投加量的增加而增加,臭氧与氯组合消毒过程与氯单独消毒过程相比,THMs生成量减少了78.08%.     

Comparison of different combined treatment processes to address the source water with high concentration of natural organic matter during snowmelt period

The source water in one forest region of the Northeast China had very high natural organic matter (NOM) concentration and heavy color during snowmelt period. The efficiency of five combined treatment processes was compared to address the high concentration of NOM and the mechanisms were also analyzed. Conventional treatment can hardly remove dissolved organic carbon (DOC) in the source water. KMnO₄ pre-oxidization could improve the DOC removal to 22.0%. Post activated carbon adsorption improved the DOC removal of conventional treatment to 28.8%. The non-sufficient NOM removal could be attributed to the dominance of large molecular weight organic matters in raw water, which cannot be adsorbed by the micropore upon activated carbon. O₃ + activated carbon treatment are another available technology for eliminating the color and UV₂₅₄ in water. However, its performance of DOC removal was only 36.4%, which could not satisfy the requirement for organicmatter. The limited ozone dosage is not sufficient to mineralize the high concentration of NOM. Magnetic ion-exchange resin combined with conventional treatment could remove 96.2% of color, 96.0% of UV₂₅₄ and 87.1% of DOC, enabling effluents to meet the drinking water quality standard. The high removal efficiency could be explained by the negative charge on the surface of NOM which benefits the static adsorption of NOM on the anion exchange resin. The results indicated that magnetic ion-exchange resin combined with conventional treatment is the best available technology to remove high concentration of NOM.     

MIEX中试实验对二级出水中有机物去除的3DEEM解析

利用三维荧光光谱研究了磁性离子交换树脂（magnetic ion exchange resin,MIEX）对污水厂二级出水中有机物的去除特征.结果表明,磁性树脂处理二级出水过程中,两级反应过程和进水流量对DOC和UV254有较显著的去除效果,去除率分别达到25.5%～53.5%和27.6%～52.2%,其中50 L.h-1流量条件下,出水中DOC和UV254浓度分别为3.29 mg.L-1和0.057cm-1.水中芳香族蛋白质或酚类物质和类腐殖酸物质荧光强度较高,磁性树脂使二级出水中色氨酸类芳香族蛋白质、芳香族蛋白质、腐殖酸类荧光强度分别下降38.2%、85.8%和85.7%,腐殖酸和富里酸峰消失,并露出溶解性微生物代谢产物荧光峰.不同进水流量条件下,色氨酸类芳香族蛋白质荧光强度下降率和芳香族蛋白质或酚类物质荧光强度下降率与进水流量的负相关性最好,50～100 L.h-1流量条件对各类荧光物质的去除率影响最大.磁性树脂与二级出水中色氨酸类芳香族蛋白质和芳香族蛋白质或酚类物质有更好的线性置换关系（R2=0.834 8）,磁性树脂对二级出水中芳香族蛋白质或酚类物质的置换作用则最显著（a=850.2）.     

制药废水二级出水中溶解性有机物混凝去除特性研究

制药废水二级出水中溶解性有机物(DOM)由于组成复杂、难去除、具有多异质性和分散性,是污水深度处理与回用的主要去除对象和关键限制因子.本论文以发酵制药废水二级出水的DOM为研究对象,采用投加聚合氯化铝(PAC)混凝剂去除DOM,考察混凝剂投加量和混凝pH值对去除效果的影响,并结合分子量分级、亲疏水性分级以及三维荧光光谱-平行因子分析方法等对DOM进行了系统表征和分析,进一步阐述混凝过程DOM的去除特征.结果表明,PAC投加量为250 mg·L~(-1)、pH=7时,混凝沉淀30 min对DOC、UV_(254)、色度和浊度的去除率分别为13.05%±0.29%、23.65%±0.75%、12.66%±1.34%、63.67%±0.89%;混凝对分子量10 kDa的组分和疏水中性(HON)组分去除效果分别为50.33%±0.98%、21.56%±0.42%,而对分子量1 kDa组分去除率较低为2.26%±0.12%;三维荧光光谱-平行因子分析将制药废水二级出水分为2个类腐殖质组分(C1、C3)和1个类蛋白组分(C2),混凝对类腐殖酸组分(C1)最大荧光强度去除率(F_(max))最高为46.22%,而亲水性的小分子和蛋白类物质混凝去除效果较差.     

Removal of fluorescence and ultraviolet absorbance of dissolved organic matter in reclaimed water by solar light

Storing reclaimed water in lakes is a widely used method of accommodating changes in the consumption of reclaimed water during wastewater reclamation and reuse. Solar light serves as an important function in degrading pollutants during storage, and its effect on dissolved organic matter(DOM) was investigated in this study. Solar light significantly decreased the UV_(254) absorbance and fluorescence(FLU) intensity of reclaimed water.However, its effect on the dissolved organic carbon(DOC) value of reclaimed water was very limited. The decrease in the UV_(254) absorbance intensity and FLU excitation–emission matrix regional integration volume(FLU volume) of reclaimed water during solar light irradiation was fit with pseudo-first order reaction kinetics. The decrease of UV_(254) absorbance was much slower than that of the FLU volume. Ultraviolet light in solar light had a key role in decreasing the UV_(254) absorbance and FLU intensity during solar light irradiation. The light fluence-based removal kinetic constants of the UV_(254) and FLU intensity were independent of light intensity. The peaks of the UV_(254) absorbance and FLU intensity with an apparent molecular weight(AMW) of 100 Da to 2000 Da decreased after solar irradiation, whereas the DOC value of the major peaks did not significantly change.     

Fouling of nanofiltration membrane by effluent organic matter： Characterization using different organic fractions in wastewater

The UF membrane with molecular weight cutoff (MWCO) ranging from 2 kDa to 100 kDa and XAD-8 resin were employed to identify the characteristic of molecular weight (MW) distribution of wastewater effluent organic matter (EfOM) in terms of TOC and UV254, as well as the amounts of the hydrophilic/hydrophobic organic fractions in different MW ranges. Then, the nanofiltration (NF) membrane fouling experiments were carried out using the above fractionated water to investigate the effect of MW distribution and hydrophilic/hydrophobic characteristics of EfOM on the membrane flux decline using the fractionated water samples above. The experimental results have shown that 45.61% of the total organics belongs to the low MW one, among which the percentage of the hydrophilic organics with low MW (less than 2 kDa) was up to 28.07%, while that of the hydrophobic organics was 17.54%. In particular, the hydrophilic fraction was found to be the most abundant fraction in the effluents. MW distribution has a significant effect on the membrane fouling. When the MW was less than 30 kDa, the lower the MW, the larger was the specific flux decline, while in the case of MW higher than 30 kDa, the higher the MW, the larger was the specific flux decline, and the decline degree of low MW organics was larger than the high MW one. With the same MW distribution range, specific flux decline of the hydrophilic organic was considerably slower than that of the hydrophobic organic, which indicated that the hydrophobic organic fractions dominantly contribute to the flux decline.     

臭氧氧化二级出水有机物可生化性研究

通过臭氧氧化北京3个典型城市污水处理厂二级出水,考察臭氧对二级出水有机物可生化性的提高作用.采用批量试验方法,通过调整臭氧投加时间控制臭氧投加浓度为2、4、6、8、10 mg/L.结果表明,UV254与比紫外消光度SUVA(UV254/DOC)随臭氧投加量而降低,臭氧投加量为6 mg/L时,UV254与SUVA分别降低54.4%与56.6%以上;BOD5/COD、BDOC与BDOC/DOC分别提高30%、360%与360%以上,表明适当的臭氧投加量可提高二级出水难降解有机物的可生化性;三维荧光指纹光谱分析臭氧氧化前后二级出水中有机物的变化规律,表明该污水处理厂二级出水的荧光有机物主要为芳香族蛋白类物质和腐殖质类物质,臭氧可显著去除该类有机物.