非均相催化臭氧处理高浓度制药废水的研究

非均相催化臭氧是一种对高浓度制药废水进行预处理的有效方法.本研究采用单一活性炭吸附、单一臭氧氧化和臭氧/活性炭联用3种体系对实际制药废水进行预处理,并对处理过程中的工艺参数进行优化.结果表明,相比单一活性炭吸附和单一臭氧降解体系,臭氧/活性炭联用体系能显著提高COD、TOC的去除率及BOD5/COD值,并显示出良好的协...     

活性炭催化臭氧氧化扑热息痛的机制研究

采用活性炭催化臭氧处理典型解热镇痛药扑热息痛,研究了活性炭/臭氧体系的协同效应,优化了工艺参数,分析了降解产物并探讨了降解机制.结果表明:在臭氧活性炭体系下,反应60 min后,TOC的去除率为55.11%,效果明显优于臭氧体系的20.22%和活性炭体系的27.39%之和,具有明显的协同作用,并且BOD5/COD比值从反应前的0.086提高到反应后的0.543,可生化性显著提高.研究了pH、臭氧投加量、污染物初始浓度和活性炭投加量等操作参数的作用规律.在此基础上,探讨了臭氧活性炭体系在不同pH下的催化反应机制,发现在酸性条件下是吸附和臭氧直接氧化共同作用,在碱性条件下以活性炭催化臭氧氧化为主.     

Effect of different molecular weight organic components on the increase of microbial growth potential of secondary effluent by ozonation

Ozonation has been widely applied in advanced wastewater treatment. In this study, the effect of ozonation on assimilable organic carbon （AOC） levels in secondary effluents was investigated, and AOC variation of different molecular weight （MW） organic components was analyzed. Although the removal efflciencies were 47%-76% and 94%-100% for UV2s4 and color at ozone dosage of 10 mg/L, dissolved organic carbon （DOC） in secondary effluents was hardly removed by ozonation. The AOC levels increased by 70%-780% at an ozone dosage range of 1-10 mg/L. AOC increased significantly in the instantaneous ozone demand phase, and the increase in AOC was correlated to the decrease in UV254 during ozonation. The results of MW distribution showed that, ozonation led to the transformation of larger molecules into smaller ones, but the increase in low MW （〈1 kDa） fraction did not contribute much to AOC production. The change of high MW （〉100 kDa and 10-100 kDa） fractions itself during ozonation was the main reason for the increase of AOC levels. Furthermore, the oxidation of organic matters with high MWs （〉 100 kDa and 10-100 kDa） resulted in more AOC production than those with low MWs （1-10 kDa and 〈1 kDa）. The results indicated that removing large molecules in secondary effluents could limit the increase of AOC during ozonation.     

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%.     

臭氧/活性炭协同作用去除二级出水中DON

为探讨臭氧氧化和活性炭吸附对城市污水厂二级出水中溶解性有机氮(DON)的去除机制,首先测定二级出水DON、溶解性有机炭(DOC)、UV254、pH值等指标.接着通过臭氧氧化试验和活性炭吸附试验来考察二级出水中DON、DOC和UV254变化,以及DON分子量分布和DON亲疏水性变化,并应用三维荧光光谱对二级出水中DON变化进行表征.结果表明,当臭氧投加量为8mg/L,DON的去除率大约为33.9%,DOC和UV254去除率约21.2%、66.7%;当活性炭投加量为2.0g/L,DON、DOC和UV254的去除率大约为43.4%、27.6%、92.2%;臭氧氧化和活性炭吸附组合试验时,对DON的去除率大约为83.3%和81.5%;臭氧氧化提高小分子量( 20kDa)的DON所占比例;活性炭吸附降低小分子量( 20kDa)DON所占比例为;臭氧氧化和活性炭吸附都提高亲水性DON所占比例,而降低疏水性和过渡性DON所占比例;三维荧光光谱证实,二级出水中DON变化与3个主要峰有关,分别代表物质为色氨酸类蛋白质、芳香族类蛋白质和富里酸类物质.     

Disinfection byproduct formation from algal organic matters after ozonation or ozone combined with activated carbon treatment with subsequent chlorination

Algal organic matter (AOM), including extracellular organic matter (EOM) and intracellular organic matter (IOM) from algal blooms, is widely accepted as essential precursors of disinfection byproducts (DBPs). This study evaluated the effect of ozonation or ozone combined with activated carbon (O₃-AC) treatment on characteristic alternation and DBP formation with subsequent chlorination of Chlorella sp.. The effects of pH and bromide concentration on DBP formation by ozonation or O₃-AC treatment were also investigated. Results showed that the potential formation of DBPs might be attributed to ozonation, but these DBP precursors could be further removed by activated carbon (AC) treatment. Moreover, the formation of target DBPs was controlled at acidic pH by alleviating the reactions between chlorine and AOM. Besides, the bromide substitution factor (BSF) value of trihalomethanes (THMs) from EOM and IOM remained constant after AC treatment. However, THM precursors could be significantly decreased by AC treatment. The above results indicated that O₃-AC was a feasible treatment method for algal-impacted water.     

城市污水再生处理过程中臭氧氧化脱色及稳定性研究

针对城市污水再生处理臭氧氧化脱色效果及稳定性开展了相关研究.结果表明,臭氧氧化处理可以有效降低二级出水的表色与真色.在自然条件模拟过程中,不同臭氧投加量的水样22 d后真色并没有明显变化,表色、叶绿素a和浊度变化呈现出良好的一致性.当臭氧投加量小于6 mg·L-1时,水样表色在12 d内缓慢增加,之后快速上升直至22 d后达到最大.低剂量的臭氧处理(小于6 mg·L-1)反而会促进藻类的繁殖,加剧水体色度的不稳定性.然而,当臭氧投加量大于8 mg·L-1时,可以明显延长水样的复色时间,表色在18 d后才略微上升.水体的色度和浊度变化主要由藻类的生长和繁殖引起的,高的臭氧剂量能够维持水体色度稳定性.因此,推荐城市污水再生处理过程臭氧投加量为8 mg·L-1.     

活性炭催化臭氧氧化处理染料废水生化出水研究

采用饱和活性炭作为臭氧氧化催化剂,对染料废水生化出水进行深度处理.以废水COD、DOC去除率为指标,考察饱和活性炭对臭氧的催化效果.使用6种不同的活性炭作为催化剂(编号1^#~6^#),并将6^#活性炭采用KMnO₄、NaOH、ZnCl₂、H₂SO₄、H₃PO₄进行表面处理,在活性炭的孔体积、酸碱基团等表面性质测定的基础上,探讨活性炭性质与催化臭氧化效率的关系.结果显示,活性炭催化效果与大孔体积密切相关;另一方面,使用微孔膜片减小臭氧气泡尺寸,增大臭氧的传质面积,提高臭氧利用率,可以改善臭氧/活性炭催化氧化处理效果.     

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.     

Degradation of endocrine disruptor bisphenol A in drinking water by ozone oxidation

The ozone oxidation of endocrine disruptor bisphenol A in drinking water was investigated. A stainless completely mixed reactor was employed to carry out the degradation experiments by means of a batch model. With an initial concentration of 11.0 mg/L, the removal efficiencies of BPA (bisphenol A) could be measured up to 70%, 82%, and 90% when the dosages of ozone were 1, 1.5, and 2 mg/L, respectively. The impacts on BPA degradation under the conditions of different ozone dosages, water background values, BPA initial concentrations, and ozone adding time were analyzed. The results showed that ozone dosage plays a dominant role during the process of BPA degradation, while the impact of the contact time could be ignored. UV wavelength scanning was used to confirm that the by-products were produced, which could be absorbed at UV254. The value of UV254 was observed to have changed during the ozonation process. Based on the change of UV254, it could be concluded that BPA is not completely degraded at low ozone dosage, while shorter adding time of total ozone dosage, high ozone dosage, and improvement of dissolved ozone concentration greatly contribute to the extent of BPA degradation. The effects of applied H₂O₂ dose in ozone oxidation of BPA were also examined in this study. The O₃-H₂O₂ processes proved to have similar effects on the degradation of BPA by ozone oxidation. Translated from Environmental Science, 2006, 27(2): 294–299 [译自: 环境科学]     

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.     

活性炭催化臭氧化表面活性剂的研究

以十二烷基苯磺酸钠(SDBS)为目标物,研究了臭氧氧化、活性炭吸附、活性炭催化臭氧化对SDBS的去除特性,并研究了天然有机物(NOMs)对催化臭氧降解SDBS的影响.结果表明,活性炭催化臭氧化较单独使用臭氧或活性炭对SDBS去除效率有显著提高,而且最有效阶段在反应初的20 min之内及臭氧和反应物浓度较高的反应阶段.时...     

Degradation and detoxification of microcystin-LR in drinking water by sequential use of UV and ozone

Microcystins (MCs) produced by cyanobacteria are strong hepatotoxins and classified as possible carcinogens.MCs pose a considerable threat to human health through tainted drinking and surface waters.Herein filtrated water from a waterworks in Harbin,China,was spiked with microcystin-LR (MC-LR) extracted from a toxic scum of microcystis aeruginosa,and the spiked sample waters were treated using UV irradiation with consequent ozonation process (UV/O3),compared with ozonation at a dose range commonly applied in water treatment plants,UV irradiation at 254 nm and UV irradiation combined with ozonation (UV+O3),respectively.The remaining of toxins were analyzed using high-performance liquid chromatography and also determined using a protein phosphatase type 2A inhibition assay,which was utilized to evaluate the reduction in toxicity.Results indicated that in comparison to other three processes (O3,UV,and UV+O3),UV/O 3 process could effectively decrease both the concentration and toxicity of MC-LR at 100 μg/L level after 5 min UV irradiation with consequent 5 min ozonation at 0.2 mg/L (below 1 μg/L),while 0.5 mg/L ozone dose was required for the level below 0.1 μg/L.The addition of an UV treatment step to the existing treatment train may induce significant transformation of micropollutants and breaks down the natural organic matters into moieties unfavorable for ozone decomposition,stabilizing the ozone residual.These findings suggested that sequential use of UV and ozone may be a suitable method for the removal of these potentially hazardous microcystins from drinking water.     

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.     

微气泡臭氧催化氧化-生化耦合工艺深度处理煤化工废水

采用微气泡臭氧催化氧化-生化耦合工艺对煤化工废水生化出水进行深度处理,考察耦合系统处理性能及不同臭氧投加量和进水COD量比值的影响.结果表明,微气泡臭氧催化氧化处理能够有效降解废水中难降解含氮芳香族污染物,去除部分COD并释放氨氮,显著提高废水可生化性,臭氧利用率接近100%,无需进行臭氧尾气处理;同时为生化处理提供充足溶解氧(DO),实现生化处理对COD和氨氮的进一步有效去除,生化处理无需曝气.在系统出水回流比为30%、臭氧投加量和进水COD量之比为0.44 mg·mg~(-1)的运行条件下,耦合系统处理性能较好.微气泡臭氧催化氧化处理对COD去除率为42.5%,臭氧消耗量与COD去除量比值为1.38 mg·mg~(-1),臭氧利用率为98.0%;生化处理对COD去除率为42.3%;耦合系统整体COD去除率为66.7%,最终平均出水COD浓度为91.5 mg·L~(-1),估算整体臭氧消耗量与COD去除量比值为0.68 mg·mg~(-1),具有较优的技术经济性能.     

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.     

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.     

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.     

紫外光和活性炭对有机物臭氧化的协同催化作用

以城市二级出水中微量有机污染物为处理的目标物质,通过静态试验分别考察了不同催化条件下臭氧对水中有机污染物的降解效果.结果表明:协同催化反应器对水体在254 nm处紫外吸光度(E₂₅₄)的去除率达87.40%,对COD_Cr的去除率可达59.79%,对臭氧的利用率可达到91.4%,因此,254 nm紫外光和活性炭对水中微量有机污染物的臭氧化过程具有协同催化作用,并大大提高了系统对臭氧的利用率;受OH－影响,碱性条件下O₃/UV/C工艺对COD_Cr和E₂₅₄的去除效果好于中性和酸性条件;不同自由基捕捉剂对臭氧化过程的影响证明,在紫外光和活性炭的协同催化作用下,臭氧分解出以羟基自由基为主的多种氧化性自由基,因此水中有机污染物的氧化降解是多种自由基反应的结果.      

臭氧氧化反渗透浓缩垃圾渗滤液动力学

采用臭氧氧化法处理经反渗透膜处理后的浓缩垃圾渗滤液,并建立了氧化降解反应动力学模型.结果表明,氧化降解初始反应速率主要与初始pH、臭氧投量、反应温度和初始COD有关.在pH 8.0,温度30℃,臭氧投量5.02 g/h,反应时间90 min的条件下,反渗透浓缩渗滤液的COD去除率达到67.6%;并且在pH为2.0～8....