O3／UV法降解水中对硝基酚

研究了臭氧，臭氧／紫外光法卫解对硝基酚过程中各种操作条件得，气相臭氧浓度，温度，初始ｐＨ值，初始ＴＯＣ值以及紫外光强度等的影响。臭氧与紫外光相结合对去除ＴＯＣ有协同效应。根据实验确定出这一过程的宏观动力学方程。     

铈负载SBA-15分子筛催化臭氧氧化水中环丙沙星

通过水热法合成纯硅介孔分子筛SBA-15,并采用等体积浸渍法制备Ce负载SBA-15分子筛催化剂(Ce/SBA-15),将其应用于催化臭氧氧化环丙沙星(CIP).小角X射线衍射(XRD)、透射电镜(TEM)表征结果表明,Ce/SBA-15保持了纯硅SBA-15有序的介孔结构.Ce/SBA-15催化臭氧氧化环丙沙星(CIP)结果显示,催化剂有良好的活性,对环丙沙星的矿化率为63.3%,比单独臭氧氧化高出22.9%;随着铈负载量增加,催化剂活性呈现先增大后减小趋势,负载量为2%时催化效果最佳;TOC去除率随着反应温度增加而提高;溶液初始pH对反应有显著的影响,pH=5.01时TOC去除率最大.以水杨酸作为羟基自由基(·OH)捕获剂,用比色法测定·OH产量为0.0072 mmol·L~(-1).溶液中投加1 mmol·L~(-1)磷酸根时,催化臭氧氧化中TOC去除率降低了25.8%,催化效果受到明显抑制,表明·OH的生成发生在Ce/SBA-15表面.     

ZnO-MgO/Al2O3吸附-臭氧催化氧化处理难降解有机废水

以活性氧化铝为载体,采用浸渍法制备催化剂,对甲基橙及草酸模拟废水进行处理.在中性条件下,臭氧催化氧化比单独臭氧氧化能提前30 min使得甲基橙溶液褪色,反应105 min时,臭氧催化氧化对TOC的去除率高达96.53%,比单独使用臭氧氧化对甲基橙TOC去除率提高了47.19%,在处理草酸废水时臭氧催化氧化对TOC去除率高达80.59%,比单独使用臭氧氧化对草酸TOC去除率提高了59.14%.在处理甲基橙及草酸的小试实验中催化剂对有机污染物的吸附作用起到了加快反应进行的作用.在对垃圾渗滤液超滤出水时,O₃与COD质量比为1:1时,臭氧催化氧化对COD去除率为49.09%,比单独使用臭氧氧化提高36.37%,臭氧催化氧化对TOC的去除率是单独使用臭氧氧化的2.54倍,在处理垃圾渗滤液纳滤浓水时,臭氧催化氧化对COD去除率高达88.72%,比单独使用臭氧氧化提高37.60%,并且臭氧催化氧化对TOC的去除率是单独臭氧氧化的1.6倍.臭氧催化氧化反应过程中产生的羟基自由基对有机物更快的反应速率.     

催化臭氧氧化去除垃圾渗滤液中难降解有机物的研究

研究了Fe(Ⅱ),Mn(Ⅱ),Cu(Ⅱ)作用下,均相催化臭氧氧化去除垃圾渗滤液中高浓度的腐殖质.分析催化剂用量、溶液pH值对腐殖质催化臭氧氧化降解的影响.结果表明,与单纯臭氧氧化比较,催化臭氧氧化对UV254和色度去除率无明显改善,但可明显提高以TOC和CODCr表征的有机物去除率;当投加催化剂过量时,以TOC和CODCr表征的有机物去除率虽降低,但仍有促进作用.但Fe2 的过量投加将明显抑制UV254和色度的去除效果.在碱性条件下,催化臭氧氧化法具有更好的去除效果.三种催化剂催化效果为Cu(Ⅱ)＞Mn(Ⅱ)＞Fe(Ⅱ).采用Cu(Ⅱ)催化臭氧氧化处理实际渗滤液生化处理出水,对CODCr,色度和UV254都显示出较好的去除效果.     

臭氧氧化法去除水中邻苯二甲酸二甲酯的初步研究

研究了水溶液中邻苯二甲酸二甲酯的臭氧氧化，考察了pH值、温度、臭氧用量等对反应的影响，结果表明：臭氧氧化使溶液的总有机碳（TOC）减少，并使紫外（UV）吸收大大降低，毛细管电泳（CE）分析证明有邻苯二甲酸的中间产物产生，采用Mn(Ⅱ）催化臭氧氧化，TOC去除率大大提高。     

冰相中对氯苯酚光转化的研究

以125W高压汞灯为光源,在低温(-12--14℃)条件下,研究了紫外光作用下冰相中对氯苯酚(4-CP)光转化反应.考察了各种因素对冰相中4-CP光转化的影响以及冰相中4-CP光转化的动力学和机理.结果表明,4-CP初始浓度,pH值和光强对冰相中4-CP光转化都有较大影响.在180min内,4-CP和TOC的转化率分别达到了96%和30%,在本实验条件下,4-CP在冰相中光转化的产物和机理与其在溶液中有所不同.     

甲醛光催化降解与过氧化氢生成的相关性研究

分别采用两种光催化剂(TiO2与Pd/TiO2)和三种紫外光源(黑光灯、杀菌灯、臭氧灯)分解水溶液中的甲醛,同时以酶法测定光催化降解过程中生成的低浓度过氧化氢.发现波长较短的紫外光源生成过氧化氢的浓度较高.当以臭氧灯为光源时,无论是否有催化剂存在,生成的过氧化氢浓度都在50mmol·m-3以上,因为185nm以下的紫外光可以直接由水与溶解氧生成臭氧,而后生成过氧化氢.不管有无催化剂存在,在臭氧灯作用下,甲醛溶液中生成的过氧化氢浓度高于纯水中生成的过氧化氢浓度.但是,在以黑光灯或臭氧灯为光源时,上述结果正好相反.此外,对于每种光源而言,当采用Pd/TiO2代替TiO2时,甲醛的分解和过氧化氢的生成都得到加强.甲醛光催化分解速率与相同条件下纯水中过氧化氢的生成速率呈正比,表明光催化降解的活性与光催化生成过氧化氢的能力近似呈正相关.     

高寒区华北落叶松林生长季内地表凋落物层碳氮磷化学计量特征

为了解青海高寒区华北落叶松地表凋落物不同分解层养分在生长季内的变化特征,分别在2015年5月1日(5/01)、6月15日(6/15)、7月30日(7/30)、9月13日(9/13)和10月28日(10/28)进行采样,将凋落物层分为未分解层(Fresh litter layer,LL)、半分解层(Fragmented litter layer,FL)和全分解层(Humified litter layer,HL),对华北落叶松凋落物总有机碳(Total organic carbon,TOC)、全氮(Total nitrogen,TN)和全磷(Total phosphorus,TP)及其化学计量比进行测定分析.结果显示:生长季内凋落物的TOC、TN、TOC/TP、TOC/TN和TN/TP均表现为LL FL HL,且各分解层之间差异显著,TP含量各分解层之间差异不显著.在生长季内,TOC、TN和TP含量及其化学计量比表现出不同的变化规律,但最大值均出现在5/01.凋落物分解层与采样时间对TOC、TN和TP储量及其化学计量特征影响的交叉分析表明,TOC、TOC/TN、TOC/TP和TN/TP的变异主要受分解层的影响,TN的变异主要受采样时间的影响,TP的变异主要受分解层和采样时间交互作用的影响,且采样时间对TP的变异没有产生显著影响.凋落物TOC、TN和TP含量及TOC/TN、TOC/TP和TN/TP的Pearson相关分析显示,TOC和TN与TOC/TN、TOC/TP和TN/TP之间呈极显著正相关关系(P 0.01),P与TOC/TN没有相关关系(P 0.05),与TOC/P显著负相关(P 0.05),与TN/TP极显著正相关(P 0.01).本研究表明,青海高寒区华北落叶松凋落物在分解过程中TOC、TN和TP化学计量均表现出明显的季节变化,季节变化和分解程度将显著影响凋落物分解过程中TOC、TN和TP含量;TOC和TN含量是影响TOC、TN和TP化学计量比的关键因子.(图1表4参42)     

颗粒活性炭催化臭氧氧化降解活性黑5

本文以深度处理后印染废水为配水模拟实际废水,对颗粒活性炭催化臭氧氧化降解活性黑5进行了研究.用低温N_2吸附-脱附等温线、SEM-EDS等对颗粒活性炭进行了表征,发现颗粒活性炭比表面积高达931 m~2·g~(-1).考察了颗粒活性炭吸附性能和催化臭氧活性,结果表明单独臭氧与颗粒活性炭催化臭氧脱色率在反应30 min内均高达100%.反应1h时,5 g·L~(-1)、10 g·L~(-1)颗粒活性炭催化臭氧TOC去除率分别为57%、74%,比单独臭氧高出33%和50%,颗粒活性炭具有良好的催化效果,能提高对污染物的矿化效果.颗粒活性炭促进了溶解性臭氧分解,重复使用6次后10 g·L~(-1)活性炭在反应时间为2 h时染料废水TOC去除率均能稳定在85%左右,多次利用后活性炭的催化活性没有明显降低.EPR检测表明,其主要机制为颗粒活性炭能够稳定地催化臭氧分子分解产生羟基自由基,实现污水中有机物的矿化.     

纳米ZnO光催化降解溴化乙锭(EB)的初步研究

对ZnO光催化降解溴化乙锭(EB)中的光源、反应介质、pH值、光催化剂用量、光照时间及氧化剂的加入等因素进行了考察.结果表明,在日光和紫外光照射下,EB都能得到较好的降解.在EB初始浓度50mg·l-1,pH 9的水溶液中,紫外光照射240min,ZnO(80mg)光催化降解EB的降解率可达到92.9%.     

Optimization of the O3/H2O2 process with response surface methodology for pretreatment of mother liquor of gas field wastewater

• Real ML-GFW with high salinity and high organics was degraded by O₃/H₂O₂ process. • Successful optimization of operation conditions was attained using RSM based on CCD. • Single-factor experiments in advance ensured optimal experimental conditions. • The satisfactory removal efficiency of TOC was achieved in spite of high salinity. • The initial pH plays the most significant role in the degradation of ML-GFW. The present study reports the use of the O₃/H₂O₂ process in the pretreatment of the mother liquor of gas field wastewater (ML-GFW), obtained from the multi-effect distillation treatment of the gas field wastewater. The range of optimal operation conditions was obtained by single-factor experiments. Response surface methodology (RSM) based on the central composite design (CCD) was used for the optimization procedure. A regression model with Total organic carbon (TOC) removal efficiency as the response value was established (R² = 0.9865). The three key factors were arranged according to their significance as: pH>H₂O₂ dosage>ozone flow rate. The model predicted that the best operation conditions could be obtained at a pH of 10.9, an ozone flow rate of 0.8 L/min, and H₂O₂ dosage of 6.2 mL. The dosing ratio of ozone was calculated to be 9.84 mg O₃/mg TOC. The maximum removal efficiency predicted was 75.9%, while the measured value was 72.3%. The relative deviation was found to be in an acceptable range. The ozone utilization and free radical quenching experiments showed that the addition of H₂O₂ promoted the decomposition of ozone to produce hydroxyl radicals (·OH). This also improved the ozone utilization efficiency. Gas chromatography-mass spectrometry (GC-MS) analysis showed that most of the organic matters in ML-GFW were degraded, while some residuals needed further treatment. This study provided the data and the necessary technical supports for further research on the treatment of ML-GFW.     

Treatment of textile dye wastewater using ozone combined with photocatalyst

Ozonolysis combined with photocatalysis was used as a new approach for the treatment of textile dye wastewater containing azo dyes. The color reduction was very fast when only ozone was used for the treatment, but a 90% Total Organic Carbon (TOC) reduction was obtained only during a combined treatment. Reactive Black 5 dye containing two different percentages of NaCl was used for the experiment. The color reduction was fast in the neutral and basic pH. However for a fast TOC reduction acidic pH was found to be more effective. On‐line UV‐Vis spectrophotometry was used to measure the color reduction.     

硝基苯水溶液的超声波降解动力学

以硝基苯为唯一底物，选择超声功率200W，400W，600W，800W，研究了超声降解硝基苯水溶液的动力学，实验证明，硝基苯超声降解属假一级动力学反应，同时得到了不同超声功率下的降解速率常数，以及速率常数与超声功率的线性相关关系和含有超声功率的动力学方程，采用色质分析，确定了硝基苯降解产物中含有邻硝基酚和对硝基酚。     

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.     

臭氧污泥减量过程中混合液各参数的变化

实验用污泥的初始浓度(MLSS)分别限定为4g/L、7g/L和11g/L,用以探讨不同浓度下臭氧氧化过程中COD、N和P浓度的变化。结果表明:臭氧氧化过程中,MLSS和MLVSS基本呈线性下降;臭氧对污泥细胞的溶解可以引起混合液中COD、N和P浓度的升高,升高速率受污泥浓度和臭氧浓度影响较大;TKN和硝态氮是N的主要存在形式,TKN和TN随时间均呈先增加后趋缓的变化规律;臭氧对氨氮和亚硝酸盐氮有较强的氧化能力,二者浓度均呈先增大后减小的规律;而硝酸盐氮呈一直增加趋势;臭氧对COD的氧化也很明显,表现为COD的增加速率随氧化时间的增加而不断降低;总磷的浓度基本呈线性增加,单位质量污泥的总磷释放量差异不大;臭氧对MLSS的彻底减量会引起臭氧溶胞利用率的降低,因此应该合理控制臭氧化反应的时间。     

偏电压对Ti/TiO2光电催化氧化富里酸的影响

采用光电催化反应器对水中天然有机物富里酸(FA)进行降解试验,考察了外加阳极偏电压对光电催化反应器降解富里酸的影响.结果表明,当外加电压为1.2V时,具有最佳的UV254和有机碳TOC去除率,当反应时间为2h时,富里酸的UV254和总有机碳TOC的去除率分别为77.4%和45.4%.另外,在反应初期(前1h内)富里酸光电催化反应动力学常数主要受外加偏电压的影响.     

Impacts of advanced treatment processes on elimination of antibiotic resistance genes in a municipal wastewater treatment plant

The distributions of ARGs were monitored in a WWTP in Harbin during six months. CASS had the best removal efficacy of ARGs compared to other processes in the WWTP. UV disinfection could effectively control the HGT. AGAC significantly remove ARGs and organics due to its high absorption capacity. Combination of ozone and AGAC significantly improve removal of ARGs and organics. Antibiotic resistance genes (ARGs) pose a serious threat to public health. Wastewater treatment plants (WWTPs) are essential for controlling the release of ARGs into the environment. This study investigated ARG distribution at every step in the treatment process of a municipal WWTP located in Harbin for six consecutive months. Changes in ARG distribution involved in two advanced secondary effluent treatment processes, ozonation and granular activated carbon (GAC) adsorption, were analyzed. Biological treatment resulted in the highest ARG removal (0.76–1.94 log reduction), followed by ultraviolet (UV) disinfection (less than 0.5-log reduction). Primary treatment could not significantly remove ARGs. ARG removal efficiency increased with an increase in the ozone dose below 40 mg/L. However, amorphous GAC (AGAC) adsorption with a hydraulic retention time (HRT) of 1 h showed better removal of ARGs, total organic carbon (TOC), total nitrogen (TN), and total phosphorus (TP) than ozonation at a 60 mg/L dose. UV treatment could efficiently reduce the relative ARG abundance, despite presenting the lowest efficiency for the reduction of absolute ARG abundance compared with GAC and ozone treatments. The combination of ozone and AGAC can significantly improve the removal of ARGs, TOC, TN and TP. These results indicate that a treatment including biological processing, ozonation, and AGAC adsorption is a promising strategy for removing ARGs and refractory organic substances from sewage.     

EDU对臭氧胁迫下菠菜急性伤害症状和光合特性的影响

如何减轻近地层臭氧(O3)体积分数持续升高对作物的影响是污染生态学研究的热点之一。运用改进的开顶式气室(open-top chambers,OTCs)装置,对嘉兴尖叶、嘉兴圆叶和荷兰35三种菠菜(Spinacia oleracea L.)进行连续5 d,每天8 h的臭氧急性暴露处理,且在暴露前24 h喷施300 mg.L-1质量浓度抗氧化剂ethylenediurea(EDU),研究EDU对臭氧胁迫下菠菜急性伤害症状及光合特性的影响。结果表明:(1)菠菜暴露于高体积分数O3时,叶片出现失水干枯、坏死斑等急性伤害症状,光合色素含量、气体交换参数和光响应参数显著降低,且下降幅度和暴露体积分数呈正相关。(2)菠菜经EDU处理后,光合特性参数明显提高。对O3和EDU作双因子分析发现,随着臭氧体积分数升高,EDU对叶片气体交换参数的影响显著,而对其他参数的影响不明显。由此可见,尽管EDU的防护作用对高体积分数的O3胁迫是有限的,但喷施EDU仍能有效减轻O3对植物的伤害,这对缓解农田生态系统O3污染灾害有积极意义。     

紫外光作用下氯酚的矿化程度比较

有关氯酚污染物光化学降解的研究,已有报道。ＨｕａｎｇＣＰ的工作较有系统性,他研究了四类深度化学氧化过程,检测指标是氯酚浓度。本文研究了在紫外光以及其它因素作用下,氯酚混合溶液的矿化程度,以溶液总有机磷浓度ＴＯＣ作为指标。所得结论,对于含有氯酚废水的治理,具有指导意义;对于难降解