真空紫外光臭氧降解偏二甲肼的研究

研究比较了臭氧氧化（O₃）、紫外臭氧（O₃/UV）和真空紫外臭氧（O₃/VUV）对推进剂——偏二甲肼的处理效果,O₃/VUV最为有效,反应速率常数分别比O₃/UV和O₃高39.8%和65.6%,中间产物——甲醛去除得更迅速,反应50 min即无法检出。初始pH 9时,O₃/VUV降解偏二甲肼的速率最快,达到0.4461 min^-1;反应速率常数随臭氧投加量的增加而线性增大;随偏二甲肼初始浓度从100 mg/L增加到2 000 mg/L,反应动力学由一级转为零级。碳酸盐浓度在0～2 mmol/L范围内对O₃/VUV降解偏二甲肼没有明显的抑制作用。偏二甲肼的无机氮产物以氨离子为主,无机氮只占总氮的40%～60%,说明仍有相当比例的氮以有机氮形式存在。     

六氯苯的O3及UV/O3高级氧化降解试验研究

采用O₃、UV/O₃高级氧化法对水中六氯苯（HCB）的降解效果及机理进行了研究，并对结果进行了比较，结果表明，UV本身对HCB的去除率贡献不大，HCB可被O₃、UV/O₃快速降解，即UV＜O₃＜UV/O₃；O₃、UV/O₃作用时，提高体系的初始pH值不利于HCB的降解，在pH＝3，HCB=0.2 mg/L，反应40 min时，HCB的去除可达50%左右，酸性条件下有利于降解反应的进行；无论是O₃单独作用还是UV/O₃联合作用，HCB的降解基本上满足准一级反应动力学规律，如果体系的pH值基本保持恒定，这种规律就更为明显。根据离子色谱(IC)、GC对六氯苯降解中间产物进行了测定，探讨了O₃、UV/O₃降解六氯苯的途径和机理。     

UV/H2O2工艺降解环丙沙星的研究

采用UV/₂O₂工艺去除水体中的喹诺酮类抗生素环丙沙星（CIP）。考察了溶液pH值、₂O₂投加量以及水体基质对环丙沙星降解效率的影响,分析了降解产物的生成情况。研究表明,环丙沙星的降解符合拟一级反应动力学模型。降解速率受溶液pH值的影响,酸性及中性条件,有利于环丙沙星的降解。₂O₂投加量的增大,使得降解速率逐渐增大,但速率增幅逐渐变缓;最佳₂O₂/环丙沙星摩尔比为2 000。实际水体中存在的NOM、NO^-₃,促进了单独UV作用下,环丙沙星的降解。水体中的?OH焠灭剂,抑制了UV/₂O₂联合作用下,环丙沙星的降解;实际水体中的光解速率常数低于超纯水中的光解速率常数。GC-MS分析表明,UV/₂O₂工艺,使环丙沙星氧化降解生成氨基乙酸、丙二酸、丙三醇和对苯二甲酸等小分子有机物。     

臭氧氧化及其他强化技术协同降解聚乙烯醇

采用O₃氧化降解水中聚乙烯醇（PVA）,考察了O₃氧化的影响因素及与其他强化技术协同下的降解效果。结果表明,经12 min处理,O₃/超声波、O₃/紫外光协同作用下PVA降解率较直接O₃氧化的63.2%有显著提高,表现出了良好的协同效应。通过比较酸性条件下添加不同量Fenton试剂的作用效果可知,·OH的氧化作用是PVA降解的重要原因。     

臭氧洗消化学战剂模拟剂DPCP试验研究

用臭氧对神经性化学战剂的模拟剂氯磷酸二苯酯（DPCP）进行洗消,试验考察了初始酸度、O₂流量、放电功率、放电室压力、反应温度、初始浓度和O₃流量等因素对DPCP降解率的影响。碱性条件下DPCP降解率高于酸性条件下的降解率;反应温度、O₃流量、放电功率的增加,DPCP降解率上升;初始浓度增加,DPCP降解率下降;氧气流量和放电室压力增加,DPCP降解率先上升,后下降。在最佳反应条件下,50 mg/L的DPCP处理16 min降解率达到98%,矿化率40.1%。     

催化臭氧化降解技术中的两个问题

探讨了有机物特性及中间产物H₂O₂在催化臭氧化中的作用。结果表明,有机物在自由基链反应过程中的特性直接影响催化臭氧化的降解效率。当目标有机物是对链反应具有促进作用的甲酸时,自由基引发反应可以明显提高甲酸的臭氧化效率。当目标有机物是对自由基链反应具有抑制剂作用的乙酸时,O₃和Fe²⁺/O₃对乙酸有着相似的降解效率。以上结果表明,自由基引发反应并不是臭氧化降解效率提高的充分条件。另外,当臭氧化过程有H₂O₂产生时,必须考虑类Fenton反应对臭氧化效率的影响。     

O3/UV预处理磺酰脲类除草剂生产废水的研究

采用O₃/UV工艺预处理磺酰脲类除草剂生产废水,考察了初始pH值、臭氧投量、叔丁醇投加等因素对废水处理效果的影响,并初步探讨了该工艺处理废水的反应机理。实验结果表明,在废水初始pH为13.59和臭氧投量为65.08 mg/min的条件下,预处理80 min后废水COD去除率达63.47%,BOD₅/COD由0.03提高至0.56,EC50从11%提高至55%。随着叔丁醇浓度的增加,废水COD去除率明显降低,证明该反应体系有?OH存在;体系中加入MnO₂后废水COD去除率下降了16%,氧化效率明显下降,证明该反应体系内中间产物H₂O₂在O₃/UV降解有机废水过程中起到了重要的作用。     

双频超声辐射协同H2O2降解偶氮染料废水的研究

采用双频超声协同H₂O₂降解酸性绿20染料废水,考察超声功率密度、染料初始浓度和pH、饱和气体及H₂O₂投加量等因素对酸性绿20降解效果的影响,结果表明,在给定实验条件下,双频降解效果优于单频超声波,且降解率随超声功率密度的增大而增大。酸性条件有利于酸性绿20的降解,当染料废水初始pH=4可取得最佳的降解效果;酸性绿20的降解效率随染料初始浓度的增大而降低,其优化初始浓度为40 mg/L。在反应体系中通入空气并投加H₂O₂,可取得最佳的降解效果。在优化实验条件下, 采用双频超声协同H₂O₂降解5 h,酸性绿20的色度和TOC去除率分别为94.6%和36.3%;分析降解前后的紫外可见光谱图可知,酸性绿20并非完全被降解为CO₂和H₂O,而是生成一些小分子有机中间体。     

活性炭纤维负载TiO2光催化降解甲醛的影响因素

利用自制光催化气体反应器体系,以活性炭纤维负载TiO₂作催化剂,在紫外光照射下模拟降解室内污染气体甲醛,测试了活性炭纤维负载TiO₂催化剂的催化活性,探讨了紫外光光强、催化剂的酸度、反应器内湿度及反应时间等控制反应的主要因素对甲醛降解率的影响。结果表明,活性炭纤维与TiO₂的协同作用大大提高了对甲醛的降解效果;紫外光强增倍对甲醛降解率有一定提高,但提高幅度仅为11.71%;活性炭纤维用pH=5的TiO₂溶胶浸泡做催化剂对甲醛的降解效果最好,60 min内降解率达到68.37％;反应器内的湿度为81%甲醛降解率最高,反应60 min后达82.2%;随着反应时间的延长,甲醛降解率的上升幅度不断减小,最高只能达到94.59%。     

微气泡曝气 O3/ H2O2处理 RO 浓水的效能及影响因素简

采用O₃/H₂O₂高级氧化工艺处理炼油厂反渗透（RO）浓水,用溶气泵加压溶气并产生微气泡强化传质,确定装置运行条件,考察气体中臭氧浓度、H₂O₂/O₃初始摩尔比、pH和温度对O₃/H₂O₂处理RO浓水效果的影响,并对RO浓水处理效能进行研究。结果表明,随着气体中臭氧浓度的增加,COD的去除率基本呈线性增加;加入适当量H₂O₂能提高臭氧氧化RO浓水的效果,H₂O₂/O₃初始摩尔比在0~0.8范围内,COD的去除率先增加后下降,H₂O₂/O₃初始摩尔比为0.5时COD去除率最大;pH从6.84增加到9.01,COD去除率逐渐增大,pH为10.03时COD去除率反而降低;在14~28℃范围内,温度低时,升高温度COD去除率增加较大,温度较高时,升高温度对COD去除率的影响较小。为考察该工艺的稳定性,在H₂O₂/O₃初始摩尔比为0.5、溶液pH为8~9、臭氧浓度为80~100 mg/L、温度为10~28℃条件下,对COD为90~140 mg/L的RO浓水氧化处理4~10 h,出水COD维持在39.9~49.9 mg/L,达到《城镇污水处理厂污染物排放标准（GB 18918-2002）》中的一级A标准;去除1 g COD消耗O₃ 1.4~3.3 g,消耗O₃与H₂O₂的总氧量为2.2~4.4 g。     

O3/H2O2处理嘧啶废水的研究

采用O3/H2O2法对嘧啶废水进行处理,考察了不同反应条件对嘧啶和COD去除率的影响,并对O3/H2O2降解嘧啶的反应机制和动力学进行了初步探讨.实验结果表明,在pH值为11,反应时间为70 min,O3流量为4g/h,H2O2投加量为50 mmol/L的条件下,废水的嘧啶和COD的去除率分别达到86.46%和74.9...     

Summertime photochemical ozone formation in Santiago,Chile

The city of Santiago, Chile experiences frequent high pollution episodes and as a consequence very high ozone concentrations, which are associated with health problems including increasing daily mortality and hospital admissions for respiratory illnesses. The development of ozone abatement strategies requires the determination of the potential of each pollutant to produce ozone, taking into account known mechanisms and chemical kinetics in addition to ambient atmospheric conditions. In this study, the photochemical formation of ozone during a summer campaign carried out from March 8–20, 2005 has been investigated using an urban photochemical box model based on the Master Chemical Mechanism (MCMv3.1). The MCM box model has been constrained with 10 min averages of simultaneous measurements of HONO, HCHO, CO, NO, j(O¹D), j(NO₂), 31 volatile organic compounds (VOCs) and meteorological parameters. The O₃–NO_x–VOC sensitivities have been determined by simulating ozone formation at different VOC and NO_x concentrations. Ozone sensitivity analyses showed that photochemical ozone formation is VOC-limited under average summertime conditions in Santiago. The results of the model simulations have been compared with a set of potential empirical indicator relationships including H₂O₂/HNO₃, HCHO/NO_y and O₃/NO_z. The ozone forming potential of each measured VOC has been determined using the MCM box model. The impacts of the above study on possible summertime ozone control strategies in Santiago are discussed.     

Atrazine removal by ozonation processes in surface waters

Abstract

Atrazine (6‐chloro‐N‐ethyl‐N'‐isopropyl‐1,3,5‐triazinedyl‐2,4‐diamine) was treated with ozone alone and in combination with hydrogen peroxide or UV radiation in three surface waters. Experiments were carried out in two bubble reactors operated continously. Variables investigated were the ozone partial pressure, temperature, pH, mass flow ratio of oxidants fed: hydrogen peroxide and ozone and the type of oxidation including UV radiation alone. Residence time for the aqueous phase was kept at 10 min. Concentrations of some intermediates, including deethylatrazine, deisopropylatrazine and deethyldeisopropylatrazine, were also followed. The nature of water, specifically the alkalinity and pH were found to be important variables that affected atrazine (ATZ) removal. Surface waters with low alkalinity and high pH allowed the highest removal of ATZ to be reached. There was an optimum hydrogen peroxide to ozone mass flow ratio that resulted in the highest ATZ removal in each surface water treated. This optimum was above the theoretical stoichiometry of the process. Therefore, to reach the maximum removal of ATZ in a O₃/H₂O₂ process, more hydrogen peroxide was needed in the surface waters treated than in ultrapure water under similar experimental conditions. In some cases, UV radiation alone resulted in the removal of ATZ higher than ozonation alone. This was likely due to the alkalinity of the surface water. Ozonation and UV radiation processes yield different amounts of hydrogen peroxide. Combined ozonations (O₃/H₂O₂ and O₃/UV) lead to ATZ removals higher than single ozonation or UV radiation but the formation of intermediates was higher.     

SMX degradation by ozonation and UV radiation: a kinetic study

The rate constants of sulfamethoxazole (SMX) degradation by ozonation and UV₂₅₄ radiation were investigated under various parameters including influent ozone gas concentration, initial SMX concentration, UV light intensity, ionic strength, water quality in terms of varying anions (bicarbonate, sulfate and nitrate), humic acid (HA) and pH. The results indicated that the removal of SMX by ozonation and UV₂₅₄ radiation fitted well to a pseudo first-order kinetic model and the rate constants were in the range of (0.9-9.8) × 10⁻³ and (1.7-18.9) × 10⁻³ s⁻¹, respectively. The second-order rate constants of SMX with ozone (k_O3), under varying operational parameters, were also determined and varied in the range of (0.60-3.38) ± 0.13 × 10⁵ M⁻¹ s⁻¹. In addition, SMX degradation through UV pretreatment followed by ozonation in the presence of HA was proved to be an effective method which can remove SMX with a low ozone dose. The results suggested that ozonation of SMX was more affected by concentration of influent ozone gas, alkalinity, and HA, while incident UV light intensity, pH, and HA were the dominant factors influencing UV degradation of SMX.     

污泥基活性炭催化臭氧氧化对氯苯甲酸效能

以城市污水处理厂剩余污泥和玉米芯为原料,用氯化锌活化法制备出污泥基活性炭(SCAC),研究了其催化臭氧氧化去除水中对氯苯甲酸(p-CBA)的效能和机理,同时,考察了臭氧浓度、SCAC投量、p-CBA初始浓度以及自由基抑制剂叔丁醇的加入对SCAC催化活性的影响。实验结果表明,SCAC的加入可以显著提高臭氧对p-CBA的氧化去除效果,在反应初期尤为明显,反应1.0 min时p-CBA的去除率由单独臭氧氧化的26.1%提高到SCAC催化臭氧氧化的60.2%。SCAC催化臭氧氧化对p-CBA的去除率随臭氧浓度的增加和p-CBA初始浓度的减小而增加。此外,在一定范围内增加催化剂的投量可以增加p-CBA的去除率。叔丁醇的加入显著减弱了SCAC催化臭氧氧化降解p-CBA的效能,表明SCAC催化臭氧氧化反应的主要活性物种为羟基自由基(·OH)。     

Removal of AOX, total nitrogen and chlorinated lignin from bleached Kraft mill effluents by UV oxidation in the presence of hydrogen peroxide utilizing TiO2 as photocatalyst

Background, aim, and scope  The pulp and paper industry is the sixth largest polluter discharging a variety of gaseous, liquid, and solid wastes into the environment. Effluents from bleached Kraft mill effluents (BKME) are polluting waters to a great extent These effluents cause considerable damage to the receiving waters if discharged untreated since they have high levels of biological oxygen demand (BOD), chemical oxygen demand (COD), chlorinated compounds (measured as AOX), suspended solids (mainly fibers), fatty acids, tannins, resin acids, lignin and its derivatives, sulfur and sulfur compounds, etc. This study aimed to remove adsorbed organic halogen (AOX), total nitrogen, and lignin-degrading products in the wastewater (4,500 m³/h) from the paper mill in the pulp and paper industry, which is discharged to sea from a plant located in western Turkey. Materials and methods  The photocatalytic degradation of AOX, total nitrogen, and chlorinated lignin in BKME have been investigated in different parameters, such as time, H₂O₂ and TiO₂ concentration. In addition, for investigating the effect of chlorine on the removal of lignin, pure lignin solution was prepared in equal amounts to chlorinated lignin degradation products found in BKME. The same experiments were conducted for this solution. Experiments were carried out in photocatalytic reactor made of Pyrex glass. The mercury lamp was used as a radiation source. All irradiation was carried out under constant stirring. The existence of dissolved O₂ is an important factor which increases the photocatalytic degradation. Hence, we used an air pump for the aeration of the wastewater solutions. The temperature of the wastewater was controlled and adjusted to 25°C by thermostat pump in conjunction with a cooler. At the end of all experiments, AOX, total nitrogen and lignin concentrations were analyzed according to standard methods. All experiments were performed in duplicate and average values were used. Results and discussion  When the effect of H₂O₂ and time were investigated, it was observed that the AOX concentration increased from 3.0 to 11.0 mg/L by only UV. However, when H₂O₂ was added, AOX concentration decreased from approximately 3.0 to 0.0 mg/L. The optimal conditions for the removal of AOX appear to be an initial H₂O₂ concentration of 20.0 mL/L and reaction time of 50 min. In addition, at the same experiment conditions, it was seen that the total nitrogen concentration decreased from 23.0 to 15.0 mg/L by only UV and by increasing H₂O₂ concentration, the concentration of 20.0 mL/L H₂O₂ appears to be optimal (9.0 mg/L). The AOX, total nitrogen and lignin degradation products and pure lignin go through a minimum when the concentration of H₂O₂ and TiO₂ increases at constant pH and UV intensity. The kinetics for the degradation of AOX, total nitrogen and lignin degradation products followed a pseudo-first order law with respect to the products, and the degradation rates (min⁻¹) for the UV/TiO₂/H₂O₂ system were higher than that of the corresponding values for the UV/H₂O₂ system. Conclusions  The AOX, total nitrogen and lignin concentration go through a minimum when the concentration of H₂O₂ and TiO₂ increases at constant pH and UV intensity. It was found that the UV/TiO₂/H₂O₂ system has proved capable of the degradation of total nitrogen as well as chlorinated and degraded lignin in BKME. Recommendations and perspectives  The photocatalytic process can be considered a suitable alternative for the remove of some compounds from the BKME. Nevertheless, further studies should be carried out to confirm the practical feasibility of BKME. Another result obtained from the study is that pre-purification carried out with UV/TiO₂/H₂O₂ photocatalytic process may constitute an important step for further purification processes such as adsorption, membrane processes, etc.     

Growth of soybean at future tropospheric ozone concentrations decreases canopy evapotranspiration and soil water depletion

Tropospheric ozone is increasing in many agricultural regions resulting in decreased stomatal conductance and overall biomass of sensitive crop species. These physiological effects of ozone forecast changes in evapotranspiration and thus in the terrestrial hydrological cycle, particularly in intercontinental interiors. Soybean plots were fumigated with ozone to achieve concentrations above ambient levels over five growing seasons in open-air field conditions. Mean season increases in ozone concentrations ([O₃]) varied between growing seasons from 22 to 37% above background concentrations. The objective of this experiment was to examine the effects of future [O₃] on crop ecosystem energy fluxes and water use. Elevated [O₃] caused decreases in canopy evapotranspiration resulting in decreased water use by as much as 15% in high ozone years and decreased soil water removal. In addition, ozone treatment resulted in increased sensible heat flux in all years indicative of day-time increase in canopy temperature of up to 0.7 °C.     

低温等离子体氧化氨气影响因素及动力学研究

采用电晕放电低温等离子体处理模拟氨气恶臭气体,考察了输入功率、初始浓度、气体湿度、停留时间等因素对降解效果和能量效率的影响,同时对反应过程进行了动力学研究。研究表明,输入功率以及停留时间对氨气降解的影响是积极的,但能量效率随着两者的增加先增大后减小。氨气的降解率随着初始浓度的增加而降低,而能量效率随着输入功率的增加而增加。氨气降解率和能量效率均随着气体湿度的增加而增加,当气体湿度为45%时达到最大值,然而随着气体湿度的进一步增加,其降解率和能量效率反而降低。反应尾气中臭氧浓度随着输入功率的增加而不断升高,而氨气的存在却使臭氧浓度有不同程度的降低。对电晕放电低温等离子体处理NH3的反应动力学进行了分析,得到NH3的反应速率常数为kNH3=0.0707 m3/(W·h)。     

A new approach to quantify the degradation kinetics of linuron with UV, ozonation and UV/O3 processes

The degradation of linuron, one of phenylurea herbicides, was investigated for its reaction kinetics by different treatment processes including ultraviolet irradiation (UV), ozonation (O₃), and UV/O₃. The decay rate of linuron by UV/O₃ process was found to be around 3.5 times and 2.5 times faster than sole-UV and ozone-alone, respectively. Experimental results also indicate overall rate constants increased exponentially with pH above 9.0 while the increase of rate constants with pH below 9 is insignificant in O₃ system. All dominant parameters involved in the three processes were determined in the assistant of proposed linear models in this study. The approach was found useful in predicting the process performances through the quantification of quantum yield (rate constant for the formation of free radical HOO⁻ from ozone decomposition at high pH), rate constant of linuron with ozone (k_O3,LNR), rate constant of linuron with hydroxyl radical (k_OH,LNR), and α (the ratio of the production rate of OH and the decay rate of ozone in UV/O₃ system).