Degradation of nitrogen containing organic compounds by combined photocatalysis and ozonation

The combination of TiO2-assisted photocatalysis and ozonation in the degradation of nitrogen-containing substrates such as alkylamines, alkanolamines, heterocyclic and aromatic N-compounds has been investigated. A laboratory set-up was designed and the influence of the structure of the N-compound, the TiO2 and ozone concentration on the formation of breakdown products were examined. The experimental results showed that a considerable increase in the degradation efficiency of the N-compounds is obtained by a combination of photocatalysis and ozonation as compared to either ozonation or photocatalysis only. The mineralization of the model substances was monitored by measurements of the TOC and ion-chromatographic determinations of the formed NO2- and NO3-. The temporal changes of concentrations of breakdown products, such as NH4+, short chain alkyl- and alkanolamines were determined by single column ion chromatography (SCIC) and as well as by electrospray mass spectrometry (EI-MS).     

光催化-臭氧氧化降解H酸的研究

采用光催化-臭氧氧化技术(催化膜/UV/O3)降解H酸.研究结果表明,光催化与臭氧氧化相结合具有明显的协同作用.实验进一步讨论了臭氧投加量、废水初始pH值和H酸初始浓度对光催化-臭氧氧化降解H酸的影响.降解后的H酸,萘环结构被破坏,可生化性提高.     

光催化-臭氧氧化降解H酸的研究

采用光催化一臭氧氧化技术（催化膜／UV／O3）降解H酸。研究结果表明，光催化与臭氧氧化相结合具有明显的协同作用。实验进一步讨论了臭氧投加量、废水初始pH值和H酸初始浓度对光催化一臭氧氧化降解H酸的影响。降解后的H酸，萘环结构被破坏，可生化性提高。     

臭氧强化光催化对垃圾渗滤液的深度处理

用臭氧强化光催化工艺对垃圾渗滤液进行了深度处理,优化了工艺参数,对比了最佳工艺条件下各时间段的出水指标.该工艺在催化剂投加量0.5 g/L,pH值8.45左右,O3流量0.4 L/min,O3浓度16.8 mg/L,初始COD浓度430 mg/L时最佳,COD和UV254的去除率均在60%以上;最佳工艺条件下1.0 h出水的BOD5提高了75.42%,2.0 h出水BOD5/COD从初始的0.05升高至0.23.结果表明,臭氧强化光催化工艺不仅可以提高处理能力,还有效地改善了出水的可生化性.     

臭氧光催化降解水中甲醛的研究

研究比较了3种光化学方法对水中低浓度甲醛的降解效果,考察了初始pH值、甲醛浓度和臭氧投加速率等因素对臭氧光催化(TiO_2/UV/O_3)降解甲醛的影响。结果表明,紫外臭氧(UV/O_3)、光催化(TiO_2/UV)和TiO_2/UV/O_3对甲醛的降解均符合表观一级反应动力学,TiO_2/UV/O_3降解甲醛的一级表观速率常数大于TiO_2/UV与UV/O_3之和,说明臭氧、光催化有明显的协同作用。pH值对臭氧光催化降解甲醛的速率几乎没有影响;甲醛初始浓度增加,表观反应速率常数下降,但甲醛的绝对去除量仍随初始浓度的增加而显著增加;臭氧投加速率增加,降解速率增加。甲醛降解的主要中间产物为甲酸,但甲酸在臭氧光催化反应过程中也快速降解而被矿化,说明臭氧光催化是一种能安全有效去除甲醛的方法。     

TiO2光催化耦合SO4-·体系对硝基苯酚的降解性能及动力学

利用溶胶-凝胶法在改性的ZSM-5分子筛上负载TiO2制备复合光催化剂TiO2/ZSM-5m,采用扫描电镜、N2吸附-脱附等温线和X射线衍射对材料进行表征。通过耦合Fe2+/S2O82-产硫酸根自由基SO4-·体系,以对硝基苯酚(pNP)为目标污染物,系统考察了初始pH、TiO2/ZSM-5m投加量、FeSO4、Na2S2O8浓度和初始浓度对pNP降解性能的影响。结果表明,在TiO2/ZSM-5m投加量为0.8 g/L,pH为4.0,FeSO4为0.4 g/L,Na2S2O8为2.4 g/L,常温下反应240 min的优化条件下,对pNP(初始浓度50 mg/L)去除率达到99.31%,光催化降解动力学符合Langmuir-Hinshelwood模型,UV-vis图谱推测对硝基苯酚分子结构发生改变,被有效降解。     

Degradation and toxicity reduction of textile effluent by combined photocatalytic and ozonation processes

To minimize the environmental impact of textile effluents, mainly related to their high coloration and the presence of toxic or carcinogenic reactive dyes, the efficiency of photochemical and ozonation processes, applied in the form of isolated and combined procedures, were evaluated. The investigation was focused on the reduction of total organic carbon content (TOC), color and acute toxicity (monitoring by inhibition of Escherichia coli respiration). For a reaction time of 60 min, the anatase TiO2-assisted photocatalytic process produces color and TOC reduction of about 90% and 50%, respectively. Meanwhile, the ozonation process gives a decolorization of about 60% but negligible TOC reduction. When the processes were applied in a simultaneous form, the decolorization was almost complete and the TOC reduction was higher than 60%. The three treatments studied yield an acute toxicity reduction of around 50%.     

臭氧催化氧化降解苯胺的机理

对臭氧单独氧化和臭氧催化氧化下的苯胺降解效率进行了比较,并通过液质联机分析了氧化过程中产物变化情况。实验结果表明,催化剂MnO2-CuO-CeO2/沸石的添加能有效地提高臭氧氧化苯胺的降解率,当苯胺初始浓度为200mg/L,反应20 min后,苯胺的去除率由原来的75%提高到89%;通过LC-MS分析,臭氧催化氧化苯胺降解过程中代谢产物依次为对亚胺醌、对苯醌、马来酸和草酸,并由此推断出了臭氧催化氧化降解苯胺的途径。     

Degradation of methylparaben in water by corona plasma coupled with ozonation

The degradation of methylparaben (MeP) in water was investigated using a pulsed corona discharge generated in oxygen, above the liquid. A comparison was made between results obtained in semi-batch corona (SBC) configuration (stationary solution, continuous gas flow) and results obtained in a semi-batch corona with recirculation combined with ozonation (SBCR?+?O₃), where the liquid is continuously circulated between a solution reservoir and the plasma reactor and the effluent gas containing ozone is bubbled through the solution in the reservoir. It was found that MeP was completely degraded after 10–15 min of treatment in both configurations. Oxidation by ozone alone, in the absence of plasma, was a slower process. The energy efficiency for MeP removal (Y _MeP) and for mineralization (Y _TOC) was significantly higher in the SBCR?+?O₃ configuration (Y _MeP?=?7.1 g/kWh at 90 % MeP removal and Y _TOC?=?0.41 g/kWh at 50 % total organic carbon (TOC) removal) than in the SBC configuration (Y _MeP?=?0.6 g/kWh at 90 % MeP removal and Y _TOC?=?0.11 g/kWh at 50 % TOC removal).     

Degradation of diuron in aqueous solution by ozonation

Degradation of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] in aqueous solution and the proposed degradation mechanism of diuron by ozonation were investigated. The factors that affect the degradation efficiency of diuron were examined. The generated inorganic ions and organic acids during the ozonation process were detected. Total organic carbon removal rate and the amount of the released Cl^? increased with increasing ozonation time, but only 80.0% of the maximum theoretical concentration of Cl^? at total mineralization was detected when initial diuron concentration was 13.8 mg L^?1. For N species, the final concentrations of NO₃ ^? and NH₄ ⁺ after 60 min of reaction time were 0.28 and 0.19 mg L^?1, respectively. The generated acetic acid, formic acid and oxalic acid were detected during the reaction process. The main degradation pathway of diuron by ozonation involved a series of dechlorination-hydroxylation, dealkylation and oxidative opening of the aromatic ring processes, leading to small organic species and inorganic species. The degradation efficiency of diuron increased with decreasing initial diuron concentration. Higher pH value, more ozone dosage, additive Na₂CO₃, additive NaHCO₃ and additive H₂O₂ were all advantageous to improve the degradation efficiency of diuron.     

Degradation of diuron in aqueous solution by ozonation

Degradation of diuron [3-(3,4-dichlorophenyl)-1,1-dimethylurea] in aqueous solution and the proposed degradation mechanism of diuron by ozonation were investigated. The factors that affect the degradation efficiency of diuron were examined. The generated inorganic ions and organic acids during the ozonation process were detected. Total organic carbon removal rate and the amount of the released Cl(-) increased with increasing ozonation time, but only 80.0% of the maximum theoretical concentration of Cl(-) at total mineralization was detected when initial diuron concentration was 13.8 mg L(-1). For N species, the final concentrations of NO3(-) and NH4+ after 60 min of reaction time were 0.28 and 0.19 mg L(-1), respectively. The generated acetic acid, formic acid and oxalic acid were detected during the reaction process. The main degradation pathway of diuron by ozonation involved a series of dechlorination-hydroxylation, dealkylation and oxidative opening of the aromatic ring processes, leading to small organic species and inorganic species. The degradation efficiency of diuron increased with decreasing initial diuron concentration. Higher pH value, more ozone dosage, additive Na2CO3, additive NaHCO3 and additive H2O2 were all advantageous to improve the degradation efficiency of diuron.     

等离子体与光催化复合空气净化技术研究

尝试了一种新的等离子体-光催化复合方式进行空气净化,研究表明该种复合方式具有较显著的协同促进效应,通过改变等离子体发生单元与光催化单元的距离以及在两者之间放置网状物,可消除等离子体单元产生的负电荷对光催化单元的不利影响,进一步提高其复合效应.还对这一复合方式产生协同效应的机理进行了分析.     

臭氧氧化法处理反渗透浓缩垃圾渗滤液

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,考察了反应时间、臭氧投量、pH和温度对COD,色度以及浓缩液中腐殖酸的去除影响,通过BOD₅/COD变化分析了臭氧氧化对浓缩液生化性的提高作用。结果表明：在pH 8.0,温度30℃,臭氧投量5 g/h,反应时间90 min的条件下,浓缩液的COD、色度以及浓缩液中腐殖酸的去除率分别达到67.6%、98.0%和86.1%, BOD₅/COD从0.008提升到0.26,生化性有很大提高。     

不同晶型二氧化锰催化臭氧化降解亚甲基蓝废水

采用水溶液化学沉积法制备纳米二氧化锰,生成了δ-MnO2、γ-MnO2、α-MnO2,采用XRD、SEM和BET等手段进行了表征。以碱性染料亚甲基蓝为目标污染物,不同晶型纳米二氧化锰作吸附剂进行了静态吸附实验;在催化臭氧化亚甲基蓝的实验中,研究了溶液的pH值、催化剂的加量以及自由基引发剂与促灭剂对催化效果的影响。结果表明：3种催化剂δ-MnO2、γ-MnO2和α-MnO2的平衡吸附量分别为58.47、50.87和40.52 mg·g-1,其中δ-MnO2的吸附性能较强;3种催化剂的吸附动力学符合准二级吸附动力学。当溶液pH=11时,催化臭氧化反应体系对亚甲基蓝的降解效果最佳。在此催化臭氧化系统下,主要遵循的是羟基自由基的反应机理。δ-MnO2应用于催化臭氧化亚甲基蓝,不仅具有良好的脱色效果,并具有一定的矿化能力。     

Degradation of recalcitrant organic matter in SAARB leachate by a combined process of coagulation and catalytic ozonation

Environmental Science and Pollution Research - A combined coagulation and γ-Al2O3 catalytic ozonation process was used to treat semi-aerobic aged refuse biofilter (SAARB) effluent from...     

Fe/TiO2光催化降解水溶液中的4-氯苯酚

以TiO2-P25及FeC2O4为前驱物制备了Fe3 掺杂TiO2光催化剂--Fe/TiO2.X射线衍射结果表明,500 ℃煅烧温度下的Fe/TiO2主要是锐态矿晶型,当掺Fe3 量为0.5%(质量分数,下同)时,Fe3 以取代掺杂形式进入TiO2晶格,而当掺Fe3 量达5.0%时,则出现α-Fe2O3的特征衍射峰;900 ℃煅烧温度下的Fe/TiO2则均为金红石晶型,掺Fe3 量达2.0%～5.0%时,出现Fe2TiO5的特征衍射峰.4-氯苯酚的光催化实验结果表明,煅烧温度及Fe3 掺杂量对Fe/TiO2的光催化活性有显著影响,以煅烧温度500 ℃及掺Fe3 量0.5%的Fe/TiO2为光催化剂,反应80 min,4-氯苯酚的降解率达100%,总有机碳去除率约95%.     

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。     

高分散纳米钙锆复合材料催化臭氧氧化降解间甲酚废水

采用共沉淀法制备了一系列Ca-Zr复合材料,探究了不同的焙烧温度对材料结构和化学性质的影响。使用X射线衍射、扫描电子显微镜及高分辨透射电镜等分析手段表征了所制备样品的物相变化和颗粒形貌特征,以间甲酚为底物,采用臭氧催化氧化方法对所得催化剂的催化性能进行了分析。结果表明：当焙烧温度升高到1 000 ℃以上时,样品晶型以斜方晶系CaZrO₃为主,随着焙烧温度的升高,颗粒更加均匀分散。在催化臭氧氧化降解间甲酚实验中,当焙烧温度为800 ℃时, TOC去除率最高可达到79%。800 ℃焙烧所得的样品由纳米颗粒组成,晶格间距为0.29 nm,说明样品的高暴露晶面为CaZrO₃的(121)晶面;XPS结果证实了样品的高活性可能是由晶格氧和表面羟基基团起重要作用而导致的。这种高效的纳米钙锆复合材料为催化臭氧氧化处理废水奠定了良好的基础。     

Degradation of some biorecalcitrant pesticides by homogeneous and heterogeneous photocatalytic ozonation

Photo-Fenton/ozone (PhFO) and TiO2-photocatalysis/ozone (PhCO) coupled systems are used as advanced oxidation processes for the degradation of the following biorecalcitrant pesticides: alachlor, atrazine, chlorfenvinfos, diuron, isoproturon and pentachlorophenol. These organic compounds are considered Priority Hazardous Substances by the Water Framework Directive of the European Commission. The degradation process of the different pesticides, that occurs through oxidation of the organic molecules by means of their reaction with generated OH radical, follows a first and zero-order kinetics, when PhFO and PhCO are applied, respectively. These two Advanced Oxidation Processes, together with the traditional ozone+UV, have been used to investigate TOC reduction of the different pesticide aqueous solutions. The best results of pesticide mineralization are obtained when PhFO is applied; with the use of this advanced oxidation process the aqueous pesticide solutions become detoxyfied except in the case of atrazine and alachlor aqueous solutions for which no detoxification is achieved at the experimental conditions used in the work, at least after 2 and 3 h of treatment, respectively.     

臭氧催化氧化-BAF组合工艺深度处理抗生素制药废水

针对抗生素制药废水组分复杂、毒性强、难生物降解的特点,以Ce负载天然沸石作为催化剂(Ce/NZ),采用臭氧催化氧化-曝气生物滤池(BAF)组合工艺对抗生素制药废水二级生化处理出水进行深度处理。结果表明,Ce/NZ催化剂可显著改善臭氧预处理单元的处理效率,在臭氧进气浓度为50 mg·L⁻¹、臭氧进气量为600 mL·min⁻¹、催化剂用量为1 g·L⁻¹、臭氧反应时间为120 min的条件下,臭氧催化氧化预处理对抗生素制药废水的COD去除率达到43%,平均COD由220 mg·L⁻¹降至125 mg·L⁻¹,BOD₅/COD由0.12升至0.28,废水的可生化性得到显著提高。臭氧预处理单元出水采用BAF进行生化处理,在进水平均COD为125 mg·L⁻¹、平均NH₄⁺-N为12 mg·L⁻¹、水力停留时间为4 h、气水比为4∶1的条件下,COD和NH₄⁺-N的平均去除率分别为62%和64%。组合工艺处理后出水平均COD和NH₄⁺-N分别为46 mg·L⁻¹和4.1 mg·L⁻¹,出水水质可以稳定达到《发酵类制药工业水污染物排放标准》(GB 21903-2008)。相较于单独BAF工艺,组合工艺出水COD和NH₄⁺-N平均去除率分别提高了66%和15%,出水水质明显优于单独BAF工艺出水。