Heterogeneous photocatalysed degradation of a herbicide derivative, isoproturon in aqueous suspension of titanium dioxide

Heterogeneous photocatalysed degradation of a herbicide derivative, N-(4-isopropylphenyl)-N',N'-dimethylurea (Isoproturon, 1) was investigated in aqueous suspensions of titanium dioxide by monitoring the change in absorption intensity and depletion in Total Organic Carbon content as a function of irradiation time. The degradation kinetics was studied under different conditions such as pH, catalyst concentration, substrate concentration, different types of TiO(2) and in the presence of electron acceptors such as hydrogen peroxide (H(2)O(2)), potassium bromate (KBrO(3)) and potassium persulphate (K(2)S(2)O(8)) besides molecular oxygen. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 was found to be more efficient as compared with other photocatalysts. An attempt was made to identify the degradation product through GC-MS analysis technique.     

Heterogeneous photocatalysed degradation of two selected pesticide derivatives, triclopyr and daminozid in aqueous suspensions of titanium dioxide

Heterogeneous photocatalysed degradation of two selected pesticide derivatives, triclopyr (1) and daminozid (2), has been investigated in aqueous suspensions of titanium dioxide by monitoring the change in substrate concentration employing the UV Spectroscopic analysis technique and depletion of Total Organic Carbon (TOC) content as a function of irradiation time. The degradation kinetics were studied under different conditions such as reaction pH, substrate and catalyst concentration, different types of TiO2 and in the presence of electron acceptors such as hydrogen peroxide (H2O2), potassium bromate (KBrO3) and ammonium persulphate (NH4)2S2O8 in addition to molecular oxygen. The degradation rates were found to be strongly influenced by all the above parameters. The photocatalyst Degussa P25 was found to be more efficient as compared with other photocatalysts. The pesticide derivative triclopyr (1) was found to degrade faster as compared to daminozid (2). An attempt was also made to identify the intermediate products formed during the photooxidation process using GC/MS analysis. Probable pathways for the formation of products have been proposed.     

用二氧化钛光催化氧化法降低丙烯腈污水中的化学需氧量

在开放的光催化反应器中,以紫外(UV)光为光源,以二氧化钛为催化剂,研究了不同水质条件下对模拟丙烯腈(AN)污水中化学需氧量(COD)的控制效果及主要影响因素。结果表明,UV光-TiO2催化体系对AN污水中COD具有良好的去除效果。当在浓度为300mg/L模拟AN污水中投加浓度为20mg/L的二氧化钛及紫外光照射180min时,污水体系中的COD残存率为7.9%。同时,反应过程中不会对环境产生二次污染。     

Intensification of degradation of aqueous solutions of rhodamine B using sonochemical reactors at operating capacity of 7 L

In the present work, degradation of rhodamine B, a typical dye effluent commonly observed in chemical processing wastewaters has been investigated using a sonochemical reactor with capacity of 7 L. The reactor consists of an ultrasonic bath equipped with a single large transducer having longitudinal vibrations with operating frequency of 25 kHz and rated power output of 1 kW. The effect of operational conditions such as the rhodamine B initial concentration, operating pH and use of additives such as H(2)O(2), CCl(4) and TiO(2) has been investigated initially. A mathematical model has also been fitted to estimate the rate constant for rhodamine B removal under different operating conditions. Intensification studies have been carried by combining sonochemical oxidation with photocatalytic oxidation under optimized conditions. In all the investigated systems, complete removal of rhodamine B (10 ppm initial concentration) was obtained using a combination of sonochemical reactor and CCl(4). Sonocatalysis (in the presence of TiO(2)) of rhodamine B showed 92% degradation, while sonophotocatalysis gave degradation of 93%. TOC analysis at various optimum conditions was also performed to quantify the extent of mineralization and it was observed that the extent of mineralization is always lower than the extent of removal of parent compound.     

Advanced oxidation treatment of pulp mill effluent for TOC and toxicity removals

Pulp mill effluent was treated by different advanced oxidation processes (AOPs) consisting of UV, UV/H2O2, TiO2-assisted photo-catalysis (UV/TiO2) and UV/H2O2/TiO2 in lab-scale reactors for total organic carbon (TOC) and toxicity removals. Effects of some operating parameters such as the initial pH, oxidant and catalyst concentrations on TOC and toxicity removals were investigated. Almost every method resulted in some degree of TOC and toxicity removal from the pulp mill effluent. However, the TiO2-assisted photo-catalysis (UV/TiO2) resulted in the highest TOC and toxicity removals under alkaline conditions when compared with the other AOPs tested. Approximately, 79.6% TOC and 94% toxicity removals were obtained by the TiO2-assisted photo-catalysis (UV/TiO2) with a titanium dioxide concentration of 0.75gl(-1) at pH 11 within 60min.     

阳离子艳红染料的光催化降解

本文研究了以沉淀法制备的TiO2为催化剂，紫外杀菌灯为光源，对阳离子艳红染料进行光催化降解的可行性，结果表明，在实验条件下，本系统对阳离子艳红染料有明显的降解效果，浓度为10mg/L的阳离子艳红染料经过30min的处理，其降解率＞88％，此外，还探讨了溶液初始pH值，催化剂的投加量，光照距离和液层高度等因素对光降解反应的影响。     

UV-H_2O_2联用工艺去除水中阿特拉津的研究

采用间歇式反应器考察了UV-H2O2高级氧化技术去除水中阿特拉津的效果及其影响因素,并进行了相关的反应动力学研究。结果表明,在pH值6.9,阿特拉津初始浓度500μg/L,紫外辐照强度172μW/cm2时,H2O2投加量50mg/L,反应10min后,阿特拉津的去除率90%。UV-H2O2联用工艺对阿特拉津的降解符合一级反应动力学。H2O2在该联用工艺降解阿特拉津中具有双重作用,一方面,当H2O2投加量较小时,一级反应速率常数随H2O2投加量的增加基本呈现线性增加的趋势;另一方面,当H2O2浓度增加到一定程度(90mg/L)后,阿特拉津的降解速率随H2O2浓度的变化已不明显,而H2O2浓度为102mg/L时,则出现了抑制作用。     

Photocatalytic activity of tungsten-doped TiO2 with hydrothermal treatment under blue light irradiation

Tungsten doping and hydrothermal treatment were found to significantly improve the visible-light photoactivity of TiO(2) synthesized by the sol-gel method. It was observed that TiO(2) doped with a 0.5% W:Ti mole ratio and treated with 4 h of hydrothermal curing showed photoactivity under blue light irradiation equal to 74% of the commercial Degussa P-25 under UV irradiation, i.e., 0.01 mM 2-chlorophenol was completely removed in 120 and 90 min, respectively. Light absorptivity and photocatalytic activity under blue light irradiation were not dependent on the crystallite structure of the TiO(2). The oxidation kinetics under blue light irradiation can be effectively explained by the Langmuir-Hinshelwood model with an apparent reaction rate constant and a Langmuir constant of 3.60 × 10(-4) mM min(-1) and 206.53 mM(-1), respectively.     

Degradation of a commercial textile biocide with advanced oxidation processes and ozone

The occurrence of significant amounts of biocidal finishing agents in the environment as a consequence of intensive textile finishing activities has become a subject of major public health concern and scientific interest only recently. In the present study, the treatment efficiency of selected, well-known advanced oxidation processes (Fenton, Photo-Fenton, TiO(2)/UV-A, TiO(2)/UV-A/H(2)O(2)) and ozone was compared for the degradation and detoxification of a commercial textile biocide formulation containing a 2,4,4'-trichloro-2'-hydroxydiphenyl ether as the active ingredient. The aqueous biocide solution was prepared to mimic typical effluent originating from the antimicrobial finishing operation (BOD(5,o) < or =5 mg/L; COD(o)=200 mg/L; DOC(o) (dissolved organic carbon)=58 mg/L; AOX(o) (adsorbable organic halogens)=48 mg/L; LC(50,o) (lethal concentration causing 50% death or immobilization in Daphnia magna)=8% v/v). Ozonation experiments were conducted at different ozone doses (500-900 mg/h) and initial pH (7-12) to assess the effect of ozonation on degradation (COD, DOC removal), dearomatization (UV(280) and UV(254) abatement), dechlorination (AOX removal) and detoxification (changes in LC(50)). For the Fenton experiments, the effect of varying ferrous iron catalyst concentrations and UV-A light irradiation (the Photo-Fenton process) was examined. In the heterogenous photocatalytic experiments, Degussa P25-type TiO(2) was used as the catalyst and the effect of reaction pH (3, 7 and 12) and H(2)O(2) addition on the photocatalytic treatment efficiency was examined. Although in the photochemical (i.e. Photo-Fenton, TiO(2)/UV-A and TiO(2)/UV-A/H(2)O(2)) experiments appreciably higher COD and DOC removal efficiencies were obtained, ozonation appeared to be equally effective to achieve dearomatization (UV(280) abatement) at all studied reaction pH. During ozonation of the textile biocide effluent, AOX abatement proceeded significantly faster than dearomatization and was complete after 20 min ozonation (267 mg O(3)). On the other hand, for complete detoxification, ozonation had to be continued for at least 30 min (corresponding to 400mg O(3)). Effective AOX and acute toxicity removal was also obtained after heterogeneous photocatalytic treatment (TiO(2)/UV-A and TiO(2)/UV-A/H(2)O(2)). The Fenton-based treatment experiments and particularly the dark Fenton reaction resulted in relatively poor degradation, dearomatization, AOX and acute toxicity removals.     

光催化氧化处理低浓度含醇废水实验

室内实验了TiO2紫外光催化氧化处理废水中的低浓度甲醇。通过对TiO2催化剂活性及添加方式、溶液pH、紫外光强与催化剂加量等参数优化,在TiO2加入浓度为300mg/L和120 W紫外灯照射条件下,对6.8L甲醇浓度为2.77%的低浓度含醇废水持续处理70min后,废水中的甲醇去除率可达98.31%。该实验为进一步处理低浓度含醇废水提供了方法依据。     

Removal of the hazardous dye rhodamine B through photocatalytic and adsorption treatments

This paper reports on photocatalytic and adsorptive treatment of a hazardous xanthene dye, Rohdamine B, in wastewater. The photocatalytic degradation was carried out in the presence of the catalyst TiO(2) and the effects of pH, concentration of the dye, amount of TiO(2), temperature and electron acceptor H(2)O(2) on the degradation process were observed. It was found that photocatalytic degradation by TiO(2) is an effective, economical and faster mode of removing Rohdamine B from aqueous solutions. Attempts were also made to utilize activated carbon and rice husk as potential adsorbents to remove Rhodamine B from wastewater. The adsorption studies were carried out at 40, 50 and 60 degrees C, and the effects of pH, temperature, amount of adsorbents, concentration of adsorbate, etc., on the adsorption were measured. On the basis of adsorption data the Langmuir and Freundlich adsorption isotherm models were also confirmed. The adsorption isotherm constants thus obtained were employed to calculate thermodynamic parameters like Gibb's free energy, change in enthalpy and entropy. In order to observe the quality of wastewater COD measurements were also carried out before and after the treatments. A significant decrease in the COD values was observed, which clearly indicates that both photocatalytic and adsorption methods offer good potential to remove Rhodamine B from industrial effluents.     

紫外光催化氧化-原子吸收分光光度法测定垃圾渗滤液中重金属的研究

本文采用二氧化钛为催化剂，通过使用光催化氧化的消解方法对垃圾渗滤液样品进行前处理，再用原子吸收分光光度法测定垃圾渗滤液中的重金属，并与常用消解方法进行对比，探讨了紫外光照射时间、紫外灯功率、H2O2的用量等因素对消解效果所产生的影响，选取了消解垃圾渗滤液的最佳条件，讨论了方法的准确度与精密度。     

光化学氧化法对阴离子表面活性剂降解的初步研究

本试验采用UV/H2O2光氧化法处理含有较高浓度阴离子表面活性剂（LAS）的模拟废水，研究了H2O2投加量、pH值、光照时间、紫外灯光强对LAS降解率的影响。     

TiO2光催化降解有机颜料艳红RGS母液研究

以TiO2为催化剂,对有机颜料艳红RGS母液进行了一系列光催化降解试验.考察了催化剂用量、溶液pH值、初始浓度、不同光源和照射时间对脱色率的影响.结果表明,溶液相对初始浓度为0.2、pH<8、催化剂用量为1g/L时,以紫外灯(254nm)为光源,反应120 min,脱色率可达93%以上.     

La掺杂TiO2/有机改性膨润土对TNT弹药废水的光催化降解性能研究

利用超声强化溶胶-凝胶法制备了La掺杂TiO2/有机改性膨润土复合光催化材料并进行了结构表征;以弹药废水中主要污染物质TNT作为目标物,考察了影响光催化降解性能的因素.结果表明：有机改性后复合材料的吸附性能和光催化性能均有所增加,对TNT的60min的吸附去除率和光催化降解率分别达到9.68％和94.53％;影响TNT光催化降解率的因素有光照时间、催化剂用量、TNT初始浓度、溶液pH值和光照强度.     

Investigation on solar photocatalytic degradation of various dyes in the presence of Er3+:YAlO3/ZnO–TiO2 composite

In this work, Er³⁺:YAlO₃/ZnO–TiO₂ and ZnO–TiO₂ composites were prepared by the ultrasonic dispersion and liquid boiling method. In succession, they were then characterized by X-ray diffraction (XRD) and scanning electron microscopy (SEM). Acid red B as a model dye compound was degraded under solar light irradiation to evaluate the photocatalytic activities of the Er³⁺:YAlO₃/ZnO–TiO₂ and ZnO–TiO₂ composites. We found that the photocatalytic activity of ZnO–TiO₂ composite can be enhanced by adding an appropriate amount of Er³⁺:YAlO₃. We reviewed influencing factors, such as Er³⁺:YAlO₃ content, heat-treated temperature and heat-treated time on the photocatalytic activity of the Er³⁺:YAlO₃/ZnO–TiO₂ composites. In addition, the effects of solar light irradiation time, dye initial concentration, Er³⁺:YAlO₃/ZnO–TiO₂ amount and solution acidity on the photocatalytic degradation of acid red B dye in aqueous solution were investigated in detail. Simultaneously, the degradation and comparison of other dyes such as methyl orange (MO), rhodamine B (RM-B), azo fuchsine (AF), congo red (CG-R) and methyl blue (MB) were also reviewed. In addition, we attempted to explore both the principle of possible excitation of Er³⁺:YAlO₃/ZnO–TiO₂ under solar light irradiation and the mechanism of photocatalytic degradation.     

HPA／ZnFe2O4-TiO2光催化剂的制备及对马拉硫磷的可见光降解

以纳米TiO2载体，利用浸渍法制备了HPA／ZnFe2O4-TiO2光催化剂。对制备的催化剂进行了XRD、BET、TEM和UV-vis DRS表征。结果表明，催化剂样品均为锐钛矿相且ZnFe2O4很好地分散在载体表面，HPA／ZnFe2O4-TiO2光催化荆的平均粒径为10nm且在380-670nm均有强的光响应；反应最佳的HPA浓度为O.08molfL，最佳的ZnFe2O4负载量为1％。考察了HPA溶液初始浓度、ZnFe2O4负载量、溶液初始pH值、H2O2用量、催化剂用量对催化剂活性的影响。在溶液初始pH=13，H2O2=6mmol／L，催化剂用量为2g/L的最优条件下，光照反应进行100min后，马拉硫磷的降解率可达87％；重复4次后马拉硫磷的降解率仍可以达到67％。     

UV/Fenton光解处理含三唑磷废水的研究

采用类UV／Fenton法对模拟三唑磷废水进行处理。在模拟废水中人工投加H2O2和Fe^3＋试剂能产生类Fenton试剂，类Fenton试剂在光照条件过程中可以产生大量活性羟基．OH，能够很好地氧化降解废水中的有机化合物。本方法可以有效的处理低浓度的含三唑磷的废水，提供三唑磷农药水样的UV／Fenton催化氧化过程的一级动力学方程。     

Fenton试剂高级氧化法降解甲基橙模拟废水研究

甲基橙是一种较难降解的有机苯环偶氮染料之一，研究其降解性能对其他染料废水体系的降解研究具有普遍参考价值。通过研究Fenton试剂降解甲基橙过程中的H202浓度、Fe2＋浓度、反应时间和反应体系pH值对甲基橙降解的影响，确定其最佳降解工艺条件为：当甲基橙浓度为20mg／L、pH值为3、Fe2＋浓度为1．5mmol／L、H2O2为32mmol/L时，降解率达到最大值（98．95％）。     

Treatment of IGCC power station effluents by physico-chemical and advanced oxidation processes

The aim of this work was to improve the quality of aqueous effluents coming from the Gasification Unit in an Integrated Gasification Combined Cycle (IGCC) Thermoelectric Power Station, with the purpose of fulfilling the future more demanding normative. To this end, an integral wastewater treatment including coagulation, flocculation, neutralization, photocatalytic oxidation, and ion-exchange has been studied. A final scheme has been proposed to remove pollutants. All the parameters of the treated wastewater are below pouring specifications. In the first stage, the wastewater was treated with CaCl2 (optimal dose=11 g CaCl2/g F-) as coagulant and a commercial anionic polyelectrolyte (optimal dose=0.02 g/g F-) as flocculant to remove fluoride ions (99%) and suspended solids (92%). The water was then neutralized, improving the degree of transmission of ultraviolet light, allowing the faster photo-degradation of pollutants. The photochemical study included different systems (H2O2, UV/H2O2, Fenton, Fenton-like, UV/Fenton, UV/Fenton-like and UV/H2O2/O2). In the Fenton-like system, the influence of two parameters (initial concentration of H2O2 and amount of Cu(II)) on the degradation of cyanide and formate (taken as the reference of the process) was studied. Experimental results were fit using neural networks (NNs). Results showed that the photocatalytic process was effective for total cyanide destruction after 60 min, while 180 min was needed to remove 80% of formates. However, a more simple system with UV/H2O2/O2 yields similar results and is preferred for industrial application due to fewer complications. Finally, an ion-exchange process with Amberlite IRA-420 was proposed to remove the excess of chlorides added as a consequence of the initial coagulation process.