Photocatalytic oxidation and ozonation of catechol over carbon-black-modified nano-TiO2 thin films supported on Al sheet

The photocatalytic activity of the carbon-black-modified nano-TiO2) (CB-TiO2) thin films was 1.5 times higher than that of TiO2 thin films in degrading Reactive Brilliant Red X-3B. Photocatalytic oxidation and ozonation of catechol over CB-TiO2 thin films supported on Al sheet was investigated. The experiments showed that ozone concentrations had an important effect on TOC removal. The combined photocatalysis with UV irradiation and ozonation (TiO2/UV/O3) process considerably increased TOC removal rate compared to combined photocatalysis with UV irradiation and oxygen oxidation (TiO2/UV/O2) process, ozonation alone (O3) process, combined ozonation and UV irradiation (UV/O3) process. The complete mineralization of catechol followed pseudo-zero-order kinetics dependent upon ozone (oxygen) concentration and indicated catechol concentration did not affect the kinetics during UV/O3 and TiO2/UV/O3 (O2) processes. The kinetic study showed that the rate constants in the complete mineralization of catechol with TiO2/UV/O3 are 1.32-1.80 times higher than that of UV/O3 with the same concentration of ozone. The rate constants are 2.56-5.36 times higher than the maximal rate constants of TiO2/UV/O2 and 4.68-9.8 times higher than the maximal rate constants of TiO2/UV.     

Ozone and photocatalytic processes to remove the antibiotic sulfamethoxazole from water

In this study, water containing the pharmaceutical compound sulfamethoxazole (SMT) was subjected to the various treatments of different oxidation processes involving ozonation, and photolysis and catalysis under different experimental conditions. Removal rates of SMT and total organic carbon (TOC), from experiments of simple UVA radiation, ozonation (O(3)), catalytic ozonation (O(3)/TiO(2)), ozone photolysis (O(3)/UVA), photocatalytic oxidation (O(2)/TiO(2)/UVA) and photocatalytic ozonation (O(3)/UVA/TiO(2)), have been compared. Photocatalytic ozonation leads to the highest SMT removal rate (pH 7 in buffered systems, complete removal is achieved in less than 5min) and total organic carbon (in unbuffered systems, with initial pH=4, 93% TOC removal is reached). Also, lowest ozone consumption per TOC removed and toxicity was achieved with the O(3)/UVA/TiO(2) process. Direct ozone and free radical reactions were found to be the principal mechanisms for SMT and TOC removal, respectively. In photocatalytic ozonation, with buffered (pH 7) aqueous solutions phosphates (buffering salts) and accumulation of bicarbonate scavengers inhibit the reactions completely on the TiO(2) surface. As a consequence, TOC removal diminishes. In all cases, hydrogen peroxide plays a key role in TOC mineralization. According to the results obtained in this work the use of photocatalytic ozonation is recommended to achieve a high mineralization degree of water containing SMT type compounds.     

活性炭及联用工艺去除自来水中有机物的效果

为保证直饮水水质并提高其安全性,采用AC、O3/AC、UV/AC、O3/UV/AC工艺对自来水进行处理,考察4种工艺对水中微量有机物的去除效果和O3/AC、UV/AC工艺出水的生物遗传毒性及水质的生物稳定性。结果表明,O3/AC工艺对TOC的去除率最高（44.85%）,其他3种工艺对TOC的去除率均在38%以上;AC工艺对UV254的去除率最低（23.96%）,其他3种工艺对UV254的去除率均高于70%。4种工艺对THMs的去除效果差异不明显,去除率均在40%左右;O3/AC和UV/AC工艺对THMFPs的去除效果好于其他2种工艺的。O3/AC和UV/AC工艺均能保证出水的β-半乳糖苷酶的被诱导活性为阴性,并可保证出水的生物稳定性。     

Discoloration and mineralization of Reactive Red HE-3B by heterogeneous photo-Fenton reaction

Discoloration and mineralization of Reactive Red HE-3B were studied by using a laponite clay-based Fe nanocomposite (Fe-Lap-RD) as a heterogeneous catalyst in the presence of H2O2 and UV light. Our experimental results clearly indicate that Fe-Lap-RD mainly consists of Fe2O3 (meghemite) and Fe2Si4O10(OH)2 (iron silicate hydroxide) which have tetragonal and monoclinic structures, respectively, and has a high specific surface area (472 m2/g) as well as a high total pore volume (0.547 cm3/g). It was observed that discoloration of HE-3B undergoes a much faster kinetics than mineralization of HE-3B. It was also found that initial HE-3B concentration, H2O2 concentration, UV light wavelength and power, and Fe-Lap-RD catalyst loading are the four main factors that can significantly influence the mineralization of HE-3B. At optimal conditions, complete discoloration of 100 mg/L HE-3B can be achieved in 30 min and the total organic carbon removal ratio can attain 76% in 120 min, illustrating that Fe-Lap-RD has a high photo-catalytic activity in the photo-assisted discoloration and mineralization of HE-3B in the presence of UV light (254 nm) and H2O2.     

南方某水厂臭氧/活性炭深度处理工艺运行效果

以南方地区微污染水源水为对象,研究臭氧/活性炭深度处理工艺对有机物综合指标UV(254)、COD(Mn)、TOC的去除效果以及对消毒副产物的控制效果,并结合三维荧光光谱技术分析溶解性有机物的荧光特性。结果表明,与常规处理工艺相比,增加臭氧/活性炭深度处理工艺后,对UV(254)、COD(Mn)、TOC、三卤甲烷前体物的去除率分别提高了47.05%、20.24%、31.11%、37.70%。三维荧光光谱分析结果表明,该地区微污染水源水主要由芳香性蛋白质类物质、溶解性微生物代谢产物类物质和富里酸类物质组成,臭氧/活性炭深度处理工艺对荧光溶解性有机物的去除效果明显。     

Hybrid photocatalysis/membrane treatment for surface waters containing low concentrations of natural organic matters

Since the mid-1990s, numerous studies on the treatment of drinking water by photocatalysis have been reported. Once optimised, the photocatalytic process can completely degrade numerous natural and artificial organic compounds. In this study, a hybrid photocatalysis/membrane process was used as a polishing treatment of surface water containing a small concentration of natural organic matters (i.e. total organic carbon (TOC) concentration of around 3mg/L) which may be difficult to remove using conventional filtration or coagulation. An optimum pH of 4.5 and a TiO(2) concentration of 0.1g/L were found to lead to the highest removal efficiencies. The relative effect of the individual processes featuring in the hybrid system (UV radiation, TiO(2) adsorption and membrane filtration) was also assessed for different pH values. The membrane separation process was accounted to remove around 18% of the initial TOC concentration, while TiO(2) adsorption alone was generally responsible for less than 5% of TOC removal during the 120 min of the experiments. However, when the natural water was only radiated by UV light, up to 70% of TOC was removed. A synergetic effect was observed when the three processes (TiO(2), UV and membrane) were used together. Comparison of removal efficiencies obtained during real and model (International Humic Substance Society) waters treatment by photocatalysis is also presented, revealing the importance of the nature of the feed in this type of treatment.     

Evaluation of the treatment performance of a multistage ozone/hydrogen peroxide process by decomposition by-products

The performance of a multistage ozone/hydrogen peroxide (O3/H2O2) process was evaluated with respect to total organic carbon (TOC) removal of waste waters. An aqueous humic acid solution (5.2 mgC l(-1) as TOC) and a sand filtered secondary sewerage effluent (5.6mgC l(-1) as TOC) were used as model waste waters. Appropriate range of hydrogen peroxide (H2O2) dose at each stage depended upon the components of the tested solutions that changed as the process proceeded. Higher hydrogen peroxide dose was required at later stages in which low reactivity compounds with hydroxyl radical (HO*), low molecular fatty acids, were predominant. And, oxalic acid concentration related to H2O2 demand at later stages. This was assumed that the slow decomposition of oxalic acid was rate-determining step for TOC removal after its accumulation. Also, it is important to maintain dissolved ozone at low concentration for efficient TOC removal because rapid ozone consumption is required for the rapid formation of hydroxyl radical (HO*).     

Kinetics and mechanisms of DMSO (dimethylsulfoxide) degradation by UV/H(2)O(2) process

The objective of this study was to elucidate the degradation pathways of dimethylsulfoxide (DMSO) during its mineralization caused by UV/H(2)O(2) treatment. In order to accomplish this, we measured the concentration time-profiles of DMSO and its degradation intermediates during the UV/H(2)O(2) treatment. In addition, we proposed a kinetic model that could account for the degradation pathways of DMSO during its UV/H(2)O(2) treatment. The results show that the degradation of DMSO by the UV/H(2)O(2) treatment can be classified into two major pathways, and this is supported by both the analysis of the intermediates and total organic carbon (TOC) measurements. Firstly, DMSO was degraded into sulfate (SO(4)(2-)) through the formation of methansulfinate (CH(3)SO(2)(-)) and methansulfonate (CH(3)SO(3)(-)) as sulfur-containing intermediates. One of the two carbon constituents of DMSO was highly resistant to mineralization, due to the formation of methansulfonate, which reacted very slowly with (.-)OH k = 0.8 x 10(7) M(-1)s(-1)). Secondly, the other carbon constituent of DMSO was relatively easily mineralized through the formation of formaldehyde (HCHO) and formate (HCO(2)(-)) as non-sulfur-containing intermediates. The kinetic model proposed in this study for the degradation of DMSO by (.-)OH in the UV/H(2)O(2) process was able to successfully predict the patterns of concentration time-profiles of all components during the UV/H(2)O(2) treatment of DMSO.     

ZnO/O3工艺降解水中微量有机物的研究

以实验室制备的粉末氧化锌(ZnO)为催化剂,考察了ZnO/O3工艺去除水中有机物的效能.采用总有机碳(TOC)指标反映水中有机污染物的含量.结果表明:臭氧投量为1 mg/L、ZnO投量为300 mg/L时,反应60 min后ZnO-O3工艺对TOC的去除率为46%,比单独臭氧化提高了1倍;反应温度明显影响该工艺对有机物的降解效果,在水温为5,10,20和25 ℃时,TOC的去除率分别为17.5%,31.5%,45.9%和51.3%.臭氧浓度和催化剂投量的增加,可以提高TOC的氧化降解效率.     

Advanced oxidation of a reactive dyebath effluent: comparison of O3, H2O2/UV-C and TiO2/UV-A processes

In the present study the treatment efficiency of different AOPs (O3/OH- H2O2/UV-C and TiO2/UV-A) were compared for the oxidation of simulated reactive dyebath effluent containing a mixture of monochlorotriazine type reactive dyes and various dye auxiliary chemicals at typical concentrations encountered in exhausted reactive dyebath liquors. A525 (color), UV280 (aromaticity) and TOC removal rates were assessed to screen the most appropriate oxidative process in terms of reactive dyebath effluent treatment. Special emphasis was laid on the effect of reaction pH and applied oxidant (O3, H2O2) dose on the observed reaction kinetics. It was established that the investigated AOPs were negatively affected by the Na2CO3 content (= 867 mg/L) which is always present at high concentrations in dychouse effluents since it is applied as a pH buffer and dye fixation agent during the reactive dyeing process. The ozonation reaction exhibited almost instantaneous decolorization kinetics and a reasonable TOC reduction rate. It appeared to be stable under the investigated advanced oxidation conditions and outranked the other studied AOPs based on the above mentioned criteria. Besides, the electrical energy requirements based on the EE/O parameter (the electrical energy required per order of pollutant removal in 1 m3 wastewater) was calculated for the homogenous AOPs in terms of decolorization kinetics. In view of the electrical energy efficiency, ozonation and H2O2/UV-C oxidation at the selected treatment conditions appear to be promising candidates for full-scale dyehouse effluent decolorization.     

Treatment of landfill leachate by combined aged-refuse bioreactor and electro-oxidation

Two-stage aged-refuse bioreactor (ARB) was applied to treat landfill leachate in Shanghai Waste Laogang Disposal Plant. The removal efficiencies of chemical oxygen demand (COD), biological oxygen demand (BOD), total organic carbon (TOC), total nitrogen (TN) and ammonia nitrogen (NH(3)-N) of landfill leachate treated by the two-stage bioreactor system were 98.5%, 99.9%, 98.0%, 64.2% and 99.9%, respectively. The COD and BOD in the second stage effluent were 239 and 7 mg l(-1), respectively. Thus three types of electrolysis were employed to further treat the second effluent, undivided electrolysis (UDE), divided electrolysis (DE) with Ti/PbO(2) cathode and DE with gas diffusion cathode. All electrolysis processes possessed good color removal effect, while the DE with gas diffusion cathode had the best TOC removal effect. The optimum electrolysis time of leachate was 30 min. The TOC removal efficiencies were 51.4% and 39.7% in anolyte and catholyte, respectively, after 30 min electrolysis at 5 V. In addition, the DE with gas diffusion cathode showed the least energy consumption of 9.8 k Whm(-3) at 30 min. The organic pollutants in the leachate were analyzed through a gas chromatography coupled with mass spectrometry (GC-MS) system. Through the two-stage ARB, the species and concentrations of organic pollutants in landfill leachate reduced greatly. Several chlorinated organic compounds were detected in the effluent after the UDE and the anolyte of the DE. In addition, the concentration of absorbable organic halogens (AOX) increased greatly during the electrolysis. Hence, careful consideration should be given in the application of electro-oxidation into the treatment of chloride-containing wastewater.     

UV/H2O2/微曝气处理微污染水中苯胺的试验研究

采用UV/H2O2/微曝气、UV/H2O2、UV/微曝气、H2O2/微曝气四种工艺处理受苯胺污染的水源水.试验结果表明,采用UV/H2O2/微曝气工艺,H2O2投加量分别为1,2,5,10和20 mL,对苯胺均有理想的去除效果.随着投加量的增加,苯胺的去除率并没有明显的提高,反应30 min后去除率分别达到94.3%,96.4%,96.5%,97.3%和96.8%.原水苯胺为0.90 mg/L时,投加1 mL H2O2反应30 min后,出水苯胺为0.06 mg/L,满足标准要求.UV/H2O2/微曝气、UV/H2O2、UV/微曝气、H2O2/微曝气四种工艺对苯胺的去除率均随着时间的增长而提高,40 min后趋于平稳,最高去除率分别为97.9%,94.5%,64.27%和13.84%,UV/H2O2/微曝气、UV/H2O2出水苯胺均低于规定限值.     

Application of O3/UV/H2O2 oxidation and process optimization for treatment of potato chips manufacturing wastewater

Effluents coming from potato chips manufacturing have high organic loads and require adequate treatment before discharge to environment. In this study, O₃/UV/H₂O₂ advanced oxidation process was applied to treat these wastewaters. With this aim, batch experiments were conducted in a reaction tank equipped with ozone injection and UV irradiation. Process variables were determined to be pH, ozone concentration, reaction time, H₂O₂ dosage and efficiency of the system was evaluated considering total organic carbon (TOC) removal. Central composite design technique was applied to examine the individual and synergetic effects of the experimental factors. A quadratic model was developed to maximize the TOC removal. Furthermore, operation costs were calculated for different experimental conditions and interactions between process variables and costs were analysed.     

Treatment of biorefractory organic compounds in wool scour effluent by hydroxyl radical oxidation

Wool scouring effluent that had been treated with chemical flocculation and aerobic biological treatment (Sirolan CFB effluent) was tertiary treated by hydroxyl radical oxidation to remove residual organic compounds. These compounds impart a high chemical oxygen demand of 500-3000 mg/L and dark colour. However, a H2O2/UV process was found to effectively treat the majority of residual compounds, with up to 75% COD, 85% total organic carbon, and 100% removal of colour (T(480 nm)) achieved. This was despite the effluent being strongly absorbing in the UV region, with a film thickness of 0.21 mm reducing T(254 nm) by 50%. Treatment was unaffected by pH over the range 3-9. H2O2/UV treatment increased the biodegradability of the effluent (5-day biochemical oxygen demand increased from < 10 to 86 mg/L), but a combined chemical and biological process did not increase maximum COD removal or overall process efficiency. The tertiary treated effluent had a final COD in the range 125-750 mg/L, equating to a total COD removal from raw wool scour effluent of approximately 97.5%. This degree of treatment is sufficient for discharge in many, but not all, circumstances.     

Advanced oxidation and adsorption technologies for organic micropollutant removal from lake water used as drinking-water supply

The goal of this research is to evaluate the effectiveness of innovative drinking-water treatments designed to remove toxic and mutagenic organic micropollutants from lake waters used for human consumption. The widely used adsorption on granular activated carbon (GAC) filter technique was compared with the more innovative resin column techniques (XAD4 and Ambersorb-563) and with the advanced oxidation processes (AOPs) with UV/O3 and UV/O3/ H2O2. The water samples, collected from lake Como, treated with these techniques were analysed for mutagenic activity using Ames assay, toxicity using bioluminescent bacteria and organic compound were characterized using the GC-MS technique. The results found a decrease of the mutagenic and toxic activities of the lake water after adsorption on GAC and resins, while the AOP process generally increased these parameters. The absence of mutagenic activity was found only when a GAC adsorption step was performed in addition to the AOP process. Similar results were obtained by the toxicological and chemical analyses. In addition, the GC-MS analysis identified some possible mutagenic agents.     

氧化剂协同即时成膜型光催化反应器降解有机物

研究了“表观”即时成膜型UV／TiO2光催化反应器降解水中有机污染物的过程中,外加氧化剂与UV／TiO2体系之间的协同效应。在UV／TiO2体系中单独投加H2O2或O3可以提高光催化氧化有机污染物的速率和效率,同时投加H2O2和O3时则光催化氧化的协同作用更加显著,可大大缩短反应时间。不同反应体系的表观速率常数排序为：UV／H2O2／O3／TiO2〉UV／O3／TiO2〉UV／H2O2／TiO2〉UV／O3〉UV／H2O2〉UV／TiO2。     

Enhancing Fenton oxidation of TNT and RDX through pretreatment with zero-valent iron

The effect of reductive treatment with elemental iron on the rate and extent of TOC removal by Fenton oxidation was studied for the explosives 2,4,6-trinitrotoluene (TNT) and hexahydro-1,3,5-trinitro-1,3,5-triazine (RDX) using a completely stirred tank reactor (CSTR). The results support the hypothesis that TNT and RDX are reduced with elemental iron to products that are oxidized more rapidly and completely by Fenton's reagent. Iron pretreatment enhanced the extent of total organic carbon (TOC) removal by approximately 20% and 60% for TNT and RDX, respectively. Complete TOC removal was achieved for TNT and RDX solutions with iron pretreatment under optimal conditions. On the other hand, without iron pretreatment, complete TOC removal of TNT and RDX solutions was not achieved even with much higher H(2)O(2) and Fe(2+) concentrations. Nitrogen was recovered as NH(4)(+) and NO(3)(-) when Fe(0)-treated TNT and RDX solutions were subjected to Fenton oxidation. The bench-scale iron treatment-Fenton oxidation integrated system showed more than 95% TOC removal for TNT and RDX solutions under optimal conditions. These results suggest that the reduction products of TNT and RDX are more rapidly and completely degraded by Fenton oxidation and that a sequential iron treatment-Fenton oxidation process may be a viable technology for pink water treatment.     

Removal of pharmaceuticals and kinetics of mineralization by O(3)/H(2)O(2) in a biotreated municipal wastewater

The ozonation of an effluent from the secondary clarifier of two Municipal Wastewater Treatment Plants was performed by using alkaline ozone and a combination of ozone and hydrogen peroxide. Alkaline ozonation achieved only a moderate degree of mineralization, essentially concentrated during the first few minutes; but the addition of hydrogen peroxide eventually led to a complete mineralization. The evolution of total organic carbon (TOC) as a measure of the extent of mineralization and the concentration of dissolved ozone were analyzed and linked in a kinetic model whose parameter represented the product of the exposure to hydroxyl radicals and the kinetic constant of indirect ozonation. This rate parameter yielded the highest values during the first part of O(3)/H(2)O(2) runs. The kinetic constant for the decomposition of ozone at the end of the run was also measured and computed for the non-oxidizable water matrix and yielded essentially the same values regardless of whether or not hydrogen peroxide was used. A group of 33 organic compounds, mainly pharmaceuticals and some relevant metabolites present in the wastewater effluents, were evaluated before and after the ozonation process using a liquid chromatography-hybrid triple-quadrupole linear ion trap system (LC-QqLIT-MS). The results demonstrate that the ozonation degrades these compounds with efficiencies of over 99% in most cases, even under low mineralization conditions in alkaline ozonation.     

Comparison of different advanced oxidation processes for phenol degradation

Advanced Oxidation Processes (O3, O3/H2O2, UV, UV/O3, UV/H2O2, O3/UV/H2O2, Fe2+ /H2O2 and photocatalysis) for degradation of phenol in aqueous solution have been studied in earlier works. In this paper, a comparison of these techniques is undertaken: pH influence, kinetic constants, stoichiometric coefficient and optimum oxidant/pollutant ratio. Of the tested processes, Fenton reagent was found to the fastest one for phenol degradation. However, lower costs were obtained with ozonation. In the ozone combinations, the best results were achieved with single ozonation. As for the UV processes, UV/H2O2 showed the highest degradation rate.     

微波/Fe-Zr联用技术处理正丁酸模拟废水的研究

采用自制的Fe—Zr为催化剂、H2O2为氧化剂、正丁酸为模拟污染物,以TOC去除率为指标,对微波／Fe—Zr联用技术进行了研究。分别考察了Fe—Zr用量、H2O2用量、微波炉的功率、微波的作用时间及Fe—Zr重复使用的次数对TOC去除率的影响;并利用一次回归正交试验确定了微波／Fe—Zr联用技术处理正丁酸模拟废水的优化条件,即处理TOC约为490mg／L的150mL正丁酸模拟废水,Fe—Zr的用量为4g、H2O2的用量为7mL、微波炉的功率为640W、微波的作用时间为10min,此时对TOC的去除率高达95％;最后在优化条件的基础上,对6种不同的处理工艺进行了比较,结果表明微彬Fe—Zr联用技术对TOC的去除率最高。