铁氧化物复合氧化铝催化臭氧化过程中溴酸盐的生成控制

以市售活性炭、硅藻土和氧化铝小球为载体，考察了负载铁基活性组分对催化臭氧化过程中溴酸盐的控制情况，其中，铁基复合氧化铝小球体现出更好的溴酸盐还原特性和催化剂稳定性，证实催化剂中铁氧化物是溴酸盐得到有效控制的主要活性组分。进一步考察了铁基复合氧化铝小球催化臭氧化处理实际原水过程中对溴酸盐的生成控制，以及反应过程中溶解性有机碳（DOC）的去除情况。结果表明，与单独臭氧化相比，该催化剂既能有效去除水中的溶解性有机物，又能明显抑制溴酸盐的生成，反应50h，其活性并没有明显下降。催化剂失活主要归因于吸附位点数量的下降，可以通过负载铁氧化物来实现催化剂的再生。     

Mn的氧化价态对Mn／γ-Al2O3催化剂催化臭氧氧化气相低浓度甲苯的影响

采用共沉淀法，以Al2O3为载体制备Mn／γ-Al2O3和Mn—Ce／Mn／γ-Al2O3催化剂，并分别在N2气氛和O2气氛下焙烧。采用固定床连续流动反应器，研究所制备催化剂在室温条件下催化臭氧氧化甲苯的性能。通过XRD、XPS和FTIR等手段对催化剂的结构和组成进行表征。结果表明，Mn／Mn／γ-Al2O3催化剂具有良好的催化臭氧氧化甲苯和催化臭氧自身分解的性能，共沉淀法制备催化剂的最佳Mn负载量为20％。O2气氛焙烧和Ce的加入，可以有效提高催化剂的活性和寿命。原因是O2气氛焙烧和Ce的加入可以提高Mn的氧化价态。催化剂失活的主要原因是有机副产物在催化剂表面吸附堆积，失活催化剂在550℃、空气气氛下焙烧可恢复催化性能。     

Catalytic oxidation of gaseous PCDD/Fs with ozone over iron oxide catalysts

Catalytic oxidation of PCDD/Fs (polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans) with ozone (catalytic ozonation) over nano-sized iron oxides (denoted as FexOy) was carried out at temperature of 120-180 degrees C. The effects of operating temperature, ozone concentration, space velocity (SV) and water vapor contents on PCDD/F removal and destruction efficiencies via catalytic ozonation were investigated. High activity of the iron oxide catalyst towards PCDD/F decomposition was observed even at low temperatures with the aid of ozone. The PCDD/F removal and destruction efficiencies achieved with FexOy/O3 at 180 degrees C reach 94% and 91%, respectively. In the absence of ozone, the destruction efficiencies of all PCDD/F congeners are below 20% and decrease with increasing chlorination level of PCDD/F congener at lower temperature (120 degrees C). However, in the presence of ozone, the destruction efficiencies of all PCDD/F congeners are over 80% on FexOy/O3 at 180 degrees C. Higher temperature and ozone addition increase the activity of iron oxide for the decomposition of PCDD/Fs. Additionally, in the presence of 5% water vapor, the destruction efficiency of the PCDD/Fs is above 90% even at lower operating temperature (150 degrees C). It indicates that the presence of appropriate amount of water vapor enhances the catalytic activity for the decomposition of gas-phase PCDD/Fs.     

铁及铁铜氧化物对臭氧氧化酸性红B的催化效能

采用自蔓延溶胶凝胶法分别制备了铁氧化物和铁铜复合氧化物催化剂,以酸性红B为降解对象,对比了单独臭氧氧化、铁氧化物和铁铜复合氧化物催化臭氧氧化对酸性红B的降解效果,考察了磁力搅拌速度(500～1 640 r/min)、溶液pH(3～11)、臭氧投加速率(3.55～28.4 mg/min)对铁铜复合氧化物催化性能的影响。结果表明,与单独臭氧氧化比较,铁氧化物和铁铜复合氧化物均能加速酸性红B的降解,促进色度和COD的去除,结合催化剂的表征结果,推断催化剂表面羟基促进臭氧分解产生.OH是其氧化性能较好的主要原因,另外,催化剂的吸附能力对催化性能也有一定影响。随着磁力搅拌速度、溶液pH、臭氧投加速率的增大,铁铜复合氧化物催化臭氧氧化酸性红B的效果越好。     

Atrazine removal by ozonation processes in surface waters

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 continuously. 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.     

Effect of manganese ion on the mineralization of 2,4-dichlorophenol by ozone

Mineralization of 2,4-dichlorophenol (DCP) was studied by ozone with Mn(2+) as an ozonation catalyst. Laboratory scale semi-batch ozonation experiments were conducted at room temperature. The results showed that trace amount of Mn(2+) accelerated the mineralization of DCP. Total organic carbon removal rate was independent on Mn(2+) dosage at its range of 0.1-0.5 mgL(-1). Dissolved ozone concentration in the solution remained low level in the catalytic ozonation process, which indicated that Mn(2+) catalyzed decomposition of ozone. DCP mineralization was inhibited in catalytic ozonation by the addition of carbonate. Electron spin resonance/spin-trapping technique was used to determine hydroxyl radicals, and the results showed that larger amounts of hydroxyl radicals were produced in catalytic ozonation system than those of single ozonation. Intermediates mainly including aliphatic carboxylic acids were determined qualitatively and semi-quantitatively by GC-MS. And, a general pathway for mineralization of DCP was proposed.     

NiO/AC催化臭氧氧化去除水中的苯酚

采用低温湿式浸渍法制备了负载氧化镍/活性炭(简称NiO/AC)催化剂。在不同pH、叔丁醇浓度等条件下,对NiO/AC与臭氧联合催化臭氧氧化苯酚的降解效果等进行了研究。用XRD、SEM及BET技术分析了活性炭与催化剂的组成、形貌及结构变化。结果表明,镍以棒状氧化镍的形式负载在活性炭表面,与AC相比,NiO/AC比表面积减少了47.9%。在O3/NiO/AC与苯酚的反应体系中,反应遵循羟基自由基(HO.)机理,苯酚的去除率比单独臭氧氧化提高了29%,且与溶液pH呈正相关。NiO/AC催化性能较稳定,镍离子最大析出浓度仅为7 mg/L,可重复使用。     

Mineralization of C.I. Reactive Yellow 84 in aqueous solution by sonolytic ozonation

The operational parameters and mechanism of mineralization of C.I. Reactive Yellow 84 (RY84), one of the azo dyes, in aqueous solution were investigated using sonolytic ozonation (US/O(3) oxidation). Of the pseudo-first-order degradation rate constants of TOC reduction, 9.0 x 10(-4), 7.3 x 10(-3) and 1.8 x 10(-2)min(-1) were observed with US, O3, and a combination of US and O3, respectively. These results illustrate that ozonation combined with sonolysis for removal of TOC is more efficient than ozonation alone or ultrasonic irradiation alone without considering the operating costs. With the initial pH value at 10.0, the ozone dose at 4.5 g h(-1), the energy density of ultrasound at 176 W l(-1), and the initial concentration of RY84 at 100 mg l(-1), the extent of mineralization measured as TOC loss was maximized. The variation of the concentrations of related ions (oxalate, formate, acetate, NO3(-), NO2(-), NH4(+), Cl(-), and SO4(2-)) during the reaction process was monitored. Other organic intermediates detected by GC/MS were N-methyleneaniline, phthalic acid, 4-hydroxyphthalic acid, isocyanatobenzene, aniline, 4-iminocyclohexa-2,5-dien-1-one, butene diacid and urea. Based on these findings, a tentative degradation pathway was proposed.     

Decomposition of 2-mercaptothiazoline in aqueous solution by ozonation

This study investigates the ozonation of 2-mercaptothiazoline (2-MT). The 2-MT is one of the important organic additives for the electroplating solution of the printed wiring board industry and has been widely used as a corrosion inhibitor in many industrial processes. It is of concern for the aquatic pollution control especially in the wastewaters. Semibatch ozonation experiments in the completely stirred tank reactor are performed under various concentrations of input ozone. The concentrations of 2-MT, sulfate, and ammonium are analyzed at specified time intervals to elucidate the decomposition of 2-MT during the ozonation. In addition, the time variation of the dissolved ozone concentration (C(ALb)) is continuously monitored in the course of experiments. Total organic carbon (TOC) is chosen and measured as a mineralization index of the ozonation of 2-MT. The results indicate that the decomposition of 2-MT is efficient, while the mineralization of TOC is limited via the ozonation only. Simultaneously, the yield of sulfate with the maximum value of about 47% is characterized by the increases of TOC removal and ozone consumption. These results can provide some useful information for assessing the feasibility of the treatment of 2-MT in the aqueous solution by the ozonation.     

Enhancement of chemical-oxygen demand and color removal of distillery spent-wash by ozonation.

Distillery spent-wash has very high organic content (75,000 to 125,000 mg/L chemical-oxygen demand [COD]), color, and contains difficult-to-biodegrade organic compounds. For example, anaerobic treatment of the distillery spent-wash used in this study resulted in 60% COD reduction and low color removal. Subsequent aerobic treatment of the anaerobic effluent resulted in enhancement of COD removal to 66%. In this paper, the effect of ozonation on various properties of the anaerobically treated distillery effluent, including the effect on its subsequent aerobic biodegradation, was investigated. Ozonation of the anaerobically treated distillery effluent at various ozone doses resulted in the reduction of total-organic carbon (TOC), COD, COD/TOC ratio, absorbance, color, and increase in the biochemical-oxygen demand (BOD)/COD ratio of the effluent. Further, ozonation of the anaerobically treated distillery effluent at an ozone dose of 2.08 mg/mg initial TOC and subsequent aerobic biodegradation resulted in 87.4% COD removal, as compared to 66% removal when ozonation was not used.     

Ozonation catalyzed by homogeneous and heterogeneous catalysts for degradation of DEHP in aqueous phase

Di-(2-ethyl hexyl) phthalate (DEHP), a recalcitrant and an endocrine disrupting chemical, was studied for its removal from wastewater by advanced oxidation process. The effects of pH, transition metal ions, and granular activated carbon (GAC) were investigated. Removal of DEHP increased with increase in pH and among metal ions Cr(III) was found to be the most active catalyst to remove DEHP. In the case of GAC, original carbon (G0) and GAC pre-ozonated in gas phase for 10 min (G10) were tested as catalysts in catalytic ozonation and found G0 to be more active than G10. This is because, during pre-ozonation, basic groups like chromene, pyrones and also graphene layers were oxidized to acidic surface oxygen groups. These basic surface groups are reported to be active catalytic centres for ozone decomposition into .OH which is a strong oxidant. According to kinetic manipulations, DEHP degradation rate constant due to .OH was affected by the catalyst while that due to direct ozonation is same in all cases with or without catalyst. G0 was doped with chromia gels (G0/CrA) to combine the benefits of homogeneous and heterogeneous catalysis. G0/CrA showed lower catalytic efficiency than that of only G0. This might be because of changes in surface structure of GAC caused by doping of chromia gel and changes in chemical nature of Cr(III) during formation of gel. A good correlation was found between the rate constants of ozone decay and DEHP degradation (R2=0.96). This correlation confirms that ozone decomposition into .OH is a critical factor for the activity of a catalyst during ozonation.     

紫外光助臭氧化处理活性艳红K-2BP废水研究

以 30 0W高压汞灯为光源 ,研究了紫外光联合臭氧化、单纯臭氧氧化及单纯紫外光照处理 4 0 0mg/L的活性艳红K 2BP废水的可行性。结果表明 :光催化臭氧化可加速有机物的矿化。在同样时间条件下 ,三者氧化能力由大至小为 :UV/O3 >单独O3 >单独UV。运用TOC、紫外 可见光谱 (UV Vis)、毛细管电泳 (CE)等分析技术初步探讨了紫外光催化臭氧化活性艳红K 2BP溶液的降解效果及降解机理。     

Catalytic degradation of Orange II by UV-Fenton with hydroxyl-Fe-pillared bentonite in water

Although homogeneous photo-Fenton system is a very efficient method for organic wastewater treatment, it suffers from costly pH adjustment as well as difficult separation of catalysts from aqueous in practical application. Through cation exchange reaction, hydroxyl-Fe-pillared bentonite (H-Fe-P-B) was successfully prepared as a solid catalyst for UV-Fenton to degrade non-biodegradable azo-dye Orange II. Compared with raw bentonite, the content of iron, interlamellar distance and external surface area of H-Fe-P-B increased remarkably. H-Fe-P-B had good photosensitivity and catalyst reactivity. And the catalytic activity of H-Fe-P-B for H(2)O(2) came from hydroxyl-Fe between sheets rather than Fe(3+) or Fe(2+) in tetrahedral or octahedral sheets of bentonite. In UVA-H(2)O(2) system, H(2)O(2) could destroy the azo bond of excited Orange II molecules but could not effectively mineralize it. After 120 min treatment, 83% discoloration was obtained while only 2% of TOC was removed. When H-Fe-P-B was used as catalyst, a significant degradation of Orange II was observed at the same condition as UVA-H(2)O(2) system. Almost 100% discoloration and more than 60% TOC removal of Orange II could be achieved after 120 min treatment. Because of the strong surface acidity and the electronegativity of H-Fe-P-B, the pH range of this catalyst in the Orange II discoloration could be extended up to 9.5. And this catalyst showed good stability during Orange II degradation in water in wide range of pH (3.0-9.5). These results indicated that the H-Fe-P-B was a promising catalyst for UV-Fenton system.     

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)。     

Degradation of atrazine by catalytic ozonation in the presence of iron scraps: performance,transformation pathway,and acute toxicity

Degradation of atrazine by catalytic ozonation in the presence of iron scraps (ZVI/O₃) was carried out. The key operational parameters (i.e., initial pH, ZVI dosage, and ozone dosage) were optimized by the batch experiments, respectively. This ZVI/O₃ system exhibited much higher degradation efficiency of atrazine than the single ozonation, ZVI, and traditional ZVI/O₂ systems. The result shows that the pseudo-first-order constant (0.0927?min^?1) and TOC removal rate (86.6%) obtained by the ZVI/O₃ process were much higher than those of the three control experiments. In addition, X-ray diffraction (XRD) analysis indicates that slight of γ-FeOOH and Fe₂O₃ were formed on the surface of iron scrap after ZVI/O₃ treatment. These corrosion products exhibit high catalytic ability for ozone decomposition, which could generate more hydroxyl radical (HO^?) to degrade atrazine. Six transformation intermediates were identified by liquid chromatography-mass spectrometry (LC-MS) analysis in ZVI/O₃ system, and the degradation pathway of atrazine was proposed. Toxicity tests based on the inhibition of the luminescence emitted by Photobacterium phosphoreum and Vibrio fischeri indicate the detoxification of atrazine by ZVI/O₃ system. Finally, reused experiments indicate the approving recyclability of iron scraps. Consequently, the ZVI/O₃ system could be as an effective and promising technology for pesticide wastewater treatment.     

Catalytic ozonation of 2,4-dichlorophenoxyacetic acid using alumina in the presence of a radical scavenger

Using a laboratory-scale mixed reactor, the performance of alumina in degrading 2,4-Dichlorophenoxyacetic acid with ozone in the presence of tert-butyl alcohol radical scavenger was studied. The operating variables investigated were the dose of alumina catalyst and solution pH. Results showed that using ozone and alumina leads to a significant increase in 2,4-D removal in comparison to non-catalytic ozonation and adsorption processes. The observed reaction rate constants (k(obs)) for 2,4-D during ozonation were found to increase linearly with increasing catalyst dose. At pH 5, the k(obs) value increased from 19.3 to 26 M(-1) s(-1) and 67 M(-1) s(-1) when varying the alumina dose from 1 to 2 and 4 g L(-1), respectively. As pH was increased, higher reaction rates were observed for both non-catalytic ozonation and catalytic ozonation processes. Thus, at pH 3 and using a catalyst dose of 8 g L(-1), the k(obs) values for non-catalytic ozonation and catalytic ozonation processes were 3.4 and 58.9 M(-1) s(-1), respectively, whereas at pH 5 reaction rate constants of 6.5 and 128.5 M(-1) s(-1) were observed, respectively. Analysis of total organic carbon suggested that catalytic ozonation with alumina achieved a considerable level of mineralization of 2,4-D. Adsorption of 2,4-D on alumina was found to play an important role in the catalytic ozonation process.     

Characteristics of MnO2 catalytic ozonation of sulfosalicylic acid and propionic acid in water

The characteristics of different types of MnO₂ catalytic ozonation of sulfosalicylic acid (SSal) and propionic acid (PPA) have been investigated in this paper. The experimental results show the dependence of catalytic activity of MnO₂ on organic compounds and the pH of solutions, but it is independent on the type of MnO₂. For example, three types of MnO₂ have not any catalytic activity when ozonation of PPA under the condition of this experiment. All MnO₂ catalytic ozonation of SSal at pH=1.0 have a greater total organic carbon removal than ozonation alone has, however, at pH=6.8 and 8.5, catalytic efficiency is not observed. Furthermore, the batch experimental results indicate that there are no direct relationship between the activity of metal oxide catalytic decomposition of ozone and that of its catalytic degradation of organic compounds.     

Ozone-driven photocatalyzed degradation and mineralization of pesticide,Triclopyr by Au/TiO2

Triclopyr is a widely used pesticide which is non-biodegradable and enters aquatic systems. The ozone facilitated photocatalyzed degradation and mineralization of Triclopyr using Au-loaded titania as heterogeneous catalyst is reported. The oxidative degradation activity of the hazardous pesticide was investigated at pH 7.8 under varied reaction conditions, including in presence and absence of ozone, titania alone, in presence and absence of light and with different loadings of Au on support. Photocatalysis with 2% Au/TiO₂ in the presence of ozone yielded 100% degradation of Triclopyr in 2 h. The extent of degradation of pesticide and its mineralization were confirmed by GC-MS. For 10 mg/L of Triclopyr, 0.1 g/L of catalyst was found to be the optimum for mineralization. Results show that photocatalyzed ozonation with Au/TiO₂ as catalyst is a very effective for its removal. No leaching of Au was observed in triplicate runs. Catalyst was fully recoverable and reusable with no loss of activity.     

Chemical oxidation of wastewater from molasses fermentation with ozone

Color removal from biologically pre-treated molasses wastewater by means of chemical oxidation with ozone has been investigated. Batch experiments have been performed in order to analyze the influence of ozone dosage and reaction time on color removal, molecular weight distribution and decolorization kinetics. Depending on the applied ozone dosage, color removal from 71% to 93% and COD reduction from 15% to 25% were reached after 30 min reaction time. TOC values remained constant throughout ozonation. Gel permeation chromatography corroborated that high molecular weight compounds, responsible for the brown color, were present in raw wastewater. UV spectral studies confirmed that these colored compounds were melanoidins. As a result of ozonation the concentration of chromophore groups decreased. Ozonation of synthetic melanoidin under the same experimental conditions provided similar color removal efficiencies. Pseudo-first order kinetics with respect to colored compounds were found.     

Cu-SBA-15催化湿式过氧化氢氧化水溶液中罗丹明B

采用水热晶化法合成了不同含铜量的Cu—SBA-15介孔分子筛，并且用XRD、N2吸附、TEM以及uV—vis对所合成的样品进行表征。以Cu—SBA-15为催化剂，H2O2为氧化剂，催化湿式过氧化水溶液中的罗丹明B，主要考察H2O2浓度、催化剂用量、处理温度、初始pH等因素对罗丹明B氧化效果的影响。结果表明，在同样的处理条件下罗丹明的脱色率明显高于TOC去除率，处理温度、初始pH对罗丹明B的脱色与氧化有重要影响。在罗丹明B初始浓度100mg／L，H2O2初始浓度1．8g／L，催化剂量0．3g／L，温度60℃，pH为7．0，处理时间100min时，罗丹明B的脱色率为98．6％，TOC去除率为62．8％。