Kinetics and Mechanism of Catalytic Ozonation of Aqueous Pollutants on Metal Oxide Catalysts

The catalytic ozonation of fenofibric and clofibric acids and the herbicides atrazine and linuron was studied using titanium dioxide, alumina, and manganese oxide supported on activated alumina and on silica SBA-15. The organics studied did not adsorb significantly either in wastewater or in phosphate-buffered water. The catalysts did not modify the rate of the hydroxyl-mediated ozonation with respect to the homogeneous value. The mode of action of metal oxide catalysts would be an enhanced generation of oxidant species from the catalytic decomposition of ozone. All catalysts increased the efficiency in the production of hydroxyl radicals from ozone.     

Study Of The Ozone - Manganese Reaction And The Interactions Of Disulfonate Indigo Carmin/Oxidized Manganese Forms As A Function Of pH

Ozone used in preoxidation for water treatment processes allows the removal of inorganic compounds such as iron and manganese. The reactivity of ozone and manganese has been studied in a wide pH range. However, some difficulties appeared in the determination of the different species because of secondary reactions, the main difficulty being the interaction between indigo (used to determine ozone concentration) and manganese dioxide formed during ozonation.     

Studies on cerium oxidation in catalytic ozonation process: A novel approach for organic mineralization

A novel regenerative catalytic system has been developed using cerium and ozone in nitric acid medium. It was found that cerium(III) was oxidized to cerium(IV) by ozone in nitric acid medium with good conversion yields. The conversion rate of Ce(III) was measured under various parameters viz. ozone–air flow rate, initial concentration of Ce(III), and concentration of nitric acid at 25 °C. It was found that the conversion of Ce(III) increased with increasing ozone flow rate and concentration of nitric acid while decreased with increasing Ce(III) concentration. The pseudo first order kinetic constants were evaluated for Ce(III) oxidation. The efficiency of this hybrid system comprising of ozone and cerium redox pair towards organic mineralization was evaluated taking phenol as the model organic pollutant and compared with Ce(III) catalyzed and uncatalyzed ozonation processes. The presence of Ce(III) catalyst increased the destruction efficiency of phenol compared to uncatalyzed ozonation whereas a synergetic effect was observed between the cerium redox pair (Ce(III) and Ce(IV)) and ozone towards phenol mineralization and a maximum TOC removal was obtained in the latter case. Kinetic interpretations have been made with some simplifying assumptions owing to the much complex nature of ozone and metal ion interactions. This hybrid catalytic ozonation process may find its suitability for continuous organic destruction at room temperature.     

Degradation of Refractory Organic Pollutants by Catalytic Ozonation—Activated Carbon and Mn-Loaded Activated Carbon as Catalysts

A novel catalyst for the ozonation process was prepared by loading manganese on the granular activated carbon (GAC). Nitrobenzene was used as a model refractory organic micropollutant in this study. The catalytic activity of GAC and the Mn-loaded GAC were studied respectively. The removal efficiency of nitrobenzene by Mn-loaded GAC catalyzed ozonation could reach 34.2–49.9%, with the oxidation efficiency being about 1.5–2.0 times higher than that achieved in GAC catalyzed ozonation and 2.0–3.0 times higher than that achieved by ozonation alone. The effect of pH and the t -butanol on the GAC/ozone process was discussed. The optimum condition for preparing the catalyst was studied.     

科研与开发MnO_x/颗粒活性炭催化臭氧氧化技术降解硝基苯效能研究

通过半动态实验,对MnOx/GAC(颗粒活性炭)催化臭氧氧化技术氧化硝基苯的降解效能与动力学规律进行了初步研究。结果表明MnOx/GAC催化臭氧氧化过程对硝基苯具有较高的催化活性,在相同的反应条件下,MnOx/GAC催化臭氧氧化技术对硝基苯的降解效率是单独臭氧氧化的2.4倍。催化剂对硝基苯有一定的吸附作用。MnOx/GAC催化剂的存在提高了臭氧的利用率。MnOx/GAC催化臭氧氧化过程存在着催化剂最佳投量,硝基苯初始浓度与反应速率常数有良好的线性相关性,水质本底对MnOx/GAC催化臭氧氧化效率也有影响。     

Manganese‐catalysed ozonation of glyoxalic acid in aqueous solutions

Manganese‐catalysed ozonation of glyoxalic acid in aqueous solutions has been investigated in the pH range 2.0–4.0. The addition of manganese ions (Mn(II) or Mn(IV)) to a glyoxalic acid–ozone system allows the substrate to be oxidized through a mechanism different from that reported for uncatalysed ozonation, as underlined by the formation of methanoic acid. The presence of solid MnO₂ results in a further increase in the system reactivity. High levels of mineralization are generally achieved during glyoxalic acid‐catalysed ozonation. © 2000 Society of Chemical Industry     

Compromise Between Bromate Ion Formation and Pesticides Degradation and/or Manganese Removal

Ozonation is a widely used technology within the water industry. Bromate ion formed by oxidation of water containing bromide ion was studied with the Gas Ozone Test and Pilot Scale Ozonation. Bromate ion formation was investigated along with the removal of triazines and/or manganese. Under identical conditions of ozonation, BrO₃ ^? formation is specific for each water and depends on parameters such as Total Organic Carbon, UV absorbance at 254 nm, applied ozone and ozone residual. Pesticides degradation by ozonation alone cannot be achieved without the formation of BrO₃ ^? at a high concentration. Hydrogen peroxide, at a constant ozone dose, reduces the BrO₃ ^? formation. However, even with the use of hydrogen peroxide, the concentration of BrO₃ ^? can remain in excess of the provisional Maximum Contaminant Level (10 μg/L). For certain types of water, pesticide degradation is difficult to achieve if the MCL for BrO₃ ^? has to be met. Manganese oxidation by ozone appears to be achieved without high bromate formation; indeed the presence of manganese hinders BrO₃ ^? formation.     

Heterogeneous Catalytic Ozonation of Sulfamethoxazole in Aqueous Solution over Composite Iron–Manganese Silicate Oxide

Composite iron–manganese silicate oxide (FMSO) was synthesized and used as a heterogeneous catalyst for the ozonation of sulfamethoxazole. Results showed that FMSO/O₃ process significantly increased the TOC removal efficiency from 27% (sole ozonation) to 79.8%. Generated intermediates exhibited much higher adsorption affinity on FMSO than sulfamethoxazole. Presence of FMSO could accelerate the mass transfer of ozone, adsorb a certain amount of ozone on its surface, and subsequently decompose ozone into hydroxyl radical. Neutral charge surface of FMSO was more favorable to interact with the ozone molecules. FMSO maintained a good catalytic activity after several repeated use and revealed low metal ion leaching during ozonation.     

The Feasibility of Using a Perfluorinated Bonded Alumina Phase in the Ozonation Process

The comparison of the efficiency of three ozonation systems (ozonation alone and ozonation in the presence of alumina or PFOA) in attempting the removal of aromatic hydrocarbons from water was made. The results obtained indicate that PFOA shows a great catalytic activity, as opposed to alumina. Moreover, ozonation in the presence of PFOA results in a much higher level of ozonation efficiency in comparison to ozonation alone. The effect of ozone dosage, catalyst dosage and pH value was investigated and was found to have a great influence on hydrocarbons removal efficiency. The degradation rate was shown to decrease with increasing ozone and catalyst dosage. The efficiency of the PFOA/O₃ system was observed to be at its greatest at the lowest pH examined.     

Application of Regression Analysis for Ozone and Catalytic Ozonation of Organic Compounds from Landfill Leachate with Ceramic Raschig Rings and Natural Manganese Ore

Treatment of landfill leachate could be improved by adding ceramic raschig rings and manganese ore as catalysts for ozonation. Regression analysis were carried out to assess effects of parameters (pH, reaction time, the amount of H₂O₂, the surface area of ceramic raschig rings and the amount of manganese ore) on removing organic compounds from landfill leachate by ozone alone, peroxone, ozone/ceramic raschig rings, peroxone/ceramic raschig rings, ozone/manganese ore and peroxone/manganese ore. Results showed that parameters of reaction time, the amount of H₂O₂ and the amount of manganese ore were the high effects on removal of organic compounds from landfill leachate, following by pH paremeter. Ceramic raschig rings did not have significant effect on color, COD and TOC removal.     

Kinetics of Organic Matter Removal in a Chemical Sequential Reactor (CSR)

The Chemical Sequential Reactor (CSR) can be considered as an advanced oxidation process able to treat wastewaters with ozone. Its operation involves a succession of acidic and alkaline pH conditions throughout continuous ozonation. The two oxidation mechanisms (direct reaction of molecular ozone and hydroxyl free radical reactions], coupled with carbon dioxide stripping, increase removal rates and ozone efficiency. Ozone efficiency is also maintained for longer periods.     

Room temperature oxidation of acetone by ozone over alumina-supported manganese and cobalt mixed oxides

Volatile organic compounds (VOCs) are among the major sources of air pollution. Catalytic ozonation is an efficient process for removing VOCs at lower reaction temperature compared to catalytic oxidation. In this study, a series of alumina supported single and mixed manganese and cobalt oxides catalysts were used for ozonation of acetone at room temperature. The influence of augmenting the single Mn and Co catalysts were investigated on the performance and structure of the catalyst. The manganese and cobalt single and mixed oxides catalysts of the formula Mn10%-CoX and Co10%-MnX (where X= 0, 2.5%, 5%, or 10%) were prepared. It was found that addition of Mn and Co at lower loading levels (2.5% or 5%) to single metal oxide catalysts enhanced the catalytic activity. The mixed oxides catalysts of (Mn10%-Co2.5%) and (Mn10%-Co5%) led to acetone conversion of about 84%. It is concluded that lower oxidation state of the secondary metal improves ozone decomposition and oxidation of acetone.     

Catalytic decomposition of ozone and para-Chlorobenzoic acid (pCBA) in the presence of nanosized ZnO

This research forwards the evaluating of the efficiency of nanosized ZnO in the application of the catalytic ozonation, determines the reaction kinetics of ozone with the nanosized ZnO, and delineates the characteristics of the decomposition of para-Chlorobenzoic acid (pCBA) and ozone in catalytic ozonation using the nanosized ZnO particles. It was found that the nanosized ZnO enhanced the degradation of ozone and the catalytic ozonation on the surface of the nanosized ZnO significantly enhanced the degradation of pCBA. In catalytic reactions the degradation of pCBA followed two-stage kinetics, initial rapid removal phase (Phase I) and a slower decomposition phase (Phase II). The total degradation rate of pCBA was well matched with the initial removal of pCBA in Phase I. The R_ct values representing the ratio of hydroxyl radicals [OH] and ozone [O₃] were found to increase with an increased concentration of the nanosized ZnO indicating the enhanced transformation of ozone into OH.     

Preliminary Results on Ozonation Enhancement by a Perfluorinated Bonded Alumina Phase

A preliminary study was undertaken in order to determine the efficiency of ozonation in the presence of perfluorooctylalumina (PFOA) for the removal of organic substances from aqueous solutions by ozone. PFOA was synthesized by reacting hydrated alumina with pentadecafluorooctanoic acid. A monomolecular layer of non-polar perfluorinated alkyl chains, orientated away from the surface of alumina, capable of dissolving ozone and organic molecules, was obtained. The efficiency of ozonation alone and ozonation in the presence of PFOA or Al₂O₃ was compared. PFOA was found to significantly enhance the degradation level of organic substances in comparison with ozonation alone. Al₂O₃ did not show any catalytic activity.     

Pilot Testing Of Trace Metals Removal With Ozone At Snowbird Ski Resort

A pilot study at the Snowbird Ski Resort in Utah evaluated feasibility of ozonation replacing chlorine and sulfur dioxide for oxidation of iron and manganese in groundwater. Ozonation also was tested for the removal of lead and cadmium, occurring at concentrations exceeding drinking water Maximum Contaminant Levels. An ozone dose of 2 mg/L, contacted with the water for 1 minute prior to filtration, was selected as optimum for iron and manganese removal from 0.4 mg/L and 40 μg/L, respectively, to below detection limits. Lead, copper, and arsenic also were removed to below detection limits. The removal of cadmium and zinc improved when ozone was contacted for 10 minutes. With metals removal through ozonation and filtration, taste and odor enhancement also were reported.     

活性炭负载Fe~(3+)催化臭氧氧化水中双酚A

采用浸渍法在活性炭上负载铁制备催化剂Fe/AC,用于催化臭氧氧化水中内分泌干扰物双酚A(BPA),研究了Fe/AC/O3体系的协同效应,探讨了Fe/AC投加浓度、臭氧浓度和BPA初始浓度等工艺参数的作用规律,并分析了Fe/AC/O3体系在不同pH值下的催化反应机制。结果表明,在Fe/AC/O3体系下,反应60 min后,BPA和COD的去除率分别为97.44%和69.47%,效果明显优于臭氧体系的70.15%、30.89%和活性炭体系的14.69%、7.53%之和,具有明显的协同作用;Fe/AC/O3体系降解BPA符合一级反应动力学,当Fe/AC的投加浓度为5.0 g/L,臭氧浓度为15.0 mg/L,BPA初始浓度为50.0 mg/L时,Fe/AC/O3体系降解BPA的反应速率常数为0.05972 min-1;其反应机制受溶液pH值的影响,在酸性条件下是吸附和臭氧直接氧化共同作用,而在碱性条件下以·OH间接氧化为主,活性炭上负载的Fe3+促进了·OH的生成,大大提高了BPA的反应效率和矿化率。     

新生态水合二氧化锰对水中酚类化合物的吸附和氧化

试验研究了新生态水合二氧化锰对水中苯酚，4－氯酚以及2，6－二氯酚的去除，结果表明水合二氧化锰对水中苯酚及氯酚均有一定的去除效果，试验中从酚的去除情况及还原性Mn^2 的生成量判断出水合二氧化锰的吸附和氧化作用程度，同时，从水合二氧化锰对水中三种酚的吸附及氧化去除结果的比较，分析出氯取代对酚在水合二氧化锰表面吸附氧化能力的影响，结果表明了氯的取代使得酚易于被二氧化锰吸附而不易于被氧化。     

Catalytic Ozonation of Sulfosalicylic Acid

The investigation of heterogeneous catalytic ozonation of sulfosalicylic acid (SSal) in aqueous solution is reported in this paper. It was found that catalytic ozonation in the presence of V-O supported on silica gel had a more positive effect on the removal rate (62% in 30 min) of total organic carbon (TOC) than that of ozonation alone (20% in 30 min), and the catalyst supported on TiO₂ had similar results. The experimental results also showed that the ozone dosage should be sufficient for achieving the catalytic effect. Efficient removal of TOC in catalytic ozonation was probably attributed to producing more powerful oxidants than molecular ozone.     

Heterogeneous Catalytic Ozonation of Refinery Wastewater over Alumina-Supported Mn and Cu Oxides Catalyst

An economical method was proposed to develop an efficient alumina-supported manganese (Mn) and copper (Cu) oxides (Mn-Cu-O/Al₂O₃) catalyst with a high surface area, 184.06 cm² g^?1. The catalyst was utilized for degradation refinery wastewater by heterogeneous catalytic ozonation. The effects of various operating variables including pH, ozone and catalyst dosages, and temperature were systematically investigated in detail to obtain the optimized conditions for accelerated degradation of refinery wastewater. The optimum values were as follows: ozone dose 50.0 mg L^?1, catalyst dose 3.0 g L^?1, initial pH = 6.8, T = 17 °C. Refinery wastewater samples were analyzed by chemical oxygen demand (COD) and the results indicated that kinetics of COD followed a pseudo–first-order degradation. Moreover, hydroxyl radical mechanism rather than absorption was proposed, indicating that the surface hydroxyl groups were the active sites that played a significant role in catalytic ozonation.     

Manganese-Based Catalysts for the Catalytic Remediation of Phenolic Acids by Ozone

Manganese-based catalysts supported on Al₂O₃, TiO₂, ZrO₂ and CeO₂ were tested for the catalytic ozonation of a simulated wastewater involving phenolic acids. Comparing the Mn-Ce catalysts preparation method, wetness impregnation and co-precipitation, the last one showed to be more active. Moreover, the increase of Mn/Ce molar proportion from 22/78 to 70/30 increased the ozonation efficiency. The catalysts stability in terms of Mn leaching, carbon adsorption and effluent biodegradability was evaluated. Mn-Ce-O (70/30) CP shows to be the most suitable catalyst to improve phenolic wastewaters catalytic remediation by ozone.