Homogeneous catalytic ozonation of C.I. Reactive Red 2 by metallic ions in a bubble column reactor

This study elucidates the decolorization of C.I. Reactive Red 2 (RR2) by homogeneous catalytic ozonation. The effects of pH and catalyst dosage were evaluated in O3/Mn(II), O3/Fe(II), O3/Fe(III), O3/Zn(II), O3/Co(II) and O3/Ni(II) systems. In O3/Mn(II), O3/Fe(II) and O3/Fe(III) systems, increasing the catalyst concentration increased the rate of RR2 decolorization; however, further increasing the catalyst concentration caused no further significant increase. When 0.6 mM catalyst was added, the decolorization rates of O3/Mn(II), O3/Fe(II), O3/Fe(III), O3/Zn(II), O3/Co(II) and O3/Ni(II) systems at pH 2 were 3.295, 1.299, 1.278, 1.015, 0.843 and 0.822 min(-1), respectively. Under all of the experimental conditions, the decolorization efficiency of catalytic ozonation exceeded that of ozonation alone. The decolorization rate markedly exceeds the TOC removal rate in all tested systems. The effect of the radical scavenger on the catalytic ozonation processes suggests that the decolorization reaction in catalytic ozonation systems proceeds by mainly radical-type mechanisms, except in the O3/Mn(II) system.     

Kinetic study of ozonation of molasses fermentation wastewater

A kinetic study of molasses wastewater ozonation was carried out in a stirred tank reactor to obtain the rate constants for the decolorization reaction and the regime through which ozone is absorbed. First, fundamental mass transfer parameters such as ozone solubility, volumetric mass transfer coefficients and ozone decomposition kinetics were determined from semi-batch experiments in organic-free solutions with an ionic composition similar that of industrial wastewater. The influence of operating variables such as the stirring rate and gas flow rate on the kinetic and mass transfer parameters was also studied. The application of film theory allows to establish that the reactions between ozone and colored compounds in wastewater take place in the fast and pseudo-first-order regime, within the liquid film. The decolorization rate constants were evaluated at pH 8.7 and 25 degrees C, varying from 0.6 x 10(7) to 3.8 x 10(7)L mol(-1)s(-1), depending on the stirring rate and the inlet gas flow.     

Efficient mineralization of dimethyl phthalate by catalytic ozonation using TiO2/Al2O3 catalyst

The removal of dimethyl phthalate (DMP), which is a pollutant of concern in water environments, was carried out by catalytic ozonation with TiO₂/Al₂O₃ catalysts. The heterogeneous catalytic ozonation was an ozonation process combined with the catalytic and adsorptive properties of the TiO₂/Al₂O₃ catalysts to significantly accelerate the mineralization efficiency. Semi-batch ozonation was performed under various experimental conditions including the fed ozone concentration, catalyst type, catalyst dosage, and ultraviolet radiation on the degradation of DMP. The complete removal of DMP was efficiently achieved by both sole and catalytic ozonation; meanwhile, the presence of the catalysts slightly accelerated the elimination rate of DMP. On the other hand, the mineralization efficiency, in terms of total organic carbon (TOC) removal, was substantially enhanced by employing the TiO₂/Al₂O₃ catalyst. The mineralization efficiency using the TiO₂/Al₂O₃ catalyst was the highest, followed in decreasing order by the Al₂O₃ catalyst, the TiO₂ catalyst, and sole ozonation. In addition, the use of the TiO₂/Al₂O₃ catalyst would increase the utilization efficiency of the fed ozone, especially in the late ozonation period. Furthermore, the decrease in the catalytic activity of the TiO₂/Al₂O₃ catalyst after multi-run experiments can be mostly recovered by an incineration process at a high temperature.     

酞菁钴负载镁铝水滑石对甲基橙的氧化脱色

通过共沉淀法制备了Mg/Al物质的量比为3∶1的镁铝水滑石,并将其作为载体负载磺化酞菁钴制得新型功能材料酞菁钴负载水滑石(CoPcTs-LDH)。通过红外和热重分析表征了CoPcTs-LDH,研究了CoPcTs-LDH/H2O2对100mL 10mg/L甲基橙的氧化脱色。实验结果表明,在25～37℃、pH值为3～9、反应7h后甲基橙的剩余率均低于30%;反应过程符合一级动力学模型,阿伦尼乌斯活化能Ea=57.64kJ/mol;反应过程中羟基自由基发挥了重要作用;CoPcTs-LDH在重复使用5次后对甲基橙仍有很好的氧化脱色能力,具有较高的重复使用性能。     

Preparation of activated carbon@ZnO composite and its application as a novel catalyst in catalytic ozonation process for metronidazole degradation

The present study aimed to investigate the efficiency of granular activated carbon modified with ZnO nanoparticles (GAC@ZnO composite) as a catalyst for metronidazole degradation using catalytic ozonation process. The catalytical properties of GAC@ZnO composite were measured by using FESEM, FT-IR, XRD, EDX, and BET advanced techniques. Also, the effects of pH factor (3, 5, 7, 9, and 11), initial concentration of contaminant (10–30 mg/L), reaction time (5–90 min), catalyst dosage (0.2–2.5 g/L), on the catalytic ozonation process, were studied. In addition, the effects of the interfering factors on the work of ozone degradation agent and hydroxyl radicals are tested. The results of characterisation study showed a successful formation of GAC@ZnO composite with favorable catalytic properties. In addition, the GAC surface properties were enhanced by the modification with ZnO nanoparticles, where more efficient reaction sites for metronidazole degradation were created onto GAC. The degradation performance of the GAC@ZnO composite was high in which 83% of metronidazole removal was achieved in optimum conditions (pH = 11, catalyst dosage = 2 g/L, and reaction time = 30 min). In addition, the degradation rate was noticeably found to be higher in case of using catalytic ozonation process than using ozonation process alone. The kinetic degradation reactions of metronidazole followed the pseudo-first-order equation. According to the results of this model’s parameters, the degradation process is occurred on or near GAC@ZnO composite surface depending on the concentration of the pollutant. From the results obtained, it can be concluded that the GAC@ZnO composite in the catalytic ozonation treatment process was efficacious catalyst as it has excellent performance toward eradication of metronidazole wastewater.     

Effects of ozonation process on lignin-derived compounds in pulp and paper mill effluents

The effect of ozonation process on pulp and paper mill effluents was investigated. The objectives were to: (1) identify various compounds in wastewater from a pulp and paper mill, (2) evaluate decolorization and organic removal efficiency by conventional bubble reactor and (3) evaluate the biodegradability at various progressive stages of ozonation. The qualitative GC/MS analyses were performed before and after the biological treatment and ozonation process. Two groups of compounds were observed in this wastewater: lignin-derived compounds and aliphatic compounds used in the pulp and paper production process (i.e. n-alkanes, fatty alcohols, fatty acid and ester). Treatment efficiency was measured by decolorization and TOC removal rates. Additionally, the utilization coefficient (k) and BOD/COD ratio were determined to observe the biodegradability of ozonized effluents. The results indicated that after 45 min, the ozonation of effluents yielded almost colorless effluent with over 90% decolorization efficiency and with corresponding ozone capacity rate of 20.0 mg O(3)L(-1). This decolorization was not always accompanied by the mineralization of the organic matters therefore ozonation was not related to TOC removal rates. The BOD/COD ratio increased from 0.10 to a maximum value of 0.32 with ozone flow rate (O/F) of 4.0 L min(-1). It was confirmed by the utilization coefficient as first order BOD equation, the magnitude k value increased from 0.21 day(-1) to maximum value of 0.47 day(-1) as the ozonation time was raised to 60 min with O/F 4.0 L min(-1).     

Decolorization of malachite green, decolorization kinetics and stoichiometry of ozone-malachite green and removal of antibacterial activity with ozonation processes

This study aimed to identify degradation intermediates and to investigate the stoichiometry of decolorization and degradation, decolorization kinetics, and removal of antibacterial activity of malachite green (MG) using ozonization processes. The decolorization of MG was optimal at an acidic pH value of 3 based on molecular ozone attack on MG molecules. The stoichiometric ratio of decolorization between ozone and MG was calculated to be 7.0 with a regression coefficient of 0.995, whereas the ratio for degradation was calculated as 13.1 with a regression coefficient of 0.998. With MG concentrations in the range of 0.30-1.82 mM, the concentration of decolorized MG increased with higher initial concentrations of MG, whereas the ozonolytic decolorization rates of MG, decreased with increasing initial concentration. The pseudo-first-order degradation rate constants (k') decreased with the initial concentration and ranged from 0.769 to 0.223 min(-1). Twelve different intermediates were produced during the ozonation of MG with ozonation times between 5 min and 30 min and were identified by GC-MS. Although 86% of MG in the reaction mixture was removed by ozonation after 10 min, the decrease of antibacterial activity was very low (10%) for Bacillus subtilis and Staphylococcus epidermidis because the degradation intermediates, phenol and benzoic acid, also have antibacterial activity. The antibacterial activity of both MG and its intermediates were removed successfully with ozonation times above 26 min.     

Combined photolysis and catalytic ozonation of dimethyl phthalate in a high-gravity rotating packed bed

In this study, a high-gravity rotating packed bed (HGRPB) was used as a catalytic ozonation reactor to decompose dimethyl phthalate (DMP), an endocrine disrupting chemical commonly encountered. The HGRPB is an effective gas-liquid mixing equipment which can enhance the ozone mass transfer coefficient. Platinum-containing catalyst (Pt/-Al2O3) of Dash 220N and ultra violet (UV) lamp were combined in the high-gravity ozonation (HG-OZ) system to enhance the self-decomposition of molecular ozone in liquid to form highly reactive radical species. Different combinations of HG-OZ with Dash 220N and UV for the degradation of DMP were tested. These include HG-OZ, HG catalytic OZ (HG-Pt-OZ), HG photolysis OZ (HG-UV-OZ) and HG-UV-Pt-OZ. The result indicated that all the above four ozonation processes result in significant decomposition of DMP and mineralization of total organic carbon (TOC) at the applied ozone dosage per volume of liquid sample of 1.2gL(-1). The UV and Pt/gamma-Al2O3 combined in HG-OZ can enhance the TOC mineralization efficiency (eta(TOC)) to 56% (via HG-UV-OZ) and 57% (via HG-Pt-OZ), respectively, while only 45% with ozone only. The process of HG-UV-Pt-OZ offers the highest eta(TOC) of about 68%.     

Decolorization of methyl orange by ozonation in combination with ultrasonic irradiation

The combination of ultrasound and ozone for the decolorization of azo dye, methyl orange, was studied. The effect of ultrasonic power, ozone gas flow rate, gaseous ozone concentration, initial dye concentration, pH and hydroxyl radical scavenger on the decolorization of methyl orange was investigated. The results showed that the synergistic effect was achieved by combining ozone with ultrasonic irradiation for the decolorization of methyl orange. The synergistic effect was more significant when the system temperature was raised due to the heat effect of ultrasonic irradiation. The decolorization of methyl orange fits the pseudo first order kinetic model. The decolorization rate increased with the increase of ultrasonic power, ozone gas flow rate, gaseous ozone concentration. However, the decolorization rate decreased with the increasing initial dye concentration. Either pH or sodium carbonate has little effect on the decolorization rate, indicating that the low frequency ultrasound enhanced ozonation process for the decolorization of methyl orange is mainly a direct reaction rather than radical reaction.     

Degradation of DMSO by ozone-based advanced oxidation processes

The present study investigates the oxidation of dimethyl sulfoxide (DMSO) by conventional ozonation and the advanced oxidation processes (AOPs). The major degradation products identified were methanesulfinate, methanesulfonate, formaldehyde, and formic acid in ozonation process. The subsequent degradation of intermediates shows that methanesulfonate is more resistance to ozonation, which reduces the mineralization rate of DMSO. The effect of t-butanol addition and ozone gas flow dosage on the degradation rate was evaluated. The rate constant of the reaction of ozone (k(D)) with DMSO was found to be 0.4162 M(-1)S(-1). In the second part of this study, DMSO degradation and TOC mineralization were investigated using O(3)/UV, O(3)/H(2)O(2) and UV/H(2)O(2) processes. In all theses processes the degradation of target organics is more pronounced than TOC removal. The efficiencies of these processes were evaluated and discussed. The formation of sulfate ion in all AOPs have been identified and compared with other processes. Overall it can be concluded that ozonation and ozone-based AOPs are promising processes for an efficient removal of DMSO in wastewater.     

Ozonation of endocrine disrupting chemical BHA under the suppression effect by salt additive--with and without H(2)O(2)

The oxidation of fresh and saline wastewater containing an endocrine disrupting chemical (butylated hydroxyanisole, BHA) under different reaction conditions by ozonation and O(3)/H(2)O(2) was investigated at various pH levels. The observed pseudo-first-order reaction kinetics was justified through a combined direct ozone and indirect radical oxidation approach for the ozonation process. The BHA decay rates increased with the increase of the solution pH, but decreased as the NaCl concentration increased because of the consumption of ozone by chloride. A kinetic model was therefore derived for predicting BHA degradation at various initial pH levels and NaCl concentrations. For the O(3)/H(2)O(2) and O(3)/H(2)O(2)/Cl(-) processes, the rate of BHA removal was investigated at hydrogen peroxide concentration ranged from 0.5 to 5mM at pH 7. Different optimal H(2)O(2) dosages and decay rates were found for both processes due to the participation of reactions among O(3), H(2)O(2), OH* and Cl(-) as discussed in the paper.     

Catalytic ozonation of dimethyl phthalate over cerium supported on activated carbon

Cerium supported on activated carbon (Ce/AC), which was prepared by dipping method, was employed to degrade dimethyl phthalate (DMP) in water. The mineral matter present in the activated carbon positively contributes to its activity to enhance DMP ozonation process. A higher dipping Ce(NO₃)₃ concentration and calcination process increase its microporous volume and surface area, and decreases its exterior surface area. The catalytic activity reaches optimal when 0.2% (w/w) cerium is deposited on activated carbon. Ce/AC catalyst was characterized by XRD, SEM and BET. The presence of either activated carbon or Ce/AC catalyst considerably improves their degradation and mineralization in the ozonation of DMP. During the ozonation (50 mg/h ozone flow rate) of a 30 mg/L DMP (initial pH 5.0) with the presence of Ce/AC catalyst, TOC removal rate reaches 68% at 60 min oxidation time, 48% using activated carbon as catalyst, only 22% with ozonation alone. The presence of tert-butanol (a well known OH radical scavenger) strongly inhibits DMP degradation by activated carbon or Ce/AC catalytic ozonation. TOC removal rate follows the second-order kinetics model well. In the ozonation of DMP with 50 mg/h ozone flow rate, its mineralization rate constant with the presence of Ce/AC catalyst is 2.5 times higher than that of activated carbon, 7.5 times higher than that of O₃ alone. Ce/AC catalyst shows the better catalytic activity and stability based on 780 min sequential reaction in the ozonation of DMP. Ce/AC was a promising catalyst for ozonizing organic pollutants in the aqueous solution.     

Electrochemical treatment of paper mill wastewater using three-dimensional electrodes with Ti/Co/SnO2-Sb2O5 anode

The properties of the interlayer and outer layer of Ti/Co/SnO2-Sb2O5 electrode were studied, and the electrochemical behavior was examined as well. As a result of unsatisfactory treatment using Ti/Co/SnO2-Sb2O5 electrode, electrochemical disposal of paper mill wastewater employing three-dimensional electrodes, combining active carbon granules serving as packed bed particle electrodes, with Ti/Co/SnO2-Sb2O5 anode, was performed. The outcome demonstrates that efficient degradation was achieved. The residual dimensionless chemical oxygen demand (COD) concentration reached 0.137, and color removal 75% applying 167 mA cm(-2) current density at pH 11 and 15 g l(-1) NaCl. The instant current efficiency, energy cost, electrochemical oxidation index (EOI) and kinetic constant of the reaction were calculated. At the same time, the influence of pH and current density on COD abatement and decolorization was also investigated, respectively.     

Catalytic activity of CuOn-La2O3/gamma-Al2O3 for microwave assisted ClO2 catalytic oxidation of phenol wastewater

In order to develop a catalyst with high activity and stability for microwave assisted ClO2 catalytic oxidation, we prepared CuOn-La2O3/gamma-Al2O3 by impregnation-deposition method, and determined its properties using BET, XRF, XPS and chemical analysis techniques. The test results show that, better thermal ability of gamma-Al2O3 and high loading of Cu in the catalyst can be achieved by adding La2O3. The microwave assisted ClO2 catalytic oxidation process with CuOn-La2O3/gamma-Al2O3 used as catalyst was also investigated, and the results show that the catalyst has an excellent catalytic activity in treating synthetic wastewater containing 100 mg/L phenol, and 91.66% of phenol and 50.35% of total organic carbon (TOC) can be removed under the optimum process conditions. Compared with no catalyst process, CuOn-La2O3/gamma-Al2O3 can effectively degrade contaminants in short reaction time and with low oxidant dosage, extensive pH range. The comparison of phenol removal efficiency in the different process indicates that microwave irradiation and catalyst work together to oxidize phenol effectively. It can therefore be concluded from results and discussion that CuOn-La2O3/gamma-Al2O3 is a suitable catalyst in microwave assisted ClO2 catalytic oxidation process.     

Decolorization of Reactive Red 2 by advanced oxidation processes: Comparative studies of homogeneous and heterogeneous systems

This study investigated the decolorization of the Reactive Red 2 in water using advanced oxidation processes (AOPs): UV/TiO2, UV/SnO2, UV/TiO2+SnO2, O3, O3+MnO2, UV/O3 and UV/O3+TiO2+SnO2. Kinetic analyses indicated that the decolorization rates of Reactive Red 2 could be approximated as pseudo-first-order kinetics for both homogeneous and heterogeneous systems. The decolorization rate at pH 7 exceeded pH 4 and 10 in UV/TiO2 and UV/TiO2+SnO2 systems, respectively. However, the rate constants in the systems (including O3) demonstrated the order of pH 10>pH 7>pH 4. The UV/TiO2+SnO2 and O3+MnO2 systems exhibited a greater decolorization rate than the UV/TiO2 and O3 systems, respectively. Additionally, the promotion of rate depended on pH. The variation of dye concentration influenced the decolorization efficiency of heterogeneous systems more significant than homogeneous systems. Experimental results verified that decolorization and desulfuration occurred at nearly the same rate. Moreover, the decolorization rate constants at pH 7 in various systems followed the order of UV/O3 > or = O3+MnO2 > or = UV/O3+TiO2+SnO2 > O3 > UV/TiO2+SnO2 > or = UV/TiO2 > UV/SnO2.     

Oxidation of methyl methacrylate from semiconductor wastewater by O3 and O3/UV processes

This study investigated the oxidation of methyl methacrylate (MMA) by sole ozonation and ozone/UV treatments. The semi-batch ozonation experiments were proceeded under different reaction conditions to study the effects of ozone dosage and UV radiation on the oxidation of MMA. The experimental results indicated that both the oxidation of MMA by the sole ozonation and O3/UV processes can completely decompose MMA to form the following intermediates within 30 min reaction time. To increase the applied ozone dosage can significantly raise the removal efficiency of MMA. However, the mineralization of MMA via the direct oxidation reaction of molecular ozone was slow, while introducing the UV radiation can promote the mineralization rate of MMA. In addition, the pH value of the oxidized solution in the O3/UV treatment decreased lower than that in the sole ozonation treatment of about 1 unit. The possible scheme of the decomposition pathway of MMA under the ozonation process is proposed in this study. Formic acid and acetic acid were found to be the main ozonated intermediates.     

Decolorization of an azo dye Orange G in aqueous solution by Fenton oxidation process: effect of system parameters and kinetic study

To establish cost-efficient operating conditions for potential application of Fenton oxidation process to treat wastewater containing an azo dye Orange G (OG), some important operating parameters such as pH value of solutions, dosages of H(2)O(2) and Fe(2+), temperature, presence/absence of chloride ion and concentration of the dye, which effect on the decolorization of OG in aqueous solution by Fenton oxidation have been investigated systematically. In addition, the decolorization kinetics of OG was also elucidated based on the experimental data. The results showed that a suitable decolorization condition was selected as initial pH 4.0, H(2)O(2) dosage 1.0 x 10(-2)M and molar ratio of [H(2)O(2)]/[Fe(2+)] 286:1. The decolorization of OG enhanced with the increasing of reaction temperature but decreased as a presence of chloride ion. On the given conditions, for 2.21 x 10(-5) to 1.11 x 10(-4)M of OG, the decolorization efficiencies within 60 min were more than 94.6%. The decolorization kinetics of OG by Fenton oxidation process followed the second-order reaction kinetics, and the apparent activation energy E, was detected to be 34.84 kJ mol(-1). The results can provide fundamental knowledge for the treatment of wastewater containing OG and/or other azo dyes by Fenton oxidation process.     

Catalytic ozonation of p-chlorobenzoic acid by activated carbon and nickel supported activated carbon prepared from petroleum coke

The aim of this research was to investigate catalytic activity of petroleum coke, activated carbon (AC) prepared from this material, Ni supported catalyst on activated carbon (Ni/AC) in the ozonation of aqueous phase p-chlorobenzoic acid (p-CBA). Activated carbon and Ni/AC catalyst were characterized by XRD and SEM. The presence of petroleum coke did not improve the degradation of p-CBA compared to ozonation alone, but it was advantageous for p-CBA mineralization (total organic carbon, TOC, reduction), indicating the generation of highly oxidant species (*OH) in the medium. The presence of either activated carbon or Ni/AC considerably improves TOC removal during p-CBA ozonation. Ni/AC catalyst shows the better catalytic activity and stability based on five repeated tests during p-CBA ozonation. During the ozonation (50 mg/h ozone flow rate) of a 10 mg/L p-CBA (pH 4.31), it can be more mineralized in the presence of Ni/AC catalyst (5.0 g/L), TOC removal rate is over 60% in 60 min, 43% using activated carbon as catalyst, only 30% with ozonation alone.     

Color removal of distillery wastewater by ozonation in the absence and presence of immobilized iron oxide catalyst

Ozone is a strong oxidant, which can oxidize both biodegradable and non-biodegradable organics. The main objective of this study was to use iron oxide as a heterogeneous catalyst to enhance the ozone oxidation process. The wastewater used in this study was distillery wastewater, which was diluted 20 times before use. The diluted distillery wastewater was fed continuously in a downflow direction in an ozonation column. The iron oxide catalyst was coated on 10.3mm diameter alumina balls (5.5 m2/g specific surface area) by using Fe(NO3)3 as a precursor. The prepared catalyst was in the form of ferric oxide, and its loading was 0.07%. From the experimental results of both with and without the iron oxide catalyst, an increase in hydraulic retention time resulted in an increase in the treatment efficiencies of both chemical oxygen demand (COD) and color reduction, since the residence time of ozone increased. When the ozone mass flow rate increased, both COD and color reduction increased, resulting from an increase in the hydroxyl radical available in the system. The ozonation system with the iron oxide catalyst gave the highest efficiency in both COD and color removals because the hydroxyl free radical generated from the catalyst is more reactive than the ozone molecule itself.     

Decomposition of dimethyl phthalate in an aqueous solution by ozonation with high silica zeolites and UV radiation

This study investigates the enhanced ozonation of dimethyl phthalate (DMP), which is a pollutant of concern in water environments, with high silica zeolites and ultraviolet (UV) radiation. Semibatch ozonation experiments are performed under various reaction conditions to examine the effects of inlet gas ozone concentration, high silica zeolite dosage, and UV radiation intensity on the decomposition of DMP. The complete removal of DMP can be efficiently achieved via both O(3) and O(3)/UV treatments. Note that the presence of high silica zeolites accelerates the decomposition rate of DMP in the O(3) process. On the other hand, the removal efficiencies of both chemical oxygen demand (COD) and total organic carbons (TOC) are significantly enhanced by employing the ozonation combined with UV radiation. The O(3)/UV process is also advantageous for the utilization efficiency of fed ozone especially in the late ozonation period. Furthermore, the correlation between the COD removal percentage (%) and the mole ratio of ozone consumed to the DMP treated (mol mol(-1)) is obtained. The clear-cut removal relationship of the TOC with COD during the ozonation of DMP has also been presented. Consequently, the results evaluate the flexibility of ozonation system associated with high silica zeolites and UV radiation for the removal of DMP and provide the useful information in engineering application.