Efficiency and Mechanism of Ciprofloxacin Hydrochloride Degradation in Wastewater by Fe3o4/Na2S2O8

ABSTRACT

The nanosized Fe₃O₄ catalyst was synthesized via a modified reverse coprecipitation method and characterized by means of a scanning electron microscope (SEM) and an X-ray diffraction (XRD) analysis instrument. The degradation efficiency and reaction rate of Fe₃O₄ in activating sodium persulfate used to degrade ciprofloxacin were determined from the catalyst dosage, oxidant concentration, and initial pH. The results showed that under the optimum conditions of a catalyst dosage of 2.0 g·L^?1, a sodium persulfate concentration of 1.0 g·L^?1, and an initial pH of 7, the degradation rate of ciprofloxacin was 93.73%, the removal rate of total organic carbon was 78%, and the first-order reaction constant was 0.06907 min^?1 within 40 min. It was also demonstrated that the reactive oxygen species in the Fe₃O₄/sodium persulfate catalytic system were mainly composed of SO₄^– and supplemented by OH· and HO₂· using probe compounds such as ethanol, tertiary butanol, and benzoquinone.     

Degradation of C.I. Basic Red 29 solution by combined ultrasound and Co-H2O2 system

Ultrasonic degradation of Basic Red 29 (BR29) textile dye in the presence of Co²⁺-H₂O₂ system was investigated in this study. The effects of presence of ultrasonic power, concentrations of cobalt (II) acetate (Co(II)Act) and H₂O₂, temperature and initial pH on the BR29 degradation were examined. Initial dye concentration of 20 mg/L BR29 was used in the study as a model solution. In sonication experiments, an ultrasonic bath at a frequency of 40 kHz was employed. Best experimental conditions were also obtained in the studies as follows: 1000 mg/L Co(II)Act, 1000 mg/L H₂O₂, 40 °C and original pH of 6.70.According to the results, after 30 min of sonication in the presence of Co²⁺-H₂O₂ dye removal efficiency of practically 100% was achieved. It was also found that US enhanced the degradation rate of BR29.     

Effectiveness and Mechanisms of Fenton-like Si-FeOOH/H2O2 in 2,4-Dichlorophenol Wastewater Treatment

This research measured the effectiveness of Si-FeOOH as a type of heterogeneous Fenton-like catalyst made from alkaline precipitation methods, in catalyzing the degradation of 2,4-dichlorophenol (2,4-DCP) wastewater. Factors including catalyst dosage, pH, and hydrogen peroxide dosage were investigated, showing: with an initial concentration of 2,4-dichlorophenol at 100 mg/L, a dosage of catalyst at 0.1 g/L, a dosage of H₂O₂ at 1.5 ml/L, pH at 5 and indoors temperature at 25 ± 1 °C, the degradation rate of 2,4-dichlorophenol, COD_Cr and TOC has reached 94.21%, 83.67%, and 76.11%, separately. Comparisons were made with FeOOH used as catalyst, showing that Fenton-like Si-FeOOH is a better catalyst than FeOOH.     

The removal of cephalexin antibiotic in aqueous solutions by ultrasonic waves/hydrogen peroxide/nickel oxide nanoparticles (US/H2O2/NiO) hybrid process

ABSTRACT

Antibiotics are non-biodegradable and can remain for a long time at aquatic environments and they have a big potential bio-accumulation in the environment. The antibiotics are broadly metabolized by humans, animals and plants and they or their metabolites, after metabolization, are entered into the aquatic environment. This study aimed to optimize the operational parameters by Taguchi design and to carry out the kinetic studies for removal of cephalexin antibiotic from aqueous solutions by US/H₂O₂/NiO hybrid process. This experimental study was performed on a laboratory scale in a 500 mL pyrex-made reactor. The main operational parameters to influence the US/H₂O₂/NiO process were identified as the initial concentration of CEX (20–80 mg/L), hydrogen peroxide (H₂O₂) (10–40 mL/L), NiO nanoparticle (2.5–10 mg/L) and reaction time (15–90 min) and therefore, the influence of these factors were studied. Under optimum conditions (pH = 3, reaction time = 90 min, CEX = 40 mg/L, NiO = 7.5 mg/L and H₂O₂ = 30 mL/L) and using the US/H₂O₂/NiO process, the removal efficiencies of CEX, COD and TOC were 93.86%, 72.46% and 54.55%, respectively. The percentage contribution of each factor was also determined. Results introduced the solution pH as the most powerful factor, and its percentage contribution value was up to 94% in the studied process. It was also identified that the removal of CEX antibiotic using the hybrid process obeys the pseudo-first-order kinetics.     

Effects of O3, O3/H2O2 and Coagulation on Natural Organic Matter and Arsenic Removal from Typical Northern Serbia Source Water

The objectives of this study were to investigate the effects of ozone and the O₃/H₂O₂ process on FeCl₃ coagulation efficiency for the removal of the high content of natural organic matter (NOM) and arsenic (As) from groundwater (DOC = 9.27 ± 0.92 mg/L; 51.7 ± 16.4 µg As/L). Arsenic and NOM removal mechanisms during coagulation/flocculation are well investigated. However, data concerning arsenic removal in the presence of NOM, which is the subject of this article, are still insufficient. Laboratory and pilot plant test results have shown that the competition of NOM and As for adsorption sites on the coagulant surface have great influence on coagulation/flocculation efficiency for their removal. With both oxidation pre-treatments, arsenic content after the coagulation process was less than 2.0 µg/L in treated water. Application of ozone has a lower influence on coagulation efficacy in terms of DOC reduction, compared to the O₃/H₂O₂ process with the same ozone dose.     

Ozonation of Reactive Orange 122 Using La3+-Doped WO3/TiO2/Sep Photocatalyst

La³⁺/WO₃/TiO₂/sep composites have been prepared by the sol–gel method. The degradation of dye was studied under the influence of various operational parameters such as initial pH, amounts of catalyst, concentrations of the dye, and ozone flow rate. The mineralization of Reactive Orange 122 has been confirmed by chemical oxygen demand measurements. The color removal of dye was found to follow a pseudo–first-order kinetics. Maximum color and chemical oxygen demand removal were 99.9% and 90% respectively, at a dye concentration of 200 mg/L, ozone flow rate of 2.0 L/min., 0.05 g/L weight of catalyst, and pH of 6.9 in 4 h. In addition, the catalyst was characterized by X-ray diffraction spectra, Fourier-Transform Infrared Spectroscopy, scanning electron microscopy, and a transmission electron microscope. This work could be a good candidate as a practical application for photocatalytic dye degradation.     

Nb2O5 as efficient and recyclable photocatalyst for indigo carmine degradation

Heterogeneous photocatalysis is a significant green technology for application in water purification. The application of Nb₂O₅ catalyst for the photodegradation of contaminants is few reported in the literature. Thus, the Nb₂O₅ catalyst was characterized by SEM, FTIR, surface area and charge surface density. This catalyst was applied to degrade indigo carmine dye, which was compared with degradation catalyzed by TiO₂ and ZnO. Almost 100% of dye degradation occurred at 20, 45 and 90 min for TiO₂, ZnO and Nb₂O₅, respectively. The effect of Nb₂O₅ catalyst concentration, pH and ionic strength (μ) was investigated. The Nb₂O₅ activity increased at 0.7 g/L and for higher catalyst concentrations the degradation was kept constant. Degradation of indigo carmine dye catalyzed by Nb₂O₅ was improved at pH < 4.0 and μ = 0.05 mol/L. TiO₂, ZnO and Nb₂O₅ were recovered and re-applied in other nine reaction cycles. While TiO₂ and ZnO have an abrupt loss of their catalytic activity, Nb₂O₅ maintained 85% of catalytic activity after 10 reaction cycles.     

Fouling Inhibition of Membrane Separation by H2O2/UV Pre-oxidation for Color Filter Effluent Reuse

This study evaluated the feasibility of treating color filter effluent by H₂O₂/UV pre-oxidation and membrane postseparation for in-house reuse. The effluent qualities were TOC of 5.8–34 mg/L, color of 46–138 ADMI, and conductivity of 1020–3500 μS/cm. Although the RO separation could directly remove TOC, color, and conductivity effectively, the serious fouling problem still existed. Through H₂O₂/UV pre-oxidation (UV = 13 W, H₂O₂ = 200 mg/L), organic and biofouling were inhibited to increase the normalized flux decline from 5% to 77%. That is, H₂O₂/UV pre-oxidation could mitigate the permeate flux decline as well as to improve the water quality for water reuse.     

Direct formation of H2O2 from H2 and O2 and decomposition/hydrogenation of H2O2 in aqueous acidic reaction medium over halide-containing Pd/SiO2 catalytic system

Formation of H₂O₂ from H₂ and O₂ and decomposition/hydrogenation of H₂O₂ have been studied in aqueous acidic medium over Pd/SiO₂ catalyst in presence of different halide ions (viz. F⁻, Cl⁻ and Br⁻). The halide ions were introduced in the catalytic system via incorporating them in the catalyst or by adding into the reaction medium. The nature of the halide ions present in the catalytic system showed profound influence on the H₂O₂ formation selectivity in the H₂ to H₂O₂ oxidation over the catalyst. The H₂O₂ destruction via catalytic decomposition and by hydrogenation (in presence of hydrogen) was also found to be strongly dependent upon the nature of the halide ions present in the catalytic system. Among the different halides, Br⁻ was found to selectivity promote the conversion of H₂ to H₂O₂ by significantly reducing the H₂O₂ decomposition and hydrogenation over the catalyst. The other halides, on the other hand, showed a negative influence on the H₂O₂ formation by promoting the H₂ combustion to water and/or by increasing the rate of decomposition/hydrogenation of H₂O₂ over the catalyst. An optimum concentration of Br⁻ ions in the reaction medium or in the catalyst was found to be crucial for obtaining the higher H₂O₂ yield in the direct synthesis.     

Fe(III)/H2O2-Like System for Removal of Azo Dye from Aqueous Solution

Fe(III)/H₂O₂ system is an effective method for separating the organic compounds from aqueous solution, whereas it is often investigated under lower pH conditions. In order to improve performance of the system, a Fe(III)/H₂O₂-like system that was composed of iron-based coagulant and H₂O₂ was developed, which has the combined effect of flocculation and oxidation. The system when used for decolorization of an organic azo dye solution, Procion Red MX-5B, under wider pH range, indicated higher decolorization efficiency. Parameters affecting the decolorization such as coagulant dosage, H₂O₂ concentration, initial solution pH, temperature, and initial dye concentration were examined in this study. The results indicated that with appropriate coagulant dosage, H₂O₂ concentration, and pH, it was more effective for the decolorization, especially in a weak alkaline environment (pH = 7-8); the pseudo-first-order kinetics could express the azo dye concentration as a function of the reaction time. This study further illustrated that the azo dye solution was degraded to a degree with 53.22% TOC removal at an initial total TOC concentration of 14.92 mg/L. Overall, the established system in this study was favorable to the decolorization of soluble azo dye.     

Oxidation of Parachloronitrobenzene in Dilute Aqueous Solution by O3 + UV and H2O2 + UV : A Comparative Study

This laboratory study was designed to investigate the degradation of 4-chloronitrobenzene ([CNB] = 2.4 × 10^?6 mol L^?1; pH = 7.5) by H₂O₂/UV and by O₃/UV oxidation processes which involve the generation of very reactive and oxidizing hydroxyl free radicals. The effects of the oxidant doses (H₂O₂ or aqueous O₃), liquid flow rate (or the contact time), and bicarbonate ions acting as OH· radical scavengers on the CNB removal rates were studied. For a constant oxidant dose, the results show that the O₃/UV system appears to be more efficient than the H₂O₂/UV system to remove CNB because of the greatest rate of OH· generation by ozone photodecomposition compared to H₂O₂ photolysis. However, for a given amount of oxidant decomposed, the H₂O₂/UV oxidant system was found to be more efficient than O₃/UV. Moreover, high levels of bicarbonate ions in solution (4 × 10^?3 mol L^?1) significantly decrease the efficiency of CNB removal by H₂O₂/UV and by O₃/UV oxidation processes.     

Study on Disposal of Textile Dyes in Aqueous Solution by TiO2 Pillared Bentonite

TiO₂/bentonite composites were prepared by a sol–gel method. X-ray diffraction measurements of the samples revealed that TiO₂ had intercalated into the layers of bentonite and existed in anatase phase of TiO₂. Acid red 3R was used as model compounds of textile dyes in this study. The effects of operational parameters, including TiO₂ content, pH, as well as catalyst dosage, on photocatalytic degradation performance were examined. The experimental results showed that the removal rate of acid red 3R can be up to 96.7% under the following conditions: the dosage of TiO₂/bentonite was 2 g/L, the content of TiO₂ was 30%, the pH value was 3. And the photocatalytic reaction followed pseudo-first-order kinetics models.     

Synthesis of magnetic Pb/Fe3O4/SiO2 and its catalytic activity for propylene carbonate synthesis via urea and 1,2-propylene glycol

To facilitate the recovery of Pb/SiO₂ catalyst, magnetic Pb/Fe₃O₄/SiO₂ samples were prepared separately by emulsification, sol-gel and incipient impregnation methods. The catalyst samples were characterized by means of X-ray diffraction and N₂ adsorption-desorption, and their catalytic activity was investigated in the reaction for synthesizing propylene carbonate from urea and 1,2-propylene glycol. When the gelatin was applied in the preparation of Fe₃O₄ at 60°C and the pH value was controlled at 4 in the preparation of Fe₃O₄/SiO₂, the Pb/Fe₃O₄/SiO₂ sample shows good catalytic activity and magnetism. Under the reaction conditions of a reaction temperature of 180°C, reaction time of 2 h, catalyst percentage of 1.7 wt-% and a molar ratio of urea to PG of 1:4, the yield of propylene carbonate attained was 87.7%.     

Isotope effect of H2/D2 and H2O/D2O for the PROX reaction of CO on the FeOx/Pt/TiO2 catalyst

The oxidation reaction of CO with O₂ on the FeOx/Pt/TiO₂ catalyst is markedly enhanced by H₂ and/or H₂O, but no such enhancement occurs on the Pt/TiO₂ catalyst. Isotope effects were studied by H₂/D₂ and H₂O/D₂O on the FeOx/Pt/TiO₂ catalyst, and almost the same magnitude of isotope effect of ca. 1.4 was observed for the enhancement of the CO conversion by H₂/D₂ as well as by H₂O/D₂O at 60 °C. This result suggests that the oxidation of CO with O₂ via such intermediates as formate or bicarbonate in the presence of H₂O, in which H₂O or D₂O acts as a molecular catalyst to promote the oxidation of CO as described below.      

Metal oxide catalysts for DME steam reforming: Ga2O3 and Ga2O3–Al2O3 catalysts

The steam reforming of dimethyl ether (DME) was performed on Ga₂O₃–Al₂O₃ mixed oxides prepared by sol–gel method. Ga₂O₃ significantly affects the catalytic performance with respect to the DME conversion and H₂ yield. The catalytic activity increases with the Ga concentration in Ga₂O₃–Al₂O₃ mixed oxides. It is very interesting that without the aid of an additional transition metal component, Ga₂O₃ and Ga₂O₃ containing Al₂O₃ mixed oxide system exhibit good activity in the reforming reaction. To the best of our knowledge, this is the first report that reveals the reforming ability of Ga₂O₃ for the production of H₂ from DME and/or methanol.     

ZnO/Cr2O3 catalyst for reverse-water-gas-shift reaction of CAMERE process

The stability and the activity of Fe₂O₃/Cr₂O₃ and ZnO/Cr₂O₃ catalysts were examined for a reverse-watergas-shift reaction (RWReaction). The initial activities of those catalysts were quite high so that the conversion reached close to equilibrium. The activity of Fe₂O₃/Cr₂O₃ catalyst decreased from 33.5 to 29.8% during the RWReaction for 75 h at 873 K with GHSV (ml/gcat · h) of 100,000. Moreover, the coke formation on the Fe₂O₃/Cr₂O₃ catalyst caused clogging in the RWReactor of the CAMERE process. On the other hand, the ZnO/Cr₂O₃ catalyst showed no coke formation and no deactivation for the RWReaction at 873 K with GHSV (ml/gcat · h) of 150,000. The ZnO/Cr₂O₃ was a good catalyst for the RWReaction of the CAMERE process.     

Partial oxidation of ethane by in situ generated H2O2

Selective partial oxidation of ethane to ethanol and acetaldehyde by in situ generated H₂O₂ has been achieved under cathodic current passing through a carbon supported Nafion-H catalytic membrane. A correlation between H₂O₂ generation rate and reaction rate has been found.     

Magnetically Separable Fe3O4 Nanoparticles-Decorated Reduced Graphene Oxide Nanocomposite for Catalytic Wet Hydrogen Peroxide Oxidation

Fe₃O₄ nanoparticles-decorated reduced graphene oxide magnetic nanocomposites (Fe₃O₄/rGO NCs) were prepared by a facile one-step strategy, and further used as heterogeneous Fenton-like catalysts for catalytic wet hydrogen peroxide oxidation (CWHPO) of methylene blue (MB) at 25 °C and atmospheric pressure. The effects of variables such as the Fe₃O₄/rGO with the mass ratio of rGO, initial pH, MB concentration and H₂O₂ dosage were investigated. The Fe₃O₄/rGO NCs with rGO mass ratio of 10.0 wt % showed the highest H₂O₂-activating ability, which was six-fold than that of pure Fe₃O₄ nanoparticles (NPs). The resulting catalysts demonstrated high catalytic activity in a broad operation pH range from 5 to 9, and still retained 90.5 % catalytic activity after reuse in five cycles. Taking advantage of the combined benefits of rGO and magnetic Fe₃O₄ NPs, these Fe₃O₄/rGO NCs were confirmed as an efficient heterogeneous Fenton-like catalyst for CWHPO to treat organic pollutants. And a reasonable catalytic mechanism of Fe₃O₄/rGO NCs was proposed to interpret the degradation process.     

Decolorization and Modeling of Synthetic Wastewater Using O3 and H2O2/O3 Processes

This research deals with the decolorization of synthetic wastewater, prepared with the acid 1:2 metal-complex textile dye C.I. Acid Blue 193, using the ozonation (O₃) and H₂O₂/O₃ processes. To minimize the number of experiments, they were performed using the 2^k factorial design. Five influential parameters were examined: initial dye concentration, ozone flow rate, initial pH value, decolorization time and H₂O₂ addition. The decolorization efficiency was 95% in 20 minutes (pH = 7; O₃ flow rate of 2 g/L.h) and a higher increase in the toxicity after the ozonation process (39%) indicates the formation of carcinogenic by-products. According to the variance test analysis, the initial dye concentration, the ozone flow rate, the initial pH value and the decolorization time and their first- and second-order interactions are significant, while the H₂O₂ addition was not important with respect to the discussed range. With the help of these significant factors a regression model was constructed and the adequacy of the model was checked. The obtained regression polynomial was used to model the relation between the absorbance and the influential parameters by fitting the response surface. This response surface may be used to predict the absorbance result from a set of influential parameters, or it can be rearranged in such a way as to predict the set of process decolorization parameters necessary to reduce the absorbance of wastewater with the given initial dye concentration, below the prescribed limit. It is also shown that the 2^k factorial design can be suitable for predicting the operating expenses of the ozonation.     

Reduction of Biocide-Polluted Wastewater Using O3 and H2O2/O3 Oxidation Processes

The objective of the presented study was to test various oxidation processes with the aim being to reduce the concentration and toxicity of biocide wastewater from a Slovenian phytopharmaceutical factory. Laboratory-scale experiments employing two AOP processes – ozonation (O₃) and peroxone (H₂O₂/O₃) – were applied to reduce the concentration of the active components involved, i.e., methylisothiazolone (MI), chloromethylisothiazolone (CMI) and dichloromethylisothiazolone (DCMI). The reduction of the biocide wastewater load for the performed oxidation processes was evaluated using ecological parameters. The H₂O₂/O₃ oxidation procedure using an O₃ flow rate of 1g/L h, at a pH value of 10 and with the addition of 5 ml of H₂O₂ (0.3 M) proved to be the most effective treatment. The toxicity of the biocide-load wastewater with an initial EC₅₀ = 0.38%, decreased to EC₅₀ (24h) >100% and EC₅₀ (48h) = 76%.