Heterogeneous sonocatalytic degradation of Bisphenol-A and the influence of the reaction parameters and ultrasonic frequency.

In the present study, the sonocatalytic oxidation of Bisphenol-A (BPA) was investigated in the presence of a LaFeO3 perovskite catalyst. The effects of the reaction temperature, initial pH, catalyst loading, presence of inorganic anions and sonication source (power and frequency) on the removal of BPA using heterogeneous sonocatalytic process were investigated. Under the studied temperature range of 288-318 K, 308 K was selected as the optimum temperature and the highest BPA removal and total oxygen demand (TOC) reduction of, 95.8% and 30.4% were achieved at that temperature. The thermodynamic parameters were calculated in the studied temperature range of 288-308 K. It was seen that an acidic pH of 3.0 was favorable for the BPA oxidation with the highest BPA removal and TOC reduction of 95.4% and 31.5%, respectively. Doubling the catalyst amount from 0.25 g/L to 0.5 g/L increased the BPA removal degree from 81.6% to 90.8%. However, further increase in catalyst amount has no remarkable positive effect on the removal of BPA. The removal of BPA was described by the first order kinetics with an activation energy of 14.9 kJ/mol. The results obtained from this study showed that the LaFeO3 perovskite catalyst was a good sonocatalyst giving high oxidation rates of BPA.

Influence of ultrasound on the heterogeneous Fenton-like oxidation of acetic acid.

The main objective of this study is to investigate the effect of ultrasound on the heterogeneous Fenton-like oxidation of acetic acid, which is one of the most resistant carboxylic acids to oxidation. For this purpose, firstly, the degradation of acetic acid was examined by using ultrasound alone and the effects of different parameters such as: type of sonication system, ultrasonic power, and addition of H2O2 were investigated on the degradation of acetic acid. There was no chemical oxygen demand (COD) reduction in the presence of sonication alone. In the presence of the heterogeneous Fenton-like oxidation process alone, at 303 K, COD reduction reached only 7.1% after 2 h of reaction. However, the combination of the heterogeneous Fenton-like oxidation process with ultrasound increased the COD reduction from 7.1% to 25.5% after 2 h of reaction in an ultrasonic bath operated at 40 kHz, while the COD reduction only increased from 7.1% to 8.9% in the ultrasonic reactor operated at 850 kHz. This result indicates that the hybrid process of ultrasound and heterogeneous Fenton-like oxidation is a promising process to degrade acetic acid.

Sonolytic degradation of butyric acid in aqueous solutions.

The sonolytic degradation of butyric acid was investigated in an ultrasonic reactor emitting waves at 850 kHz. The effects of the ultrasonic power, the initial concentration of butyric acid, and the addition of H2O2 were studied on the degradation of butyric acid. In the sonication of butyric acid, degradation degrees as high as 31.5% could be achieved at a power of 31 W, at an initial concentration of 2.8 mM butyric acid with the addition of 0.34 M H2O2 for a sonication time of 5 h. The degradation of butyric acid increased with irradiation time, indicating first order kinetics.

Synergistic effect of sonication on photocatalytic oxidation of pharmaceutical drug carbamazepine.

Photocatalytic, sono-photocatalytic oxidation of pharmaceutical drug of carbamazepine was successfully carried out using Ag/AgCl supported BiVO4 catalyst. For this purpose, firstly, photocatalytic oxidation was optimized by central composite design methodology and then synergistic effect of sonication was investigated. Low frequency (20 kHz) probe type and high frequency (850 kHz) plate type sonication at pulse and continuous mode were studied to degrade the carbamazepine (CBZ) containing wastewater. Pulse duties of 1:5 and 5:1 (on : off) were tested using the high frequency sonication system in the sono-photocatalytic oxidation of CBZ. The effects of frequency, power density measured from calorimetry by changing amplitudes were discussed in the sono-photocatalytic oxidation of CBZ. Complete carbamazepine removal was achieved at the optimum conditions of 5 ppm CBZ initial concentration with 1.5 g/L of catalysts loading and at an alkaline pH of 10 at the end of 4 h of photocatalytic reaction under visible LED light irradiation. Both low frequency and high frequency sonication systems caused an increase in photocatalytic efficiency in a shorter treatment time of 60 min. CBZ removal increased from 44% to 65.42% in low frequency sonication of 20 kHz at the amplitude of 20% (0.15 W/mL power density). In the case of high frequency ultrasonic system (850 kHz), CBZ removal increased significantly from 44% to 89.5 % at 75% amplitude (0.12 W/mL power density) within 60 min of reaction. Continuous mode sonication was observed to be more effective than that of pulse mode sonication not only for degradation efficiency and also for electrical energy consumption needed to degrade CBZ. Sono-catalytic oxidation was also conducted with simulated wastewater that contains SO42-, CO32-, NO3-, Cl- anions and natural organic component of fulvic acid. The CBZ degradation was inhibited slightly in the presence of NO3- and Cl-, and fulvic acid, however, the existence of SO42- and CO32- increased the degradation degree of CBZ. Toxicity tests were performed to determine the toxicity of untreated CBZ, and treated CBZ by photocatalytic, and sono-photocatalytic oxidations.

Effects of catalyst preparation method and reaction parameters on the ultrasound assisted Photocatalytic oxidation of reactive yellow 84 dye.

In this study, the Heterogeneous Sono-photocatalytic Process was used to degrade Reactive Yellow 84 (RY 84) dye dissolved in water over iron containing TiO2 and TiO2-Ce catalysts. The catalysts were prepared by sol-gel and incipient wetness impregnation methods and characterized using XRD, SEM, Nitrogen adsorption, UV-Vis DRS and ICP-AES measurements. The TiO2 catalyst containing 1% (in weight) iron, prepared by incipient wetness impregnation technique and calcined at 300 °C (1%Fe/TiO2-300 °C (IW)) was found to be the most effective catalyst. Parametric study was carried out over this catalyst and COD removal of 55% and TOC removal of 38% were achieved while the decolorization efficiency reached 100% after 45 min of reaction at the optimum conditions of, (25 mg/L of RY 84 solution, 0.5 g/L of catalyst, 5 mM of H2O2, a temperature of 25 °C, pH = 6 and US at a power of 40 W). Decolorization of RY 84 obeyed the first order kinetics with an activation energy of 20.7 kJ/mol. Sonication increased the decolorization efficiency of the heterogeneous Fenton process (UV + Catalyst+H2O2) from 92.7% to 97.5% after 30 min of reaction, with the COD and TOC reductions increasing from 87% to 90% and 48% to 57% after 120 min of reaction, respectively. US also decreased the toxicity of the RY 84 dye. The results obtained from this study show that, iron containing TiO2 and TiO2-Ce catalysts could be efficiently used in the hybrid process of ultrasound assisted heterogeneous photocatalytic oxidation in a wide range of experimental conditions.

Sono-photo-Fenton oxidation of bisphenol-A over a LaFeO3 perovskite catalyst.

In this study, oxidation of bisphenol-A (IUPAC name - 2,2-(4,4-dihydroxyphenyl, BPA), which is an endocrine disrupting phenolic compound used in the polycarbonate plastic and epoxy resin industry, was investigated using sono-photo-Fenton process under visible light irradiation in the presence of an iron containing perovskite catalyst, LaFeO3. The catalyst prepared by sol-gel method, calcined at 500°C showed a catalytic activity in BPA oxidation using sono-photo-Fenton process with a degradation degree and a chemical oxygen demand (COD) reduction of 21.8% and 11.2%, respectively. Degradation of BPA was studied by using individual and combined advanced oxidation techniques including sonication, heterogeneous Fenton reaction and photo oxidation over this catalyst to understand the effect of each process on degradation of BPA. It was seen, the role of sonication was very important in hybrid sono-photo-Fenton process due to the pyrolysis and sonoluminescence effects caused by ultrasonic irradiation. The prepared LaFeO3 perovskite catalyst was a good sonocatalyst rather than a photocatalyst. Sonication was not only the effective process to degrade BPA but also it was the cost effective process in terms of energy consumption. The studies show that the energy consumption is lower in the sono-Fenton process than those in the photo-Fenton and sono-photo- Fenton processes.

Degradation of a textile dye, Rhodamine 6G (Rh6G), by heterogeneous sonophotoFenton process in the presence of Fe-containing TiO2 catalysts.

In this study, degradation of Rhodamine 6G (Rh6G) was investigated with ultrasound-assisted heterogeneous photoFenton process by iron-containing TiO2 catalysts. The catalysts were prepared by incipient wetness impregnation method and characterized by XRD, SEM, FT-IR, nitrogen adsorption, and ICP-AES measurements. Almost complete color removal (99.9 %) was achieved after a reaction time of 90 min while chemical oxygen demand (COD) could be removed by 24 % only with the 1 wt% iron-containing TiO2 catalyst. Initial color removal after 15 min of reaction and total COD abatement after 90 min of reaction decreased with increasing calcination temperature of the catalyst from 573 to 973 K. This indicated that the catalytic activity of the catalyst depend on the percentage of anatase phase in the TiO2, which was decreased with increasing calcination temperature.

The sonochemical decolourisation of textile azo dye Orange II: effects of Fenton type reagents and UV light.

The removal of Orange II (O-II) from aqueous solution under irradiation at 850 kHz has been studied. The effects of both homogeneous (with FeSO4/H2O2), and heterogeneous (Fe containing ZSM-5 zeolite/H2O2) Fenton type reagents are reported together with the effect of UV irradiation in combination with ultrasound both alone and with homogeneous Fenton-type reagent. Degrees of decolourisation of 6.5% and 28.9% were observed using UV radiation and ultrasound, respectively, whereas under the simultaneous irradiation of ultrasound and UV light, the decolourisation degree reached 47.8%, indicating a synergetic effect of ultrasound and UV light. The decolourisation was increased with the addition of Fenton's reagent with an optimal Fenton molar reagent ratio, Fe(2+):H2O2 of 1:50. In the combined process of ultrasound and UV light with the homogeneous Fenton system 80.8% decolourisation could be achieved after 2h indicating that UV improves this type of Orange II degradation. The degree of decolourisation obtained using the heterogeneous sono-Fenton system (Fe containing ZSM-5 zeolite catalysts+H2O2+ultrasound) were consistently lower than the traditional homogeneous ultrasound Fenton system. This can be attributed to the greater difficulty of the reaction between Fe ions and hydrogen peroxide. In all cases the Orange II ultrasonic decolourisation was found to follow first order kinetics.