Degradation of C.I. Acid Orange 7 by the advanced Fenton process in combination with ultrasonic irradiation

The combination of ultrasound and the advanced Fenton process (AFP, zero-valent iron and hydrogen peroxide) for the degradation of C.I. Acid Orange 7 was studied. The effect of hydrogen peroxide concentration, initial pH, ultrasonic power density, dissolved gas, and iron powder addition on the decolorization of C.I. Acid Orange 7 was investigated. A modified pseudo-first order kinetic model was used to simulate the experimental results. The results showed that the decolorization rate increased with the increase of hydrogen peroxide concentration and power density, but decreased with the increase of initial pH value. There existed an optimal iron powder addition when decolorization rate was concerned. The decolorization efficiency also increased with the increase of hydrogen peroxide concentration, but decreased with the increase of initial pH value. It varied little at different power densities or iron powder additions at the fixed hydrogen peroxide concentration. The presence of dissolved gas would enhance color removal, and the enhancement was more significant when dissolved oxygen was present. More hydrogen peroxide dosage and reaction duration are required to achieve a relatively high COD removal than those employed to simply break the chromophore group.     

Mineralisation of 2,4-dichlorophenoxyacetic acid by acoustic or hydrodynamic cavitation in conjunction with the advanced Fenton process

The mineralisation of 2,4-dichlorophenoxyacetic acid (2,4-D) in the presence of zero-valent iron and hydrogen peroxide (the advanced Fenton process--AFP) whilst being subjected to acoustic or hydrodynamic cavitation is reported. If the reaction is merely stirred then there is 57% removal of TOC whilst on irradiation the figure is 64% although the latter reaction is more rapid. Use of ultrasound alone results in only 11% TOC removal in 60 min of treatment time. Addition of iron powder marginally enhances the extent of degradation but an appreciable increase is observed in the presence of hydrogen peroxide which acts as a source for hydroxyl radicals by Fenton chemistry as well as by dissociation in the presence of ultrasound. The use of hydrodynamic cavitation in conjunction with the advanced Fenton process has also been found to be a useful tool for continuous remediation of water contaminated with 2,4-D. After 20 min of treatment the residual TOC is reduced to 30% and this probably represents the remaining highly recalcitrant small organic molecules.     

Treatment of industrial wastewater effluents using hydrodynamic cavitation and the advanced Fenton process

For the first time, hydrodynamic cavitation induced by a liquid whistle reactor (LWR) has been used in conjunction with the advanced Fenton process (AFP) for the treatment of real industrial wastewater. Semi-batch experiments in the LWR were designed to investigate the performance of the process for two different industrial wastewater samples. The effect of various operating parameters such as pressure, H2O2 concentration and the initial concentration of industrial wastewater samples on the extent of mineralization as measured by total organic carbon (TOC) content have been studied with the aim of maximizing the extent of degradation. It has been observed that higher pressures, sequential addition of hydrogen peroxide at higher loadings and lower concentration of the effluent are more favourable for a rapid TOC mineralization. In general, the novel combination of hydrodynamic cavitation with AFP results in about 60-80% removal of TOC under optimized conditions depending on the type of industrial effluent samples. The combination described herein is most useful for treatment of bio-refractory materials where the diminution in toxicity can be achieved up to a certain level and then conventional biological oxidation can be employed for final treatment. The present work is the first to report the use of a hydrodynamic cavitation technique for real industrial wastewater treatment.     

Sonoelectrocatalytic decomposition of methylene blue using Ti/Ta2O5–SnO2 electrodes

Sonoelectrochemical decomposition of organic compounds is a developing technique among advanced oxidation processes (AOPs). It has the advantage over sonication alone that it increases the efficiency of the process in terms of a more rapid decrease in chemical oxygen demand (COD) and in total organic carbon (TOC) and accelerates electrochemical oxidation which normally requires a lengthy period of time to achieve significant mineralisation. Moreover the use of an electrocatalytic electrode in the process further accelerates the oxidation reaction rates. The aim of this study was to improve the decomposition efficiency of methylene blue (MB) dye by sonoelectrochemical decomposition using environmentally friendly and cost-effective Ti/Ta₂O₅–SnO₂ electrodes. Decolourisation was used to assess the initial stages of decomposition and COD together with TOC was used as a measure of total degradation. The effect of a range of sonication frequencies 20, 40, 380, 850, 1000 and 1176 kHz at different powers on the decolourisation efficiency of MB is reported. Frequencies of 850 and 380 kHz and the use of higher powers were found more effective towards dye decolourisation. The time for complete MB degradation was reduced from 180 min using electrolysis and from 90 min while carrying out sonolysis to 45 min when conducting a combined sonoelectrocatalytic experiments. The COD reduction of 85.4% was achieved after 2 h of combined sonication and electrolysis which is a slightly higher than after a single electrolysis (78.9%) and twice that of sonolysis (40.4%). A dramatic improvement of mineralisation values were observed within 2 h of sonoelectrocatalytic MB degradation. The TOC removal efficiency increased by a factor of 10.7 comparing to sonication alone and by a factor of 1.5 comparing to the electrolytic process. The energy consumption (kWh/m³) required for the complete degradation of MB was evaluated.     

Improvement in sonochemical degradation of 4-chlorophenol by combined use of Fenton-like reagents

Studies on the sonolysis of a wide range of organic compounds have demonstrated that ultrasonic irradiation has potential for decomposition of organic pollutants in hazardous wastewater. However, the ultrasonic irradiation alone cannot provide high enough rate of decomposition to be used practically. One of the solutions to increase the degradation efficiency is to combine the ultrasound application with other advanced chemical oxidation processes (AOPs). In this study, in order to increase the efficiency of ultrasonically assisted degradation of organic pollutants in water, we examined effects of three kinds of solid Fe-containing catalysts, namely iron powder, basic oxygen furnace (BOF) slag and mill scale on the degradation rate of 4-CP (4-chlorophenol) in aqueous solutions containing hydrogen peroxide. In the experiments, 4-CP was considered as a model organic compound. All three Fe-containing matters when react with hydrogen peroxide are involved in the Fenton-like reaction system, which is one of the promising AOPs. The results showed that both the iron powder and mill scale additions can accelerate the degradation of 4-CP, although the effect is dependent on the solution pH. All 4-CP could be decomposed for 2 min at pH=3 and for 1h at pH=5.6. On the other hand, the BOF slag had no catalysis effect on the 4-CP degradation because of higher concentration of calcium and lower concentration of iron.     

Enhancement of saccharin removal from aqueous solution by activated carbon adsorption with ultrasonic treatment

This study investigates the use of ultrasonication as a pretreatment process and its effect on the adsorption characteristics of saccharin onto activated carbon (AC). Ultrasonic decomposition of saccharin was performed at a frequency of 500 kHz under argon and O2/N2 (20/80 vol%) atmospheres. Adsorption was carried out using a commercial activated carbon. The behavior of total organic carbon (TOC) during ultrasonication was investigated. Saccharin removal after 180 min of ultrasonication under Ar and O2/N2 atmospheres are 38% and 26%, respectively, while the amount of saccharin removed by activated carbon adsorption without US pretreatment is 40% after 16 h. After 16 h of AC adsorption with 180 min of ultrasonic pretreatment under Ar and O2/N2 atmospheres, both removal ratios increased to 75%. These results indicated that the pretreatment of sonication under O2/N2 leads to the increase in the amount of saccharin adsorbed on AC. On the other hand, the TOC removal by decomposition by ultrasound is not more than 5% in both Ar and O2/N2 atmospheres after 180 min ultrasonication. However, the TOC removal increased to 54% and 69% after 16 h of adsorption of saccharin pretreated by ultrasonication for 180 min under Ar and O2/N2 atmospheres, respectively. About 13% and 16% TOC removal in Ar and in O2/N2, respectively, were achieved due to adsorption of the by-products. It is considered that the improvement in TOC removal is also brought about by the formation of the by-products that were adsorbed onto AC.     

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 SO₄^2-, CO₃^2–, NO^3–, 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 SO₄^2- and CO₃^2– 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.     

A new development of dyestuffs degradation system using ultrasound

Dyestuffs are often present in industrial wastewaters and can consist of hazardous substances which have a serious impact on the environment and personal health. This report describes a system developed to degrade these substances using sonochemical reactions. Ultrasonic frequencies of 118, 224, 404 and 651 kHz and power input values of 11.4, 29.0 and 41.5 W were tested on Rhodamine B and Orange II dyestuff solutions in order to find the best degradation conditions. The ultrasonic irradiation of air-saturated solutions produces free radicals that combine and generates hydrogen peroxide, and compared to the production of hydrogen peroxide when irradiating water, a decrease was found during the irradiation to dyestuff solutions, indicating that some of the free radicals were consumed in the dyestuffs degradation process. The effects of the ultrasonic irradiation conditions on the pH, nitric and nitrous acid formations as well as the total organic carbon value (TOC) were also investigated. For the ultrasonic frequencies of 224, 404 and 651 kHz, the degradation rates were very similar, however, the 118 kHz system presented a degradation rate of about one-third that of the higher frequencies for both dyestuffs. The Rhodamine B solutions were decolorized within 2 h of ultrasonic irradiation for all systems with the exception of the 118 kHz one. For Orange II, except for the 118 kHz system, all solutions were decolorized within 4 h of ultrasonic irradiation. All reactions were carried out at 25 degrees C and the total ultrasonic irradiation time was 10 h.     

Evaluation of ammonia–nitrogen removal efficiency from aqueous solutions by ultrasonic irradiation in short sonication periods

In this study, mechanisms and efficiency of ammonia–nitrogen removal from aqueous solutions by ultrasonic irradiation were investigated. Depending on the factors affecting the sonication (initial concentration, initial pH, ultrasonic power density and sonication period), sonication tests were carried out and ammonium–nitrogen removal efficiency by ultrasonic irradiation was determined. In these experiments, ammonia–nitrogen removal efficiency was achieved in the range of 8–64%. In short sonication periods, the best ammonia–nitrogen removal efficiency was achieved at pH 8.2–11. Lower ammonia–nitrogen removal efficiency was observed in high initial ammonia–nitrogen concentration of solutions. It was observed that high initial ammonia–nitrogen concentrations may led to decreased ammonia–nitrogen removal efficiency however quantity of ammonia–nitrogen removal was higher. Because high initial concentration had a negative impact on the sonochemical reactions the heat of cavitation bubbles was reduced. Ammonia–nitrogen removal efficiency was increased with ultrasonic density and sonication period. This study showed that effective ammonia–nitrogen removal could be achieved by the ultrasonic irradiation in short sonication periods (as 60–600 s). Specific cost of ammonia–nitrogen removal by the ultrasonic irradiation from simulated ground water, surface water, wastewater and landfill leachate was also calculated. The specific removal cost was varied between 0.01 and 0.25 $/g ammonia–nitrogen.     

Degradation of Acid Blue 25 in aqueous media using 1700 kHz ultrasonic irradiation: ultrasound/Fe(II) and ultrasound/H2O2 combinations

In this work, the sonolytic degradation of an anthraquinonic dye, C.I. Acid Blue 25 (AB25), in aqueous phase using high frequency ultrasound waves (1700 kHz) for an acoustic power of 14 W was investigated. The sonochemical efficiency of the reactor was evaluated by potassium iodide dosimeter, Fricke reaction and hydrogen peroxide production yield. The three investigated methods clearly show the production of oxidizing species during sonication and well reflect the sonochemical effects of high frequency ultrasonic irradiation. The effect of operational conditions such as the initial AB25 concentration, solution temperature and pH on the degradation of AB25 was studied. Additionally, the influence of addition of salts on the degradation of dye was examined. The rate of AB25 degradation was dependent on initial dye concentration, pH and temperature. Addition of salts increased the degradation of dye. Experiments conducted using distilled and natural waters demonstrated that the degradation was more efficient in the natural water compared to distilled water. To increase the efficiency of AB25 degradation, experiments combining ultrasound with Fe(II) or H₂O₂ were conducted. Fe(II) induced the dissociation of ultrasonically produced hydrogen peroxide, leading to additional OH radicals which enhance the degradation of dye. The combination of ultrasound with hydrogen peroxide looks to be a promising option to increase the generation of free radicals. The concentration of hydrogen peroxide plays a crucial role in deciding the extent of enhancement obtained for the combined process. The results of the present work indicate that ultrasound/H₂O₂ and ultrasound/Fe(II) processes are efficient for the degradation of AB25 in aqueous solutions by high frequency ultrasonic irradiation.