Degradation of orange-G by advanced oxidation processes

The degradation and mineralization of orange-G (OG) in aqueous solutions by means of ultrasound irradiation at a frequency of 213 kHz and its combination with a heterogeneous photocatalyst (TiO₂) were investigated. The effects of various operational parameters such as, the concentration of the dye and solution pH on the degradation efficiency were studied. The degradation of the dye followed first-order like kinetics under the conditions examined. The sonolytic degradation of OG was relatively higher at pH 5.8 than that at pH 12. However, an alkaline pH was favoured for the photocatalytic degradation of OG using TiO₂. Total organic carbon (TOC) measurements were also carried out in order to evaluate the mineralization efficiency of OG using sonolysis, photocatalysis and sonophotocatalysis. The hybrid technique of sonophotocatalytic degradation was compared with the individual techniques of photocatalysis and sonolysis. A simple additive effect was observed during the sonophotocatalytic oxidation of OG using TiO₂ indicating that the combined treatment offers no synergistic enhancement. TOC results also support the additive effect in the dual treatment process.     

Development of dispersed-type sonophotocatalytic process using piezoelectric effect caused by ultrasonic resonance

Recently, degradation of persistent organic pollutants (POPs) with low biodegradability in the environment and in industrial and municipal wastewaters has gained importance. In this study, a dispersed-type sonophotocatalysis (SP) process, which is a combination of sonolysis and photocatalysis with dispersed light sources, has been proposed for the effective and energy-efficient degradation of POPs. In this method, the piezoelectric effect caused by ultrasonic resonance in a piezoelectric element is used for producing luminescence in a LED. A luminescent device composed of eight UV-LEDs and a piezoelectric element was designed for dispersion of UV light in water; this device was confirmed to show luminescence under ultrasonic irradiation. Sonophotocatalytic degradation experiments were carried out using several such devices, and the results were compared with those obtained in sonolysis, photocatalysis, and fixed-type SP. The comparison showed that the degradation rate constants in fixed-type and dispersed-type SP were larger than the sum of the rate constants obtained for sonolysis and photocatalysis; further, the synergetic effect caused by the combination of sonolysis and photocatalysis was 7.5% and 18% in fixed-type and dispersed-type SP, respectively.     

Sonolytic degradation of hazardous organic compounds in aqueous solution

Benzene, chlorobenzene, 1,2-, 1,3-, 1,4-dichlorobenzene, biphenyl, and polychlorinated biphenyls such as 2-, 4-chlorobiphenyl and 2,2′-dichlorobiphenyl in aqueous solutions have been subjected to sonolysis with 200 kHz ultrasound at an intensity of 6 W cm⁻² under an argon atmosphere. 80–90% of initial amount of these compounds were degraded by 30–60 min of sonication when the initial concentrations were 10–100 μmol l⁻¹. The degradation rate of these compounds increased with increase in their vapor pressures. In all cases of sonolysis of chlorinated organic compounds, an appreciable amount of liberated chloride ion was observed.     

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.     

Visible light induced sonophotocatalytic degradation of Reactive Red dye 198 using dye sensitized TiO2

In this paper we are reporting the accelerated sonophotocatalytic degradation of Reactive Red (RR) 198 dye under visible light using dye sensitized TiO(2) activated by ultrasound. The effect of sonolysis, photocatalysis and sonophotocatalysis under visible light has been examined to study the influence on the degradation rates by varying the initial substrate concentration, pH and catalyst loading to ascertain the synergistic effect on the degradation techniques. Ultrasonic activation at 47kHz contributes through cavitation leading to the splitting of H(2)O(2) produced by both photocatalysis and sonolysis. This results in the formation of oxidative species, such as singlet oxygen ((1)O(2)) and superoxide (O2-*) radicals in the presence of oxygen. Sonication increases the amount of reactive radical species, inducing faster oxidation of the substrate and degradation of intermediates and also the deaggregation of the photocatalyst which are responsible for the observed synergy. Further, the photocatalytic activity of RR 198 dye sensitized TiO(2) is demonstrated by the degradation of phenol under visible light and ultrasound. A comparative study using TiO(2), Hombikat UV 100 and ZnO was also carried out.     

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.     

Sonophotocatalysis of oxalic acid solution

Sonophotocatalysis of oxalic acid was performed in various atmospheric conditions. Sonophotocatalysis means a coupled reaction of sonolysis and photocatalysis. CO(2), CO and H(2) were obtained. The yield of CO(2) was twice larger than the sum of yields of photocatalysis and sonolysis in an Ar atmosphere. Namely, synergistic effect was observed. Further improvement was observed after pre-sonication. Hydrogen peroxide produced during sonication is a key material for the synergistic effect. In surroundings including O(2), however, synergistic effect could not be observed. The role of ultrasonic waves on the sonophotocatalysis of organic compounds was investigated.     

Degradation of methyl tert-butyl ether in water: effects of the combined use of sonolysis and photocatalysis

The degradation of methyl tert-butyl ether (MTBE) in water was kinetically investigated in a O(2)/Ar 80:20 atmosphere employing either sonolysis at 20 kHz, or photocatalysis on TiO(2) (with 315 nm< lambda(irr) <400 nm), or simultaneous sonolysis and photocatalysis (i.e. sonophotocatalysis), as degradation techniques. In all investigated conditions, MTBE concentration decreased according to a first order rate law; under ultrasound the degradation rate was stirring-dependent. The time profile of the reaction intermediates gave information on the reaction paths prevailing under the different experimental conditions. The energy consumption of the employed degradation techniques was also evaluated, which might be decisive for their practical application.     

Study of the sonophotocatalytic degradation of basic blue 9 industrial textile dye over slurry titanium dioxide and influencing factors

The sonophotocatalytic degradation of basic blue 9 industrial textile dye has been studied in the presence of ultrasound (20 kHz) over a TiO(2) slurry employing an UV lamp (15 W, 352 nm). It was observed that the color removal efficiency was influenced by the pH of the solution, initial dye concentration and TiO(2) amount. It was found that the dye degradation followed apparent first order kinetics. The rate constant increased by decreasing dye concentration and was affected by the pH of the solution with the highest degradation obtained at pH 7. The first order rate constants obtained with sonophotocatalysis were twofold and tenfold than those obtained under photocatalysis and sonolysis, respectively. The chemical oxygen demand was abated over 80%.     

Sonocatalytic degradation of Acid Blue 92 using sonochemically prepared samarium doped zinc oxide nanostructures

Pure and Sm-doped ZnO nanoparticles were synthesized applying a simple sonochemical method. The nanocatalysts were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS) techniques which confirmed the successful synthesis of the doped sonocatalyst. The sonocatalytic degradation of Acid Blue 92 (AB92), a model azo dye, was more than that with sonolysis alone. The 6% Sm-doped ZnO nanoparticles had a band gap of 2.8 eV and demonstrated the highest activity. The degradation efficiency (DE%) of sonolysis and sonocatalysis with undoped ZnO and 6% Sm-doped ZnO was 45.73%, 63.9%, and 90.10%, after 150 min of treatment, respectively. Sonocatalytic degradation of AB92 is enhanced with increasing the dopant amount and catalyst dosage and with decreasing the initial AB29 concentration. DE% declines with the addition of radical scavengers such as chloride, carbonate, sulfate, and tert-butanol. However, the addition of enhancers including potassium periodates, peroxydisulfate, and hydrogen peroxide improves DE% by producing more free radicals. The results show adequate reusability of the doped sonocatalyst. Degradation intermediates were recognized by gas chromatography–mass spectrometry (GC–MS). Using nonlinear regression analysis, an empirical kinetic model was developed to estimate the pseudo-first-order constants (k_app) as a function of the main operational parameters, including the initial dye concentration, sonocatalyst dosage, and ultrasonic power.     

Synergistic degradation of methyl orange in an ultrasound intensified photocatalytic reactor

An original ultrasound (US) directly intensified photocatalytic reactor was designed to degrade azo dye pollutant methyl orange (MeO) using Degussa TiO(2) as the photocatalyst. The sonolytic, photocatalytic and sonophotocatalytic degradation of MeO in the new reactor and the synergistic effect between sonolysis and photocatalysis were investigated. Effects of operation parameters i.e., US power, TiO(2) dosage, liquid circulation velocity and air flow rate on degradation efficiency were investigated and optimized. The results showed that all parameters have optimal values for the sonophotocatalytic degradation of MeO, and the optimum conditions for the new process are US power 600 W, TiO(2) dosage 3g/L, liquid circulation velocity 4.05×10(-2) m/s and air flow rate 0.2 L/min. Under the optimum conditions, 91.52% MeO had been degraded within 1h, and the combination of sonolysis and TiO(2) photocatalysis exhibited an obvious synergetic effect.     

Phenol degradation under visible light irradiation in the continuous system of photocatalysis and sonolysis

The combination of photocatalysis under visible light irradiation and sonolysis in the continuous system has been used to degrade an aqueous solution of phenol. ZnFe₂O₄/TiO₂–GAC was employed as the photocatalysts which were obtained by sol–gel process and characterized by spectroscopic X-ray diffraction (XRD), scanning electron microscopy with energy dispersive X-ray microanalyses (SEM–EDX) and Brunauer–Emmett–Teller sorptometer (BET). It was observed that the rates of phenol degradation were affected by the initial pH value of phenol solution, salt addition, gas supplying and the recycling times of the recovered photocatalyst. The kinetic law for the phenol degradation can be apparently expressed as the first-order with respect to the concentration of phenol. Degradation of phenol solution in the continuous system, i.e., photocatalysis and sonolysis has synergistic effect in comparison with the photocatalytic reaction and sonolysis, respectively.     

Degradation of Acid Orange 7 in aqueous solution by zero-valent aluminum under ultrasonic irradiation

Degradation of azo dye Acid Orange 7 (AO7) by zero-valent aluminum (ZVAl) in combination with ultrasonic irradiation was investigated. The preliminary studies of optimal degradation methodology were conducted with sole ultrasonic, sole ZVAl/air system, ultrasonication + ZVAl/air system (US-ZVAl). In ZVAl/air system, the degradation of AO7 could almost not be observed within 30 min. The degradation of AO7 by ZVAl/air system was obviously enhanced under ultrasound irradiation, and the enhancement is mainly attributed to that the production of hydroxyl radicals in ultrasound-ZVAl process was much higher than that in sole ultrasonic or in sole ZVAl/air system. The variables considered for the effect of degradation were the power of ultrasound, the initial concentration of AO7, as well as the initial pH value and the dosage of zero-valent aluminum. The results showed that the decolorization rate increased with the increase of power density and the dosage of ZVAl, but decreased with the increase of initial pH value and initial concentration of AO7. More than 96% of AO7 removal was achieved within 30 min under optimum operational conditions (AO7: 20 mg/L, ZVAl: 2 g/L, pH: 2.5, ultrasound: 20 kHz, 300 W). This study demonstrates that ultrasound-ZVAl process can effectively decolorize the azo dye AO7 in wastewater.     

Individual and combined effects of ultrasound, ozone and UV irradiation: a case study with textile dyes

Comparative degradation of azo dyes by 520 kHz ultrasonic irradiation and its combinations with ozone and/or ultraviolet light (UV) was investigated using a probe dye C.I. Acid Orange 7. Operation parameters such as ultrasonic power density, ozone flow, UV intensity, and type and injection mode of the bubbling gas were optimized based on the rate of absorption decay in the visible and UV bands as estimated by regression analysis of absorption-time data. At equivalent initial dye concentrations and contact times, individual effects of UV irradiation, ultrasound and ozone were "no effect", "bleaching", and "bleaching/organic carbon degradation", respectively. UV irradiation, however, was found to induce a catalytic effect when applied in combination with either ultrasound or ozone schemes; and the overall degradation process was most rapid under simultaneous operation of the three in the presence of a continuous flow of a gas mixture made of argon and oxygen. The synergy observed in combined schemes was attributed to enhanced ozone diffusion by mechanical effects of ultrasound, and the photolysis of ultrasound-generated H(2)O(2) to produce hydroxyl radicals.     

Degradation of organic water pollutants through sonophotocatalysis in the presence of TiO(2)

The degradation of 2-chlorophenol and of the two azo dyes acid orange 8 and acid red 1 in aqueous solution was investigated kinetically under sonolysis at 20 kHz and under photocatalysis in the presence of titanium dioxide particles, as well as under simultaneous sonolysis and photocatalysis, i.e. sonophotocatalysis. The influence on the degradation and mineralisation rates of the initial substrate concentration and of the photocatalyst amount was systematically investigated to ascertain the origin of the synergistic effect observed between the two degradation techniques. The evolution of hydrogen peroxide during kinetic runs was also monitored. Small amounts of Fe(III) were found to affect both the adsorption equilibria on the semiconductor and the degradation paths. Ultrasound may modify the rate of photocatalytic degradation by promoting the deaggregation of the photocatalyst, by inducing the desorption of organic substrates and degradation intermediates from the photocatalyst surface and, mainly, by favouring the scission of the photocatalytically and sonolytically produced H(2)O(2), with a consequent increase of oxidising species in the aqueous phase.     

Sonochemical degradation of martius yellow dye in aqueous solution

The sonolytic degradation of the textile dye martius yellow, also known as either naphthol yellow or acid orange 24, was studied at various initial concentrations in water. The degradation of the dye followed first-order kinetics under the conditions examined. Based on gas chromatographic results and sonoluminescence measurements of sonicated aqueous solutions of the dye, it is concluded that pyrolysis does not play a significant role in its degradation. The chromatographic identification of hydroxy added species indicates that an OH radical induced reaction is the main degradation pathway of the dye. Considering the non-volatility and surface activity of the dye, the degradation of the dye most probably takes place at the bubble/solution interface. The quantitative and qualitative formation of the degradation intermediates and final products were monitored using HPLC and ESMS. The analytical results suggest that the sonolytic degradation of the dye proceeds via hydroxylation of the aryl ring and also by C-N bond cleavage of the chromophoric ring, either through OH radical attack or through another unidentified process. The identification of various intermediates and end products also imply that the degradation of martius yellow proceeds through multiple reaction pathways. Total organic carbon (TOC) analyses of the dye solutions at various times following sonication revealed that sonolysis was effective in the initial degradation of the parent dye but very slow in achieving mineralization. The slow rate of mineralization is likely to be due to the inability of many of the intermediate products such as, the carboxylic acids, to accumulate at the bubble (air/water) interface and undergo decomposition due to their high water solubility (low surface activity).     

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.     

Sonocatalytic degradation of a textile dye over Gd-doped ZnO nanoparticles synthesized through sonochemical process

The present study was performed to sonochemically synthesize Gd_xZn_1 − xO (x = 0–0.1) nanoparticles for sonocatalysis of Acid Orange 7 (AO7) in an aqueous medium. The results of X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR) and X-ray photoelectron spectroscopy (XPS) analysis confirmed proper synthesis of Gd-doped sonocatalyst. 5% Gd-doped ZnO nanoparticles with band gap of 2.8 eV exhibited the highest sonocatalytic decolorization efficiency of 90% at reaction time of 90 min. The effects of initial dye concentration and sonocatalyst dosage on decolorization efficiency were evaluated. In the presence of sodium sulfate, sodium carbonate and sodium chloride the decolorization efficiency decreased from 90 to 78, 65 and 56%, respectively. Among various enhancers, the addition of potassium periodate improved the decolorization efficiency from 90 to 100%. The highest decolorization efficiency was obtained at pH value of 6.34 (90%). The decolorization efficiency decreased only 6% after 4 repeated runs. Therefore, Gd-doped ZnO nanoparticles can be used as a promising catalyst for degradation of organic pollutants with great reusability potential.     

Sonophotocatalytic decomposition of water using TiO(2) photocatalyst

Sonophotocatalytic reaction is a photocatalytic reaction with ultrasonic irradiation or the simultaneous irradiation of ultrasound and light with a photocatalyst. The possibility of the effect of hybrid of sonochemical and photocatalytic reactions was examined. Liquid water was hardly decomposed to H(2) and O(2) by photocatalysis or sonolysis, independently. In order to decompose water, powdered TiO(2) photocatalyst suspended in distilled water should be simultaneously irradiated by light and ultrasound. This sonophotocatalytic reaction was effective on the decomposition of water to H(2) and O(2).     

Removal of organic matter and ammonia nitrogen from landfill leachate by ultrasound

Experiments on the removal of organic matters and ammonia nitrogen from landfill leachate by ultrasound irradiation were carried out. The effects of COD reduction and ammonia removal of power input, initial concentration, initial pH and aeration were studied. It was found that the sonolysis of organic matters proceeds via reaction with ()OH radicals; a thermal reaction also occurs with a small contribution. The rise of COD at some intervals could be explained by the complexity of organic pollutant sonolysis in landfill leachate. Ultrasonic irradiation was shown to be an effective method for the removal of ammonia nitrogen from landfill leachate. After 180 min ultrasound irradiation, up to 96% ammonia nitrogen removal efficiency can be obtained. It was found that the mechanism of ammonia nitrogen removal by ultrasound irradiation is largely that the free ammonia molecules in leachate enter into the cavitation bubbles and transform into nitrogen molecules and hydrogen molecules via pyrolysis under instant high temperature and high pressure in the cavitation bubbles.