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1.
Sonochemical degradation of 4-chlorophenol, phenol, catechol and resorcinol was studied under Ar at 200 kHz in the absence and presence of Na2SO4 or NaCl. The rates of sonochemical degradation in the absence of salts decreased in the order 4-chlorophenol > phenol > catechol > resorcinol and this order was in good agreement with the order of log P (partition coefficient) value of each phenolic compound. The effects of salts on the rates of sonochemical degradation consisted of no effect or slight negative or positive effects. We discussed these unclear results based on two viewpoints: one was based on the changes in pseudo hydrophobicity and/or diffusion behavior of phenolic compounds and the other was based on the changes in solubility of Ar gas. The measured log P value of each phenolic compound slightly increased with increasing salt concentration. In addition, the dynamic surface tension for 4-chlorophenol aqueous solution in the absence and presence of Na2SO4 or NaCl suggested that phenolic compounds more easily accumulated at the interface region of bubbles at higher salt concentration. These results indicated that the rates of sonochemical degradation should be enhanced by the addition of salts. On the other hand, the calculated Ar gas solubility was confirmed to decrease with increasing salt concentration. The yield of H2O2 formed in the presence of Na2SO4 or NaCl decreased with increasing salt concentration. These results suggested that sonochemical efficiency decreased with decreasing gas amount in aqueous solution: a negative effect of salts was observed. Because negative and positive effects were induced simultaneously, we concluded that the effects of salts on the rates of sonochemical degradation of phenolic compounds became unclear. The products formed from sonochemical degradation of 4-chlorophenol were also characterized by HPLC analysis. The formation of phenol and 4-chloro-1,3-dihydroxy benzene was confirmed and these concentrations were affected by the presence of salts.  相似文献   

2.
The effects of critical factors such as Henry’s Law constant, atmospheric OH rate constant, initial concentration, H2O2, FeSO4 and tert-butanol on the sonochemical degradation of fumaric acid have been investigated. The pseudo first-order rate constant for the sonochemical degradation of 1 mM fumaric acid is much lower than those for chloroform and phenol degradation, and is related to solute concentration at the bubble/water interface and reactivity towards hydroxyl radicals. Furthermore, fumaric acid is preferentially oxidized at the lower initial concentration. It is unreactive to H2O2 under agitation at room temperature. However, the degradation rate of fumaric acid increases with the addition of H2O2 under sonication. 0.1 mM of fumaric acid suppresses H2O2 formation thanks to water sonolysis, while degradation behavior is also dramatically affected by the addition of an oxidative catalyst (FeSO4) or radical scavenger (tert-butanol), indicating that the degradation of fumaric acid is caused by hydroxyl radicals generated during the collapse of high-energy cavities.  相似文献   

3.
《Ultrasonics sonochemistry》2014,21(5):1778-1786
The present work deals with application of sonochemical reactors for the treatment of imidacloprid containing wastewaters either individually or in combination with other advanced oxidation processes. Experiments have been performed using two different configurations of sonochemical reactors viz. ultrasonic horn (20 kHz frequency and rated power of 240 W) and ultrasonic bath equipped with radially vibrating horn (25 kHz frequency and 1 kW rated power). The work also investigates the effect of addition of process intensifying agents such as H2O2 and CuO, which can enhance the production of free radicals in the system. The combination studies with advanced oxidation process involve the advanced Fenton process and combination of ultrasound with UV based oxidation. The extent of degradation obtained using combination of US and H2O2 at optimum loading of H2O2 was found to be 92.7% whereas 96.5% degradation of imidacloprid was achieved using the combination of US and advanced Fenton process. The process involving the combination of US, UV and H2O2 was found to be the best treatment approach where complete degradation of imidacloprid was obtained with 79% TOC removal. It has been established that the use of cavitation in combination with different oxidation processes can be effectively used for the treatment of imidacloprid containing wastewater.  相似文献   

4.
In the present work, combination of ultraviolet (UV) irradiations (using 8 W UV tube) with ultrasonic (US) irradiations (rated power 1 kW and frequency of 25 kHz) has been investigated for the degradation of phenol at pilot scale of operation. Different modes of operation viz. UV alone, US alone, UV/US, UV/TiO2 (photocatalysis), UV/H2O2, UV/NaCl, UV/US/TiO2 (sonophotocatalysis) and H2O2 assisted sonophotocatalysis have been investigated with an objective of maximizing the extent of phenol degradation. Effect of presence of hydrogen peroxide and sodium chloride at a concentration of 10 g/l and TiO2 over a range of 0.5–2.5 g/l has been investigated. It has been observed that 2.0 g/l of TiO2 is the optimum concentration, beyond which a decrease in the extent of degradation is observed. Maximum extent of degradation of phenol was 37.75% for H2O2 assisted photosonocatalysis at pH of 2. The present work is first of its kind to report the use of combined ultrasonic and UV irradiations at pilot scale operation and obtained results should induce some degree of certainty in proposed industrial applications of sonochemical reactors for wastewater treatment.  相似文献   

5.
《Ultrasonics sonochemistry》2014,21(5):1787-1796
Application of Advanced Oxidation Processes (AOP) such as sono, photo and sonophoto catalysis in the purification of polluted water under ambient conditions involve the formation and participation of Reactive Oxygen Species (ROS) like OH, HO2, O2, H2O2 etc. Among these, H2O2 is the most stable and is also a precursor for the reactive free radicals. Current investigations on the ZnO mediated sono, photo and sonophoto catalytic degradation of phenol pollutant in water reveal that H2O2 formed in situ cannot be quantitatively correlated with the degradation of the pollutant. The concentration of H2O2 formed does not increase corresponding to phenol degradation and reaches a plateau or varies in a wave-like fashion (oscillation) with well defined crests and troughs, indicating concurrent formation and decomposition. The concentration at which decomposition overtakes formation or formation overtakes decomposition is sensitive to the reaction conditions. Direct photolysis of H2O2 in the absence of catalyst or the presence of pre-equilibrated (with the adsorption of H2O2) catalyst in the absence of light does not lead to the oscillation. The phenomenon is more pronounced in sonocatalysis, the intensity of oscillation being in the order sonocatalysis > photocatalysis  sonophotocatalysis while the degradation of phenol follows the order sonophotocatalysis > photocatalysis > sonocatalysis > sonolysis > photolysis. In the case of sonocatalysis, the oscillation continues for some more time after discontinuing the US irradiation indicating that the reactive free radicals as well as the trapped electrons and holes which interact with H2O2 have longer life time (memory effect).  相似文献   

6.
Pharmaceutical products are often present in wastewater treatment effluents, rivers, lakes and, more rarely, in groundwater. The advanced oxidation methods, like ultrasound, find a promising future in the area of wastewater treatment. The aim of this paper is to evaluate the influence of several parameters of the ultrasound process on the degradation of paracetamol, a widely used non-steroidal anti-inflammatory recalcitrant drug found in water and levodopa, the most frequently prescribed drug for the treatment of Parkinson disease. Experiments were carried out at 574, 860 and 1134 kHz of ultrasonic frequency with horn-type sonicator and actual power values of 9, 17, 22 and 32 W at 20 °C. Initial concentrations of 25, 50, 100 and 150 mg L?1 of both products were used. Treatment efficiency was assessed following changes in pharmaceuticals concentration and chemical oxygen demand.The sonochemical degradation of both products follows a pseudo-first-order reaction kinetics. Complete removal of pharmaceuticals was achieved in some cases but some dissolved organic carbon remains in solution showing that long lived intermediates were recalcitrant to ultrasound irradiation. Pollutants conversion and COD removal were found to decrease with increasing the initial solute concentration and decreasing power. The best results were obtained with 574 kHz frequency. Investigations using 1-butanol as radical scavenger and H2O2 as promoter revealed that pollutants degradation proceeds principally through radical reactions, although some differences were observed between both molecules. Addition of H2O2 had a positive effect on degradation rate, but the optimum concentration of hydrogen peroxide depends on the pollutant.  相似文献   

7.
Kinetics of hydrogen formation was explored as a new chemical dosimeter allowing probing the sonochemical activity of argon-saturated water in the presence of micro- and nano-sized metal oxide particles exhibiting catalytic properties (ThO2, ZrO2, and TiO2). It was shown that the conventional sonochemical dosimeter based on H2O2 formation is hardly applicable in such systems due to catalytic degradation of H2O2 at oxide surface. The study of H2 generation revealed that at low-frequency ultrasound (20 kHz) the sonochemical water splitting is greatly improved for all studied metal oxides. The highest efficiency is observed for relatively large micrometric particles of ThO2 which is assigned to ultrasonically-driven particle fragmentation accompanied by mechanochemical water molecule splitting. The nanosized metal oxides do not exhibit particle size reduction under ultrasonic treatment but nevertheless yield higher quantities of H2. The enhancement of sonochemical water splitting in this case is most probably resulting from better bubble nucleation in heterogeneous systems. At high-frequency ultrasound (362 kHz), the effect of metal oxide particles results in a combination of nucleation and ultrasound attenuation. In contrast to 20 kHz, micrometric particles slowdown the sonolysis of water at 362 kHz due to stronger attenuation of ultrasonic waves while smaller particles show a relatively weak and various directional effects.  相似文献   

8.
A novel H3PW12O40/TiO2 (anatase) composite photocatalyst was prepared by a high-intensity ultrasonic method using a lower temperature (80 °C) and was characterized by XRD and FT-IR. Its photocatalytic activity, using solar light, was evaluated through the degradation of organic dye methylene blue (MB) in aqueous. When MB solution (50 mg/l, 200 ml) containing H3PW12O40/TiO2 (anatase) (0.4 g) was degraded by solar irradiation after 90 min, the removal of concentration and TOC of MB reached 95% and 73%, respectively. The photocatalyst activity of H3PW12O40/TiO2 (anatase) was much higher than TiO2 which was prepared in the same way. H3PW12O40/TiO2 remained efficient after five repeated experiments.  相似文献   

9.
The mineralization of industrial wastewater coming from food industry using an emerging homogeneous sonophotolytic oxidation process was evaluated as an alternative to or a rapid pretreatment step for conventional anaerobic digestion with the aim of considerably reducing the total treatment time. At the selected operation conditions ([H2O2] = 11,750 ppm, pH = 8, amplitude = 50%, pulse length (cycles) = 1), 60% of TOC is removed after 60 min and 98% after 180 min when treating an industrial effluent with 2114 ppm of total organic carbon (TOC). This process removed completely the toxicity generated during storing or due to intermediate compounds.An important synergistic effect between sonolysis and photolysis (H2O2/UV) was observed. Thus the sonophotolysis (ultrasound/H2O2/UV) technique significantly increases TOC removal when compared with each individual process.Finally, a preliminary economical analysis confirms that the sono-photolysis with H2O2 and pretreated water is a profitable system when compared with the same process without using ultrasound waves and with no pretreatment.  相似文献   

10.
Degradation of C.I. Direct Black 168 from aqueous solution using Fenton-like reactions combining ultrasound was investigated. In the presence of H2O2, the effect of the heterogeneous catalysts, such as fly ash, kaolinite or diatomaceous earth on the degradation of Direct Black 168 was observed under ultrasound. The fly ash was the most efficient catalyst. It is apparent that ultrasound can prompt the reaction to take place and give in higher degradation. In the combination of ultrasound and fly ash/H2O2, the effect of different system variables namely concentration of the dye, dosage of fly ash, concentration of H2O2, pH of solution and the addition of NaCl were studied. 99.0% removal ratio was achieved at initial concentration 100 mg/L, pH 3.0, and dosage of fly ash 2.0 g/L, as well as 2.94 mM H2O2. NaCl exhibited only a minor effect on the dye removal.  相似文献   

11.
Natural pyrite (NP) was treated using oxygen and nitrogen non-thermal plasmas to form modified catalysts. Cleaning effect of the O2 plasma by chemical etching leads to removal of impurities from catalyst surface and sputtering effect of the N2 plasma results in formation of pyrite nanorods. The mentioned plasmas were applied separately or in the order of first O2 and then N2, respectively. The catalytic performance of the plasma-modified pyrites (PMPs) is better than the NP for treatment of Reactive Blue 69 (RB69) in heterogeneous sono-Fenton process (US/H2O2/PMP). The NP and the most effective modified pyrite (PMP4) samples were characterized by XRD, FT-IR, SEM, EDX, XPS and BET analyses. The desired amounts were chosen for operational parameters including initial pH (5), H2O2 concentration (1 mM), PMP4 dosage (0.6 g/L), dye concentration (20 mg/L), and ultrasonic power (300 W). Moreover, the effects of peroxydisulfate and inorganic salts on the degradation efficiency were investigated. Gas chromatography–mass spectrometry (GC–MS) method was applied to identify the generated intermediates and a plausible pathway was proposed for RB69 degradation. Environmentally-friendly modification of the NP, low amount of leached iron and repeated reusability at milder pH are the significant privileges of the PMP4. The phytotoxicity test using Spirodela polyrrhiza verified the remarkable toxicity removal of the RB69 solution after the treatment process.  相似文献   

12.
《Ultrasonics sonochemistry》2014,21(3):1026-1029
Sonoluminescence spectra collected from 0.1 to 3.0 M aqueous solutions of formic acid sparged with argon show the OH(A2Σ+−X2Πi) and C2(d3Πg  a3Πu) emission bands and a broad continuum typical for multibubble sonoluminescence. The overall intensity of sonoluminescence and the sonochemical yield of HCOOH degradation vary in opposite directions: the sonoluminescence is quenched while the sonochemical yield increases with HCOOH concentration. By contrast, the concentration of formic acid has a relatively small effect on the intensity of C2 Swan band. It is concluded that C2 emission originates from CO produced by HCOOH degradation rather than from direct sonochemical degradation of HCOOH. The intensity of C2 band is much stronger at high ultrasonic frequency compared to 20 kHz ultrasound which is in line with higher yields of CO at high frequency. Another product of HCOOH sonolysis, carbon dioxide, strongly quenches sonoluminescence, most probably via collisional non-radiative mechanism.  相似文献   

13.
The current work is a “first of a kind” report on the feasibility and efficacy of hydrodynamic cavitation integrated Advanced Oxidation Processes (AOP’s) towards treatment of a real life greywater stream in form of kitchen wastewater. The work has been carried out in a sequential manner starting with geometry optimization of orifice plate (cavitating device) followed by studying the effects of inlet pressure, pH, effluent dilution ratio on degradation of TOC and COD. Under optimized conditions of pH 3, 4 bar pressure, TOC and COD reduction of 18.23 and 25% were obtained using HC for a period of 120 min. To improve the performance of HC, further studies were carried out by integrating H2O2 and O3 with HC. Using 5 g/h optimum dosage of H2O2, 87.5% reduction in COD was obtained beyond which it started decreasing. Moreover, integrating O3 (57.5% reduction in COD) increased the treatment cost. However, a hybrid process (HC + H2O2 + O3) yielded 76.26 and 98.25% reductions in TOC and COD within 60 min. The energetics of all the processes and the treatment costs were studied in detail and it was concluded that combined process of HC + H2O2 + O3 surpassed by far the performances of HC + H2O2 and HC + O3.  相似文献   

14.
《Solid State Ionics》2006,177(26-32):2363-2368
The mechanism and kinetics of water incorporation in the double perovskites Ва4Ca2Nb2O11 and Sr6Ta2O11 has been investigated (T = 300÷500 °C and aH2O = 1 · 10 3÷2.2 · 10 2). The formation of hydration products Ba4Ca2Nb2O11·xH2O and Sr6Ta2O11·xH2O (0.2 < x < 0.50) was limited by the diffusion of H2O. It has been found that the concentration dependences of H2O are the same for both samples: small increasing of H2O with increasing x. The temperature dependences of the chemical diffusion coefficients of water for compositions of Ba4Ca2Nb2O11·0.35H2O and Sr6Ta2O11·0.35H2O could be described with close activation energies of Ea = 0.38 ± 0.03 eV and Ea = 0.49 ± 0.03 eV, respectively. The chemical diffusion coefficients of water are nearly one order of magnitude smaller for tantalate Sr6Ta2O11. This result correlates with lower oxygen and proton conductivities in Sr6Ta2O11 as the consequence of lower mobilities.  相似文献   

15.
《Ultrasonics sonochemistry》2014,21(3):1244-1257
In this study, the effects of some additives [manganese (III) oxide (Mn3O4), Cu+2, Fe0 and potassium iodate (KIO3)] and some radical scavengers [sodium carbonate (Na2CO3), perfluorohexane (C6F14) and t-butyl alcohol (C4H10O)] on the sonication of olive mill effluent wastewater (OMW) were investigated since the wastewaters of this industry are removed with low efficiencies. The maximum total phenol and total aromatic amines (TAAs) removal efficiencies were 88% and 79%, respectively, at 60 °C with only 150 min sonication. The maximum phenol removal was found as 98% with 19 mg L−1 perfluorohexane and 5 mg L−1 Fe0 while the maximum TAAs removal was 99% with 16 mg L−1 KIO3. Catechol, tyrosol, quercetin, caffeic acid, 4-methyl catechol, 2-phenylphenol (2-PHE) and 3-phenyl phenol (3-PHE) were detected as phenol intermediates while trimethlyaniline, aniline, o-toluidine, o-anisidine, dimethylaniline, ethylbenzene and durene were identified as TAAs in the OMW. The maximum acute toxicity removals were 96% and 99% in Vibrio fischeri and Daphnia magna, respectively. Total phenol, TAAs and the toxicity in an OMW were removed efficiently and cost-effectively through sonication.  相似文献   

16.
The study is about the degradation of a widely used pharmaceutical and personal care product-salicylic acid by sonocatalysis, and the experimental design of the reaction system. The first part of the study consists of sonication (572 kHz) in the presence of zero-valent iron (ZVI) with or without H2O2 to select and optimize the operational parameters as frequency, time, initial solute concentration, dose of reagents and pH. The second part consists of the use of response surface methodology and multiple regression to develop an experimental design modeland to assess the individual and interactive effects of pH, power (Po), ZVI dose and H2O2. The results showed that the optimal conditions predicted by the model without defining any restrictions are: pH = 2.0, Po = 120 W, ZVI = 24 mg L−1, which provide total salicyclic acid and 48% TOC decay. However, the prediction implies intensive consumption of energy and reagents, and must therefore be modified by restricting the value of TOC decay to a lower value and that of pH to a higher one. Cross-validation tests showed that the prediction accuracy of the model was considerably high with 5.0–9.4% deviation from the experimental data.  相似文献   

17.
In this work, the influence of CCl4 on the sonochemical decolorization of anthraquinonic dye Acid Blue 25 (AB25) in aqueous medium was investigated using high frequency ultrasound (1700 kHz). This frequency, reputed ineffective, was tested in order to introduce the ultrasound waves with high frequency in the field of degradation or removal of dyes from wastewater, due to its limited use in this field, and to increase the application of high frequency ultrasound wave in the field of environmental protection. The effects of various parameters such as the concentration of CCl4, frequency (22.5 and 1700 kHz), solution pH, temperature and tert-butyl alcohol adding on the decolorization rate of AB25 was studied. The obtained results clearly demonstrated the significant intensification of AB25 decolorization in the presence of CCl4. The enhancement effect of CCl4 increased by decreasing temperature and by increasing the CCl4 concentration. The pH has a significant influence on the bleaching of dye both in the absence and presence of CCl4. The three investigated dosimeter methods (KI oxidation, Fricke reaction and H2O2 production) well corroborate the improvement of the sonochemical effects in the presence of CCl4. The best sonochemical decolorization rate of AB25 in aqueous solution both in the absence and presence of CCl4 is observed to occur at 1700 kHz compared to 22.5 kHz. The sonochemical oxidation of CCl4 generates oxidizing species in the liquid phase that are highly beneficial for oxidation of hydrophilic and non-volatile pollutant, such as dyes, because they are less susceptible to free radical attack due to lower stability of the generated free radicals.  相似文献   

18.
The photo-Fenton degradation of carbamazepine (CBZ) assisted with ultrasound radiation (US/UV/H2O2/Fe) was tested in a lab thin film reactor allowing high TOC removals (89% in 35 min). The synergism between the UV process and the sonolytic one was quantified as 55.2%.To test the applicability of this reactor for industrial purposes, the sono-photo-degradation of CBZ was also tested in a thin film pilot plant reactor and compared with a 28 L UV-C conventional pilot plant and with a solar Collector Parabolic Compound (CPC). At a pilot plant scale, a US/UV/H2O2/Fe process reaching 60% of mineralization would cost 2.1 and 3.8 €/m3 for the conventional and thin film plant respectively. The use of ultrasound (US) produces an extra generation of hydroxyl radicals, thus increasing the mineralization rate.In the solar process, electric consumption accounts for a maximum of 33% of total costs. Thus, for a TOC removal of 80%, the cost of this treatment is about 1.36 €/m3. However, the efficiency of the solar installation decreases in cloudy days and cannot be used during night, so that a limited flow rate can be treated.  相似文献   

19.
《Ultrasonics sonochemistry》2014,21(4):1358-1365
Ultrasonic-assisted heterogeneous Fenton reaction was used for degradation of nitrobenzene (NB) at neutral pH conditions. Nano-sized oxides of α-Fe2O3 and CuO were prepared, characterized and tested in degradation of NB (10 mg L−1) under sonication of 20 kHz at 25 °C. Complete degradation of NB was effected at pH 7 in presence of 10 mM H2O2 after 10 min of sonication in presence of α-Fe2O3 (1.0 g L−1), (k = 0.58 min−1) and after 25 min in case of CuO (k = 0.126 min−1). α-Fe2O3 showed also effective degradation under the conditions of 0.1 g L−1 oxide and 5.0 mM of H2O2, even though with a lower rate constant (0.346 min−1). Sonication plays a major role in enhancing the production of hydroxyl radicals in presence of solid oxides. Hydroxyl radicals-degradation pathway is suggested and adopted to explain the differences noted in rate constants recorded on using different oxides.  相似文献   

20.
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.  相似文献   

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