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1.
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   

2.
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   

3.
《Ultrasonics sonochemistry》2014,21(5):1881-1885
In this work, the decolorization of C.I. Reactive Blue 181 (RB181), an anthraquinone dye, by Ultrasound and Fe2+ H2O2 processes was investigated. The effects of operating parameters, such as Fe2+ dosage, H2O2 dosage, pH value, reaction time and temperature were examined. Process optimisation [pH, ferrous ion (Fe2+), hydrogen peroxide (H2O2), and reaction time], kinetic studies and their comparison were carried out for both of the processes. The Sono-Fenton process was performed by indirect sonication in an ultrasonic water bath, which was operated at a fixed 35-kHz frequency. The optimum conditions were determined as [Fe2+] = 30 mg/L, [H2O2] = 50 mg/L and pH = 3 for the Fenton process and [Fe2+] = 10 mg/L, [H2O2] = 40 mg/L and pH = 3 for the Sono-Fenton process. The colour removals were 88% and 93.5% by the Fenton and Sono-Fenton processes, respectively. The highest decolorization was achieved by the Sono-Fenton process because of the production of some oxidising agents as a result of sonication. The paper also discussed kinetic parameters. The decolorization kinetic of RB181 followed pseudo-second-order reaction (Fenton study) and Behnajady kinetics (Sono-Fenton study).  相似文献   

4.
In this study, synergistic degradation of antibiotic norfloxacin (NOR) was obtained in a novel sonochemical ultrasound/zero-valent iron/tetraphosphate system (US/ZVI/TPP). Compared to three common organic ligands (EDTA, EDDS, and DTPA), TPP could perform more excellently in activation of O2 to produce reactive oxidative species (ROS) and lead to efficient Fenton-like oxidative degradation of NOR in the sonochemical in situ chemical oxidation (ISCO) system. An optimized initial condition was obtained as 10 mg/L NOR, 0.3 mM TPP, 1 g/L ZVI and initial pH 7, and the US/ZVI/TPP system would effectively degrade NOR with relative low dosage of ZVI and ligand as well as broad pH work range 3–9. It was found that three ROS (OH, O2 and H2O2) instead of OH only would participate in the NOR degradation, while the in situ generation of H2O2 during the series of Fe-TPP reactions should be more critical. Fourteen organic intermediates and four inorganic products were detected during the NOR decomposition, suggesting that two main degradation pathways would occur under OH oxidation via cleavage of the piperazine ring and defluorination of the benzene ring, respectively. Finally, an integrated reaction mechanism in the US/ZVI/TPP system was proposed including solid-liquid interfacial iron corrosion as well as bulk homogenous oxygen activation and Fenton reactions, wherein US would play mechanically and chemically promotional roles. Besides, triple-repeated treatments suggested the relative long-term re-usage of ZVI particles and low effluent dissolved iron (<0.6 mg/L).  相似文献   

5.
《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   

6.
Hydrogen peroxide (H2O2) and hydroperoxy (HO2) reactions present in the H2O2 thermal decomposition system are important in combustion kinetics. H2O2 thermal decomposition has been studied behind reflected shock waves using H2O and OH diagnostics in previous studies (Hong et al. (2009) [9] and Hong et al. (2010) [6,8]) to determine the rate constants of two major reactions: H2O2 + M  2OH + M (k1) and OH + H2O2  H2O + HO2 (k2). With the addition of a third diagnostic for HO2 at 227 nm, the H2O2 thermal decomposition system can be comprehensively characterized for the first time. Specifically, the rate constants of two remaining major reactions in the system, OH + HO2  H2O + O2 (k3) and HO2 + HO2  H2O2 + O2 (k4) can be determined with high-fidelity.No strong temperature dependency was found between 1072 and 1283 K for the rate constant of OH + HO2  H2O + O2, which can be expressed by the combination of two Arrhenius forms: k3 = 7.0 × 1012 exp(550/T) + 4.5 × 1014 exp(?5500/T) [cm3 mol?1 s?1]. The rate constants of reaction HO2 + HO2  H2O2 + O2 determined agree very well with those reported by Kappel et al. (2002) [5]; the recommendation therefore remains unchanged: k4 = 1.0 × 1014 exp(?5556/T) + 1.9 × 1011+exp(709/T) [cm3 mol?1 s?1]. All the tests were performed near 1.7 atm.  相似文献   

7.
《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   

8.
Zerovalent iron (ZVI) has been demonstrated to be suitable for the dehalogenation of environmental pollutants such as chloroethenes. The construction of ZVI reactive barriers by conventional engineering measures is expensive and limited to shallow aquifers. The use of nanosized ZVI particles opens new opportunities to construct ZVI barriers with less invasive techniques. However, nanosized particles of pure ZVI are pyrophoric and react spontaneously with atmospheric oxygen.In this study, nanosized air-stable ZVI particles were produced by applying ultrasound to a solution of Fe(CO)5 in edible oil. The resulting iron nanoparticles were dispersed in a carbon matrix, and coated with a non-crystalline carbon layer of approx. 2.5 nm. Although, these nanoparticles are non-pyrophoric and stable in air, dechlorination of tetrachloroethene was demonstrated in synthetic aqueous medium and in polluted groundwater. Additionally, hydrogen was formed. Due to the larger surface area, significantly higher mass-normalized reaction rates of the novel carbon-coated nanoparticles were obtained as compared to conventional bulk ZVI material. Surface normalized pseudo-first-order-reaction rates of kSA = 3.49 × 10?3 L h?1 m?2 and 2.33 × 10?2 L h?1 m?2 were calculated for the nano-ZVI and the bulk ZVI, respectively. Dechlorination reaction products of the novel nano-ZVI were trichloroethene, cis-dichloroethene, vinyl chloride, ethene, and ethane.  相似文献   

9.
The study is about the assessment of single and multi-frequency operations for the overall degradation of a widely consumed analgesic pharmaceutical-ibuprofen (IBP). The selected frequencies were in the range of 20–1130 kHz emissions coming from probes, baths and piezo-electric transducers attached to plate-type devices. Multi-frequency operations were applied either simultaneously as “duals”, or sequentially at fixed time intervals; and the total reaction time in all operations was 30-min. The work also covers evaluation of the effect of zero-valent iron (ZVI) on the efficiency of the degradation process and the performance of the reaction systems. It was found that low-frequency probe type devices especially at 20 kHz were ineffective when applied singly and without ZVI, and relatively more effective in combined-frequency operations in the presence of ZVI. The power efficiencies of the reactors and/or reaction systems showed that 20-kHz probe was considerably more energy intensive than all others, and was therefore not used in multi-frequency operations. The most efficient reactor in terms of power consumption was the bath (200 kHz), which however provided insufficient mineralization of the test chemical. The highest percentage of TOC decay (37%) was obtained in a dual-frequency operation (40/572 kHz) with ZVI, in which the energy consumption was neither low nor exceptionally too high. A sequential operation (40 + 200 kHz) in that respect was more efficient, because it required much less energy for a similar TOC decay performance (30%). In general, the degradation of IBP increased with increased power consumption, which in turn reduced the sonochemical yield. The study also showed that advanced Fenton reactions with ZVI were faster in the presence of ultrasound, and the metal was very effective in improving the performance of low-frequency operations.  相似文献   

10.
H2O2 is one of the most important species in dimethyl ether (DME) oxidation, acting not only as a marker for low temperature kinetic activity but also responsible for the “hot ignition” transition. This study reports, for the first time, direct measurements of H2O2 and CH3OCHO, among other intermediate species concentrations in helium-diluted DME oxidation in an atmospheric pressure flow reactor from 490 to 750 K, using molecular beam electron-ionization mass spectrometry (MBMS). H2O2 measurements were directly calibrated, while a number of other species were quantified by both MBMS and micro gas chromatography to achieve cross-validation of the measurements. Experimental results were compared to two different DME kinetic models with an updated rate coefficient for the H + DME reaction, under both zero-dimensional and two-dimensional physical model assumptions. The results confirm that low and intermediate temperature DME oxidation produces significant amounts of H2O2. Peroxide, as well as O2, DME, CO, and CH3OCHO profiles are reasonably well predicted, though profile predictions for H2/CO2 and CH2O are poor above and below ~625 K, respectively. The effect of the collisional efficiencies for the H + O2 + M = HO2 + M reaction on DME oxidation was investigated by replacing 20% He with 20% CO2. Observed changes in measured H2O2 concentrations agree well with model predictions. The new experimental characterizations of important intermediate species including H2O2, CH2O and CH3OCHO, and a path flux analysis of the oxidation pathways of DME support that kinetic parameters for decomposition reactions of HOCH2OCO and HCOOH directly to CO2 may be responsible for model under-prediction of CO2. The H abstraction reactions for DME and/or CH2O and the unimolecular decomposition of HOCH2O merit further scrutiny towards improving the prediction of H2 formation.  相似文献   

11.
《Solid State Ionics》2006,177(26-32):2407-2411
Electrical conduction of Sr-doped LaP3O9 ([Sr]/{[La] + [Sr]} = 2–10 mol%) was investigated under 0.4–5 kPa of p(H2O) and 0.01–100 kPa of p(O2) or 0.3–3 kPa of p(H2) at 573–973 K. Sr-doped LaP3O9 showed apparent H/D isotope effect on conductivity regardless of the Sr-doping level under both H2O/O2 oxidizing and H2/H2O reducing conditions at investigated temperatures. Conductivities of the material were almost independent of p(O2) and p(H2O). These results demonstrated that the Sr-doped LaP3O9 exhibited protonic conduction under wide ranges of p(O2), p(H2O) and temperature. The conductivity of the Sr-doped LaP3O9 increased with increasing Sr concentration up to its solubility limit, ca. 3 mol%, while the further Sr-doping slightly degraded the conductivity. These indicate that Sr2+ substitution for La3+ leads to proton dissolution into the material and induced protonic conduction. Conductivities of the 3 mol% Sr-doped sample were 2 × 10- 6–5 × 10 4 S cm 1 at 573–973 K.  相似文献   

12.
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   

13.
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   

14.
Simultaneous direct irradiation with microwaves and ultrasound was used to determine total Kjeldahl nitrogen. The method involves chemical digestion in two steps, mineralization with sulfuric acid and oxidation with H2O2. The most influential variables for the microwave/ultrasound (MW/US)-assisted digestion were optimized using tryptophan as the model substance. The optimum conditions were: H2SO4 volume, 10 mL; H2O2 volume, 5 mL; weight of sample, 0.05 g; MW power, 500 W; US power, 50 W; digestion time, 7 min (i.e., 5 min mineralization and 2 min oxidation). A modification of the classical Kjeldahl (Hach) method and an US-assisted digestion method were used for comparison. The latter was also optimized; the optimum conditions were: H2SO4 volume, 10 mL; H2O2 volume, 5 mL; sonication time with H2SO4, 15 min; sonication time with H2O2,10 min; US power, 50 W; weight of sample, 0.05 g. Five pure amino acids and two certified reference materials (NIST standard reference materials 1547 (peach leaves), and soil, NCS DC 73322) were analyzed to assess the accuracy of our new MW/US-assisted digestion method, that was successfully applied to five real samples. The significant reduction in digestion time (being 30 min and 25 min for classical Kjeldahl and US-assisted digestion methods, respectively) and consumption of reagents show that simultaneous and direct MW/US irradiation is a powerful and promising tool for low-pressure digestion of solid and liquid samples.  相似文献   

15.
《Ultrasonics sonochemistry》2014,21(6):1976-1981
This report describes the effects of H2O2 concentration (0.01, 0.1, 1, and 10 mM) on the sonochemical degradation of phenol and bisphenol A (BPA) using an ultrasonic source of 35 kHz and 0.08 W/mL. The concentration of the target pollutants (phenol or BPA), total organic carbon (TOC), and H2O2 were monitored for each input concentration of H2O2. The effects of H2O2 on the sonochemical degradation of phenol was more significant than that of BPA because phenol has a high solubility and low octanol–water partition coefficient (Kow) value and is subsequently very likely to remain in the aqueous phase, giving it a greater probability of reacting with H2O2. The removal of TOC was also enhanced by the addition of H2O2. Some intermediates of BPA have a high Kow value and subsequently have a greater probability of pyrolyzing by the high temperatures and pressures inside of cavitation bubbles. Thus the removal efficiency of TOC in BPA was higher than that of phenol. The removal efficiencies of TOC were lower than the degradation efficiencies of phenol and BPA. This result is due to the fact that some intermediates cannot readily degrade during the sonochemical reaction. The H2O2 concentration decreased but was not completely consumed during the sonochemical degradation of pollutants. The initial H2O2 concentration and the physical/chemical characteristics of pollutants were considered to be important factors in determining the formation rate of the H2O2. When high concentration of H2O2 was added to the solution, the formation rates were relatively low compared to when low concentrations of H2O2 were used.  相似文献   

16.
Ignition delay time measurements of H2/O2/NO2 mixtures diluted in Ar have been measured in a shock tube behind reflected shock waves. Three different NO2 concentrations have been studied (100, 400 and 1600 ppm) at three pressure conditions (around 1.5, 13, and 30 atm) and for various H2–O2 equivalence ratios for the 100 ppm NO2 case. Results were compared to some recent ignition delay time measurements of H2/O2 mixtures. A strong dependence of the ignition delay time on the pressure and the NO2 concentration was observed, whereas the variation in the equivalence ratio did not exhibit any appreciable effect on the delay time. A mechanism combining recent H2/O2 chemistry and a recent high-pressure NOx sub-mechanism with an updated reaction rate for H2 + NO2 ? HONO + H was found to represent correctly the experimental trends over the entire range of conditions. A chemical analysis was conducted using this mechanism to interpret the experimental results. Ignition delay time data with NO2 and other NOx species as additives or impurities are rare, and the present study provides such data over a relatively wide pressure range.  相似文献   

17.
Herein, we report the sonochemical reactions with MSU-X mesoporous alumina (m-Al2O3) in aqueous solutions. Sonication (f = 20 kHz, I = 30 W cm?2, Waq = 0.67 W mL?1, T = 36–38 °C, Ar) causes significant acceleration of m-Al2O3 dissolution in the pH range of 4–11. Moreover, power ultrasound has a dramatic effect on the textural properties and phase composition of m-Al2O3. Short-time sonication at pH = 4 leads to the formation of nanorods and nanofibers of boehmite, AlO(OH). Prolonged ultrasonic treatment causes high aspect morphology transformation to aggregated nanosheets in weakly acid solutions or plated nanocrystals in alkaline solutions. Sonochemical products in alkaline medium are composed principally from boehmite and small amounts of bayerite, Al(OH)3. Silent hydrolysis of m-Al2O3 yields boehmite at pH = 4 and bayerite at pH = 11. The effect of ultrasound on the textural properties of mesoporous alumina as well as on the transformation of nanosized bayerite to boehmite can be consistently attributed to the transient strong heating of the liquid shell surrounding the cavitation bubble which caused the chemical processes similar to those occurred during hydrothermal treatment.  相似文献   

18.
By means of a high-temperature gravimetry, the defect chemical relationships between oxygen nonstoichiometry and water content in BaCe0.9M0.1O3?δ (M = Y and Yb) were investigated as functions of partial pressure of oxygen, P(O2), partial pressure of water vapor, P(H2O), and temperature. Concentrations of protonic defect and that of oxygen vacancy strongly depend on P(H2O) and temperature, while the dependences on P(O2) were weak. The equilibrium constants of the water vapor incorporation reaction H2O + VO??? + OO× = 2OHO? were determined. Concentrations of hole, [h?], in the dry-atmospheres were determined by the weight gain by the incorporation of oxygen from the gas atmospheres. The [h?] values increased with decreasing temperature. The [h?] values were estimated to be about 2 to 3 orders of magnitude less than [OHO?] values measured in the wet-atmospheres.  相似文献   

19.
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, Fe2+: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 2 h 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.  相似文献   

20.
The heterogeneous catalytic reaction of H2O2 with iron oxides is an important reaction for the environment since both H2O2 and iron oxides are common constituents of natural and atmospheric waters. In this work, three ferrihydrites, labeled Fh-1, -2 and -3, were prepared by different procedures. Fh-1 was prepared by adding alkali solution to ferric solution under stirring. In the preparation of Fh-2, the mixing procedure of the two solutions was reversed. Fh-3 was obtained by adding alkali solution and ferric solution simultaneously into a certain amount of water. The heterogeneous catalytic reaction of H2O2 with three ferrihydrites in aqueous solution was investigated in detail. The results demonstrated that the apparent reaction rate was affected by the preparation procedure of ferrihydrite besides pH, temperature and the dose of catalyst. The activation energy of the decomposition reaction of H2O2 was determined to be 76.13, 59.41 and 68.05 kJ mol?1 for Fh-1, -2 and -3, respectively. The activation enthalpy of the reaction were determined to be 73.59, 56.56 and 65.76 kJ mol-1 and the activation entropy of the reaction were determined to be ?69.65, ?119.67 and ?90.58 J mol?1 K?1, respectively.  相似文献   

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