Intensification of sonophotocatalytic degradation of p-nitrophenol at pilot scale capacity

Sonophotocatalysis involves the use of a combination of ultrasonic irradiation, ultraviolet radiation and a semiconductor photocatalyst, which enhances the rates of chemical reactions by the formation of enhanced amounts of free radicals. In the present work, the sonophotocatalytic degradation of p-nitrophenol has been investigated using low frequency ultrasound waves (25 kHz) with an acoustic power of 1 kW and UV tube of 11 W power rating at an operating volume of 7 L. The efficacy of combination of sonochemistry and photocatalysis has been initially compared with the individual operation of sonolysis and photocatalytic oxidation. The effect of operational conditions such as the initial p-nitrophenol concentration, pH and catalyst concentration on the extent of degradation has been investigated using sonophotocatalysis. The initial concentration of the pollutant was varied in the range 10 to 100 ppm whereas pH in the range of 2.5-11 and catalyst loading in the range of 0.5-4 g/l. Intensification studies have been carried out using hydrogen peroxide and Fenton chemistry. In all the systems investigated, maximum extent of degradation (94.6%) was observed for 10 ppm of p-nitrophenol initial concentration (w/v) using combination of sonophotocatalysis and optimum quantity of H(2)O(2). Use of Fenton chemistry also plays an effective role in enhancing the extent of degradation though the concentration of additive needs to be carefully adjusted in order to get maximum beneficial effects.     

Production of tung oil epoxy resin using low frequency high power ultrasound

Epoxy resins made from vegetable oils are an alternative to synthesize epoxy resins from renewable sources. Tung oil is rich in α -eleostearic fatty acid, which contains three double bonds producing epoxy resins with up to three epoxy groups per fatty acid. This work studied the production of tung oil epoxy resin using hydrogen peroxide as an oxidizing agent and acetic and formic acid as percarboxylic acid precursors, applying low frequency high power ultrasound. This study evaluated the effects of ultrasound power density, hydrogen peroxide concentration, acetic acid concentration, and formic acid concentration on the yield into epoxy resin, selectivity, and by-products formation. Application of ultrasound was carried out using a 19 kHz probe ultrasound (horn ultrasound) with a 1.3 cm diameter titanium probe, 500 W nominal power, 2940 W L⁻¹ maximum effective power density applied to the reaction mixture. Ultrasound technology yielded up to 85% of epoxy resin in 3 h of reaction. The use of formic acid resulted in a slightly lower oil conversion than acetic acid but with a much higher selectivity towards epoxidized tung oil. However, using acetic acid resulted in the production of high-value by-products, such as 2-heptenal and 2,4-nonadienal. The ultrasound-assisted epoxidation showed to be particularly efficient when applied to oils containing conjugated double-bonds.     

（CTAB）_9[Sb_1W_9O_（33）]的制备及其光谱分析

利用溶胶-凝胶法合成了K9[Sb1W9O33],用十六烷基三甲基溴化铵（CTAB）对K9[Sb1W9O33]改性,得到了（CTAB）9[Sb1W9O33],以过氧化氢氧化环己醇制取环己酮为探针反应,考察了n（Sb）∶n（W）对催化剂催化活性的影响,评价结果表明：催化剂金属原子配比n（Sb）∶n（W）=1∶9,催化活性最高,在该条件下,环己酮的选择性达到了最大值99.2%。通过XRD、FT IR的检测,揭示了（CTAB）9[Sb1W9O33]的微观结构和内在规律性,[Sb1W9O33]9-与CTAB＋之间存在协同效应,实验结果为工业装置的技术改造提供了较好的实验依据。     

Interaction of Cholesterol with Dimethyl and Diethyl Sulfoxides

The complexing of cholesterol with dimethyl and diethyl sulfoxides in carbon tetrachloride is investigated by the method of IR spectroscopy. It is established that the hydrogen bond is formed between the oxygen of the sulfoxide group of sulfoxides and the hydrogen of the hydroxyl group of cholesterol. The equilibrium constants (K _eq) of the complexes of cholesterol with dimethyl sulfoxide (K _eq = 93 liters/mole) and diethyl sulfoxide (K _eq = 98 liters/mole) at 23°C are determined.     

Ascorbic acid vibrational spectra in sulfoxide solvents

Ascorbic acid in dimethyl-and diethylsulfoxide solutions has been studied using vibrational (Fourier transform IR and Raman) spectroscopy. Noticeable changes observed in the range of S=O-group vibrations can be explained by the presence of a hydrogen bond between ascorbic acid and sulfoxides. Various types of ascorbic acid/sulfoxide hydrogen-bonded complexes were revealed based on spectral analysis data. The results showed that the ascorbic acid/dimethylsulfoxide system has predominantly one type of complexes whereas the ascorbic acid/diethylsulfoxide system can contain three types of complexes. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 5, pp. 653–658, September–October, 2008.     

The effects of liquid height/volume,initial concentration of reactant and acoustic power on sonochemical oxidation

Even though much knowledge on acoustic cavitation and its application has been accumulated over the past decades, further research is still required to develop industrial uses of acoustic cavitation. It is because the available information is mainly based on small-scale sonoreactors and the design and optimization of sonoreactors for large-scale applications have not been widely studied. In this study, the effects of liquid height/volume, initial concentration of the reactant and input acoustic power on sonochemical oxidation reactions including iodide ion oxidation, As(III) oxidation, and hydrogen peroxide generation were investigated using a 291 kHz sonoreactor with various liquid height/volumes (50, 100, 200, 300, 500, and 1000 mL) and input powers (23, 40, and 82 W). As the liquid height/volume and the input power changed, the power density varied from 23 to 1640 W/L and the maximum cavitation yields of triiodide ion for 23, 40, and 82 W were observed at 0.05, 0.1, and 0.2/0.3 L, respectively. It was found that low power was more effective for the small volume and the large volume required high power level and the moderate power density, approximately 400 W/L, was suggested for the sonochemical oxidation of iodide ion in the 291 kHz sonoreactor in this study. Similar results were observed in the generation of hydrogen peroxide and the sonochemical oxidation of As(III) to As(V). It was also revealed that KI dosimetry could be applicable for the estimation of the sonochemical reactions of non-volatile compounds such as As(III).     

中低温太阳能-甲醇重整互补供能系统动力学提升与系统优化

本文考察了中低温-甲醇重整互补制氢及其与高温质子交换膜燃料电池(HT-PEMFC)结合的中低温太阳能-甲醇重整互补发电系统,并分析、优化了两供能系统的性能.从动力学性能优化角度,研发了一种适用于甲醇重整制氢反应的新型复合金属氧化物纳米催化剂,并测试了不同反应物体积流量与反应温度下的催化剂性能.基于动力学实验结果,模拟了...     

Degradation of methylparaben by sonocatalysis using a Co–Fe magnetic carbon xerogel

The degradation of methylparaben (MP) through 20 kHz ultrasound coupled with a bimetallic Co-Fe carbon xerogel (CX/CoFe) was investigated in this work. Experiments were performed at actual power densities of 25 and 52 W/L, catalyst loadings of 12.5 and 25 mg/L, MP concentrations between 1 and 4.2 mg/L and initial pH values between 3 and 10 in ultrapure water (UPW). Matrix effects were studied in bottled water (BW) and secondary treated wastewater (WW), as well as in UPW spiked with bicarbonate, chloride or humic acid. The pseudo–first order kinetics of MP degradation increase with power and catalyst loading and decrease with MP concentration and matrix complexity; moreover, the reaction is also favored at near–neutral conditions and in the presence of dissolved oxygen. The contribution of the catalyst is synergistic to the sonochemical degradation of MP and the extent of synergy is quantified to be >45%. This effect was ascribed to the ability of CX/CoFe to catalyze the dissociation of hydrogen peroxide, formed through water sonolysis, to hydroxyl radicals. Experiments in UPW spiked with an excess of tert-butanol (radical scavenger), sodium dodecyl sulfate or sodium acetate (surfactants) led to substantially decreased rates (i.e. by about 8 times), thus implying that the liquid bulk and the gas-liquid interface are major reaction sites. The stability of CX/CoFe was shown by performing reusability cycles employing magnetic separation of the catalyst after the treatment stage. It was found that the CX/CoFe catalyst can be reused in up to four successive cycles without noteworthy variation of the overall performance of the sonocatalytic process.     

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.     

Electrosynthesis of hydrogen peroxide via the reduction of oxygen assisted by power ultrasound

The electrosynthesis of hydrogen peroxide using the oxygen reduction reaction has been studied in the absence and presence of power ultrasound in a non-optimized sono-electrochemical flow reactor (20 cm cathodic compartment length with 6.5 cm inner diameter) with reticulated vitreous glassy carbon electrode (30 x 40 x 10 mm, 10 ppi, 7 cm(2)cm(-3)) as the cathode. The effect of several electrochemical operational variables (pH, volumetric flow, potential) and of the sono-electrochemical parameters (ultrasound amplitude and horn-to-electrode distance) on the cumulative concentration of hydrogen peroxide and current efficiency of the electrosynthesis process have been explored. The application of power ultrasound was found to increase both the cumulative concentration of hydrogen peroxide and the current efficiency. The application of ultrasound is therefore a promising approach to the increased efficiency of production of hydrogen peroxide by electrosynthesis, even in the solutions of lower pH (<12). The results demonstrate the feasibility of at-site-of-use green synthesis of hydrogen peroxide.     

Degradation of dichlorvos containing wastewaters using sonochemical reactors

The present work deals with application of sonochemical reactors for the degradation of dichlorvos containing wastewaters. The sonochemical reactor used in the work is a simple ultrasonic horn type operating at 20 kHz with a power rating of 270 W. The effect of different operating parameters such as operating pH, temperature and power density on the extent of degradation has been investigated initially followed by intensification studies using additives such as hydrogen peroxide, Fenton's reagent and CCl(4). It has been observed that low frequency sonochemical reactors can be effectively used for treatment of pesticide wastewaters and acidic conditions and optimum values of temperature and power dissipation favors the degradation of dichlorvos. The efficacy of sonochemical reactors can be further enhanced by using different additives at optimized loadings. Complete removal of the pesticide at the given loading has been obtained using an optimized combination of ultrasound and Fenton's chemistry. The controlling mechanism for the sonochemical degradation has been confirmed to be the free radical attack based on the studies involving radical scavengers. The novelty of the present work is clearly established as there have been no earlier studies dealing with degradation of dichlorvos pesticide using sonochemical reactors operating at low frequency which offers distinct advantage in terms of cost and the stability of the reactor.     

Intensification of heterogeneously catalyzed Suzuki-Miyaura cross-coupling reaction using ultrasound: Understanding effect of operating parameters

Palladium-catalyzed Suzuki-Miyaura cross-coupling reaction is a significant reaction for obtaining industrially important products. The current research work deals with intensification of reaction of 4-bromoanisole and phenylboronic acid catalyzed with 5 wt% Pd/C (5% by weight Pd supported on C available as commercial catalyst) using ultrasound and more importantly, without use of any additional phase transfer catalyst. Heterogeneous catalyst has been selected in the present work so as to harness the benefits of easy separation and the possible limitations of heterogeneous operation are minimized by introducing ultrasonic irradiations. The effect of operating parameters such as ultrasound power, temperature, catalyst loading and molar ratio on the progress of reaction has been investigated. It has been observed that an optimum power, temperature and catalyst loading exist for maximum benefits whereas higher molar ratio was found to be favourable for the progress of the reaction. Also, the use of ultrasound reduced the reaction time from 70 min required in conventional approach to only 35 min under conditions of frequency of 22 kHz, power dissipation of 40 W and catalyst loading as 1.5 mol% (refers to total quantum of catalyst used in the work) in ethanol-water system under ambient conditions. The work also demonstrated successful results at ten times higher volume as compared to the normally used volumes in the case of simple ultrasonic horn. Overall, the work has successfully demonstrated process intensification benefits obtained due to the use of ultrasound for heterogeneously catalyzed Suzuki-Miyaura cross-coupling reaction.     

Catalytic-oxidative/adsorptive denitrogenation of model hydrocarbon fuels under ultrasonic field using magnetic reduced graphene oxide-based phosphomolybdic acid (PMo-Fe3O4/rGO)

In this work, the effect of ultrasound irradiation on the catalytic oxidative/adsorptive denitrogenation (COADN) of model hydrocarbon fuels (composed of pyrrole or indole as an organonitrogen compounds dissolved in n-nonane) has been investigated using magnetic reduced graphene oxide supported with phosphomolybdic acid (PMo-Fe₃O₄/rGO) as a heterogeneous catalyst/adsorbent and hydrogen peroxide as an oxidant. The synthesized PMo-Fe₃O₄/rGO nanocomposite was characterized by XRD, FE-SEM, VSM and BET surface area analysis methods. Moreover, different experimental variables including catalyst dose, initial pyrrole/indole concentration, H₂O₂ to pyrrole/indole molar ratio, ultrasound power and sonication time have been studied on the COADN process. The regeneration/recyclability of PMo-Fe₃O₄/rGO catalyst was also examined. Experimental results revealed that, the ultrasound treatment significantly improved the adsorption process of organonitrogen compounds from model fuels (q_e increased by 50.3% for pyrrole and 18% for indole). Furthermore, high ultrasound-aided catalytic oxidative denitrogenation efficiency (85.6% for pyrrole and 90% for indole) has been attained under optimal conditions (ultrasonic power = 200 W, sonication time = 240 min, catalyst dose = 2 g/L, and H₂O₂:pyrrole/indole molar ratio = 5). The recyclability of catalyst displayed that the prepared catalyst can be reused five times without any significant reduction in its performance.     

Formation of reactive species in gliding arc discharges with liquid water

The effects of gas composition on gliding arc (glidarc) electrical discharge reactors with pure water have been studied. The glidarc reactors utilized AC electrical discharges with two different electrode configurations. In one case a set of two stainless steel electrodes connected to a single power supply was placed in the gas phase over the liquid surface (power=250–300 W, maximum voltage=12 kV). The second experimental arrangement utilized a reactor with a set of three stainless steel electrodes supplied by two identical high-voltage transformers, where the electrodes were placed over the water surface or with the water sprayed directly in the plasma formed between the electrodes (power=500–600 W, maximum voltage=12 kV). The variation of pH and conductivity and the formation of hydrogen peroxide, ozone, nitrate, and hydrogen were measured. The effects of the type of gas, including pure oxygen, pure nitrogen, and dry air, were determined.     

Sonochemical degradation of 3-methylpyridine (3MP) intensified using combination with various oxidants

3-Methyl pyridine (3MP) is a toxic and hazardous organic compound having considerable negative impact on environment and living organisms. The objective of this work to report a novel treatment strategy based on sonochemical degradation of 3MP, in combination with oxidants such as hydrogen peroxide, Fenton’s reagent, peroxymonosulphate (PMS), and potassium persulphate (KPS) as well as solar irradiations. A bath sonicator operating at 25 kHz frequency and rated power dissipation of 100 W was applied in the work to study different approaches with an objective to enhance the removal of 3MP in lesser time. Effect of operating parameters such as pH (over the range of 2–10), treatment time, temperature (25–55 °C) and ultrasonic power (25 W to 150 W) on the degradation has been studied and the best conditions were used in subsequent combination approaches. It was demonstrated that ultrasound in combination with PMS, ferrous sulphate (FeSO₄) and solar irradiations (approach of US/PMS/FeSO₄/solar irradiation) is the best treatment strategy yielding maximum degradation as 97.4% with highest cavitational yield as 1.920 × 10⁻⁴ mg/J and highest synergetic Index as 2.70. Kinetic analysis revealed that first order mechanism fitted well to all the approaches involving different combinations of ultrasound, oxidising agents and solar irradiation. Degradation products were also analysed that established the degradation mechanism as C₂ and C₃ ring cleavages forming 1, 4-dihydro3-methylpyridine followed by Levulinic acid as non -toxic main by-product. Overall the work clearly demonstrated an effective treatment approach involving combined sonication with oxidants for remediation of 3MP also providing insights on kinetics and mechanism of degradation.     

Isotope effect in hydrogen peroxide formation during H2O and D2O sonication

The kinetics of hydrogen peroxide formation have been studied during H2O and D2O sonication in the presence of argon and oxygen (f = 22 kHz, I = 3.0 W cm-2, Pac = 0.52 W ml-1, V = 20 ml, T = 20 degrees C). It was found that the sonochemical reaction rate W has a zero order with respect to hydrogen peroxide (H2O, D2O or DHO2) concentration. In argon atmosphere the kinetic isotope effect was found to be equal to alpha = WH2O/WD2O = 2.2 +/- 0.3. The alpha value decreases in H2O-D2O mixtures with increasing H2O concentration. In oxygen atmosphere the isotope effect is not observed (alpha = 1.05 +/- 0.10). It is assumed that the revealed isotope effect is related to the mechanism of water sonolysis including the H2O-Ar* and D2O-Ar* energy transition, where Ar* is an argon atom in an excited state, in nonequilibrium plasma generated by the shock-wave.     

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.     

Characteristic of peroxyoxalate-chemiluminescence intensity in the presence of Chlorpheniramine maleate and its analytical application

It has been shown that Chlorpheniramine maleate (CPM) increases chemiluminescence intensity of bis-(2,4,6-trichlorophenyl)oxalate (TCPO) with hydrogen peroxide in the presence of biphenylquinoxaline as a fluorophore. In this work, the effect of CPM on the intensity of chemiluminescence (CL) in the system of (TCPO-sodium salicylate-fluorophore-hydrogen peroxide) was investigated. The fall and rise rates constants were also studied. A pooled-intermediate model was used for determining the kinetics parameters of CL with and without CPM. Results indicated that addition of CMP to this system increases the fall rate constant and decreases the rise rate constant. Results also specified that there is a linear relationship between CPA concentration and chemiluminescence intensity in the range 0.66-21.5 μg/ml. Detection limit 0.18 μg/ml and the relative standard deviation (RSD) <7% was obtained. This work is introduced as a new method for the determination of CMP.     

Investigation on the transition crystal of ordinary rutile TiO2 powder by microwave irradiation in hydrogen peroxide solution and its sonocatalytic activity

The transition crystal TiO(2) catalyst with high sonocatalytic activity was obtained utilizing the microwave irradiation in hydrogen peroxide solution. At the same time a series of affecting factors (microwave irradiation time, heat-treated time and heat-treated temperature) to prepare the TiO(2) catalyst on the sonocatalytic degradation of parathion were considered in this paper. The ultrasound of low power was used as an irradiation source to induce treated TiO(2) particles to perform catalytic activity. The results show that the sonocatalytic activity of the transition crystal TiO(2) powder is obviously higher than those of pure ordinary rutile and anatase TiO(2) powders. At last, the parathion in aqueous solution was degraded completely and became some simple inorganic ions such as NO(3)(-), PO(4)(3-), SO(4)(2-), etc. The degradation ratio of parathion in the presence of the transition crystal TiO(2) catalyst attains nearly 80% within 60 min ultrasonic irradiation, while corresponding ones are only 65.23% and 53.88%, respectively, for pure ordinary rutile and anatase TiO(2) powders.     

荧光光度法测定雨水中的H2O2含量

研究了在pH4.48的HAc-NaAc缓冲溶液中,邻苯二胺(OPDA)与过氧化氢反应生成新物质2,3-二氨基吩嗪(DAPN)的荧光光谱变化,通过跟踪DAPN的荧光强度建立了过氧化氢测定的新方法,该方法由于采用二元体系,实验操作简单,灵敏度较高。实验结果表明,过氧化氢含量在9.0×10-7～3.6×10-5mol.L-1范围内与荧光强度的变化呈良好的线性关系,线性方程为:F=1.15c(μmol.L-1) 398.6,相关系数r=0.9991,最低检出限为2.7×10-7mol.L-1(3Ds/斜率,n=11)。对含量为7.5×10-6mol.L-1和3.0×10-5mol.L-1的H2O2的标准溶液进行了11次平行测定,其相对标准偏差分别为2.2%和1.0%。考察了多种共存离子的影响。该方法用于雨水中微量H2O2的测定,测定结果令人满意。