Sonochemical and hydrodynamic cavitation reactors for laccase/hydrogen peroxide cotton bleaching

The main goal of this work is to develop a novel and environmental-friendly technology for cotton bleaching with reduced processing costs. This work exploits a combined laccase–hydrogen peroxide process assisted by ultrasound. For this purpose, specific reactors were studied, namely ultrasonic power generator type K8 (850 kHz) and ultrasonic bath equipment Ultrasonic cleaner USC600TH (45 kHz). The optimal operating conditions for bleaching were chosen considering the highest levels of hydroxyl radical production and the lowest energy input. The capacity to produce hydroxyl radicals by hydrodynamic cavitation was also assessed in two homogenizers, EmulsiFlex®-C3 and APV-2000. Laccase nanoemulsions were produced by high pressure homogenization using BSA (bovine serum albumin) as emulsifier. The bleaching efficiency of these formulations was tested and the results showed higher whiteness values when compared to free laccase. The combination of laccase–hydrogen peroxide process with ultrasound energy produced higher whiteness levels than those obtained by conventional methods. The amount of hydrogen peroxide was reduced 50% as well as the energy consumption in terms of temperature (reduction of 40 °C) and operating time (reduction of 90 min).     

Ultrasonic pilot-scale reactor for enzymatic bleaching of cotton fabrics

The potential of ultrasound-assisted technology has been demonstrated by several laboratory scale studies. However, their successful industrial scaling-up is still a challenge due to the limited pilot and commercial sonochemical reactors. In this work, a pilot reactor for laccase-hydrogen peroxide cotton bleaching assisted by ultrasound was scaled-up. For this purpose, an existing dyeing machine was transformed and adapted by including piezoelectric ultrasonic devices. Laboratory experiments demonstrated that both low frequency, high power (22 kHz, 2100 W) and high frequency, low power ultrasounds (850 kHz, 400 W) were required to achieve satisfactory results. Standard half (4 g/L H₂O₂ at 90 °C for 60 min) and optical (8 g/L H₂O₂ at 103 °C for 40 min) cotton bleaching processes were used as references. Two sequential stages were established for cotton bleaching: (1) laccase pretreatment assisted by high frequency ultrasound (850 kHz, 400 W) and (2) bleaching using high power ultrasound (22 kHz, 2100 W). When compared with conventional methods, combined laccase-hydrogen peroxide cotton bleaching with ultrasound energy improved the whitening effectiveness. Subsequently, less energy (temperature) and chemicals (hydrogen peroxide) were needed for cotton bleaching thus resulting in costs reduction. This technology allowed the combination of enzyme and hydrogen peroxide treatment in a continuous process. The developed pilot-scale reactor offers an enhancement of the cotton bleaching process with lower environmental impact as well as a better performance of further finishing operations.     

Effects of ultrasound and temperature on copper electro reduction in Deep Eutectic Solvents (DES)

This paper concerns a preliminary study for a new copper recovery process from ionic solvent. The aim of this work is to study the reduction of copper in Deep Eutectic Solvent (choline chloride–ethylene glycol) and to compare the influence of temperature and the ultrasound effects on kinetic parameters. Solutions were prepared by dissolution of chloride copper salt CuCl₂ (to obtain Copper in oxidation degree II) or CuCl (to obtain Copper in oxidation degree I) and by leaching metallic copper directly in DES. The spectrophotometry UV–visible analysis of the leached solution showed that the copper soluble form obtained is at oxidation degree I (Copper I). Both cyclic voltammetry and linear voltammetry were performed in the three solutions at three temperatures (25, 50 and 80 °C) and under ultrasonic conditions (F = 20 kHz, PT = 5.8 W) to calculate the mass transfer diffusion coefficient kD and the standard rate coefficient k°. These parameters are used to determine that copper reduction is carried out via a mixed kinetic-diffusion control process. Temperature and ultrasound have the same effect on mass transfer for reduction of Cu^II/Cu^I. On the other hand, temperature is more beneficial than ultrasound for mass transfer of Cu^I/Cu. Standard rate constant improvement due to temperature increase is of the same order as that obtained with ultrasound. But, by combining higher temperature and ultrasound (F = 20 kHz, PT = 5.6 W at 50 °C), reduction limiting current is increased by a factor of 10 compared to initial conditions (T = 25 °C, silent), because ultrasonic stirring is more efficient in lower viscosity fluid. These values can be considered as key-parameters in the design of copper recovery in global processes using ultrasound.     

Formation and its mechanism of copper metal layers at surface by annealing in reduced atmosphere in CuO–Li2O–Nb2O5–SiO2 glass

A trace amount (0.5 mol%) of CuO-doped 40Li₂O–32Nb₂O₅–28SiO₂ glass (mol%) exhibits the formation of copper metal layers at the glass surface by annealing at temperatures (530 °C) below the glass transition temperature (544 °C) in the reduced atmosphere of 7% H₂–93%Ar. The coordination state of copper ions is examined from optical absorption and Fourier transform infrared (FT-IR) spectrum measurements, indicating the formation of Si–OH and Si–H bonds due to the diffusion of hydrogen into the inside of the glass and the reduction of Cu⁺ and Cu²⁺ ions. The mechanism of the formation of copper metals at the surface is proposed, in which the key points are the reduction of Cu²⁺ to Cu⁺ ions due to the hydrogen and the migration of Cu⁺ ions in the interior of the glass to the surface. The first finding on copper metal layers at the glass surface might have a potential for practical applications such as electrodes in glass.     

Ultrasound-assisted copper deposition on a polymer membrane and application for methanol steam reforming

Copper particles were electrolessly deposited on a palladium aerosol activated polymer membrane in the presence of ultrasound. An application of ultrasound introduced a faster deposition (220 μg min^?1 in deposition rate) and finer copper particles (9 nm in crystallite size) than those (11 and 41 μg min^?1; 27 and 32 nm) in the absence of ultrasound (i.e. respectively 20 and 45 °C in bath temperature with mechanical agitation). A better performance of methanol steam reforming (0.59 in mean conversion during 5 h operation; 1.3 and 1.6 times respectively higher than those from 20 to 45 °C cases) at a 300 °C reaction temperature was materialized for the ultrasound application, probably due to a finer (i.e. a more textured) copper particle deposition on a polymer membrane.     

Ultrasound assisted synthesis of performic acid in a continuous flow microstructured reactor

The present work establishes in depth study of ultrasound assisted preparation of performic acid (PFA) in a continuous flow microstructured reactor. The influence of various parameters viz. formic acid: hydrogen peroxide molar ratio, flow rate, temperature and catalyst loading on the PFA formation were studied in a continuous flow microstructured reactor. In a continuous microstructured reactor in the presence of ultrasonic irradiation, the formation of PFA was found to be dependent on the molar ratio of formic acid: hydrogen peroxide, flow rate of reactants, temperature and catalyst loading (Amberlite IR-120H). The optimized parameter values are 1:1 M ratio, 50 mL/h, 40 °C and 471 mg/cm³ respectively. Further, the performance of Amberlite IR-120H catalyst was evaluated for three successive cycles in continuous microstructured reactor. The performance of catalyst was found to be decreased with the usage of the catalyst and is attributed to neutralization of the sulfonic acid groups, catalyst shrinkage, or loss in pore sites. The experimental results revealed that, for an ultrasound assisted synthesis of PFA in continuous microstructured reactor the observed reaction time was even less than 10 min. The observed intensification in the PFA synthesis process can be attributed to the intense collapse of the cavities formed at low temperature during ultrasonic irradiations, which further improved the heat and mass transfer rates with the formation of H₂O₂ during the reaction. The combined use of ultrasound and a continuous flow microstructured reactor has proved beneficial process of performic acid synthesis.     

Mechanistic study on ultrasound assisted pretreatment of sugarcane bagasse using metal salt with hydrogen peroxide for bioethanol production

This study presents the ultrasound assisted pretreatment of sugarcane bagasse (SCB) using metal salt with hydrogen peroxide for bioethanol production. Among the different metal salts used, maximum holocellulose recovery and delignification were achieved with ultrasound assisted titanium dioxide (TiO₂) pretreatment (UATP) system. At optimum conditions (1% H₂O₂, 4 g SCB dosage, 60 min sonication time, 2:100 M ratio of metal salt and H₂O₂, 75 °C, 50% ultrasound amplitude and 70% ultrasound duty cycle), 94.98 ± 1.11% holocellulose recovery and 78.72 ± 0.86% delignification were observed. The pretreated SCB was subjected to dilute acid hydrolysis using 0.25% H₂SO₄ and maximum xylose, glucose and arabinose concentration obtained were 10.94 ± 0.35 g/L, 14.86 ± 0.12 g/L and 2.52 ± 0.27 g/L, respectively. The inhibitors production was found to be very less (0.93 ± 0.11 g/L furfural and 0.76 ± 0.62 g/L acetic acid) and the maximum theoretical yield of glucose and hemicellulose conversion attained were 85.8% and 77%, respectively. The fermentation was carried out using Saccharomyces cerevisiae and at the end of 72 h, 0.468 g bioethanol/g holocellulose was achieved. Fourier transform infrared spectroscopy (FTIR) and X-ray diffraction (XRD) analysis of pretreated SCB was made and its morphology was studied using scanning electron microscopy (SEM). The compounds formed during the pretreatment were identified using gas chromatography–mass spectrometry (GC–MS) analysis.     

Synthesis of TiO2/WO3 nanoparticles via sonochemical approach for the photocatalytic degradation of methylene blue under visible light illumination

Through an ultrasound assisted method, TiO₂/WO₃ nanoparticles were synthesized at room temperature. The XRD pattern of as-prepared TiO₂/WO₃ nanoparticles matches well with that of pure monoclinic WO₃ and rutile TiO₂ nanoparticles. TEM images show that the prepared TiO₂/WO₃ nanoparticles consist of mixed square and hexagonal shape particles about 8–12 nm in diameter. The photocatalytic activity of TiO₂/WO₃ nanoparticles was tested for the degradation of a wastewater containing methylene blue (MB) under visible light illumination. The TiO₂/WO₃ nanoparticles exhibits a higher degradation rate constant (6.72 × 10⁻⁴ s⁻¹) than bare TiO₂ nanoparticles (1.72 × 10⁻⁴ s⁻¹) under similar experimental conditions.     

Ultrasound assisted extraction of pectin from waste Artocarpus heterophyllus fruit peel

Four factors three level face centered central composite response surface design was employed in this study to investigate and optimize the effect of process variables (liquid-solid (LS) ratio (10:1–20:1 ml/g), pH (1−2), sonication time (15–30 min) and extraction temperature (50–70 °C)) on the maximum extraction yield of pectin from waste Artocarpus heterophyllus (Jackfruit) peel by ultrasound assisted extraction method. Numerical optimization method was adapted in this study and the following optimal condition was obtained as follows: Liquid-solid ratio of 15:1 ml/g, pH of 1.6, sonication time of 24 min and temperature of 60 °C. The optimal condition was validated through experiments and the observed value was interrelated with predicted value.     

Evaluation on the air-borne ultrasound-assisted hot air convection thin-layer drying performance of municipal sewage sludge

The thin-layer drying behavior of the municipal sewage sludge in a laboratory-scale hot air forced convective dryer assisted with air-borne ultrasound was investigated in between 70 and 130 °C hot air temperatures. The drying kinetics in the convective process alone were compared to that for ultrasound-assist process at three ultrasound powers (30, 90, 150 W). The average drying rates within whole drying temperature range at ultrasound powers of 30, 90 and 150 W increased by about 22.6%, 27.8% and 32.2% compared with the convective drying alone (without ultrasound). As the temperature increasing from 70 °C to 130 °C, there were maximum increasing ratios for the effective moisture diffusivities of the sewage sludge in both falling rate periods at ultrasonic power of 30 W in comparison with other two high powers. In between the ultrasound powers of 0 and 30 W, the effect of the power on the drying rate was significant, while its effect was not obvious over 30 W. Therefore, the low ultrasonic power can be just set in the drying process. The values of the apparent activation energy in the first falling rate period were down from 13.52 to 12.78 kJ mol⁻¹, and from 17.21 to 15.10 kJ mol⁻¹ for the second falling rate period with increasing the ultrasonic power from 30 to 150 W. The values of the apparent activation energy in two falling rate periods with the ultrasound-assist were less than that for the hot air convective drying alone.     

Thermosonication as a potential quality enhancement technique of apple juice

Enzymatic browning and microbial growth lead to quality losses in apple products. In the present study, fresh apple juice was thermosonicated using ultrasound in-bath (25 kHz, 30 min, 0.06 W cm⁻³) and ultrasound with-probe sonicator (20 kHz, 5 and 10 min, 0.30 W cm⁻³) at 20, 40 and 60 °C for inactivation of enzymes (polyphenolase, peroxidase and pectinmethylesterase) and microflora (total plate count, yeast and mold). Additionally, ascorbic acid, total phenolics, flavonoids, flavonols, pH, titratable acidity, ^°Brix and color values influenced by thermosonication were investigated. The highest inactivation of enzymes was obtained in ultrasound with-probe at 60 °C for 10 min, and the microbial population was completely inactivated at 60 °C. The retention of ascorbic acid, total phenolics, flavonoids and flavonols were significantly higher in ultrasound with-probe than ultrasound in-bath at 60 °C. These results indicated the usefulness of thermosonication for apple juice processing at low temperature, for enhanced inactivation of enzymes and microorganisms.     

Preparation of carbon nanoparticles from electrolysis of molten carbonates and use as anode materials in lithium-ion batteries

The electrochemical reduction of molten Li–Na–K carbonates at 450 °C provides “quasi-spherical” carbon nanoparticles with size comprised between 40 and 80 nm (deduced from AFM measurements). XRD analyses performed after washing and heat-treatment at various temperatures have revealed the presence of graphitised and amorphous phases. The d₀₀₂ values were close to the ideal one obtained for pure graphite. Raman spectroscopy has pointed out surface disordering which increases with increasing temperature of the heat-treatment. The presence of Na and Li on the surface of the carbon powder has been evidenced by SIMS. The maximum Na and Li contents were observed for carbon samples heat-treated at 400 °C. Their electrochemical performances vs. the insertion/deinsertion of lithium cations were studied in 1 M LiPF₆–EC : DEC : DMC (2 : 1 : 2). The first charge–discharge cycle is characterised by a high irreversible capacity as in the case of hard-disordered carbon materials. However, the potential profile in galvanostatic mode is intermediate between that usually observed for graphite and amorphous carbon: rather continuous charge–discharge curves sloping between 1.5 and 0.3 V vs. Li / Li⁺, and successive phase transformations between 0.3 and 0.02 V vs. Li / Li⁺. The best electrochemical performances were obtained with carbon powders heat-treated at 400 °C which exhibits a reversible capacity value of 1080 mAh g^− 1 (composition of Li_2.9C₆). This sample has also both the lowest surface disordering (deduced from Raman spectroscopy), and the highest Na and Li surface contents (deduced from SIMS).     

Influence of low ultrasound intensity on the degradation of dextran catalyzed by dextranase

In our current research work, the effect of ultrasound irradiation on the enzymatic activity and enzymatic hydrolysis kinetic parameters of dextran catalysis by dextranase were investigated. Furthermore, the effects of ultrasound irradiation on the structure of dextranase were investigated with the aid of fluorescence spectroscopy and circular dichroism (CD) spectroscopy. The maximum activity of dextranase was observed when the sample was treated with ultrasound at 25 kHz, 40 W for 15 min, under which the enzyme activity increased by 13.43% compared the routine thermal incubation at 50 °C. Experimental Kinetics results, demonstrated that, both the V_max and K_M values of dextranase increased with ultrasound-treated compared with the incubation at 50 °C. Likewise, both the catalytic and specificity constants were higher under the effects of an ultrasonic field, indicating that, the substrate is converted into the product at an increased rate when compared with the incubation at 50 °C.On the other hand, fluorescence and CD spectra reflected that the ultrasound irradiation had increased the number of tryptophan on dextranase surface with increased α-helix by 15.74% and reduced random coil by 5.41% upon ultrasound-treated dextranase protein compared to the control, which were helpful for the improvement of its activity.     

Effect of processing conditions on sonochemical synthesis of nanosized copper aluminate powders

Nanosized copper aluminate (CuAl₂O₄) spinel particles have been prepared by a precursor approach with the aid of ultrasound radiation. Mono-phasic copper aluminate with a crystallite diameter of 17 nm along the (3 1 1) plane was formed when the products were synthesized using Cu(NO₃)₂·6H₂O and Al(NO₃)₃·9H₂O as starting materials, with urea as a precipitation agent at a concentration of 9 M. The reaction was carried out under ultrasound irradiation at 80 °C for 4 h and a calcination temperature of 900 °C for 6 h. The synthesized copper aluminate particles and the effect of different processing conditions such as the copper source, precipitation agents, sonochemical reaction time, calcination temperature and time were analyzed and characterized by the techniques of powder X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), atomic force microscopy (AFM) and Fourier transformation infrared spectroscopy (FT–IR).     

Decolorization of azo dye Orange G by aluminum powder enhanced by ultrasonic irradiation

In this work, the decolorization of azo dye Orange G (OG) in aqueous solution by aluminum powder enhanced by ultrasonic irradiation (AlP-UI) was investigated. The effects of various operating operational parameters such as the initial pH, initial OG concentration, AlP dosage, ultrasound power and added hydrogen peroxide (H₂O₂) concentration were studied. The results showed that the decolorization rate was enhanced when the aqueous OG was irradiated simultaneously by ultrasound in the AlP-acid systems. The decolorization rate decreased with the increase of both initial pH values of 2.0–4.0 and OG initial concentrations of 10–80 mg/L, increased with the ultrasound power enhancing from 500 to 900 W. An optimum value was reached at 2.0 g/L of the AlP dosage in the range of 0.5–2.5 g/L. The decolorization rate enhanced significantly by the addition of hydrogen peroxide in the range of 10–100 mM to AlP-UI system reached an optimum value of 0.1491 min⁻¹. The decolorization of OG appears to involve primarily oxidative steps, the cleavage of NN bond, which were verificated by the intermediate products of OG under the optimal tested degradation system, aniline and 1-amino-2-naphthol-6,8-disulfonate detected by the LC–MS.     

Thermal and sonochemical synthesis of porous (Ce,Zr)O2 mixed oxides from metal β-diketonate precursors and their catalytic activity in wet air oxidation process of formic acid

Porous (Ce_0.5Zr_0.5)O₂ solid solutions were prepared by thermolysis (T = 285 °C) or sonolysis (20 kHz, I = 32 W cm⁻², P_ac = 0.46 W mL⁻¹, T = 200 °C) of Ce(III) and Zr(IV) acetylacetonates in oleylamine or hexadecylamine under argon followed by heat treatment of the precipitates obtained in air at 450 °C. Transmission Electron Microscopy images of the samples show nanoparticles of ca. 4–6 nm for the two synthetic approaches. The powder X-ray diffraction, scanning electron microscopy, energy dispersive X-ray and μ-Raman spectroscopy of solids obtained after heat treatment indicate the formation of (Ce_0.5Zr_0.5)O₂ solid solutions with a metastable tetragonal crystal structure for the two synthetic routes. The specific surface area of the samples varies between 78 and 149 m² g⁻¹ depending on synthesis conditions. The use of Barrett–Joyner–Halenda and t-plot methods reveal the formation of mixed oxides with a hybrid morphology that combines mesoporosity and microporosity regardless of the method of preparation. Platinum nanoparticles were deposited on the surface of the mixed oxides by sonochemical reduction of Pt(IV). It was found that the materials prepared by sonochemistry exhibit better resistance to dissolution during the deposition process of platinum. X-ray photoelectron spectroscopy analysis shows the presence of Pt(0) and Pt(II) on the surface of mixed oxides. Porous (Ce_0.5Zr_0.5)O₂ mixed oxides loaded with 1.5 %wt. platinum exhibit high activity in catalytic wet air oxidation of formic acid at 40 °C.     

Ultrasound assisted co-precipitation synthesis and catalytic performance of mesoporous nanocrystalline NiO-Al2O3 powders

Mesoporous nanocrystalline NiO-Al₂O₃ powders with high surface area were synthesized via ultrasound assisted co-precipitation method and the potential of the selected samples as catalyst was investigated in dry reforming reaction for preparation of synthesis gas. The prepared samples were characterized by N₂ adsorption (BET), X-ray diffraction (XRD), Temperature programmed reduction and oxidation (TPR, TPO) and scanning electron microscopy (SEM) techniques. The effects of pH, power of ultrasound irradiation, aging time and calcination temperature on the textural properties of the catalysts were studied. The sample prepared under specified conditions (pH10, 70 W, without aging time and calcined at 600 °C) exhibited the highest surface area (249.7 m² g⁻¹). This catalyst was calcined at different temperature and employed in dry reforming of methane and the catalytic results were compared with those obtained over the catalysts prepared by impregnation and co-precipitation methods. The results showed that the catalyst prepared by ultrasound assisted co-precipitation method exhibited higher activity and stability with lower degree of carbon formation compared to catalysts prepared by co-precipitation and impregnation methods.     

Hydrogen permeation of tungsten phosphate glass thin films

Thin films of tungsten phosphate glasses were deposited on a Pd substrate by a pulsed laser deposition method and the flux of hydrogen passed thorough the glass film was measured with a conventional gas permeation technique in the temperature range 300–500 °C. The glass film deposited at low oxygen pressure was inappropriate for hydrogen permeation because of reduction of W ions due to oxygen deficiency. The membrane used in the hydrogen permeation experiment was a 3-layered membrane and consisted of Pd film (~ 20 nm), the glass film (≤ 300 nm) and the Pd substrate (250 µm). When the pressure difference of hydrogen and thickness of the glass layer were respectively 0.2 MPa and ~ 100 nm, the permeation rate through the membrane was 2.0 × 10^? 6 mol cm^? 2 s^? 1 at 500 °C. It was confirmed that the protonic and electronic mixed conducting glass thin film show high hydrogen permeation rate.     

Intensification of ultrasound-assisted process for the preparation of spindle-shape sodium zinc molybdate nanoparticles

In the present work, sodium zinc molybdate (SZM) nanoparticles were prepared using conventional and an innovative ultrasound assisted co-precipitation of sodium molybdate, zinc oxide and HNO₃ at different temperatures. Prepared product was characterized by XRD, TEM, FT-IR, particle size distribution (PSD), TGA and DTA techniques. TEM analysis shows the spindle-shaped morphology of the formed SZM nanoparticles. The average particle size of SZM nanoparticles is found to be lower in case of sonochemical method (78.3 nm) compared to conventional method (340.2 nm) which is attributed to faster solute transfer rate due to ultrasonic irradiation leading to rapid nucleation and restricted growth of SZM nanoparticles. Further, the kinetics of synthesis of SZM nanoparticles are studied using the sonochemical method at different operating temperature and conventional method at 80 °C. It is shown that the rate of reaction is significantly faster at 40 °C compared to other temperatures and also conventional method. This can be attributed to intense cavity collapse at lower temperature (low vapour pressure) compared to higher temperature (high vapour pressure) of the reaction mixture.     

Ce0.8Sm0.2O1.9 synthesis for solid oxide fuel cell electrolyte by ultrasound assisted co-precipitation method

In this study, the synthesis of Ce_0.8Sm_0.2O_1.9 (SDC) solid electrolyte by the ultrasound assisted co-precipitation method was accomplished to explore the effects of ultrasound power, ultrasound pulse ratio and probe type upon the ionic conductivity of SDC as well as the lattice parameter, the microstructure and the density. Fine powders of uniform crystallite sizes (average 11.70 ± 0.62 nm) were obtained, needing lower sintering temperature. The SDC powders were successfully sintered to a relative density of over 95% at 1200 °C (5 °C min^?1) for 6 h. The micrograph of SDC pellets showed non-agglomerated and well-developed grains with average size of about 200 nm. X-ray diffraction analysis showed that the lattice parameter increased with increasing acoustic intensity and reached a maximum for the 14.94 W cm^?2. Further, a linear relationship was detected between the lattice parameter and the ionic conductivity, inspiring a dopant like effect of US on the electrolyte properties. The highest ionic conductivity as σ_800°C = 3.07 × 10^?2 S cm^?1 with an activation energy E_a = 0.871 kJ mol^?1 was obtained with pulsed ultrasound for an acoustic intensity of 14.94 W cm^?2, using 19 mm probe and 8:2 pulse ratio.