Mass transfer enhancement in supercritical fluids extraction by means of power ultrasound

The use of high-intensity ultrasound represents an efficient manner of producing small scale agitation, enhancing mass transfer on supercritical fluids (SF) extraction processes. In this way, a supercritical CO(2) extraction of oil from particulate almonds using power ultrasound was studied. To examine the effect of the acoustic waves all experiments were performed with and without ultrasound. A power ultrasonic transducer for a working frequency of about 20 kHz was constructed and installed inside a high-pressure 5 l SF extractor. The experimental tests were carried out with CO(2) at 280 bar and 55 degrees C. Grounded almonds with an oil content of about 55%, in an amount of 1500 g were deposited inside the SF reactor where the solvent was introduced at a flow rate of 20 kg/h. The results show that the kinetics and the extraction yield of the oil were enhanced by 30% and 20% respectively, when a power of about 50 W was applied to the transducer. The average time of each extraction process was of about 8 h and 30 min. In addition, the transducer was also used as a sensitive probe capable to detect the phase behavior of supercritical fluids when it was driven with low power signals.     

Study on the changes of ultrasonic parameters over supercritical Ni-Co electroplating process

This work discusses the influence of changes to ultrasound (US) parameters over the nickel cobalt (Ni-Co) metal thin film properties produced by supercritical CO₂ (SC-CO₂) electroplating. Additionally, Ni-Co films were produced by conventional electroplating and silent SC-CO₂ and compared against each other.The discussion on metal thin film properties revolves around variations to the bath type ultrasonic power (15 W and 20 W) and frequency (42 k Hz and 72 kHz) during experiments. The properties provided by the three electroplating processes and analyzed include: grain sizes, film elemental content analyses, surface microstructures, film hardness, corrosion resistance, surface roughness, crystalline structure and preferential growth, etc. From the results it was clear that quality of films produced by US-SC-CO₂ was improved compared to that of films produced by silent SC-CO₂, which itself was better than those produced by conventional electroplating. However, when US power was varied we observed a decline in the mechanical properties of the produced films.The combination of ultrasonic agitation with SC-CO₂ allows for improved mechanical properties such as: lower surface roughness, finer grain size and surface morphologies, increased corrosion resistance and film hardness. The ultrasound agitation applied to SC-CO₂ electroplating enhanced the formation of alloyed metal as ultrasonic agitation increased the electrolyte flowability during electroplating process resulting in increased mass transfer while at the same time achieving a surface cleaning effect which removed metal ions with poor adhesion and other unwanted particles. Moreover, application of ultrasonic agitation avoids the use of surfactants so only changes to the physical phenomena and no changes to the chemical composition of the deposited thin films were observed, meaning less pollution to the electrolyte and higher purity of the deposited films.The US-SC-CO₂ electroplating method described in this work effectively enhanced the mechanical properties of the deposited thin films compared to those produced by both silent SC-CO₂ and conventional electroplating processes.     

A comparative study between classical stirred and ultrasonically-assisted dead-end ultrafiltration

The aim of this work was to determine mass transfer coefficients in the cases of ultrasonically-assisted and classical stirred dead-end ultrafiltration. A comparative study was then performed, and mass transfer coefficients obtained under ultrasonic conditions are described by an empirical model. This correlation results from an analogy with what is observed using a stirred cell and involves the ultrasonic power as the main parameter. The hydrodynamics are assumed to depend on the intensity of the ultrasound effects illustrated by the agitation arising within the cell. This agitation is due to convective currents as well as physical effects due to cavitation. The concentration polarization phenomenon is therefore affected by this action of ultrasonic waves.     

Application of ultrasound in combination with other technologies in food processing: A review

The use of non-thermal processing technologies has been on the surge due to ever increasing demand for highest quality convenient foods containing the natural taste & flavor and being free of chemical additives and preservatives. Among the various non-thermal processing methods, ultrasound technology has proven to be very valuable. Ultrasound processing, being used alone or in combination with other processing methods, yields significant positive results on the quality of foods, thus has been considered efficacious. Food processes performed under the action of ultrasound are believed to be affected in part by cavitation phenomenon and mass transfer enhancement. It is considered to be an emerging and promising technology and has been applied efficiently in food processing industry for several processes such as freezing, filtration, drying, separation, emulsion, sterilization, and extraction. Various researches have opined that ultrasound leads to an increase in the performance of the process and improves the quality factors of the food. The present paper will discuss the mechanical, chemical and biochemical effects produced by the propagation of high intensity ultrasonic waves through the medium. This review outlines the current knowledge about application of ultrasound in food technology including processing, preservation and extraction. In addition, the several advantages of ultrasound processing, which when combined with other different technologies (such as microwave, supercritical CO₂, high pressure processing, enzymatic extraction, etc.) are being examined. These include an array of effects such as effective mixing, retention of food characteristics, faster energy and mass transfer, reduced thermal and concentration gradients, effective extraction, increased production, and efficient alternative to conventional techniques. Furthermore, the paper presents the necessary theoretical background and details of the technology, technique, and safety precautions about ultrasound.     

Phase-transfer catalysis and ultrasonic waves. I. Cannizzaro reaction

The aim of this work is to study the effect of an ultrasonic wave on the Cannizzaro reaction catalyzed by a phase-transfer catalyst. The reaction of benzaldehyde with potassium hydroxide was chosen as the reference reaction. The kinetics of the reaction was followed by the amount of benzoic acid which is well characterized and easily isolatable. Investigations were made on variables such as the kind of aldehyde, the phase-transfer catalyst, the temperature and the frequency of ultrasonic wave. As the phase-transfer catalyst depends strongly on mass transfer between two phases, it is well understood that ultrasonic waves have a greater efficiency of interface mixing than conventional agitation. The results showed that an ultrasonic wave of 20 kHz dramatically accelerates on the reaction.     

Green ultrasound-assisted extraction of carotenoids from pomegranate wastes using vegetable oils

The objective of this work was to develop a new process for pomegranate peels application in food industries based on ultrasound-assisted extraction of carotenoids using different vegetable oils as solvents. In this way, an oil enriched with antioxidants is produced. Sunflower oil and soy oil were used as alternative solvents and the effects of various parameters on extraction yield were studied. Extraction temperature, solid/oil ratio, amplitude level, and extraction time were the factors investigated with respect to extraction yield. Comparative studies between ultrasound-assisted and conventional solvent extraction were carried out in terms of processing procedure and total carotenoids content. The efficient extraction period for achieving maximum yield of pomegranate peel carotenoids was about 30 min. The optimum operating conditions were found to be: extraction temperature, 51.5 °C; peels/solvent ratio, 0.10; amplitude level, 58.8%; solvent, sunflower oil. A second-order kinetic model was successfully developed for describing the mechanism of ultrasound extraction under different processing parameters.     

Numerical simulations and electrochemical experiments of the mass transfer of microvias electroforming under ultrasonic agitation

This paper explores the mass transfer mechanism of microvias electroforming under ultrasonic agitation by numerical simulations and electrochemical experiments. Firstly, the velocity distribution of electroforming solution inside the microvias under ultrasound treatment is simulated by COMSOL Multiphysics software. The ultrasonic frequency is that of 120 kHz. The ultrasonic powers are 100 W, 200 W, 300 W and 400 W, respectively. The simulation results indicate that the mean liquid velocity inside the microvias increases with the increasing of acoustic power. In addition, under a certain ultrasonic power, the mean liquid velocity will decrease with increasing the distance between microvias and transducer, the aspect ratio of microvias and the distance between cathode and central position. Secondly, electrochemical experiments are presented to investigate the effect of ultrasonic agitation on the electrode kinetics of microvias electroforming. It is found that ultrasonic treatment decreases the thickness of diffusion layer, increases the limiting diffusion current densities and further enhances the mass transfer of microvias electroforming. Compared with the silent condition, the diffusion layer thicknesses with the acoustic power of 100 W, 200 W, 300 W, 400 W are decreased by 50.0%, 64.1%, 69.3% and 74.5%, respectively. Finally, according to the results above, the 200 × 200 metal micro-column array structures are fabricated by ultrasonic electroforming under the condition of 120 kHz and 200 W. The metal micro-column is 250 μm high and has a diameter of 80 μm. The results show that ultrasonic electroforming can enhance the mass transfer of microvias electroforming, and further solve the problem of porous structure in electroforming layer. This work contributes to expanding the application of ultrasonic agitation in the microvias electroforming.     

Numerical Investigation of Heat Transfer Characteristics of scCO2 Flowing in a Vertically-Upward Tube with High Mass Flux

In this work, the heat transfer characteristics of supercritical pressure CO₂ in vertical heating tube with 10 mm inner diameter under high mass flux were investigated by using an SST k-ω turbulent model. The influences of inlet temperature, heat flux, mass flux, buoyancy and flow acceleration on the heat transfer of supercritical pressure CO₂ were discussed. Our results show that the buoyancy and flow acceleration effect based on single phase fluid assumption fail to explain the current simulation results. Here, supercritical pseudo-boiling theory is introduced to deal with heat transfer of scCO₂. scCO₂ is treated to have a heterogeneous structure consisting of vapor-like fluid and liquid-like fluid. A physical model of scCO₂ heat transfer in vertical heating tube was established containing a gas-like layer near the wall and a liquid-like fluid layer. Detailed distribution of thermophysical properties and turbulence in radial direction show that scCO₂ heat transfer is greatly affected by the thickness of gas-like film, thermal properties of gas-like film and turbulent kinetic energy in the near-wall region. Buoyancy parameters Bu < 10⁻⁵, Bu* < 5.6 × 10⁻⁷ and flow acceleration parameter K_v < 3 × 10⁻⁶ in this paper, which indicate that buoyancy effect and flow acceleration effect has no influence on heat transfer of scCO₂ under high mass fluxes. This work successfully explains the heat transfer mechanism of supercritical fluid under high mass flux.     

Effects of ultrasonic agitation on adhesion strength of micro electroforming Ni layer on Cu substrate

Micro electroforming is an important technology, which is widely used for fabricating micro metal devices in MEMS. The micro metal devices have the problem of poor adhesion strength, which has dramatically influenced the dimensional accuracy of the devices and seriously limited the development of the micro electroforming technology. In order to improve the adhesion strength, ultrasonic agitation method is applied during the micro electroforming process in this paper. To explore the effect of the ultrasonic agitation, micro electroforming experiments were carried out under ultrasonic and ultrasonic-free conditions. The effects of the ultrasonic agitation on the micro electroforming process were investigated by polarization and alternating current (a.c.) impedance methods. The real surface area of the electroforming layer was measured by cyclic voltammetry method. The compressive stress and the crystallite size of the electroforming layer were measured by X-ray Diffraction (XRD) method. The adhesion strength of the electroforming layer was measured by scratch test. The experimental results show that the imposition of the ultrasonic agitation decreases the polarization overpotential and increases the charge transfer process at the electrode–electrolyte interface during the electroforming process. The ultrasonic agitation increases the crystallite size and the real surface area, and reduces the compressive stress. Then the adhesion strength is improved about 47% by the ultrasonic agitation in average. In addition, mechanisms of the ultrasonic agitation improving the adhesion strength are originally explored in this paper. The mechanisms are that the ultrasonic agitation increases the crystallite size, which reduces the compressive stress. The lower the compressive stress is, the larger the adhesion strength is. Furthermore, the ultrasonic agitation increases the real surface area, enhances the mechanical interlocking strength and consequently increases the adhesion strength. This work contributes to fabricating the electroforming layer with large adhesion strength.     

Ultrasound-assisted extraction of hesperidin from Penggan (Citrus reticulata) peel

Hesperidin, an abundant and inexpensive bioflavonoid in Penggan (Citrus reticulata) peel, has been reported to possess a wide range of pharmacological properties. Ultrasonic extraction is an effective technique for the isolation of bioactive compounds from vegetable materials. In this study, the application of ultrasonic method was shown to be more efficient in extracting hesperidin from Penggan (C. reticulata) peel than the classical method. The effects of main ultrasonic-assisted extraction conditions on extraction yields of hesperidin from Penggan (C. reticulata) peel were evaluated, including extraction solvents, solvent volume, temperature, extraction time, ultrasonic power, ultrasonic frequency. Results showed that solvent, frequency and processing temperature were the most important factors for improving the extracting yields of hesperidin. When performed at the same temperature under the same time using three frequencies, methanol as the solvent improved the extraction yield evidently compared with ethanol or isopropanol; by comparison of the frequency influence, the yield of hesperidin was higher at 60 kHz than at 20 kHz and 100 kHz. The optimum ultrasonic conditions were determined as: methanol, frequency of 60 kHz, extraction time of 60 min, and temperature of 40 degrees C. In addition, the ultrasonic power had a weak effect on the yields of hesperidin within the experimental range. Extending ultrasonic treatment times did not result in degradation of hesperidin; the rotary beaker for materials can increase the yields of hesperidin.     

Extraction of natural products using supercritical fluids and pressurized liquids assisted by ultrasound: Current status and trends

Natural products are a source of a wide range of chemical compounds, from pigments to bioactive compounds, which can be extracted and used in different applications. Due to consumer awareness, the interest in natural compounds significantly increased in the last decades, prompting the search for more efficient and environmentally friendly extraction techniques and methods. Pressurized liquids and fluids (sub and supercritical) are being explored to extract natural compounds within the green process concept. The combination of these techniques with ultrasound has emerged as an alternative to intensify the extraction process efficiently. In this context, this work presents a comprehensive review and current insights into the use of high-pressure systems, specifically supercritical fluid extraction and pressurized liquid extraction assisted by ultrasound, as emerging technologies for extracting bioactive compounds from natural products. The extraction mechanisms, applications, and the influence of operational parameters in the process are addressed, in addition to an analysis of the main challenges to be overcome for widespread application.     

Enhancing the adhesion strength of micro electroforming layer by ultrasonic agitation method and the application

Micro electroforming is widely used for fabricating micro metal devices in Micro Electro Mechanism System (MEMS). However, there is the problem of poor adhesion strength between micro electroforming layer and substrate. This dramatically influences the dimensional accuracy of the device. To solve this problem, ultrasonic agitation method is applied during the micro electroforming process. To explore the effect of the ultrasonic agitation on the adhesion strength, micro electroforming experiments were carried out under different ultrasonic power (0 W, 100 W, 150 W, 200 W, 250 W) and different ultrasonic frequencies (0 kHz, 40 kHz, 80 kHz, 120 kHz, 200 kHz). The effects of the ultrasonic power and the ultrasonic frequency on the micro electroforming process were investigated by polarization method and alternating current (a.c.) impedance method. The adhesion strength between the electroforming layer and the substrate was measured by scratch test. The compressive stress of the electroforming layer was measured by X-ray Diffraction (XRD) method. The crystallite size of the electroforming layer was measured by Transmission Electron Microscopy (TEM) method. The internal contact surface area of the electroforming layer was measured by cyclic voltammetry (CV) method. The experimental results indicate that the ultrasonic agitation can decrease the polarization overpotential and increase the charge transfer process. Generally, the internal contact surface area is increased and the compressive stress is reduced. And then the adhesion strength is enhanced. Due to the different depolarization effects of the ultrasonic power and the ultrasonic frequency, the effects on strengthening the adhesion strength are different. When the ultrasonic agitation is 200 W and 40 kHz, the effect on strengthening the adhesion strength is the best. In order to prove the effect which the ultrasonic agitation can improve the adhesion strength of the micro devices, micro pillar arrays were fabricated under ultrasonic agitation (200 W, 40 kHz). The experimental results show that the residual rate of the micro pillar arrays is increased about 17% by ultrasonic agitation method. This work contributes to fabricating the electroforming layer with large adhesion strength.     

Effects of ultrasonic agitation and surfactant additive on surface roughness of Si (1 1 1) crystal plane in alkaline KOH solution

In the silicon wet etching process, the “pseudo-mask” formed by the hydrogen bubbles generated during the etching process is the reason causing high surface roughness and poor surface quality. Based upon the ultrasonic mechanical effect and wettability enhanced by isopropyl alcohol (IPA), ultrasonic agitation and IPA were used to improve surface quality of Si (1 1 1) crystal plane during silicon wet etching process. The surface roughness R_q is smaller than 15 nm when using ultrasonic agitation and R_q is smaller than 7 nm when using IPA. When the range of IPA concentration (mass fraction, wt%) is 5–20%, the ultrasonic frequency is 100 kHz and the ultrasound intensity is 30–50 W/L, the surface roughness R_q is smaller than 2 nm when combining ultrasonic agitation and IPA. The surface roughness R_q is equal to 1 nm when the mass fraction of IPA, ultrasound intensity and the ultrasonic frequency is 20%, 50 W and 100 kHz respectively. The experimental results indicated that the combination of ultrasonic agitation and IPA could obtain a lower surface roughness of Si (1 1 1) crystal plane in silicon wet etching process.     

Ultrasound-assisted extraction of rare-earth elements from carbonatite rocks

In view of the increasing demand for rare-earth elements (REE) in many areas of high technology, alternative methods for the extraction of these elements have been developed. In this work, a process based on the use of ultrasound for the extraction of REE from carbonatite (an igneous rock) is proposed to avoid the use of concentrated reagents, high temperature and excessive extraction time. In this pioneer work for REE extraction from carbonatite rocks in a preliminary investigation, ultrasonic baths, cup horn systems or ultrasound probes operating at different frequencies and power were evaluated. In addition, the power released to the extraction medium and the ultrasound amplitude were also investigated and the temperature and carbonatite mass/volume of extraction solution ratio were optimized to 70 °C and 20 mg/mL, respectively. Better extraction efficiencies (82%) were obtained employing an ultrasound probe operating at 20 kHz for 15 min, ultrasound amplitude of 40% (692 W dm⁻³) and using a diluted extraction solution (3% v/v HNO₃ + 2% v/v HCl). It is important to mention that high extraction efficiency was obtained even using a diluted acid mixture and relatively low temperature in comparison to conventional extraction methods for REE. A comparison of results with those obtained by mechanical stirring (500 rpm) using the same conditions (time, temperature and extraction solution) was carried out, showing that the use of ultrasound increased the extraction efficiency up to 35%. Therefore, the proposed ultrasound-assisted procedure can be considered as a suitable alternative for high efficiency extraction of REE from carbonatite rocks.     

Estimation of the Axial Dispersion Effect on Supercritical Fluid Extraction from Bidisperse Packed Beds

The general hydrodynamic equations of a mathematical model for supercritical fluid extraction are derived within the framework of the continuum mechanics approach. The shrinking core concept is used to describe the mass transfer on the solid-liquid interface. The complete system of macroscopic differential mass-balance equations is reduced to a one-dimensional approximation and accounts for the axial dispersion effect. Correlation formulas available in the literature are used to calculate the axial dispersion coefficient for the conditions of supercritical CO₂ filtration. The effect of axial dispersion on the characteristics of the macroscopic process is analyzed for the typical laboratory-scale extraction conditions in the framework of the suggested model. The numerical simulations demonstrate that the difference between the values of the current mass of accumulated extract calculated in terms of the complete approach, which accounts for the axial dispersion, and the one related to the simplified model (in which the axial dispersion is neglected), is less than 10%. The same comparison is made for the outlet concentrations of the target compounds; the difference reaches 200%.     

Mixing and Characterization of Nanosized Powders: An Assessment of Different Techniques

The objective of this paper was to gain an understanding of the mixing and characterization of nanosized powders. Three different nanosized material systems were selected based on their physical and chemical properties. Mixing experiments of the selected nanopowders were performed using a variety of environmentally friendly dry powder processing devices and the rapid expansion of supercritical CO₂ suspensions (RESS process) and compared with solvent-based methods coupled with ultrasonic agitation. A number of imaging techniques, including FESEM, AFM, TEM, EELS and EDS were used to characterize the degree of mixing or homogeneity of the mixtures obtained.The results indicate that only some of the imaging techniques are capable of determining the quality of nanoparticle mixing, depending on the physical and chemical properties of the nanopowders. For example, field emission scanning electron microscope (FESEM) is suitable for characterizing powder mixtures having a distinct difference in particle shape, or with a large difference in atomic number of the metallic element of the two constituents. Only electron energy loss spectroscopy (EELS) was able to fully characterize nanopowder mixtures of SiO₂ and TiO₂ at the nanoscale. Energy dispersive X-ray spectroscopy (EDS) provided information on mixing quality, but only on a scale of about 1m. The results also show that solvent-based mixing methods coupled with ultrasonic agitation, and RESS generally perform better than dry powder processing systems, with the exception of the hybridizer, in generating a homogeneous mixture.     

Optimization of ultrasonic extraction of 23 elements from cotton

Optimization of ultrasonic extraction of 23 elements from cotton was performed with different solvent volume ratios. For this purpose nitric acid, hydrochloric acid and water were mixed and applied in a mixture for the extraction of elements adsorbed on cotton material. The elements chosen for the extraction procedure (Al, As, Be, Bi, Ca, Cd, Co, Cr, Cu, Fe, Hg, K, Mg, Mn, Mo, Na, Ni, Pb, Sb, Si, Sn, Tl and Zn) were those that are important in textile processing. Some of them cause problems during fiber processing, dyeing or bleaching. The removal of elements from the processed fabric can be successfully done with ultrasonic extraction in the ultrasonic bath. Extraction procedure was optimized by software package Design Expert 6 (DX6) and the optimum of ultrasonic extraction was achieved with the mixture of 1M HCl-1M HNO(3)-H(2)O=3.32/2.83/93.85 (v/v). Ultrasonic extraction was a fast and efficient extraction procedure easily applied on cotton textile material.     

Ultrasonic cavitation in CO2-expanded N,N-dimethylformamide (DMF)

Due to the tunability in mass transfer, solvation and solubility, gas-expanded liquids show advantages over traditional organic solvents in many characteristics. Ultrasonication is a commonly used method to promote heat and mass transfer. The introduction of ultrasonic technology into the gas-expanded liquid system can promote the polymerization of polymer monomers, enhance extraction efficiency, and control the growth size of nanocrystals, etc. Although acoustic cavitation has been extensively explored in aqueous solutions, there are still few studies on cavitation in organic liquids, especially in gas-expanded liquid systems. In this article, the development of cavitation bubble cloud structure in CO₂-expanded N, N-dimethylformamide (DMF) was observed by a high-speed camera, and the cavitation intensity was recorded using a spherical hydrophone. It was found that the magnitude of the transient cavitation energy was not only related to input power, but also closely related to CO₂ content. The combination of ultrasound (causing a rapid alternation of gas solubility) and gas-expanded liquid system (causing a decrease in viscosity and surface tension of liquids) is expected to provide a perfect platform for high-speed mass transfer.     

Macrosonics in industry: 4. Chemical processing

Acoustic irradiation can result in increased inter-phase mass and heat transfer rates. The second-order acoustic effects of cavitation, interfacial instability, radiation pressure and acoustic streaming are responsible for the enhancement in these rate processes. The application of sonic and ultrasonic energy in industrial processing is reviewed. A number of units using acoustic energy to enhance rates of conventional unit processes, for example, drying, solid-liquid extraction, etc, are described. In addition, new applications in waste water treatment and oil-water emulsion fuels are described. The development of newer, more efficient generators should lead to a greater use of acoustic energy for large-scale industrial processing.     

Currents on Ultrasound‐Assisted Extraction for Sample Preparation and Spectroscopic Analytes Determination

Abstract

This review reports recent applications of the ultrasonic energy for extracting inorganic and organic analytes from diverse solid samples devoted to spectroscopic analyses. The main advantages resulting from ultrasound comprise the reduction of the procedural time and reagent consumption. In this sense, ultrasound‐assisted extractions can be considered as an efficient tool for improving the analytical performance of procedures employed in analytical chemistry and natural products chemistry. However, a rigorous experimental control is strongly recommended in order to avoid losses in precision and accuracy. Uncontrolled ultrasound‐assisted extraction procedure is also discussed, since ultrasonic irradiation can provoke decompositions of molecules, hindering organic compounds extraction.