Effects of ultrasonic frequency and liquid height on sonochemical efficiency of large-scale sonochemical reactors

The sonochemical efficiency of a cylindrical sonochemical reactor has been investigated as a function of frequency and liquid height. The irradiation frequencies were 45, 129, 231 and 490 kHz. The liquid height was varied from 10 to 700 mm. The sonochemical efficiency of the cylindrical reactor was evaluated by potassium iodide (KI) dosimetry and calorimetry. In our study, the sonochemical efficiency depended on the frequency and liquid height; further, the plots of sonochemical efficiency against liquid height exhibit one or two peaks for each frequency. The sonochemical efficiency up to the first peak increased monotonically with the logarithm of the frequency, and the liquid height for the first peak was inversely proportional to the frequency. From these results, the optimum frequency for a sonochemical reactor can be determined if the liquid height is specified for scale-up of the sonochemical reactor.     

Intensification of hydroxyl radical production in sonochemical reactors

The efficacy of sonochemical reactors in chemical processing applications has been well established in the laboratory scale of operation though at a given set of operating parameters and no efforts have been directed in terms of maximizing the free radical production. In the present work, the effect of different operating parameters viz. pH, power dissipation into the system, effect of additives such as air, haloalkanes, titanium dioxide, iron and oxygen on the extent of hydroxyl radical formation in a sonochemical reactor have been investigated using salicylic acid dosimetry. Possible mechanisms for oxidation of salicylic acid in the presence of different additives have also been established. It has been observed that acidic conditions under optimized power dissipation in the presence of iron powder and oxygen result in maximum liberation of hydroxyl radicals as quantified by the kinetic rate constant for production of 2,5- and 2,3-dihydroxybenzoic acid. The study has enabled the optimization of the conditions for maximum efficacy of sonochemical reactors where free radical attack is the controlling mechanism for the chemical processing applications.     

频率对双频超声辐照声化学产额增强效应的影响

本文采用电学法研究了２８ｋＨｚ分别与０．８７ＭＨｚ、１ＭＨｚ、１．７ＭＨｚ组成的双频超声辐照的声化学效应。结果表明，双频辐照增强声化学产额具有明显的频率效率。     

Some aspects of the design of sonochemical reactors

The magnitudes of collapse pressures and temperatures as well as the number of free radicals generated at the end of cavitation events are strongly dependent on the operating parameters of the equipment namely, intensity and frequency of irradiation along with the geometrical arrangement of the transducers and the liquid phase physicochemical properties, which affect the initial size of the nuclei and the nucleation process. In the present work, the effect of these parameters on the collapse pressure generated and the maximum size of the cavity during the cavitation phenomena have been studied using the bubble dynamics equation, which considers the compressibility of the medium and a single bubble in isolation. The different liquid phase properties considered include, liquid vapor pressure, viscosity, bulk liquid temperature, surface tension and nature of dissolved gases (polytropic constant of the gas). The theoretical predictions have been also compared with the experimental results observed in the literature qualitatively and some recommendations have been made for the selection of the operating parameters so as to achieve maximum benefits. The work presented here is novel in sense that no earlier studies have considered the compressibility of the liquid medium and tried to evaluate the effect of all the operating parameters on the cavitational activity.     

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.     

Comments on the use of loop reactors in sonochemical processes

For sonochemical processing on an industrial scale the traditional choice is either a batch or flow system. The former is straightforward in concept but it requires large scale powerful ultrasonic transducers capable of delivering high intensity ultrasound to large volumes of liquid. Unfortunately at the moment the cost and problems involved in building very large sonication devices for batch processes cannot justify the replacement of existing industrial processes. For this reason most sonochemists prefer some form of flow system where small quantities of reagents can be treated as they are pumped from a large vat of reagents through a smaller sonochemical reactor where high intensity ultrasound can be applied. In this short paper we draw attention to a problem which seems common in a number of papers dealing with such flow systems – a confusion between the terms continuous reactor and loop reactor. Further we emphasise the importance of calculating the actual amount of ultrasonic processing experienced by the reaction mixture within the sonication zone of a loop reactor during its operation. The parameters required for such a calculation are: ultrasonic processor volume (R_v in L), pump flow rate (F_r in L/min), stock solution volume in the reservoir (S_v in L) and the overall system operating time (S_o in min).     

Simulation of the spatial distribution of the acoustic pressure in sonochemical reactors with numerical methods: A review

Numerical methods for the calculation of the acoustic field inside sonoreactors have rapidly emerged in the last 15 years. This paper summarizes some of the most important works on this topic presented in the past, along with the diverse numerical works that have been published since then, reviewing the state of the art from a qualitative point of view. In this sense, we illustrate and discuss some of the models recently developed by the scientific community to deal with some of the complex events that take place in a sonochemical reactor such as the vibration of the reactor walls and the nonlinear phenomena inherent to the presence of ultrasonic cavitation. In addition, we point out some of the upcoming challenges that must be addressed in order to develop a reliable tool for the proper designing of efficient sonoreactors and the scale-up of sonochemical processes.     

Ultrasound pressure distributions generated by high frequency transducers in large reactors

The performance of an ultrasound reactor chamber relies on the sound pressure level achieved throughout the system. The active volume of a high frequency ultrasound chamber can be determined by the sound pressure penetration and distribution provided by the transducers. This work evaluated the sound pressure levels and uniformity achieved in water by selected commercial scale high frequency plate transducers without and with reflector plates. Sound pressure produced by ultrasonic plate transducers vertically operating at frequencies of 400 kHz (120 W) and 2 MHz (128 W) was characterized with hydrophones in a 2 m long chamber and their effective operating distance across the chamber’s vertical cross section was determined. The 2 MHz transducer produced the highest pressure amplitude near the transducer surface, with a sharp decline of approximately 40% of the sound pressure occurring in the range between 55 and 155 mm from the transducer. The placement of a reflector plate 500 mm from the surface of the transducer was shown to improve the sound pressure uniformity of 2 MHz ultrasound. Ultrasound at 400 kHz was found to penetrate the fluid up to 2 m without significant losses. Furthermore, 400 kHz ultrasound generated a more uniform sound pressure distribution regardless of the presence or absence of a reflector plate. The choice of the transducer distance to the opposite reactor wall therefore depends on the transducer plate frequency selected. Based on pressure measurements in water, large scale 400 kHz reactor designs can consider larger transducer distance to opposite wall and larger active cross-section, and therefore can reach higher volumes than when using 2 MHz transducer plates.     

Cavity cluster approach for quantification of cavitational intensity in sonochemical reactors

The mechanism involved in the spectacular effects from cavitation phenomenon is very complex and there have been several proposed theories to explain the observed results. The experimental as well as the visual observations indicate that a single collapsing cavity is also influenced by the dynamics of the surrounding cavities, which are very near to the collapsing cavity. The observed effects and erosion patterns cannot be explained properly on the basis of a single cavity collapse and hence in this study a cavity cluster (group of cavities) has been considered to understand the mechanism of cavitational effects. The effect of intensity, frequency of ultrasound, initial size of the cluster and the fraction of energy transferred from the collapsing cavities to the surrounding cavities on the cavitational intensity quantified in terms of the pressure pulse generated at the collapse of cavities as well as the active zone of cavitation has been investigated using bubble/cavity dynamics equations, numerically. On the basis of the trends obtained, empirical correlations estimating the collapse pressure and active volume of cavitation, have been developed.     

Synthesis of biodiesel from waste cooking oil using sonochemical reactors

Investigation into newer routes of biodiesel synthesis is a key research area especially due to the fluctuations in the conventional fuel prices and the environmental advantages of biodiesel. The present work illustrates the use of sonochemical reactors for the synthesis of biodiesel from waste cooking oil. Transesterification of used frying oil with methanol, in the presence of potassium hydroxide as a catalyst has been investigated using low frequency ultrasonic reactor (20 kHz). Effect of different operating parameters such as alcohol–oil molar ratio, catalyst concentration, temperature, power, pulse and horn position on the extent of conversion of oil have been investigated. The optimum conditions for the transesterification process have been obtained as molar ratio of alcohol to oil as 6:1, catalyst concentration of 1 wt.%, temperature as 45 °C and ultrasound power as 200 W with an irradiation time of 40 min. The efficacy of using ultrasound has been compared with the conventional stirring approach based on the use of a six blade turbine with diameter of 1.5 cm operating at 1000 rpm. Also the purification aspects of the final product have been investigated.     

Dependence of the characteristics of bubbles on types of sonochemical reactors

Computer simulations of bubble oscillations in liquid water irradiated by an ultrasonic wave have revealed that the characteristic of bubbles depends on types of sonochemical reactors: a horn-type reactor and a standing-wave type reactor. When the acoustic amplitude is large at 20 kHz, the bubble content is mostly water vapor even at the end of the bubble collapse and the temperature inside a bubble at the collapse is relatively low. On the other hand, when the acoustic amplitude is relatively low, the bubble content is mostly noncondensable gas at the end of the bubble collapse and the bubble temperature is relatively high. In a horn-type sonochemical reactor, the former type of bubbles are dominant because many bubbles exist near the horn-tip where the acoustic amplitude is large, while in a standing-wave type reactor the latter type of bubbles are dominant because the Bjerknes force gathers bubbles at a region where acoustic amplitude is relatively low.     

Mapping the efficacy of new designs for large scale sonochemical reactors

Sonochemical reactors have a great promise for many physical and chemical processing applications but its applicability at pilot or industrial scale levels is hindered by lack of novel designs which can reproduce the spectacular effects generated at the laboratory scale. The present work evaluates the efficacy of two new designs, operating at a liquid capacity of 7l. Mapping of the cavitational activity has been carried out using measurements of local pressure using hydrophone and cativational intensity using Cavitation Activity Indicator (Model IC-3, N. Deznukov, Belarus State University, Minsk, Belarus). Aim has been to identify the distribution of the cavitational activity in radial and axial directions and possibly characterizing the zones with very high and very low cavitational activity in these reactor configurations. It has been observed that the cavitational activity is substantially uniform in both the reactors unlike the conventional single transducer based reactors. The study clearly indicates the feasibility of these designs for future large scale applications.     

Investigation of induction of air due to ultrasound source in the sonochemical reactors

A detailed investigation into the phenomena of induction of air using a novel arrangement of the ultrasonic horn (tip is located just above the liquid surface) has been made with the quantification of the extent of induction in terms of the air entrainment rate and the gas–liquid mass transfer coefficient for the transfer of air into the system. The measurement of air entrainment rate was found to be quite difficult and hence focus was kept on the quantification in terms of the gas–liquid mass transfer coefficient. The effect of ultrasonic power dissipation and type of the liquid medium (water, sodium chloride and sodium laruyl sulphate [surfactant] solution) on the mass transfer coefficient has been studied and correlations have been developed for the prediction of the same. Comparison with the mechanically agitated surface aerators has enabled us to understand the controlling mechanism in the induction and subsequent distribution of the air i.e. turbulence or convective motion. The present work should open an entirely new field of research in the area of design of sonochemical gas–liquid reactors operating possibly as a combination of gas-inducing reactors and cavitational reactors.     

Comparison of several methods to characterise the high frequency behaviour of piezoelectric ceramics for transducer applications

Thickness mode resonances in commercial piezoelectric ceramics have been characterised as a function of frequency by two methods. The first is based on a fit on the electrical impedance for the fundamental and the overtones. This method has been applied to a large number of PZT ceramic samples and frequency dependence for all the parameters is investigated, in particular for the piezoelectric coefficient e33. The second is based on the measurement of the mechanical displacement at the centre of the surface of a PZT ceramic disk. With a modified KLM scheme, this displacement is modelled. The dielectric, elastic and piezoelectric parameters are extracted and compared for the fundamental and the third overtone. The results are found to be in good agreement.     

Experimental quantification of cavitation yield revisited: focus on high frequency ultrasound reactors

Acoustic cavitation plays an important role in enhancing the reaction rate of chemical processes in sonochemical systems. However, quantification of cavitation intensity in sonochemical systems is generally limited to low frequency systems. In this study, an empirical determination of cavitation yield in high frequency ultrasound systems was performed by measuring the amount of iodine liberated from the oxidation of potassium iodide (KI) solution at 1.7 and 2.4 MHz. Experiments for determining cavitation were carried out at various solute (KI) concentrations under constant temperature, obtained by direct cooling of the solution and variable temperature conditions, in the absence of external cooling. Cavitation yield measurements, reported in this work, extend previously reported results and lend credence to the two step reaction pathway in high frequency systems. Additionally, the concentration of KI and temperature affect the cavitation yield of a system such that the iodine production is proportional to both conditions. It is proposed that direct cooling of sonicated KI solution may be advantageous for optimization of cavitation intensity in high frequency sonochemical reactors.     

Material characterization of ER fluids at high frequency

In this paper, the material characterization of ER fluids at high frequencies is studied. To characterize the properties at high frequencies, an experimental apparatus is provided, based upon the wave transmission through ER fluids in the presence of electric field. Details of the experiment and how to extract the complex shear modulus of ER fluids are addressed. A moderate increase in the storage modulus and loss modulus was observed when the weight ratio of ER particles and the electric field were increased. The proposed method is a comprehensive material characterization of ER fluids in high frequencies for ER smart structures.     

Modeling of three-dimensional pressure fields in sonochemical reactors with an inhomogeneous density distribution of cavitation bubbles. Comparison of theoretical and experimental results

During the last 50 years extensive experimental investigation has been carried out on the chemical effects of ultrasound, but limited work has been reported on modeling. This paper presents a new model in which a numerical calculation of the three-dimensional linear sound pressure field distribution in a commonly used sonoreactor containing three transducers is carried out. In this model the inhomogeneous three-dimensional time-dependent wave equation was solved using the finite difference approach. The modeled results are then compared with the experimentally measured values, and the agreement, in general, is found to be good. Further, our modeling studies have an advantage, since they clearly describe the continuous sound pressure field structure, unlike previously reported results in which some information is missing due to limited intermittent measured points.     

Comparative study of sonochemical reactors with different geometry using thermal and chemical probes

Laboratory scale 20 kHz sonochemical reactors with different geometries have been tested using thermal probes, the kinetics of H(2)O(2) formation, and the kinetics of diphenylmethane (DPhM) sonochemical darkening. Results revealed that the overall sonochemical reaction rates in H(2)O and DPhM are driven by the total absorbed acoustic energy and roughly independent the geometry of the studied reactors. However, the sonochemical efficiency, defined as eta=VG/S, where G is a sonochemical yield of H(2)O(2), V is a volume of sonicated liquid, and S is a surface of the sonotrode, was proved to increase with the decrease of S. This phenomenon was explained by growing of the maximum cavitating bubble size with ultrasonic intensity and its independence towards the specific absorbed acoustic power. For the cleaning bath reactor the kinetics of the sonochemical reactions in H(2)O and DPhM depends strongly on the reaction vessel materials: the reaction rates decreased with the increase of the materials elasticity. Kinetic study of H(2)SO(4) sonolysis using a sonoreactor without direct contact with titanium sonotrode showed that sulphate anion is an effective scavenger of OH() radicals formed during water sonolysis.     

An alternative technique for determining the number density of acoustic cavitation bubbles in sonochemical reactors

The present paper introduces a novel semi-empirical technique for the determination of active bubbles’ number in sonicated solutions. This method links the chemistry of a single bubble to that taking place over the whole sonochemical reactor (solution). The probe compound is CCl₄, where its eliminated amount within a single bubble (though pyrolysis) is determined via a cavitation model which takes into account the non-equilibrium condensation/evaporation of water vapor and heat exchange across the bubble wall, reactions heats and liquid compressibility and viscosity, all along the bubble oscillation under the temporal perturbation of the ultrasonic wave. The CCl₄ degradation data in aqueous solution (available in literature) are used to determine the number density through dividing the degradation yield of CCl₄ to that predicted by a single bubble model (at the same experimental condition of the aqueous data). The impact of ultrasonic frequency on the number density of bubbles is shown and compared with data from the literature, where a high level of consistency is found.     

Simple sonochemical synthesis and characterization of HgSe nanoparticles

Mercury selenide (HgSe) nanostructures were synthesized via a sonochemical method based on the reaction between HgCl(2), SeCl(4) and hydrazine hydrate (N(2)H(4)·H(2)O) in water, in presence of various capping agents. The effects of preparation parameters such as: the kind of capping agent and its amount, ultrasonic power, reaction time and temperature were investigated. It was found that morphology, particle size and phase of the products could be greatly affected by these parameters. HgSe nanostructures were characterized by X-ray powder diffraction (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), photoluminescence spectroscopy (PL) and X-ray energy dispersive spectroscopy (EDS).