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.     

Degradation of dichlorvos using hydrodynamic cavitation based treatment strategies

The degradation of an aqueous solution of dichlorvos, a commonly used pesticide in India, has been systematically investigated using hydrodynamic cavitation reactor. All the experiments have been carried out using a 20 ppm solution of commercially available dichlorvos. The effect of important operating parameters such as inlet pressure (over a range 3-6 bar), temperature (31 °C, 36 °C and 39 °C) and pH (natural pH = 5.7 and acidic pH = 3) on the extent of degradation has been investigated initially. It has been observed that an optimum value of pressure gives maximum degradation whereas low temperature and pH of 3 are favorable. Intensification studies have been carried out using different additives such as hydrogen peroxide, carbon tetrachloride, and Fenton’s reagent. Use of hydrogen peroxide and carbon tetrachloride resulted in the enhancement of the extent of degradation at optimized conditions but significant enhancement was obtained with the combined use of hydrodynamic cavitation and Fenton’s chemistry. The maximum extent of degradation as obtained by using a combination of hydrodynamic cavitation and Fenton’s chemistry was 91.5% in 1 h of treatment time. The present work has conclusively established that hydrodynamic cavitation in combination with Fenton’s chemistry can be effectively used for the degradation of dichlorvos.     

Sonochemical reactors: scale up aspects

The present work deals with the discussion on the engineering aspects of the design of large-scale sonochemical reactors using the solutions of the bubble dynamics equations as well as experimentation with different reactor types and reactions. Design correlations for the collapse pressure and its relation to the cavitational yield have also been given which should assist the designers in the choice of the operating parameters for a desired cavitational effect. Some techniques for the intensification of cavitational activity (with the use of additives) with an aim of reducing the cost of operation have also been discussed. The guidelines for the future work to be carried out to remove the lacunae in the design information with an aim of developing industrial scale efficient sonochemical reactors have also been mentioned.     

Degradation of imidacloprid containing wastewaters using ultrasound based treatment strategies

The present work deals with application of sonochemical reactors for the treatment of imidacloprid containing wastewaters either individually or in combination with other advanced oxidation processes. Experiments have been performed using two different configurations of sonochemical reactors viz. ultrasonic horn (20 kHz frequency and rated power of 240 W) and ultrasonic bath equipped with radially vibrating horn (25 kHz frequency and 1 kW rated power). The work also investigates the effect of addition of process intensifying agents such as H₂O₂ and CuO, which can enhance the production of free radicals in the system. The combination studies with advanced oxidation process involve the advanced Fenton process and combination of ultrasound with UV based oxidation. The extent of degradation obtained using combination of US and H₂O₂ at optimum loading of H₂O₂ was found to be 92.7% whereas 96.5% degradation of imidacloprid was achieved using the combination of US and advanced Fenton process. The process involving the combination of US, UV and H₂O₂ was found to be the best treatment approach where complete degradation of imidacloprid was obtained with 79% TOC removal. It has been established that the use of cavitation in combination with different oxidation processes can be effectively used for the treatment of imidacloprid containing wastewater.     

Ultrasonic degradation of polymers: effect of operating parameters and intensification using additives for carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA)

Use of ultrasound can yield polymer degradation as reflected by a significant reduction in the intrinsic viscosity or the molecular weight. The ultrasonic degradation of two water soluble polymers viz. carboxymethyl cellulose (CMC) and polyvinyl alcohol (PVA) has been studied in the present work. The effect of different operating parameters such as time of irradiation, immersion depth of horn and solution concentration has been investigated initially using laboratory scale operation followed by intensification studies using different additives such as air, sodium chloride and surfactant. Effect of scale of operation has been investigated with experiments in the available different capacity reactors with an objective of recommending a suitable type of configuration for large scale operation. The experimental results show that the viscosity of polymer solution decreased with an increase in the ultrasonic irradiation time and approached a limiting value. Use of additives such as air, sodium chloride and surfactant helps in increasing the extent of viscosity reduction. At higher frequency operation the viscosity reduction has been found to be negligible possibly attributed to less contribution of the physical effects. The viscosity reduction in the case of ultrasonic horn has been observed to be more as compared to other large capacity reactors. Kinetic analysis of the polymer degradation process has also been performed. The present work has enabled us to understand the role of the different operating parameters in deciding the extent of viscosity reduction in polymer systems and also the controlling effects of low frequency high power ultrasound with experiments on different scales of operation.     

Treatment of cyanide containing wastewater using cavitation based approach

Industrial wastewater streams containing high concentrations of biorefractory materials like cyanides should ideally be treated at source. In the present work, degradation of potassium ferrocyanide (K₄F_e(CN)₆) as a model pollutant has been investigated using cavitational reactors with possible intensification studies using different approaches. Effect of different operating parameters such as initial concentration, temperature and pH on the extent of degradation using acoustic cavitation has been investigated. For the case of hydrodynamic cavitation, flow characteristics of cavitating device (venturi) have been established initially followed by the effect of inlet pressure and pH on the extent of degradation. Under the optimized set of operating parameters, the addition of hydrogen peroxide (ratio of K₄F_e(CN)₆:H₂O₂ varied from 1:1 to 1:30 mol basis) as process intensifying approach has been investigated. The present work has conclusively established that under the set of optimized operating parameters, cavitation can be effectively used for degradation of potassium ferrocyanide. The comparative study of hydrodynamic cavitation and acoustic cavitation suggested that hydrodynamic cavitation is more energy efficient and gives higher degradation as compared to acoustic cavitation for equivalent power/energy dissipation. The present work is the first one to report comparison of cavitation based treatment schemes for degradation of cyanide containing wastewaters.     

Depolymerization using sonochemical reactors: A critical review

Ultrasonic irradiation has been proposed as a novel approach for degradation of polymer compounds, especially considering the fact that the reduction in the molecular weight (also the intrinsic viscosity) is simply by splitting the most susceptible chemical bond without causing any changes in the chemical nature. An overview of the application of ultrasound for the polymer degradation has been presented in this work, discussing the mechanism of degradation, kinetic modeling, effect of operating parameters and the type of reactors generally used for depolymerization. The effect of important operating parameters such as initial polymer concentration, presence of functional groups in the polymer chain, reaction volume, initial molecular weight, temperature, operating frequency, power dissipation and use of process intensifying additives have been discussed also giving guidelines about selection of the optimum parameters. It has been observed that the low concentrations and higher power dissipation (till an optimum) are favorable resulting in higher extents of degradation. Typically low frequency is recommended but for the case of water soluble polymers, higher frequencies would also give similar results due to the dominant action of chemical effects of cavitation. It has been demonstrated that the alkyl group substituent also affects the degradation rate of polymer. An overview of degradation using combined approach based on ultrasound and additives with comparison with individual approach has also been presented. It has been observed that the main contributing factor for the synergy of the combined approach is the selection of optimum loading of additives. Overall, it has been observed that efficient polymer degradation can be achieved using combined process based on the use of ultrasound.     

The effect of solution level on calorific and dosimetric results in a 70 kHz tower type sonochemical reactor

In order to design and optimise sonochemical reactors it is important to study the impact of liquid level, or path length, on the standing wave phenomena and the influence this has on temperature increase and OH radical rate of production. In this work, an ultrasonic tower type reactor operating at 70 kHz is investigated with results from variations to liquid levels reported. Calorimetry data was obtained using a modified reactor set up with temperature change monitored at selected points within the chamber. OH radical rate of formation was shown via chemical dosimetry, following the conversion of terephthalic acid (TA) to 2-hydroxyterephthalic acid (HTA). The results obtained have shown that changes in solution depth of a few millimetres significantly impacts on the interaction of the propagated and reflected waveforms with the results of calorific measurements and HTA rates of formation varying by 90% (750 J) and 88% (80 mmol dm(-3) min(-1)) between the operational extremes over the studied depth range.     

Kinetics analysis for development of a rate constant estimation model for ultrasonic degradation reaction of methylene blue

Ultrasound has been used as an advanced oxidation method for wastewater treatment. Sonochemical degradation of organic compounds in aqueous solution occurs by pyrolysis and/or reaction with hydroxyl radicals. Moreover, kinetics of sonochemical degradation has been proposed. However, the effect of ultrasonic frequency on degradation rate has not been investigated. In our previous study, a simple model for estimating the apparent degradation rate of methylene blue was proposed. In this study, sonochemical degradation of methylene blue was performed at various frequencies. Apparent degradation rate constant was evaluated assuming that sonochemical degradation of methylene blue was a first-order reaction. Specifically, we focused on effects of ultrasonic frequency and power on rate constant, and the applicability of our proposed model was demonstrated. Using this approach, maximum sonochemical degradation rate was observed at 490 kHz, which agrees with a previous investigation into the effect of frequency on the sonochemical efficiency value evaluated by KI oxidation dosimetry. Degradation rate increased with ultrasonic power at every frequency. It was also observed that threshold power must be reached for the degradation reaction to progress. The initial methylene blue concentration and the apparent degradation rate constant have a relation of an inverse proportion. Our proposed model for estimating the apparent degradation rate constant using ultrasonic power and sonochemical efficiency value can apply to this study which extended the frequency and initial concentration range.     

Ultrasound-based treatment approaches for intrinsic viscosity reduction of polyvinyl pyrrolidone (PVP)

The present work deals with achieving viscosity reduction in polymer solutions using ultrasound-based treatment approaches. Use of simple additives such as salts, or surfactants and introduction of air at varying flow rates as process intensifying parameters have been investigated for enhancing the degradation of polyvinyl pyrrolidone (PVP) using ultrasonic irradiation. Sonication is carried out using an ultrasonic horn at 36 kHz frequency at an optimized concentration (1%) of the polymer. The degradation behavior has been characterized in terms of the change in the viscosity of the aqueous solution of PVP. The intrinsic viscosity of the polymer has been shown to decrease to a limiting value, which is dependent on the operating conditions and use of different additives. Similar extent of viscosity reduction has been observed with 1% NaCl or 0.1% TiO₂ at optimized depth of horn and 27 °C, indicating the superiority of titanium dioxide as an additive. The combination of ultrasound and ultraviolet (UV) irradiation results in a significantly faster viscosity reduction as compared to the individual operations. A kinetic analysis for the degradation of PVP has also been carried out. The work provides a detailed understanding of the role of the operating parameters and additives in deciding the extent of reduction in the intrinsic viscosity of PVP solutions.     

Removal of 2,4-dinitrophenol using hybrid methods based on ultrasound at an operating capacity of 7 L

Sonochemical removal of 2,4-dinitrophenol (DNP) has been investigated using ultrasonic bath, with an operating capacity of 7 L, fitted with a large transducer with longitudinal vibrations having a 1 kW rated power output and operating frequency of 25 kHz. It has been revealed from calorimetric studies that maximum power is dissipated at a capacity of 7 L. The concentration of DNP has been monitored with an objective of evaluation of the efficacy of ultrasonic reactor in combination with process intensifying approaches for the removal of DNP. The effect of operating pH and additives such as hydrogen peroxide and ferrous iron activated persulfate on the extent of removal of DNP has been investigated. It has been observed that the extent of removal is greater at lower pH (pH 2.5 and 4) than at higher pH (pH 10). The combined treatment strategies such as ultrasound (US)/Fenton, US/advanced Fenton and US/CuO/H₂O₂ have also been investigated with an objective of obtaining complete removal of DNP using hybrid treatment strategies. The extent of removal has been found to increase significantly in US/Fenton process (98.7%) as compared to that using US alone (5.8%) which demonstrates the efficacy of the combined process. First order kinetics has been fitted for all the approaches investigated in the work. Calculations of cavitational yield indicated the superiority of the reactor design as compared to the conventional ultrasonic horn type reactors. The main intermediates formed during the process of removal of DNP have been identified.     

A review and assessment of hydrodynamic cavitation as a technology for the future

In the present work, the current status of the hydrodynamic cavitation reactors has been reviewed discussing the bubble dynamics analysis, optimum design considerations, design correlations for cavitational intensity (in terms of collapse pressure)/cavitational yield and different successful chemical synthesis applications clearly illustrating the utility of these types of reactors. The theoretical discussion based on the modeling of the bubble dynamics equations aims at understanding the design information related to the dependency of the cavitational intensity on the operating parameters and recommendations have been made for the choice of the optimized conditions of operating parameters. The design information based on the theoretical analysis has also been supported with some experimental illustrations concentrating on the chemical synthesis applications. Assessment of the hydrodynamic cavitation reactors and comparison with the sonochemical reactors has been done by citing the different industrially important reactions (oxidation of toluene, o-xylene, m-xylene, p-xylene, mesitylene, o-nitrotoluene, p-nitrotoluene, m-nitrotoluene, o-chlorotoluene and p-chlorotoulene, and trans-esterification reaction i.e., synthesis of bio-diesel). Some recommendations have also been made for the future work to be carried out as well as the choice of the operating conditions for realizing the dream of industrial scale applications of the cavitational reactors.     

Sonochemical and photochemical oxidation of organic matter

Recent developments in sonochemistry have led us to study its use to treat water and wastewater. The effects of ultrasound wave in hydrophilic chemical oxidations are mainly due to hydroxyl radical production during the cavitation-induced water decomposition. Currently, the sonochemical destruction of aromatic compounds in water solution is obtained with low rates. The aim of this work is to evaluate the efficiency of the sonochemical effect in conjunction with a photochemical irradiation. Taking phenol as an example, the combined action of sonochemistry and photochemistry has been considered in a ‘sonuv’ reactor. An important enhancement of the degradation rate of phenol has been observed. It may be the result of three different oxidative processes: direct photochemical action, high frequency sonochemistry and reaction with ozone (produced by UV irradiation of air). The process has been successfully tested to lower the chemical oxygen demand of a municipal wastewater.     

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.     

Investigation of design parameters in ultrasound reactors with confined channels

This paper presents a three-dimensional numercial simulation of sonochemical degradation upon cavitational activity. The model relates the simulation of the acoustic pressure distribution to the sonochemical reaction rate. As a case study, the thermal degradation of carbon tetrachloride during sonication is studied in a tubular milliscale reactor. The model is used to optimize the reactor diameter, ultrasound frequency and power dissipated to the ultrasound transducers. The results indicate that multiple transducers at a moderate power level are more efficient than one transducer with high power level. Furthermore, the average cavity volume fraction is proposed as a reaction independent parameter to estimate the optimal reactor design. Within the results obtained in this paper, it appears possible to optimise reactor design based on this parameter.     

Degradation of pentachlorophenol aqueous solutions using a continuous flow ultrasonic reactor: experimental performance and modelling

The degradation of aqueous solutions of pentachlorophenol (PCP) in a three-stage sonochemical reactor operating in the continuous flow mode has been investigated. The experimental reactor may be considered as a series of three high-frequency ultrasonic units. The influence of several parameters such as ultrasonic power, reactor volume and volumetric feed flow rate on the reactor performance is reported. Application of classical basic chemical engineering principles leads to a model that enables us to predict the PCP concentration within the reactor. In steady state, experimental conversion rates are shown to be in good agreement with model predictions.     

Sonochemical degradation of poly- and perfluoroalkyl substances – A review

Poly- and perfluoroalkyl substances (PFAS) have received considerable attention from environmental scientists and engineers because of their stability and widespread. Sonochemical process has been widely used in the environmental field to remove pollutants due to its advantages in terms of operational simplicity, no secondary pollutant formation and safety. Currently, many studies have reported sonochemical degradation of various PFAS in laboratory settings and showed excellent removal potential. This article reviewed the effects of different power densities, ultrasonic frequencies, temperatures, atmosphere conditions, additives, and initial concentration and chemical properties of PFAS on the sonochemical degradation of PFAS. Sonochemical methods combined with conventional techniques for PFAS removal were elaborated as well. Additionally, this article discussed the challenges and prospects of using sonochemical approaches for PFAS remediation.     

Intensification of esterification of acids for synthesis of biodiesel using acoustic and hydrodynamic cavitation

Cavitation results in conditions of turbulence and liquid circulation in the reactor which can aid in eliminating mass transfer resistances. The present work illustrates the use of cavitation for intensification of biodiesel synthesis (esterification) reaction, which is mass transfer limited reaction considering the immiscible nature of the reactants, i.e., fatty acids and alcohol. Esterification of fatty acid (FA) odour cut (C(8)-C(10)) with methanol in the presence of concentrated H(2)SO(4) as a catalyst has been studied in hydrodynamic cavitation reactor as well as in the sonochemical reactor. The different reaction operating parameters such as molar ratio of acid to alcohol, catalyst quantity have been optimized under acoustic as well as hydrodynamic cavitating conditions in addition to the optimization of the geometry of the orifice plate in the case of hydrodynamic cavitation reactors. Few experiments have also been carried out with other acid (lower and higher)/methanol combination viz. caprylic acid and capric acids with methanol with an aim of investigating the efficacy of cavitation for giving the desired yields and also to quantify the degree of process intensification that can be achieved using the same. It has been observed that ambient operating conditions of temperature and pressure and reaction times of <3h, for all the different combinations of acid (lower and higher)/methanol studied in the present work, was sufficient for giving >90% conversion (mol%). This clearly establishes the efficacy of cavitation as an excellent way to achieve process intensification of the biodiesel synthesis process.     

Velocity study in an ultrasonic reactor

In order to determine the parameters required to describe and to optimize sonochemical reactors, we have investigated the water flow inside such a reactor. With this aim, the experimental velocity field has been measured by tomography laser. The influence of certain parameters such as the electric power, the water height and the fluid viscosity has been evaluated. At the same time, the water movement has been studied theoretically using Nyborg's model. We have tried to improve this model by considering a three-dimensional velocity.     

Degradation of imidacloprid using combined advanced oxidation processes based on hydrodynamic cavitation

The harmful effects of wastewaters containing pesticides or insecticides on human and aquatic life impart the need of effectively treating the wastewater streams containing these contaminants. In the present work, hydrodynamic cavitation reactors have been applied for the degradation of imidacloprid with process intensification studies based on different additives and combination with other similar processes. Effect of different operating parameters viz. concentration (20–60 ppm), pressure (1–8 bar), temperature (34 °C, 39 °C and 42 °C) and initial pH (2.5–8.3) has been investigated initially using orifice plate as cavitating device. It has been observed that 23.85% degradation of imidacloprid is obtained at optimized set of operating parameters. The efficacy of different process intensifying approaches based on the use of hydrogen peroxide (20–80 ppm), Fenton’s reagent (H₂O₂:FeSO₄ ratio as 1:1, 1:2, 2:1, 2:2, 4:1 and 4:2), advanced Fenton process (H₂O₂:Iron Powder ratio as 1:1, 2:1 and 4:1) and combination of Na₂S₂O₈ and FeSO₄ (FeSO₄:Na₂S₂O₈ ratio as 1:1, 1:2, 1:3 and 1:4) on the extent of degradation has been investigated. It was observed that near complete degradation of imidacloprid was achieved in all the cases at optimized values of process intensifying parameters. The time required for complete degradation of imidacloprid for approach based on hydrogen peroxide was 120 min where as for the Fenton and advance Fenton process, the required time was only 60 min. To check the effectiveness of hydrodynamic cavitation with different cavitating devices, few experiments were also performed with the help of slit venturi as a cavitating device at already optimized values of parameters. The present work has conclusively established that combined processes based on hydrodynamic cavitation can be effectively used for complete degradation of imidacloprid.