Degradation of a cationic dye (Rhodamine 6G) using hydrodynamic cavitation coupled with other oxidative agents: Reaction mechanism and pathway

In the present study, decolorization and mineralization of a cationic dye, Rhodamine 6G (Rh6G), has been carried out using hydrodynamic cavitation (HC). Two cavitating devices such as slit and circular venturi were used to generate cavitation in HC reactor. The process parameters such as initial dye concentration, solution pH, operating inlet pressure, and cavitation number were investigated in detail to evaluate their effects on the decolorization efficiency of Rh6G. Decolorization of Rh6G was marginally higher in the case of slit venturi as compared to circular venturi. The kinetic study showed that decolorization and mineralization of the dye fitted first-order kinetics. The loadings of H₂O₂ and ozone have been optimized to intensify the decolorization and mineralization efficiency of Rh6G using HC. Nearly 54% decolorization of Rh6G was obtained using a combination of HC and H₂O₂ at a dye to H₂O₂ molar ratio of 1:30. The combination of HC with ozone resulted in 100% decolorization in almost 5–10 min of processing time depending upon the initial dye concentration. To quantify the extent of mineralization, total organic carbon (TOC) analysis was also performed using various processes and almost 84% TOC removal was obtained using HC coupled with 3 g/h of ozone. The degradation by-products formed during the complete degradation process were qualitatively identified by liquid chromatography-mass spectrometry (LC-MS) and a detailed degradation pathway has been proposed.     

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.     

Wastewater treatment: a novel energy efficient hydrodynamic cavitational technique

A novel method of treating a dye solution has been studied by hydrodynamic cavitation using multiple hole orifice plates. The present work deals with the effect of geometry of the multiple hole orifice plates on the degradation of a cationic dye rhodamine B (rhB) solution. The efficiency of this technique has been compared with the cavitation generated by ultrasound and it has been found that there is substantial enhancement in the extent of degradation of this dye solution using hydrodynamic cavitation. Large-scale operation coupled with better energy efficiency makes this technique a viable alternative for conventional cavitational reactors.     

Quantifying OH radical generation in hydrodynamic cavitation via coumarin dosimetry: Influence of operating parameters and cavitation devices

Hydrodynamic cavitation (HC) has been extensively investigated for effluent treatment applications. Performance of HC devices or processes is often reported in terms of degradation of organic pollutants rather than quantification of hydroxyl (OH) radicals. In this study, generation of OH radicals in vortex based cavitation device using coumarin dosimetry was quantified. Coumarin was used as the chemical probe with an initial concentration of 100 µM (15 ppm). Generation of OH radicals was quantified by analysing generated single hydroxylated products. The influence of operating parameters such as pH and type of acid used to adjust pH, dissolved oxygen, and inlet and outlet pressures was investigated. Acidic pH was found to be more conducive for generating OH radicals and therefore subsequent experiments were performed at pH of 3. Sulphuric acid was found to be more than three times effective than hydrochloric acid in generating OH radicals. Effect of initial levels of dissolved oxygen was found to influence OH radical generation. Performance of vortex based cavitation device was then compared with other commonly used cavitation devices based on orifice and venturi. The vortex based cavitation device was found to outperform the orifice and venturi based devices in terms of initial per-pass factor. Influence of device scale (nominal flow rate through the device) on performance was then evaluated. The results presented for these devices unambiguously quantifies their cavitational performance. The presented results will be useful for evaluating computational models and stimulate further development of predictive computational models in this challenging area.     

Degradation of benzene present in wastewater using hydrodynamic cavitation in combination with air

The degradation of benzene present in wastewater using hydrodynamic cavitation (HC) alone as well as in combination with air has been studied using nozzles as cavitating device of HC reactor. Initially, the energy efficiency of the HC reactor operated at different inlet pressures was determined using the calorimetric studies. Maximum energy efficiency of 53.4% was obtained at an inlet pressure of 3.9 bar. The treatment processes were compared under adiabatic as well as isothermal conditions and it was observed that under the adiabatic condition, the extent of degradation is higher as compared to isothermal condition. Studies related to the understanding the effect of inlet pressure (range of 1.8–3.9 bar) revealed that the maximum degradation as 98.9% was obtained at 2.4 bar pressure using the individual operation of HC under adiabatic conditions and in 70 min of treatment. The combination of HC with air was investigated at different air flow rates with best results for maximum degradation of benzene achieved at air flow rate of 60 mL/sec. A novel approach of using cavitation for a limited fraction of total treatment time was also demonstrated to be beneficial in terms of the extent of degradation as well as energy requirements and cost of operation. Based on the cavitational intensity, the resonant radius of aggregates of cavitation bubbles was also determined for distilled water as well as for aqueous solution of benzene. Overall, significant benefits of using HC combined with air have been demonstrated for degradation of benzene along with fundamental understanding into cavitation effects.     

Effect of process intensifying parameters on the hydrodynamic cavitation based degradation of commercial pesticide (methomyl) in the aqueous solution

Methomyl, a carbamate pesticide, is classified as a pesticide of category-1 toxicity and hence shows harmful effects on both human and aquatic life. In the present work, the degradation of methomyl has been studied by using hydrodynamic cavitation reactor (HC) and its combination with intensifying agents such as H₂O₂, fenton reagent and ozone (hybrid processes). Initially, the optimization of operating parameters such pH and inlet pressure to the cavitating device (circular venturi) has been carried out for maximizing the efficacy of hydrodynamic cavitation. Further degradation study of methomyl by the application of hybrid processes was carried out at an optimal pH of 2.5 and the optimal inlet pressure of 5 bar. Significant synergetic effect has been observed in case of all the hybrid processes studied. Synergetic coefficient of 5.8, 13.41 and 47.6 has been obtained by combining hydrodynamic cavitation with H₂O₂, fenton process and ozone respectively. Efficacy of individual and hybrid processes has also been obtained in terms of energy efficiency and extent of mineralization. HC + Ozone process has proved to be the most effective process having highest synergetic coefficient, energy efficiency and the extent of mineralization. The study has also encompassed the identification of intermediate by-products generated during the degradation and has proposed the probable degradation pathway. It has been conclusively established that hydrodynamic cavitation in the presence of intensifying agents can effectively be used for complete degradation of methomyl.     

Decolourization of Rhodamine B: A swirling jet-induced cavitation combined with NaOCl

A hydrodynamic cavitation reactor (Ecowirl) based on swirling jet-induced cavitation has been used in order to allow the degradation of a waste dye aqueous solution (Rhodamine B, RhB). Cavitation generated by Ecowirl reactor was directly compared with cavitation generated by using multiple hole orifice plates. The effects of operating conditions and parameters such as pressure, pH of dye solution, initial concentration of RhB and geometry of the cavitating devices on the degradation rate of RhB were discussed. In similar operative conditions, higher extents of degradation (ED) were obtained using Ecowirl reactor rather than orifice plate. An increase in the ED from 8.6% to 14.7% was observed moving from hole orifice plates to Ecowirl reactor. Intensification in ED of RhB by using hydrodynamic cavitation in presence of NaOCl as additive has been studied. It was found that the decolourization was most efficient for the combination of hydrodynamic cavitation and chemical oxidation as compared to chemical oxidation and hydrodynamic cavitation alone. The value of ED of 83.4% was reached in 37 min using Ecowirl combined with NaOCl (4.0 mg L⁻¹) as compared to the 100 min needed by only mixing NaOCl at the same concentration. At last, the energetic consumptions of the cavitation devices have been evaluated. Increasing the ED and reducing the treatment time, Ecowirl reactor resulted to be more energy efficient as compared to hole orifice plates, Venturi and other swirling jet-induced cavitation devices, as reported in literature.     

Degradation of diclofenac sodium using combined processes based on hydrodynamic cavitation and heterogeneous photocatalysis

Diclofenac sodium, a widely detected pharmaceutical drug in wastewater samples, has been selected as a model pollutant for degradation using novel combined approach of hydrodynamic cavitation and heterogeneous photocatalysis. A slit venturi has been used as cavitating device in the hydrodynamic cavitation reactor. The effect of various operating parameters such as inlet fluid pressure (2–4 bar) and initial pH of the solution (4–7.5) on the extent of degradation have been studied. The maximum extent of degradation of diclofenac sodium was obtained at inlet fluid pressure of 3 bar and initial pH as 4 using hydrodynamic cavitation alone. The loadings of TiO₂ and H₂O₂ have been optimised to maximise the extent of degradation of diclofenac sodium. Kinetic study revealed that the degradation of diclofenac sodium fitted first order kinetics over the selected range of operating protocols. It has been observed that combination of hydrodynamic cavitation with UV, UV/TiO₂ and UV/TiO₂/H₂O₂ results in enhanced extents of degradation as compared to the individual schemes. The maximum extent of degradation as 95% with 76% reduction in TOC has been observed using hydrodynamic cavitation in conjunction with UV/TiO₂/H₂O₂ under the optimised operating conditions. The diclofenac sodium degradation byproducts have been identified using LC/MS analysis.     

Optimization of biodiesel production in a hydrodynamic cavitation reactor using used frying oil

The present work demonstrates the application of a hydrodynamic cavitation reactor for the synthesis of biodiesel with used frying oil as a feedstock. The synthesis involved the transesterification of used frying oil (UFO) with methanol in the presence of potassium hydroxide as a catalyst. The effect of geometry and upstream pressure of a cavitating orifice plate on the rate of transesterification reaction has been studied. It is observed that the micro level turbulence created by hydrodynamic cavitation somewhat overcomes the mass transfer limitations for triphasic transesterification reaction. The significant effects of upstream pressure on the rate of formation of methyl esters have been seen. It has been observed that flow geometry of orifice plate plays a crucial role in process intensification. With an optimized plate geometry of 2 mm hole diameter and 25 holes, more than 95% of triglycerides have been converted to methyl esters in 10 min of reaction time with cavitational yield of 1.28 × 10^?3 (Grams of methyl esters produced per Joule of energy supplied). The potential of UFO to produce good quality methyl esters has been demonstrated.     

Dynamics of cavitational bubbles and design of a hydrodynamic cavitational reactor: cluster approach

In the present work, a cavity cluster of predetermined size has been considered to study the bubble dynamics in the hydrodynamic cavitation reactor. The effect of different operating and system parameters on the cavitational intensity has been numerically investigated. The yield of any cavitationally induced physical/chemical transformations depends not only on the collapse pressure of the cavities but also on the active volume of cavitation within the reactor. Empirical correlations have been developed to predict the collapse pressure and the active volume of cavitation as a function of different operating parameters based on the bubble dynamics studies. Recommendations are made for designing a cavitational reactor on the basis of the proposed empirical correlations. This work is a first step towards the designing and optimization of hydrodynamic cavitational reactor with cluster approach.     

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.     

Degradation of 2,4-dinitrophenol using a combination of hydrodynamic cavitation,chemical and advanced oxidation processes

In the present work, degradation of 2,4-dinitrophenol (DNP), a persistent organic contaminant with high toxicity and very low biodegradability has been investigated using combination of hydrodynamic cavitation (HC) and chemical/advanced oxidation. The cavitating conditions have been generated using orifice plate as a cavitating device. Initially, the optimization of basic operating parameters have been done by performing experiments over varying inlet pressure (over the range of 3–6 bar), temperature (30 °C, 35 °C and 40 °C) and solution pH (over the range of 3–11). Subsequently, combined treatment strategies have been investigated for process intensification of the degradation process. The effect of HC combined with chemical oxidation processes such as hydrogen peroxide (HC/H₂O₂), ferrous activated persulfate (HC/Na₂S₂O₈/FeSO₄) and HC coupled with advanced oxidation processes such as conventional Fenton (HC/FeSO₄/H₂O₂), advanced Fenton (HC/Fe/H₂O₂) and Fenton-like process (HC/CuO/H₂O₂) on the extent of degradation of DNP have also been investigated at optimized conditions of pH 4, temperature of 35 °C and inlet pressure of 4 bar. Kinetic study revealed that degradation of DNP fitted first order kinetics for all the approaches under investigation. Complete degradation with maximum rate of DNP degradation has been observed for the combined HC/Fenton process. The energy consumption analysis for hydrodynamic cavitation based process has been done on the basis of cavitational yield. Degradation intermediates have also been identified and quantified in the current work. The synergistic index calculated for all the combined processes indicates HC/Fenton process is more feasible than the combination of HC with other Fenton like processes.     

Ultrasonic bath with longitudinal vibrations: a novel configuration for efficient wastewater treatment

Efficacy of a novel configuration for large-scale wastewater treatment applications has been investigated using formic acid degradation as a model reaction. The reactor is first characterized using energy efficiency measurements and the optimum operating volume for maximum transfer of supplied energy and hence maximum cavitational effects has been established. Effect of initial concentration of the pollutant on the rates of degradation has been investigated. Comparison has been also made with the conventional ultrasonic horn in terms of energy efficiency and cavitational yield for the model reaction. With an aim of possible reduction in the total treatment time, some intensification studies have been undertaken considering hydrogen peroxide as an additional source of free radicals.     

不同超声作用方式对葛根有效部位提取率的影响

研究不同的超声作用方式对葛根总黄酮的提取率的影响.采用单频,双频（包括槽式双频以及槽式＋探头式双频）,及三频等不同的处理方法,对超声作用参数,如时间,声强及处理量的多少进行研究,采用两个超声特性参数即能量效率和空化产量来对比不同容积、频率的超声作用效果.目前的研究表明：多频超声耦合时,可以获得较高的能量效率和空化产量.     

Scale-up of vortex based hydrodynamic cavitation devices: A case of degradation of di-chloro aniline in water

Hydrodynamic cavitation (HC) is being increasingly used in a wide range of applications. Unlike ultrasonic cavitation, HC is scalable and has been used at large scale industrial applications. However, no information about influence of scale on performance of HC is available in the open literature. In this work, we present for the first time, experimental data on use of HC for degradation of complex organic pollutants in water on four different scales (~200 times scale-up in terms of capacity). Vortex based HC devices offer various advantages like early inception, high cavitational yield and significantly lower propensity to clogging and erosion. We have used vortex based HC devices in this work. 2,4 dichloroaniline (DCA) – an aromatic compound with multiple functional groups was considered as a model pollutant. Degradation of DCA in water was performed using vortex-based HC devices with characteristic throat dimension, d_t as 3, 6, 12 and 38 mm with scale-up of almost 200 time based on the flow rates (1.3 to 247 LPM). Considering the experimental constraints on operating the largest scale HC device, the experimental data is presented here at only one value of pressure drop across HC device (280 kPa). A previously used per-pass degradation model was extended to describe the experimental data for the pollutant used in this study and a generalised form is presented. The degradation performance was found to decrease with increase in the scale and then plateaus. Appropriate correlation was developed based on the experimental data. The developed approach and presented results provide a sound basis and a data set for further development of comprehensive multi-scale modelling of HC devices.     

Degradation of orange-G by advanced oxidation processes

The degradation and mineralization of orange-G (OG) in aqueous solutions by means of ultrasound irradiation at a frequency of 213 kHz and its combination with a heterogeneous photocatalyst (TiO₂) were investigated. The effects of various operational parameters such as, the concentration of the dye and solution pH on the degradation efficiency were studied. The degradation of the dye followed first-order like kinetics under the conditions examined. The sonolytic degradation of OG was relatively higher at pH 5.8 than that at pH 12. However, an alkaline pH was favoured for the photocatalytic degradation of OG using TiO₂. Total organic carbon (TOC) measurements were also carried out in order to evaluate the mineralization efficiency of OG using sonolysis, photocatalysis and sonophotocatalysis. The hybrid technique of sonophotocatalytic degradation was compared with the individual techniques of photocatalysis and sonolysis. A simple additive effect was observed during the sonophotocatalytic oxidation of OG using TiO₂ indicating that the combined treatment offers no synergistic enhancement. TOC results also support the additive effect in the dual treatment process.     

Limitations of the Weissler reaction as a model reaction for measuring the efficiency of hydrodynamic cavitation

The Weissler reaction in which iodide is oxidised to a tri-iodide complex (I(3)(-)) has been widely used for measurement of the intensity of ultrasonic and hydrodynamic cavitation. It was used in this work to compare ultrasonic cavitation at 24kHz with hydrodynamic cavitation using two different devices, one a venturi and the other a sudden expansion, operated up to 8.7bar. Hydrodynamic cavitation had a maximum efficiency of about 5x10(-11) moles of I(3)(-) per joule of energy compared with the maximum of almost 8x10(-11)molJ(-1) for ultrasonic cavitation. Hydrodynamic cavitation was found to be most effective at 10 degrees C compared with 20 degrees C and 30 degrees C and at higher upstream pressures. However, it was found that in hydrodynamic conditions, even without cavitation, I(3)(-) was consumed at a rapid rate leading to an equilibrium concentration. It was concluded that the Weissler reaction was not a good model reaction for the assessment of the effectiveness of hydrodynamic cavitation.     

Effect of molecular weight on the ultrasonic degradation of poly(vinyl-pyrrolidone)

The ultrasonic degradation of poly(vinyl-pyrrolidone) (PVP) of different initial molecular weights was studied at a fixed temperature. The effect of solution concentration on the rate of degradation was investigated. A method of viscometry was used to study the degradation behavior and kinetic model was developed to estimate the degradation rate constant. The results were indicated that the rate of ultrasonic degradation increased with increasing molecular weight. It was found that rate constant decreases as the concentration increases. The calculated rate constants correlated in terms of inverse concentration and relative viscosity of PVP solutions. This behavior in the rate of degradation was interpreted in terms of viscosity and concentration of polymer solution. With increasing solution concentration, viscosity increases and it causes a reduction in the cavitation efficiency thus, the rate of degradation will be decreased. The experimental results show that the viscosity of polymers decreased with ultrasonic irradiation time and approached a limiting value, below which no further degradation took place. This study confirms the general assumption that the shear forces generated by the rapid motion of the solvent following cavitational collapse are responsible for the breakage of the chemical bonds within the polymer. The effect of polymer concentration can be interpreted in terms of the increase in viscosity with concentration, causing the molecules to become less mobile in solution and the velocity gradients around the collapsing bubbles to, therefore, become smaller.     

Performance evaluation of a novel pilot-scale pinned disc rotating generator of hydrodynamic cavitation

This study investigates hydrodynamic performance of a novel pinned disc rotating generator of hydrodynamic cavitation in comparison with a serrated disc variant on a pilot-scale. Experimental results show that at a given rotational speed and liquid flow rate, the pinned disc generates more intense cavitation (i.e. lower cavitation number, higher volume fraction of vapor and higher amplitude of pressure fluctuations) than the serrated disc, while also consuming less energy per liquid pass (i.e., higher flow rate and pumping pressure difference of water at similar power consumption). Additionally, mechanical and chemical wastewater treatment performance of the novel cavitator was evaluated on an 800 L influent sample from a wastewater treatment plant. Mechanical effects resulted in a reduction of average particle size from 148 to 38 µm and increase of specific surface area, while the oxidation potential was confirmed by reduction of COD, TOC, and BOD up to 27, 23 and 30% in 60 cavitation passes, respectively. At optimal operating conditions and 30 cavitation passes, pinned disc cavitator had a 310% higher COD removal capacity while consuming 65% less energy per kg of COD removed than the serrated disc cavitator. Furthermore, the specific COD-reduction energy consumption of the pinned disc cavitator on the pilot scale is comparable to the best cases of lab-scale orifice and venturi devices operating at much lower wastewater processing capacity.