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.     

Biodiesel production process intensification using a rotor-stator type generator of hydrodynamic cavitation

Triglyceride transesterification for biodiesel production is a model reaction which is used to compare the conversion efficiency, yield, reaction time, energy consumption, scalability and cost estimation of different reactor technology and energy source. This work describes an efficient, fast and cost-effective procedure for biodiesel preparation using a rotating generator of hydrodynamic cavitation (HC). The base-catalyzed transesterification (methanol/sodium hydroxide) has been carried out using refined and bleached palm oil and waste vegetable cooking oil. The novel HC unit is a continuous rotor-stator type reactor in which reagents are directly fed into the controlled cavitation chamber. The high-speed rotation of the reactor creates micron-sized droplets of the immiscible reacting mixture leading to outstanding mass and heat transfer and enhancing the kinetics of the transesterification reaction which completes much more quickly than traditional methods. All the biodiesel samples obtained respect the ASTM standard and present fatty acid methyl ester contents of >99% m/m in both feedstocks. The electrical energy consumption of the HC reactor is 0.030 kW h per L of produced crude biodiesel, making this innovative technology really quite competitive. The reactor can be easily scaled-up, from producing a few hundred to thousands of liters of biodiesel per hour while avoiding the risk of orifices clogging with oil impurities, which may occur in conventional HC reactors. Furthermore it requires minimal installation space due to its compact design, which enhances overall security.     

Novel utilization of waste marine sponge (Demospongiae) as a catalyst in ultrasound-assisted transesterification of waste cooking oil

This study demonstrates the potential of Na-silica waste sponge as a source of low cost catalyst in the transesterification of waste cooking oil aided by ultrasound. In this work an environmentally friendly and efficient transesterification process using Na-loaded SiO₂ from waste sponge skeletons as a solid catalyst is presented. The results showed that the methyl esters content of 98.4 ± 0.4 wt.% was obtainable in less than an hour (h) of reaction time at 55 °C. Optimization of reaction parameters revealed that MeOH:oil, 9:1; catalyst, 3 wt.% and reaction duration of 30 min as optimum reaction conditions. The catalyst is able to tolerant free fatty acid and moisture content up to 6% and 8%, respectively. In addition, the catalyst can be reused for seven cycles while maintaining the methyl esters content at 86.3%. Ultrasound undoubtedly assisted in achieving this remarkable result in less than 1 h reaction time. For the kinetics study at 50–60 °C, a pseudo first order model was proposed, and the activation energy of the reaction is determined as 33.45 kJ/mol using Arrhenius equation.     

Development of a novel electric field-assisted modified hydrodynamic cavitation system for disintegration of waste activated sludge

In this current study, we present a modified hydrodynamic cavitation device that combines an electric field to substitute for the chemical addition. A modified HC system is basically an orifice plate and crisscross pipe assembly, in which the crisscross pipe imparts some turbulence, which creates collision events. This study shows that for maximizing disintegration, combining HC system, which called electric field-assisted modified orifice plate hydrodynamic cavitation (EFM-HC) in this study, with an electric field is important. Various HC systems were compared in terms of disintegration of WAS, and, among them, the EFM-HC system exhibited the best performance with the highest disintegration efficiency of 47.0 ± 2.0% as well as the destruction of WAS morphological characteristics. The experimental results clearly show that a conventional HC system was successfully modified. In addition, electric field has a great potential for efficient disintegration of WAS for as a additional option in a combination treatment. This study suggests continued research in this field may lead to an appropriate design for commercial use.     

Extraction of tungsten from scheelite using hydrodynamic and acoustic cavitation

The primary purpose of this study is to investigate the effects of hydrodynamic and acoustic cavitation (HAC) on the leaching efficiency of tungsten. The aim is to reduce energy use and to improve the recovery rate. The goal is also to carry out a leaching process at a much lower temperature than in an autoclave process that is currently used in the industry. Energy-efficient initiation and collapse of cavitation bubbles require optimization of (i) vibro-acoustic response of the reactor structure, (ii) multiple excitation frequencies adapted to the optimized reactor geometry, and (iii) hydrodynamic cavitation with respect to orifice geometry and flow conditions. The objective is to modify and apply a previously in house developed high power cavitation reactor in order to recover tungsten by leaching of the dissolution of scheelite in sodium hydroxide. In this process, various experimental conditions like dual-frequency excitation, different orifice geometry have been investigated. The numerically optimized reactor concept was excited by two frequencies 23 kHz and 39–43 kHz in various flow conditions. The effects of leaching time, leaching temperature, ultrasonic power and geometry of orifice plates have been studied. The leaching temperature was varied from 40 °C to 80 °C. The concentration of leaching reagent sodium hydroxide (NaOH) was 10 mol/L.The results were compared to conventional chemical leaching. Energy supplement with acoustic cavitation of 130 kWh/kg concentrate resulted in a leaching recovery of tungsten (WO₃) of 71.5%, compared to 36.7% obtained in absence of ultrasound. The results confirm that the method developed is energy efficient and gives a recovery rate potentially better than current autoclave technology.     

Ultrasonic biodiesel synthesis from crude Jatropha curcas oil with heterogeneous base catalyst: Mechanistic insight and statistical optimization

This paper reports studies in ultrasound-assisted heterogeneous solid catalyzed (CaO) synthesis of biodiesel from crude Jatropha curcas oil. The synthesis has been carried out in two stages, viz. esterification and trans-esterification. The esterification process is not influenced by ultrasound. The transesterification process, however, shows marked enhancement with ultrasound. A statistical experimental design has been used to optimize the process conditions for the synthesis. XRD analysis confirms formation of Ca(OMe)₂, which is the active catalyst for transesterification reaction. The optimum values of parameters for the highest yield of transesterification have been determined as follows: alcohol to oil molar ratio ≈ 11, catalyst concentration ≈ 5.5 wt.%, and temperature ≈ 64 °C. The activation energy of the reaction is calculated as 133.5 kJ/mol. The heterogeneity of the system increases mass transfer constraints resulting in approx. 4× increase in activation energy as compared to homogeneous alkali catalyzed system. It is also revealed that intense micro-convection induced by ultrasound enhances the mass transfer characteristics of the system with ∼20% reduction in activation energy, as compared to mechanically agitated systems. Influence of catalyst concentration and alcohol to oil molar ratio on the transesterification yield is inter-linked through formation of methoxy ions and their diffusion to the oil–alcohol interface, which in turn is determined by the volume fractions of the two phases in the reaction mixture. As a result, the highest transesterification yield is obtained at the moderate values of catalyst concentration and alcohol to oil molar ratio.     

Biodiesel production from palm oil using combined mechanical stirred and ultrasonic reactor

This paper investigates the production of biodiesel from palm oil using a combined mechanical stirred and ultrasonic reactor (MS–US). The incorporation of mechanical stirring into the ultrasonic reactor explored the further improvement the transesterification of palm oil. Initial reaction rate values were 54.1, 142.9 and 164.2 mmol/L min for the mechanical-stirred (MS), ultrasonic (US) and MS–US reactors, respectively. Suitable methanol to oil molar ratio and the catalyst loading values were found to be 6 and 1 of oil, respectively. The effect of ultrasonic operating parameters; i.e. frequency, location, and number of transducer, has been investigated. Based on the conversion yield at the reactor outlet after 1 h, the number of transducers showed a relevant role in the reaction rate. Frequency and transducer location would appear to have no significant effect. The properties of the obtained biodiesel (density, viscosity, pour point, and flash point) satisfy the ASTM standard. The combined MS–US reactors improved the reaction rate affording the methyl esters in higher yield.     

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.     

Transesterification of soybean oil by using the synergistic microwave-ultrasonic irradiation

Microwave and ultrasound have been demonstrated to be outstanding process intensification techniques for transesterification of oil. According to their mechanisms, simultaneous effects can surely bring about better enhancement than sole microwave or ultrasound. Therefore, this study aimed to investigate the important factors and their suitable levels in the KOH-catalyzed transesterification of soybean oil with methanol by using synergistic assistance of microwave-ultrasound (CAMU). The feasibility of application of CAMU in transesterification of oil was demonstrated. When the dosage of methanol, soybean oil and KOH were 15.4 g, 34.7 g (with methanol-to-oil molar ratio of 12:1) and 1 g, respectively, and the microwave power, ultrasonic power, ultrasonic mode, reaction temperature and reaction time were 700 W, 800 W, 1:0, 65 °C and 6 min, respectively, the transesterification reached 98.0% of yield, being the highest yield among all the results obtained; while by using 600 W of microwave plus stirring instead of CAMU, only 57.4% of yield could be obtained. Compared with other reaction techniques, the transesterification by applying novel CAMU was found to have remarkable advantages. Furthermore, by monitoring the variation of real-time temperature and microwave power during transesterification reactions with different microwave operation time and by taking comparison of the corresponding yield, it was demonstrated that the main reason for the acceleration of microwave-assisted transesterification was the polarization and further activation of reactants caused by microwave irradiation, but not the factor of fast heating.     

Improved synthesis of sucrose fatty acid monoesters under ultrasonic irradiation

Sucrose fatty acid esters were synthesized by the transesterification of sucrose with aliphatic esters under ultrasound irradiation in good yield (?73%). The optimum reaction conditions for the transesterification reaction include a molar ratio of sucrose to fatty acid ethyl ester of 2:1 and the use of a 13% mol anhydrous K₂CO₃ catalyst. The optimum reaction temperature was set at 70 °C, the optimum reaction time was 2 h, and the optimum reaction pressure was 11 kPa. The reaction had excellent monoester selectivity. The proportion of monoester (6-monoester + 6′-monoester) in the purified products was up to 92–95% via flash column chromatography over silica gel, the ratios of 6-monoester/6′-monoester are 2.1–2.7, and the sucrose monoesters were identified by HPLC–MS, NMR and IR.     

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.     

Mechanistic insight into sonochemical biodiesel synthesis using heterogeneous base catalyst

The beneficial effect of ultrasound on transesterification reaction is well known. Heterogeneous (or solid) catalysts for biodiesel synthesis have merit that they do not contaminate the byproduct of glycerol. In this paper, we have attempted to identify the mechanistic features of ultrasound–enhanced biodiesel synthesis with the base–catalyst of CaO. A statistical design of experiments (Box–Behnken) was used to identify the influence of temperature, alcohol to oil molar ratio and catalyst loading on transesterification yield. The optimum values of these parameters for the highest yield were identified through Response Surface Method (with a quadratic model) and ANOVA. These values are: temperature = 62 °C, molar ratio = 10:1 and catalyst loading = 6 wt.%. The activation energy was determined as 82.3 kJ/mol, which is higher than that for homogeneous catalyzed system (for both acidic and basic catalyst). The experimental results have been analyzed vis–à–vis simulations of cavitation bubble dynamics. Due to 3–phase heterogeneity of the system, the yield was dominated by intrinsic kinetics, and the optimum temperature for the highest yield was close to boiling point of methanol. At this temperature, the influence of cavitation bubbles (in terms of both sonochemical and sonophysical effect) is negligible, and ultrasonic micro–streaming provided necessary convection in the system. The influence of all parameters on the reaction system was found to be strongly inter–dependent.     

Ultrasound assisted enzymatic conversion of non edible oil to methyl esters

Conventional and ultrasound-assisted hydrolysis and subsequent esterification of Nagchampa oil under mild operating conditions have been investigated with an objective of intensification of methyl esters production using a sustainable approach. The effect of ratio of reactants, temperature, enzyme loading, pretreatment of enzyme (using ultrasonic irradiations) on the hydrolysis and esterification reaction has been studied. Optimum conditions for hydrolysis were observed to be 1:1 weight ratio of oil: water for Lip Z and 1:3 for Lip 2 enzymes, enzyme loading of 400 units for Lip Z and 800 mg for Lip 2 enzymes and reaction time of 6 h. In the case of esterification reaction, optimum conditions obtained were oil to methanol molar ratio of 1:2, enzyme loading of 1000 mg and reaction time of 20 h. Use of pretreated enzyme (using ultrasonic irradiations) was found to increase the extent of esterification reaction from 75% to 92.5%. It was observed that use of ultrasound in the reaction significantly intensified the esterification reaction with time requirement reducing from 20 h for conventional stirring based approach to only about 7.5 h in the presence of ultrasound. The extent of esterification obtained with sonicated enzyme also increased to 96% from 75% with unsonicated enzyme.     

Ultrasound assisted two-stage biodiesel synthesis from non-edible Schleichera triguga oil using heterogeneous catalyst: Kinetics and thermodynamic analysis

Present work deals with the ultrasound-assisted biodiesel production from low cost, substantial acid value kusum (Schleichera triguga) oil using a two-step method of esterification in presence of acid (H₂SO₄) catalyst followed by transesterification using a basic heterogeneous barium hydroxide (Ba(OH)₂) catalyst. The initial acid value of kusum oil was reduced from 21.65 to 0.84 mg of KOH/g of oil, by acid catalyzed esterification with 4:1 methanol to oil molar ratio, catalyst concentration 1% (v/v), ultrasonic irradiation time 20 min at 40 °C. Then, Ba(OH)₂ concentration of 3% (w/w), methanol to oil molar ratio of 9:1, ultrasonic irradiation time of 80 min, and temperature of 50 °C was found to be the optimum conditions for transesterification step and triglyceride conversion of 96.8% (wt) was achieved. This paper also examined the kinetics as well as the evaluation of thermodynamic parameters for both esterification and transesterification reactions. The lower value of activation energy and higher values of kinetic constants indicated a fast rate of reaction, which could be attributed to the physical effect of emulsification, in which the microturbulence generated due to radial motion of bubbles, creates an intimate mixing of the immiscible reactants causing the increase in the interfacial area, giving faster reaction kinetics. The positive values of Gibbs-free energy (ΔG), enthalpy (ΔH) and negative value of entropy (ΔS) revealed that both the esterification and transesterification were non-spontaneous, endothermic and endergonic reactions. Therefore, the present work has not only established the escalation obtained due to ultrasonication but also exemplified the two-step approach for synthesis of biodiesel from non-edible kusum oil based on the use of heterogeneous catalyst for the transesterification step.     

Cavitation milling of natural cellulose to nanofibrils

Cavitation holds the promise of a new and exciting approach to fabricate both top down and bottom up nanostructures. Cavitation bubbles are created when a liquid boils under less than atmospheric pressure. The collapse process occurs supersonically and generates a host of physical and chemical effects. We have made an attempt to fabricate natural cellulose material using hydrodynamic as well as acoustic cavitation. The cellulose material having initial size of 63 micron was used for the experiments. 1% (w/v) slurry of cellulose sample was circulated through the hydrodynamic cavitation device or devices (orifice) for 6 h. The average velocity of the fluid through the device was 10.81 m/s while average pressure applied was 7.8 kg/cm². Cavitation number was found to be 2.61. The average particle size obtained after treatment was 1.36 micron. This hydrodynamically processed sample was sonicated for 1 h 50 min. The average size of ultrasonically processed particles was found to be 301 nm. Further, the cellulose particles were characterized with X-ray diffraction (XRD) and differential scanning calorimetry (DSC) to see the effect of cavitation on crystallinity (X_c) as well as on melting temperature (T_m). Cellulose structures consist of amorphous as well as crystalline regions. The initial raw sample was 86.56% crystalline but due to the effect of cavitation, the crystallinity reduced to 37.76%. Also the melting temperature (T_m) was found to be reduced from 101.78 °C of the original to 60.13 °C of the processed sample. SEM images for the cellulose (processed and unprocessed) shows the status and fiber–fiber alignment and its orientation with each other. Finally cavitation has proved to be very efficient tool for reduction in size from millimeter to nano scale for highly crystalline materials.     

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.     

Ultrasound assisted enzyme catalyzed transesterification of waste cooking oil with dimethyl carbonate

This work reports the production of biodiesel with waste cooking oil and dimethyl carbonate in solvent free system through transesterification by immobilized enzyme (Novozym 435) under the influence of ultrasound irradiation. The experiments were conducted in an ultrasonic water bath under three different conditions i.e. ultrasonic irradiation (UI) without stirring, UI coupled with stirring and only stirring to compare their overall effects on fatty acid methyl esters (FAME) conversion. As compared with the conventional stirring method, where FAME conversion was 38.69% at 4 h, the UI without stirring significantly enhanced the conversion of enzymatic transesterification to 57.68% for the same reaction time. However the reaction rate was further increased under the condition of ultrasonication coupled with stirring and resulted into higher conversion of 86.61% for the same reaction time. Effects of reaction parameters, such as temperature, ratio of DMC/oil, speed of agitation and enzyme loading on the conversion were investigated. Furthermore, repeated use of Novozym 435 showed gradual decline in both conversion as well as enzyme activity.     

Intensification of biogas production using pretreatment based on hydrodynamic cavitation

The present work investigates the application of hydrodynamic cavitation (HC) for the pretreatment of wheat straw with an objective of enhancing the biogas production. The hydrodynamic cavitation reactor is based on a stator and rotor assembly. The effect of three different speeds of rotor (2300, 2500, 2700 rpm), wheat straw to water ratios (0.5%, 1% and 1.5% wt/wt) and also treatment times as 2, 4 and 6 min have been investigated in the work using the design of experiments (DOE) approach. It was observed that the methane yield of 31.8 ml was obtained with untreated wheat straw whereas 77.9 ml was obtained with HC pre-treated wheat straw confirming the favourable changes during the pre-treatment. The combined pre-treatment using KOH and HC gave maximum yield of biogas as 172.3 ml. Overall, it has been established that significant enhancement in the biogas production can be obtained due to the pretreatment using HC which can also be further intensified by combination with chemical treatment.     

Time reducing process for biofuel production from non edible oil assisted by ultrasonication

Limited resources of conventional fuels such as petrodiesel have led to the search for alternative fuels. Various convention batch/continuous processes for the biodiesel production have been developed before the recent year. All processes are time consuming with high labor cost. Thus, we need a new process for biodiesel production which reduces the reaction time and production cost as well as save the energy. In this work, ultrasonic assisted transesterification of Jatropha curcas oil is carried out in the presence of methanol and potassium hydroxide (KOH) as catalyst, keeping the molar ratio of oil to alcohol 1:5, catalyst concentration 0.75 wt% of oil, ultrasonic amplitude 50% and pulse 0.3 cycle, 7 min reaction time under atmospheric condition. Ultrasonic mixing has increased the rate of transesterification reaction as compare to the mechanical mixing.     

Performance and energetic analysis of hydrodynamic cavitation and potential integration with existing advanced oxidation processes: A case study for real life greywater treatment

The current work is a “first of a kind” report on the feasibility and efficacy of hydrodynamic cavitation integrated Advanced Oxidation Processes (AOP’s) towards treatment of a real life greywater stream in form of kitchen wastewater. The work has been carried out in a sequential manner starting with geometry optimization of orifice plate (cavitating device) followed by studying the effects of inlet pressure, pH, effluent dilution ratio on degradation of TOC and COD. Under optimized conditions of pH 3, 4 bar pressure, TOC and COD reduction of 18.23 and 25% were obtained using HC for a period of 120 min. To improve the performance of HC, further studies were carried out by integrating H₂O₂ and O₃ with HC. Using 5 g/h optimum dosage of H₂O₂, 87.5% reduction in COD was obtained beyond which it started decreasing. Moreover, integrating O₃ (57.5% reduction in COD) increased the treatment cost. However, a hybrid process (HC + H₂O₂ + O₃) yielded 76.26 and 98.25% reductions in TOC and COD within 60 min. The energetics of all the processes and the treatment costs were studied in detail and it was concluded that combined process of HC + H₂O₂ + O₃ surpassed by far the performances of HC + H₂O₂ and HC + O₃.