Degradation of magenta dye using cavitation-based transducers to glass marble: Lab to semi-pilot scale operations.

In the present work, the degradation of magenta dye has been investigated using ultrasonic (US) and ultraviolet (UV) irradiation at a laboratory scale. Additionally, the investigation was conducted at a semi-pilot scale by employing hydrodynamic cavitation and a novel air-marble cavitation reactor. Initially, optimization studies such as the effect of initial dye concentration and catalyst loading of TiO2 and MnO2 followed by the effect of combined catalyst loading (TiO2 /MnO2 ) on the extent of degradation have been studied at a capacity of 3 L. It was observed that the US irradiation results in 87.1% and 68.2% of degradation, whereas the UV irradiation results in 79.8% and 56.4% extent of degradation at 1 g/l of TiO2 and 0.8 g/l of MnO2 , respectively. The maximum degradation was 92.1% at the combined loading of 0.6 g/l (1:0.8; TiO2 :MnO2 ) using US irradiation with a capacity of 3 L and 81.3% using a hydrodynamic cavitation reactor with a semi-pilot scale capacity of 7 L. The chemical oxygen demand (COD) analysis also showed the highest COD removal of 92% at a small scale using the US irradiation and 76% at a semi-pilot scale using hydrodynamic cavitation. On a small scale, the cost of a US/TiO2 + MnO2 treatment scheme is US$ 0.01/L, whereas on a semi-pilot scale using HC/TiO2 + MnO2 , the cost is US$ 0.04/L. Both of these treatment schemes offer viable pathways for degradation based on energy and economic assessments. Overall, the current work has clearly demonstrated the effectiveness of the cavitational reactor for the efficient degradation of magenta dye from lab to semi-pilot scale operation. PRACTITIONER POINTS: Small-scale dye containing wastewater treatment using ultrasound and ultraviolet irradiation Combined use of catalysts at large-scale operations with novel cavitation techniques Novel cavitation techniques studied for dye degradation. Energy efficiency and cost analysis evaluated for AOPs studies.

Intensified synthesis of medium chain triglycerides using ultrasonic reactors at a capacity of 4L.

Lipids are considered as one of the most crucial nutrients for humans and among the various classes, medium chain triglycerides (MCTs) are considered as the most important functional foods and nutraceuticals. The present work deals with the intensification of synthesis of MCTs at a large capacity of 4L based on the use of ultrasonic bath and ultrasonic longitudinal horn. The effect of operating parameters like molar ratio of the reactants, type of catalyst and catalyst loading as well as the temperature on the extent of conversion has been investigated. The effect of molar ratio of lauric acid and glycerol was investigated over the range of 1:2 to 1:8 whereas the effect of loading of sulfuric acid was studied over the range of 4 ml/L-10 ml/L and zinc chloride loading over the range of 1 g/L-4 g/L. The effect of temperature was also studied using the conventional approach where it has been observed that 90 °C is an optimum temperature giving the extent of conversion as 72%. Also, the use of homogeneous catalyst as sulphuric acid was found to be more effective as compared to the solid catalyst as zinc chloride. It was observed that the maximum extent of conversion as 77.5% was obtained at 8 ml/L of sulfuric acid and molar ratio of 1:6 using ultrasonic longitudinal horn with US bath giving lower conversion as compared to US longitudinal horn but higher than the conventional approach under same operating conditions. The present work clearly established the intensification benefits in terms of reduction in time and higher conversion using cavitational reactors.

Improved crystallization of ammonium sulphate using ultrasound assisted approach with comparison with the conventional approach.

In chemical processing industries, crystallization is one of the most important operations to obtain solid products with desired purity and characteristics. With distinct processing problems for the conventional approaches for crystallization, research into alternate approaches such as ultrasound assisted crystallization has been on the forefront. The present work deals with comparison of the conventional approach and ultrasound assisted approach for crystallization of ammonium sulphate followed by detailed understanding into the effect of important operating parameters (initial concentration, pH, agitation speed, depth of horn, and cooling approach) on the metastable zone width and average crystal size. Ultrasound assisted crystallization has been investigated using both ultrasonic bath and ultrasonic horn to understand the effect of type of irradiation. It has been observed that the maximum reduction in the MSZW was obtained using ultrasonic horn under conditions of optimized initial concentration. The order of average crystal size obtained for ammonium sulphate was conventional cooling crystallization>ultrasonic bath>ultrasonic horn. The average crystal size obtained was in the range of 411-450µm for conventional approach of cooling crystallization, 350-400µm using ultrasonic bath and 200-250µm using ultrasonic horn. The analysis of crystal size distribution and surface characteristics using the SEM analysis was also performed under set of optimized parameters established using the particle size analysis. Overall the work has clearly established that the ultrasound assisted crystallization gave better results as compared to the conventional cooling crystallization in terms of reduced metastable zone width, better crystal characteristics and less agglomeration.

Intensification of esterification of non edible oil as sustainable feedstock using cavitational reactors.

Using sustainable feed stock such as non-edible oil for the biodiesel production can be one of the cost effective approaches considering the ever growing interest towards renewable energy and problems in existing approaches for production. However, due to the high free fatty acid content, non-edible oils require considerable preprocessing before the actual transesterification reaction for biodiesel production. The present work focuses on intensification of the esterification reaction used as preprocessing step based on acoustic and hydrodynamic cavitation also presenting the comparison with the conventional approach. Karanja oil with initial acid value as 14.15mg of KOH/g of oil has been used as a sustainable feedstock. Effect of operating parameters such as molar ratio, catalyst loading, temperature and type of catalyst (sulfuric acid and Amberlyst-15) on the acid value reduction has been investigated. The maximum reduction in the acid value (final acid value as 2.7mg of KOH/g of oil) was obtained using acoustic cavitation at optimum molar ratio of oil to methanol as 1:5 and 2% sulfuric acid loading at ambient temperature. In the case of hydrodynamic cavitation, acid value reduced upto 4.2mg of KOH under optimized conditions of first stage processing. In the second stage esterification using hydrodynamic cavitation and conventional approach, the final acid value was 3.6 and 3.8mg of KOH/g of oil respectively. Energy requirement analysis for ultrasound and conventional approaches clearly established the superiority of the ultrasound based approach. The present study clearly demonstrated that significant intensification benefits can be obtained in terms of the reduction in the molar ratio and operating temperature for the case of acoustic cavitation as compared to the conventional approach with somewhat lower effects for the hydrodynamic cavitation.

Degradation of magenta dye using different approaches based on ultrasonic and ultraviolet irradiations: Comparison of effectiveness and effect of additives for intensification.

The conventional chemical oxidation methods have not been very successful for the treatment of dyes due to higher stability against the oxidizing agents. The present work investigates the application of an improved treatment approach based on the ultrasonic and ultraviolet irradiations for treatment of dye containing wastewaters. Magenta dye, which is commonly used in textile industries, has been used as a model compound. Initially, the experiments have been performed using individual operation of ultrasonic and ultraviolet irradiations. Studies related to effect of concentration revealed that the extent of degradation increased with an increase in the concentration of dye solution till an optimum loading. Intensification of the extent of degradation using ultrasonic irradiation has been investigated using different additives such as NaCl, TiO2, air and starch. Also the efficacy of combined treatment approaches based on different approaches involving ultrasound, ultraviolet irradiation and additives for the removal of magenta dye from the aqueous solution have been evaluated. For the use of additives, maximum intensification was achieved for TiO2 followed by use of NaCl and least effect was observed for starch. For the combined treatment approaches, the maximum extent of degradation (98.8%) and maximum COD removal (94.0%) has been obtained for the combination of ultrasound with 1 g/L TiO2 and air. The present work has clearly demonstrated the efficacy of combined treatment approaches for removal of dyes from the wastewater.

Sonocatalytic and sonophotocatalytic degradation of Rhodamine 6G containing wastewaters.

The present work deals with degradation of aqueous solution of Rhodamine 6G (Rh 6G) using sonocatalytic and sonophotocatalytic treatment schemes based on the use of cupric oxide (CuO) and titanium dioxide (TiO2) as the solid catalysts. Experiments have been carried out at the operating capacity of 2 L and constant initial pH of 12.5. The effect of catalyst loading on the sonochemical degradation has been investigated by varying the loading over the range of 1.5-4.5 g/L. It has been observed that the maximum degradation of 52.2% was obtained at an optimum concentration of CuO as 1.5 g/L whereas for TiO2 maximum degradation was observed as 51.2% at a loading of 4 g/L over similar treatment period. Studies with presence of radical scavengers such as methanol (CH3OH) and n-butanol (C4H9OH) indicated lower extents of degradation confirming the dominance of radical mechanism. The combined approach of ultrasound, solid catalyst and scavengers has also been investigated at optimum loadings to simulate real conditions. The optimal solid loading was used for studies involving oxidation using UV irradiations where 26.4% and 28.9% of degradation was achieved at optimal loading of CuO and TiO2, respectively. Studies using combination of UV and US irradiations have also been carried out using the optimal concentration of the catalysts. It has been observed that maximum degradation of 63.3% is achieved using combined US and UV with TiO2 (4 g/L) as the photocatalyst. Overall it can be said that the combined processes give higher extent of degradation as compared to the individual processes based on US or UV irradiations.

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.

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.