Treatment of complex sulfur-containing solutions in ammonia desulfurization ammonium sulfate production by ultrasonic-assisted ozone technology

In this work, the cause of abnormal color in ammonium sulfate products formed by flue gas desulfurization is revealed by investigating the conversion relationship between different sulfur-containing ions and their behavior in a sulfuric acid medium. Both thiosulfate (S₂O₃²⁻) and sulfite (SO₃²⁻ ＆ HSO₃⁻) impurities affect the quality of ammonium sulfate. The S₂O₃²⁻ is the main reason for the yellowing of the product due to the formation of sulfur impurities in concentrated sulfuric acid. To address the yellowing of ammonium sulfate products, a unified technology (US/O₃), using ozone (O₃) and ultrasonic waves (US) simultaneously, is exploited to remove both thiosulfate and sulfite impurities from the mother liquor. The effect of different reaction parameters on the degree of removal of thiosulfate and sulfite is investigated. The synergistic effect of ultrasound and ozone on ion oxidation is further explored and demonstrated by the comparative experiments with O₃ and US/O₃. Under the optimized conditions, the thiosulfate and sulfite concentration in the solution is 2.07 and 5.93 g/L, respectively, and the degree of removal is 91.39 and 90.83%, respectively. The product obtained after evaporation and crystallization is pure white and meets the national standard requirements for ammonium sulfate products. Under the same conditions, the US/O₃ process has apparent advantages, such as saving reaction time compared with the O₃ process alone. Introducing an ultrasonically intensified field improves the generation of oxidation radicals ·OH, ¹O₂, and ·O₂^– in the solution. Furthermore, the effectiveness of different oxidation components in the decolorization process is studied by adding other radical shielding agents using the US/O₃ process supplemented with EPR analysis. The order of the different oxidation components is O₃(86.04%) > ¹O₂(6.53%) > •OH(4.45%) > •O₂^–(2.97%) for the oxidation of thiosulfate, and it is O₃(86.28%) > •OH(7.49%) > ¹O₂(4.99%) > •O₂^–(1.25%) for the oxidation of sulfite.     

Effective removal of organics from Bayer liquor through combined sonolysis and ozonation: Kinetics and mechanism

The presence of organic compounds in the waste liquor is of serious environmental concern that has plagued the development of alumina industry (Bayer Process). The present work attempts to develop a green and efficient process for removal of organics utilizing combined effect of sonolysis and ozonation (US/O₃). The effects of reaction duration, ozone concentration and ultrasonic power are assessed for sonolysis (US), ozonation (O₃) and combination of sonolysis and ozonation (US/O₃). The optimal conditions for US/O₃ treatment system is identified to be a reaction duration of 7 h, ozone concentration of 7.65 g/h, and ultrasonic power of 600 W. The total organic carbon (TOC) removal and decolorization are 60.13% and 87.1%, respectively. The process can be scaled-up to industrial scale, which could potentially serve to be a convenient, safe and sustainable alternative to the exisiting treatment technologies. Additionally, the treated waste water can be reused contributing to an improvement in the overall economics.     

Mechanism and dynamic study of reactive red X-3B dye degradation by ultrasonic-assisted ozone oxidation process

The effectiveness of ozone combined with ultrasound techniques in degrading reactive red X-3B is evaluated. A comparison among ozone (O₃), ultrasonic (US), ozone/ultrasonic (O₃/US) for degradation of reactive red X-3B has been performed. Results show that O₃/US system was the most effective and the optimally synergetic factor reaches to 1.42 in O₃/US system. The cavitation of ultrasound plays an important role during the degradation process. It is found that 99.2% of dye is degraded within 6 min of reaction at the initial concentration of 100 mg·L⁻¹, pH of 6.52, ozone flux of 40 L·h⁻¹ and ultrasonic intensity of 200 W·L⁻¹. Ozonation reactions in conjunction with sonolysis indicate that the decomposition followed pseudo-first-order reaction kinetics but the degradation efficiencies are affected by operating conditions, particularly initial pH and ultrasonic intensity. A kinetic model is established based on the reaction corresponding to operational parameters. In addition, the main reaction intermediates, such as p-benzoquinone, catechol, hydroquinone, phthalic anhydride and phthalic acid, are separated and identified using GC/MS and a possible degradation pathway is proposed during the O₃/US process.     

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.     

Enhanced mechanism of catalytic ozonation by ultrasound with orthogonal dual frequencies for the degradation of nitrobenzene in aqueous solution

The experiments have been performed with a semi-continuous batch reactor to investigate the degradation efficiency of nitrobenzene in aqueous solution by ultrasound with the different orthogonal dual frequencies catalytic ozonation. The introduction of ultrasound can enhance the degradation efficiency of nitrobenzene compared to the results obtained from the processes of ozonation alone and ultrasound alone. The degradation of nitrobenzene is found to be zero-order in the two systems of ultrasound alone, and the reactions follow the pseudo-first-order kinetic model in the processes of ozone alone and ozone/ultrasound. The investigation confirms that the degradation of nitrobenzene follows the mechanism of hydroxyl radical (^•OH) oxidation, and the enhancement function is even more pronounced in the presence of ultrasound with the greater difference between the orthogonal dual frequencies due to the obvious synergetic effect between ozone and ultrasound, which increases the utilization efficiency of ozone, and accelerates the initiation of ^•OH and the formation of H₂O₂, resulting in the rapid formation of an increasing diversity of byproducts and the advancement degree of mineralization of total organic carbon (TOC). The oxidative byproducts have been, respectively identified in the different processes selected, including o, p, m-nitrophenols, phenol, malonic acid, 4-nitrocatechol, nitrate ion, maleic acid, oxalic acid, hydroquinone, p-quinone, 1,2,3-trihydroxy-5-nitrobenzene and acetic acid.     

Novel approaches based on ultrasound for treatment of wastewater containing potassium ferrocyanide

Industrial wastewaters containing biorefractory compounds like cyanide offer significant environmental problems attributed to the fact that the conventional methods have limited effectiveness and hence developing efficient treatment approaches is an important requirement. The present work investigates the use of novel treatment approach of ultrasound (US) combined with advanced oxidation techniques for the degradation of potassium ferrocyanide (KFC) for the first time. An ultrasonic bath equipped with longitudinal horn (1 kW rated power and 25 kHz frequency) has been used. The effect of initial pH (2–9) on the progress of degradation has been investigated initially and subsequently using the optimized pH, effect of addition of hydrogen peroxide (ratio of KFC:H₂O₂ varied over the range of 1:0.5–1:5) and TiO₂ in the presence of H₂O₂ (1:1 ratio by weight of TiO₂) as process intensifying approach has been studied. Combination of ultrasonic irradiation with ozone (O₃) (100–400 mg/h) and ultraviolet irradiation (UV) has also been investigated. Use of combination of US with H₂O_2, H₂O₂ + TiO₂ and ozone resulted in extent of KFC degradation as 54.2%, 74.82% and 82.41% respectively. Combination of US with both UV and ozone was established to be the best approach yielding 92.47% degradation. The study also focused on establishing kinetic rate constants for all the treatment approaches which revealed that all the approaches followed first order kinetic mechanism with higher rate constants for the combination approaches. Overall, it has been conclusively established that ultrasound based combined treatment schemes are very effective for the treatment of KFC containing wastewaters.     

A review on hybrid techniques for the degradation of organic pollutants in aqueous environment

The creation of the modern world requires many industrial sectors, however, sustainability needs to be considered while developing industries. In particular, organic pollutants generated by many of these industries contaminate the environment leading to health and other issues. Advanced oxidation processes (AOPs) have been introduced to remove organic pollutants present in wastewater. Sonolytic degradation of organic pollutants is considered as one of the AOPs, however, this process has its limitations. In order to overcome the limitations, hybrid techniques involving ultrasound and other AOPs have been developed. That is, ultrasound combined with heterogeneous AOPs (ultrasound/metal ions, ultrasound/metal oxides, and ultrasound/photocatalysis) and homogeneous AOPs (ultrasound/ozone, ultrasound/H₂O₂, and ultrasound/persulfate) for the degradation/mineralization of organic pollutants. This review highlights the advantages of using hybrid techniques involving ultrasound for the degradation of organic pollutants in aqueous solutions.     

Intensification of degradation of methomyl (carbamate group pesticide) by using the combination of ultrasonic cavitation and process intensifying additives

In the present work, the degradation of methomyl has been carried out by using the ultrasound cavitation (US) and its combination with H₂O₂, Fenton and photo-Fenton process. The study of effect of operating pH and ultrasound power density has indicated that maximum extent of degradation of 28.57% could be obtained at the optimal pH of 2.5 and power density of 0.155 W/mL. Application of US in combination with H₂O₂, Fenton and photo-Fenton process has further accelerated the rate of degradation of methomyl with complete degradation of methomyl in 27 min, 18 min and 9 min respectively. Mineralization study has proved that a combination of US and photo-Fenton process is the most effective process with maximum extent of mineralization of 78.8%. Comparison of energy efficiency and cost effectiveness of various processes has indicated that the electrical cost of 79892.34 Rs./m³ for ultrasonic degradation of methomyl has drastically reduced to 2277.00 Rs./m³, 1518.00 Rs./m³ and 807.58 Rs./m³ by using US in combination with H₂O₂, Fenton and photo-Fenton process respectively. The cost analysis has also indicated that the combination of US and photo-Fenton process is the most energy efficient and cost effective process.     

Application of hybrid oxidative processes based on cavitation for the treatment of commercial dye industry effluents

The present work demonstrates the significant role of ultrasound (US) in intensifying the efficacy of the combination with Fenton reagent and/or ozone for the treatment of real dye industry industrial effluent procured from the local industry. Initial part of the work focused on analysing the literature based on combination approaches of US with different oxidants applied for the treatment of real and simulated effluents focusing on the dyes. The work also provides guidelines for the selection of optimal operating parameters for maximizing the intensification of the degradation. The second part of the work presents an experimental study into combined approaches of ultrasound with ozone (O₃) and Fenton’s reagent for treatment of real effluent. Under optimized conditions (100 W, 20 kHz and duty cycle of 70%), maximum COD reductions of 94.79% and 51% were observed using a combined approach of US + Fenton oxidation followed by lime treatment for the treatment of effluent-I and effluent-II respectively at H₂O₂ loading of 17.5 g/L, H₂O₂/Fe²⁺ ratio of 3, pH of 4, CaO dose of 1 g/L and an overall treatment time of 70 min. US + Fenton + O₃ followed by lime was also applied for treatment under ozone loading of 1 g/h for the treatment of effluent-I and it was found that maximum COD reduction of 95.12% was obtained within 30 min of treatment time, indicating use of ozone did not result in significant value addition in terms of COD reduction but resulted in faster treatment. HC (inlet pressure: 4 bar) + Fenton + Lime scheme was successfully replicated on a pilot-scale resulting in maximum COD reduction of 57.65% within 70 min of treatment time. Overall, it has been concluded that the hybrid oxidative processes as US + Fenton followed by lime treatment is established as the best approach ensuring effective COD reduction at the same time obtaining final colourless/reusable effluent.     

Sonozonation (sonication/ozonation) for the degradation of organic contaminants – A review

Ozonation (OZ) is an important advanced oxidation process to purify water and wastewater. Because of the lower solubility and instability of ozone (O₃), selective oxidation and dependence on pH value, the industrial applications of OZ have been hindered by the following disadvantages: incomplete removal of pollutants, lower mineralization efficiency and the formation of toxic by-products. Meanwhile, OZ seems to have higher processing costs than other technologies. To improve the treatment efficiency and O₃ utilization, several combined processes, such as H₂O₂/O₃, UV/O₃, and Cavitation/O₃, have been explored, while the combined method of ultrasonication (US) with OZ is a promising treatment technology with a complex physicochemical mechanism. In US alone, the sonolysis of water molecules can produce more powerful unselective oxidant hydroxyl radicals (OH), and directly cause the sonochemical pyrolysis of volatile pollutants. In US/OZ, US can promote the mass transfer of O₃, and also drive the chemical conversion of O₃ to enhance the formation of OH. Various layouts of US/OZ devices and the interactive effects of US/OZ (synergism or antagonism) on the degradation of various organics are illustrated in this review. The main factors, including US frequency, pH value, and radical scavengers, significantly affect the mass transfer and decomposition of O₃, the formation of OH and H₂O₂, the degradation rates of organics and the removal efficiencies of COD and TOC (mineralization). As a result, US can significantly increase the yield of OH, thereby improving the degradation efficiency and mineralization of refractory organics. However, US also enhances the decomposition of ozone, thereby reducing the concentration of O₃ in water and impairing the efficiency of selective oxidation with O₃ molecules.     

Environmentally superior cleaning of diatom frustules using sono-Fenton process: Facile fabrication of nanoporous silica with homogeneous morphology and controlled size

Existing techniques for the preparation of silica structures from diatom cells include cleaning of frustules through baking at high temperature and oxidant cleaning using concentrated sulfuric acid, hydrogen peroxide, nitric acid, or sodium dodecyl sulfate (SDS)/ethylenediaminetetraacetic acid (EDTA). In this study, sono-Fenton (SF) process was examined to prepare nanoporous silica through cleaning diatom frustules, while preserving their structural features. Single colonies of Cyclotella sp. were cultivated in batch mode f/2-enriched seawater. Combination of Fenton process with ultrasonication was found to be more efficient than the sum of individual processes in the removal of organic compounds from Cyclotella sp. structure. The optimized amounts of operational parameters were determined as suspension pH of 3, diatom cell density of 4.8 × 10⁵ cell mL⁻¹, H₂O₂ concentration of 60 mM, Fe²⁺ concentration of 15 mM, ultrasound irradiation power of 400 W and the temperature of 45 °C. The results of energy-dispersive X-ray spectroscopy (EDX) and thermal gravimetry (TG) analyses proved that organic materials covering the cell wall were significantly removed from the frustules through SF process. Scanning electron microscopy (SEM) images showed that after SF treatment, silica nanostructures were produced having uniform pores less than 15 nm in diameter. N₂ adsorption–desorption isotherms demonstrated that almost non-porous structure of diatom frustules became mesoporous during removing the organic matrix. Lipids, amino acids, carbohydrates and organic acids or their oxidized products were identified using GC–MS analysis as the main organic compounds released from diatom cells to the solution after SF treatment. Treated frustules exhibited adsorption capability of 91.2 mg/g for Methylene Blue, which was almost 2.5 times higher than that of untreated frustules (34.8 mg/g).     

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.     

Intensification of depolymerization of polyacrylic acid solution using different approaches based on ultrasound and solar irradiation with intensification studies

Depolymerization of polyacrylic acid (PAA) as sodium salt has been investigated using ultrasonic and solar irradiations with process intensification studies based on combination with hydrogen peroxide (H₂O₂) and ozone (O₃). Effect of solar intensity, ozone flow and ultrasonic power dissipation on the extent of viscosity reduction has been investigated for individual treatment approaches. The combined approaches such as US + solar, solar + O₃, solar + H₂O₂, US + H₂O₂ and US + O₃ have been subsequently investigated under optimum conditions and established to be more efficient as compared to individual approaches. Approach based on US (60 W) + solar + H₂O₂ (0.01%) resulted in the maximum extent of viscosity reduction as 98.97% in 35 min whereas operation of solar + H₂O₂ (0.01%), US (60 W), H₂O₂ (0.3%) and solar irradiation resulted in about 98.08%, 90.13%, 8.91% and 90.77% intrinsic viscosity reduction in 60 min respectively. Approach of US (60 W) + solar + ozone (400 mg/h flow rate) resulted in extent of viscosity reduction as 99.47% in 35 min whereas only ozone (400 mg/h flow rate), ozone (400 mg/h flow rate) + US (60 W) and ozone (400 mg/h flow rate) + solar resulted in 69.04%, 98.97% and 98.51% reduction in 60 min, 55 min and 55 min respectively. The chemical identity of the treated polymer using combined approaches was also characterized using FTIR (Fourier transform infrared) spectra and it was established that no significant structural changes were obtained during the treatment. Overall, it can be said that the combination technique based on US and solar irradiations in the presence of hydrogen peroxide is the best approach for the depolymerization of PAA solution.     

Processing of coked Pt-Re/γ-Al<Subscript>2</Subscript>O<Subscript>3</Subscript> catalysts with high-concentration ozone dissolved in supercritical carbon dioxide

The potentialities of low-temperature (50–150°C) regeneration of coked Pt-Re/γ-Al₂O₃ bimetallic catalysts of reforming with high-concentration ozone dissolved in supercritical carbon dioxide (SC-CO₂) are examined. Raman spectroscopy, thermogravimetric, and differential microcalorimetric studies show that solid organic deposit (coke), a by-product of the reforming process, can be partially removed from the mesoporous surface of a coked catalyst by processing with an O₃/SC-CO₂ mixture without any loss of the active components (Pt, Re). Treatment of coked Pt-Re/γ-Al₂O₃ catalysts with an O₃/SC-CO₂ mixture causes changes in the parameters (extent of conversion, selectivity) of the catalytic reforming of n-heptane.     

Synergetic decolorization of azo dyes using ultrasounds,photocatalysis and photo-fenton reaction

In the present work, ultrasound irradiation, photocatalysis with TiO₂, Fenton/Photo-Fenton reaction, and the combination of those techniques were investigated for the decolorization of industrial dyes in order to study their synergy. Three azo dyes were selected from the weaving industry. Their degradation was examined via UV illumination, Fenton and Photo-Fenton reaction as well as ultrasound irradiation at low (20 kHz) and high frequencies (860 kHz). In these experiments, we investigated the simultaneous action of the ultrasound and UV irradiation by varying parameters like the duration of photocatalysis and ultrasound irradiation frequency. At the same time, US power, temperature, amount of TiO₂ photocatalyst and amount of Fenton reagent remained constant. Due to their diverse structure, each azo dye showed different degradation levels using different combinations of the above-mentioned Advanced Oxidation Processes (AOPs). The Photo-Fenton reagent is more effective with US 20 kHz and US 860 kHz for the azo dyes originated from the weaving industry at pH = 3 as compared to pH = 6.8. The combination of the Photo-Fenton reaction with 860 kHz ultrasound irradiation for the same dye gave an 80% conversion at the same time. Experiments have shown a high activity during the first two hours. After that threshold, the reaction rate is decreased. FT-IR and TOC measurements prove the decolorization due to the destruction of the chromophore groups but not complete mineralization of the dyes.     

Sonochemical effectiveness factor (eUS) in the reactors for wastewater treatment by sono-Fenton oxidation: Novel considerations

A comprehensive algorithm was recently proposed for calculation of the sonochemical effectiveness factor and wastewater treatment modeling. The presented approach implies that ultrasound is an auxiliary source of free radicals in Fenton type reactions; introduction of ultrasound represents an enhancement of pollutant degradation rates. The sonochemical effectiveness factor was introduced in kinetic models as the e_US factor (Gr?i? et al., 2012 [1]). As a substantial follow-up, this study presents novel considerations. The e_US factor was modeled as a function of employed frequency, actual cavitation-related power intensity of ultrasound and a portion of the cavitationally active zone, i.e. dimensionless active volume. The effect of temperature was disregarded in the present model considerations. Cavitationally active zone in reactors was determined based on the erosion of aluminum foil, resulting in cone-shaped space arising from transducer.In the present study, sonochemical treatment of industrial wastewater containing HCOONa as organic pollutant was performed using different equipment: ultrasonic baths (UB1, UB2 and UB3), cylindrical reactor with homogenizer (HCR) and three-frequency hexagonal cell, i.e. ultrasonic pilot reactor prototype (PP). Explored frequency range was from 20 to 120 kHz. Homogeneous and heterogeneous Fenton-type sonochemical processes, US/Fe(II)(FeSO₄,aq.)/H₂O₂ and US/Fe(II)(steel-plate)/H₂O₂, respectively, applied to industrial wastewater were investigated in terms of mineralization kinetics. Newly modeled e_US factor was introduced in corresponding kinetic models and the overall model was validated. Kinetic parameters of Fenton process were treated as independent of ultrasound, since e_US factor consists of cavitation-related phenomena responsible for the mineralization rate enhancement. In average, a 21% increase of mineralization efficiency was achieved using a single frequency, while more than 70% increase can be achieved by combining 20, 68 and 120 kHz in PP.     

Intensified recovery of lipids,proteins, and carbohydrates from wastewater-grown microalgae Desmodesmus sp. by using ultrasound or ozone

This study evaluates the effect of ultrasound and ozone pretreatments for the subsequent recovery of Desmodesmus sp. biocomponents—lipids, proteins, and carbohydrates—using a response surface methodology. Both pretreatments impact on the recovered lipids quality, solvent waste production and extraction time is analysed for process intensification purposes. For ultrasound pretreatment, independent parameters were energy applied (50–200 kWh/kg dry biomass), biomass concentration (25–75 g/L), and ultrasonic intensity (0.32 and 0.53 W/mL). While for ozone pretreatment, independent parameters were ozone concentration (3–9 mg O₃/L), biomass concentration (25–75 g/L), and contact time (5–15 min). In the case of ultrasound pretreatment, recovery yield reached 97 ± 0.4%, 89 ± 3%, and 73 ± 0.6% for proteins, carbohydrates and lipids respectively. Given process required: energy applied of 50 kWh/kg dry biomass, 75 g/L of biomass concentration, 0.32 W/mL of ultrasonic intensity, and 56 min of time process. Ultrasound caused high cell disruption releasing all proteins, thereby obviating downstream processing for its recovery. Ozone pretreatment recovery yield was 85 ± 2%, 48 ± 1.4%, and 25 ± 1.3%, for carbohydrates, lipids and proteins respectively, under the following conditions: 9 mg O₃/L of ozone concentration, 25 g/L of biomass concentration, and 5 min of contact time that depicts an energy consumption of 30.64 kWh/kg dry biomass. It was found that ultrasound and ozone pretreatments intensified the lysis and biocomponents recovery process by reducing solvent consumption by at least 92% and extraction time between 80% and 90% compared with extraction of untreated biomass biocomponents. Both pretreatments improve the composition of the recovered lipids. It was noted that the yield of neutral lipids increased from 28% to 67% for ultrasound pretreatment while for ozone pretreatment from 49% to 63%. The method used for lipid extraction may also have an effect but here it was kept constant.     

Effects of organic acids on the size-controlled synthesis of rutile TiO2 nanorods

Size-controlled synthesis of pure rutile-phase TiO₂ nanorods was carried out by a hydrothermal method using different organic acids as modifiers, and metatitanic acid and concentrated sulfuric acid as raw materials. The synthesized rutile TiO₂ nanorods were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). The effects of organic acid modifiers on the sizes of rutile TiO₂ nanorods were investigated. It was found that the steric effect occurred by the organic modifiers and non-polarity of organic acids were beneficial to the formation of small-sized rutile TiO₂ nanorods. The strongly coordinative interaction between the carboxyl (or hydroxyl) group of the modifier and the surface of TiO₂ nanoparticles effectively inhibited the crystal growth.     

Combined treatment approaches based on ultrasound for removal of triazophos from wastewater

Pesticides have been the major contributors to the growth of agricultural productivity, but the wide spread use in the fields and discharge from the manufacturing industries have also contributed to environmental concerns. In the present work, degradation of triazophos (O,O-diethyl-O-(1-phenyl-1H-1,2,4-triazol-3-yl) phosphorothioate) as a model pollutant has been investigated using high volume continuous ultrasonic flow cell for the first time. Effect of power dissipation and initial pH on the extent of triazophos degradation using acoustic cavitation has been investigated initially. Under the optimized set of operating power dissipation and pH, effect of addition of hydrogen peroxide (ratio of C₁₂H₁₆N₃O₃PS (Triazophos):H₂O₂ over the range of 1:1–1:5), ozone (over the flow rate of 100–400 mg/h) and Fenton’s reagent (C₁₂H₁₆N₃O₃PS:FeSO₄:H₂O₂ ratio over the range of 1:1:1–1:4:4) has been investigated as possible process intensification strategy. Combined operation of US with H₂O₂ and Ozone resulted in 48.6% and 54.6% triazophos degradation respectively whereas combination of US and Fenton’s reagent resulted in maximum degradation as 92.2% and also resulted in maximum COD removal as 88.5%. The study also focused on identification of intermediate products formed during the degradation as well as establishing the kinetic rate constants and the synergistic index for different approaches. The study has established that cavitation can be effectively used for triazophos degradation with significant intensification benefits based on the use of combination approach.