A combination of ultrasound and inorganic catalyst: removal of 2-chlorophenol from aqueous solution

Removal of 2-chlorophenol by ultrasonic waves (sonolysis), inorganic catalyst, and a combination of the two processes was tested and compared with each technique. In sonolysis, 2-chlorophenol mostly degraded indirectly in the bulk of solution by the radicals produced in the cavitation process. In catalyst treatment, the removal was performed in the presence of Al2O3, TiO2 and CuO. The highest removal was achieved in the presence of TiO2 for this pollutant. In the combined method an enhancement was observed for the removal of 2-chlorophenol. This could be attributed primarily to the continuous cleaning and chemical activation of the catalyst by acoustic cavitation. The mass transfer between the liquid phase and the catalyst and also the surface area of the catalyst are accelerated by the ultrasonic waves. The removal of 2-chlorophenol was performed under different intensities of irradiation, temperatures and quantities of catalyst. Some experiments were conducted in the presence of a Fenton reagent. In kinetic point of view, the removal of pollutant showed a pseudo-first order behavior. The combined method had a higher rate coefficient than sonolysis and catalyst treatment individually. Under some conditions, the presence of ultrasound has increased the rate coefficient of removal to about 10 times that in the absence of ultrasound.     

The removal of MO molecules from aqueous solution by the combination of ultrasound/adsorption/photocatalysis

Methyl orange (MO) molecules had been removed from aqueous solution by nano-TiO(2)/exfoliated graphite composites with the combination of ultrasound/adsorption/photocatalysis. The experimental results had showed that nano-TiO(2)/exfoliated graphite composites provided with the adsorptive capability of exfoliated graphite and the photocatalysis capability of nano-TiO(2) synchronously. It had been proved that the removal ratios related to the adsorption and photocatalysis capability of the composites and were influenced by US and UV irradiation, the reaction times, the reaction temperatures, the initial pH values, the dosages and the initial MO solution concentrations. Moreover, it had been illuminated that the combination was very effective and useful on removing MO molecules from aqueous solution.     

Removal of disperse blue 2BLN from aqueous solution by combination of ultrasound and exfoliated graphite

This paper reports an efficient and convenient removal of disperse blue 2BLN from aqueous solution by the combination of ultrasound and exfoliated graphite. The various affecting factors were studied. The removal ratio of disperse blue 2BLN is 96.9% for the initial concentration of 200 mg/L using 600 mg/L exfoliated graphite (exfoliation volume of 300 mL/g) at 45 degrees C within 120 min under ultrasound. The combination method was more effective than sonolysis or exfoliated graphite treatment individually.     

Fast and efficient removal of Reactive Black 5 from aqueous solution by a combined method of ultrasound and sorption process

Removal of Reactive Black 5 (RB5) from aqueous solutions was carried by the sorption process in the presence and in the absence of ultrasound. Sorption of the dye on the solid phase was investigated in a series of batch sorption experiments to determine the influence of different parameters such as contact time, amount of sorbent and concentration of pollutant on the removal efficiency of RB5 with and without ultrasound. The experimental data were fitted properly to the Freundlich model and the isotherm constants were 28.2 and 7.4 for k(f) and 0.13 and 0.38 for 1/n in the presence and in the absence of ultrasound (20 kHz) respectively. The data were analyzed with different sorption kinetic models and were better fitted with a pseudo-second-order kinetic model. Two ultrasonic generators at 20 and 500 kHz were used for sonication of the system. This investigation also reveals that RB5 can be removed by higher frequency apparatus (500 kHz) without sorbent in about 60 min sonication. The rate of removal was higher at the higher frequency than at the lower one.     

Gallium- and iodine-co-doped titanium dioxide for photocatalytic degradation of 2-chlorophenol in aqueous solution: Role of gallium

Visible-light-driven TiO₂-based catalysts for the degradation of pollutants have become the focus of attention. In the present work, iodine-doped titania photocatalysts (I-TiO₂) were improved by doping with gallium (Ga,I-TiO₂) and the resulting physicochemical properties and photocatalytic activity were investigated. The structural properties of the catalysts were determined by X-ray diffraction, UV-vis diffuse reflectance spectroscopy, X-ray photoelectron spectroscopy, Brunauer-Emmett-Teller analysis and transmission electron microscopy. We found that Ga probably enters the TiO₂ framework for doping levels <0.5 mol%. A further increase in Ga content probably leads to dispersal of excess Ga on the TiO₂ surface. The photocatalytic activity of Ga,I-TiO₂ catalysts was evaluated using 2-chlorophenol (2-CP) as a model compound under visible and UV-vis light irradiation. The results indicate that 0.5 mol% Ga loading and calcination at 400 °C represent optimal conditions in the calcining temperature range 400-600 °C and with doping levels from 0.1% to 1 mol%. The effective enhancement of 2-CP degradation might be attributed to the formation of oxygen vacancies by Ga doping, which could decrease the recombination of electron-hole pairs.     

Sonolysis of 4-chlorophenol in aqueous solution: effects of substrate concentration, aqueous temperature and ultrasonic frequency

The sonolysis of 4-chlorophenol (4-CP) in O2-saturated aqueous solutions is investigated for a variety of operating conditions with the loss of 4-CP from solution following pseudo-first-order reaction kinetics. Hydroquinone (HQ) and 4-chlorocatechol (4-CC) are the predominant intermediates which are degraded on extended ultrasonic irradiation. The final products are identified as Cl-, CO2, CO, and HCO2H. The rate of 4-CP degradation is dependent on the initial 4-CP concentration with an essentially linear increase in degradation rate at low initial 4-CP concentrations but with a plateauing in the rate increase observed at high reactant concentrations. The results obtained indicate that degradation takes place in the solution bulk at low reactant concentrations while at higher concentrations degradation occurs predominantly at the gas bubble-liquid interface. The aqueous temperature has a significant effect on the reaction rate. At low frequency (20 kHz) a lower liquid temperature favours the sonochemical degradation of 4-CP while at high frequency (500 kHz) the rate of 4-CP degradation is minimally perturbed with a slight optimum at around 40 degrees C. The rate of 4-CP degradation is frequency dependent with maximum rate of degradation occurring (of the frequencies studied) at 200 kHz.     

Decomposition of an azo dye in aqueous solution by combination of ultrasound and visible light

The degradation of Acid Orange 7 in aqueous solution has been investigated under the irradiation of ultrasound and visible light respectively and simultaneously. We have observed that the maximum removal percentage K increases from 4% to 35% when the ultrasonic frequency f and power P change from f=20 KHz and P=3 W to f=1 MHz and P=40 W. On the other hand, the K-value is approximately 3% under the irradiation of visible light at 632 nm and 100 mW/mm(2). Under the simultaneous irradiation of ultrasound (1 MHz, 40 W) and visible light (632 nm, 100 mW/mm(2)), the K-value reaches to approximately 65%, indicating a synergistic effect of ultrasound and visible light irradiations. A simple model based on the band gap theory and cavitation theory is proposed to explain the synergistic phenomenon.     

Sono-sorption as a new method for the removal of methylene blue from aqueous solution

The sorption of methylene blue as a basic dye onto cellulosic materials such as waste newspaper was examined kinetically in the presence of ultrasound (sono-sorption) and in its absence (conventional method). The effects of various experimental parameters such as the amount of sorbent, type of cellulosic sorbents, initial dye concentration, temperature, and contact time have been investigated using a batch sorption technique. The information obtained can be used for treating effluents from the dye industry which deals with this kind of dye. The results show that as the amount of sorbent is increased, the dye removal in conventional method increases accordingly. In case of sono-sorption, it was stopped at specific amount of sorbent. More than 98% removal of the dye could be achieved in a very short period of time of sonication with respect to the conventional method. This behavior is related to the cavitation process which facilitates the removal of dye from aqueous solution. The method mentioned could be employed as a low cost alternative to the commercial activated carbon currently used in wastewater treatment for the removal of dyes.     

Ultrasound-assisted removal of malachite green from aqueous solution by dead pine needles

The dead needles of Aleppo pine (Pinus halepensis) were tested as a possible sorbent for the removal of malachite green from aqueous solutions in the absence and presence of ultrasound. Batch process was employed for sorption kinetic and equilibrium studies. Sorption experiments indicated that the sorption capacity was dependent of operating variables. Both the rate and the amount of malachite green sorption are markedly increased in the presence of the ultrasonic field. The dye removal with the assistance of ultrasound was enhanced with the increase of sorbate initial concentration and temperature, and with the decrease of sorbent dosage and ionic strength. The combination of stirring and ultrasound leads to an improvement of the removal of dye. The sorption kinetics was controlled by the intraparticle diffusion. The intraparticle diffusion coefficient increased 1.7 times in the presence of ultrasound and up to 3.6 times in the combined process. The sorption capacity, estimated according to the Freundlich model, indicates that ultrasound enhanced the sorption properties of the sorbent. The effect of ultrasound on the improvement of dye sorption is due to a variety of physical and mechanical effects as well as to thermal properties. The combination of ultrasound and stirring for the sorption process was shown to be of interest for the treatment of wastewaters contaminated with malachite green.     

Organic dye removal from aqueous solution by pulsed discharge on the pinhole

Various active chemical species such as hydroxyl radicals, oxygen radical, hydrogen peroxide and ozone etc. can be produced by pulsed discharge. These active species can remove organic pollutants from the aqueous phase effectively. In present work pulsed discharge was formed on the pinhole of an insulating plate which was inserted between two plate electrodes. The characteristic of methyl orange decoloration by the discharge was investigated. The results of experimentation showed that peak voltage, pulsed frequency, initial solution conductivity and gas species impact the decoloration rate of the methyl orange (MO) significantly. The decoloration rate of MO solution is increased with increasing of the peak voltage, pulsed frequency, and decreasing initial solution conductivity. When the MO solution was treated with different gases bubbling, different decoloration rate was obtained and the order of decoloration rate is: oxygen > air > nitrogen.     

Adsorptive removal of congo red dye from aqueous solution using bael shell carbon

This study investigates the potential use of bael shell carbon (BSC) as an adsorbent for the removal of congo red (CR) dye from aqueous solution. The effect of various operational parameters such as contact time, temperature, pH, and dye concentration were studied. The adsorption kinetics was modeled by first-order reversible kinetics, pseudo-first-order kinetics, and pseudo-second-order kinetics. The dye uptake process obeyed the pseudo-second-order kinetic expression at pH 5.7, 7 and 8 whereas the pseudo-first-order kinetic model was fitted well at pH 9. Langmuir, Freundlich and Temkin adsorption models were applied to fit adsorption equilibrium data. The best-fitted data was obtained with the Freundlich model. Thermodynamic study showed that adsorption of CR onto BSC was endothermic in nature and favorable with the positive ΔH° value of 13.613 kJ/mol.     

Mercury removal from aqueous solution and flue gas by adsorption on activated carbon fibres

The use of two activated carbon fibres, one laboratorial sample prepared from a commercial acrylic textile fibre and one commercial sample of Kynol^®, as prepared/received and modified by reaction with powdered sulfur and H₂S gas in order to increase the sulfur content were studied for the removal of mercury from aqueous solution and from flue gases from a fluidized bed combustor. The sulfur introduced ranged from 1 to 6 wt.% depending on the method used. The most important parameter for the mercury uptake is the type of sulfur introduced rather than the total amount and it was found that the H₂S treatment of ACF leads to samples with the highest mercury uptake, despite the lower sulfur amount introduced. The modified samples by both methods can remove HgCl₂ from aqueous solutions at pH 6 within the range 290-710 mg/g (ACF) which can be favourably compared with other studies already published. The use of a filter made with an activated carbon fibre modified by powdered sulfur totally removed the mercury species present in the flue gases produced by combustion of fossil fuel.     

Enhancement of saccharin removal from aqueous solution by activated carbon adsorption with ultrasonic treatment

This study investigates the use of ultrasonication as a pretreatment process and its effect on the adsorption characteristics of saccharin onto activated carbon (AC). Ultrasonic decomposition of saccharin was performed at a frequency of 500 kHz under argon and O2/N2 (20/80 vol%) atmospheres. Adsorption was carried out using a commercial activated carbon. The behavior of total organic carbon (TOC) during ultrasonication was investigated. Saccharin removal after 180 min of ultrasonication under Ar and O2/N2 atmospheres are 38% and 26%, respectively, while the amount of saccharin removed by activated carbon adsorption without US pretreatment is 40% after 16 h. After 16 h of AC adsorption with 180 min of ultrasonic pretreatment under Ar and O2/N2 atmospheres, both removal ratios increased to 75%. These results indicated that the pretreatment of sonication under O2/N2 leads to the increase in the amount of saccharin adsorbed on AC. On the other hand, the TOC removal by decomposition by ultrasound is not more than 5% in both Ar and O2/N2 atmospheres after 180 min ultrasonication. However, the TOC removal increased to 54% and 69% after 16 h of adsorption of saccharin pretreated by ultrasonication for 180 min under Ar and O2/N2 atmospheres, respectively. About 13% and 16% TOC removal in Ar and in O2/N2, respectively, were achieved due to adsorption of the by-products. It is considered that the improvement in TOC removal is also brought about by the formation of the by-products that were adsorbed onto AC.     

Facile preparation of mesoporous titanium nitride microspheres as novel adsorbent for trace Cd2+ removal from aqueous solution

A simple and facile route is developed for the preparation of mesoporous titanium nitride (TiN) microspheres with a large surface area and a highly porous structure. This method involves the preparation of an amorphous precursor via a solvothermal reaction and subsequent short-time nitridation process to mesoporous TiN. X-ray diffraction and X-ray photoelectron spectroscopy analyses confirm the composition of the resultant sample. The mesoporous structure of the as-prepared TiN sample has been studied by nitrogen adsorption/desorption measurement. The surface area obtained by the Brunauer–Emmett–Teller method is 50.6 m² g⁻¹ and the pore sizes are in the range of 2.0–4.0 nm. In addition, the obtained sample is evaluated as a new sorbent for Cd²⁺ removal. Experimental parameters such as solution pH, contact time and concentration of adsorbate are optimized. The maximum adsorption capacity for Cd²⁺ removal is found to be 12.40 mg g⁻¹ and it is a potentially attractive adsorbent for Cd²⁺ removal from aqueous solution.     

Effect of biotite content of hydrogels on enhanced removal of methylene blue from aqueous solution

A series of chitosan-g-poly(acrylic acid)/biotite (CTS-g-PAA/BT) hydrogels with unique clay biotite (BT) were prepared and used to remove cationic dye methylene blue (MB) from aqueous solution by batch adsorption experiments. Variables of the system including BT content, initial pH, contact time, initial concentration, and temperature affecting the adsorption efficiency of MB by CTS-g-PAA/BT hydrogels were investigated. Kinetic studies indicated that the adsorption data well followed pseudo-second-order kinetics. Langmuir and Freundlich isotherm models were applied to experimental equilibrium data of MB adsorption depending on temperature. The adsorption equilibrium data obeyed Langmuir isotherm, and the monolayer adsorption capacity calculated from the Langmuir isotherm was 2,125.70 mg/g for CTS-g-PAA/10% BT at 30 °C. The adsorption capacity was much higher compared with other hydrogels with the same content of other clays. The introduction of BT into the hydrogel could effectively improve its adsorption properties and reduce the cost. Thermodynamic parameters were evaluated for the dye-adsorbent systems and revealed that the adsorption process was spontaneous and exothermic in nature. All the information gave an indication that CTS-g-PAA/10% BT could potentially be applied as an efficient adsorbent for cationic dye removal from aqueous solution.     

Adsorptive removal and kinetics of methylene blue from aqueous solution using NiO/MCM-41 composite

Highly ordered mesoporous material MCM-41 was synthesized from tetraethylorthosilicate (TEOS) as Si source and cetyltrimethylammonium bromide (CTAB) as template. Well-dispersed NiO nanoparticles were introduced into the highly ordered mesoporous MCM-41 by chemical precipitation method to prepare the highly ordered mesoporous NiO/MCM-41 composite. X-ray diffraction (XRD) analysis, transmission electron microscopy (TEM) and high-resolution TEM (HRTEM), and nitrogen adsorption–desorption measurement were used to examine the morphology and the microstructure of the obtained composite. The morphological study clearly revealed that the synthesized NiO/MCM-41 composite has a highly ordered mesoporous structure with a specific surface area of 435.9 m² g⁻¹. A possible formation mechanism is preliminary proposed for the formation of the nanostructure. The adsorption performance of NiO/MCM-41 composite as an adsorbent was further demonstrated in the removal azo dyes of methyl orange (MO), Congo red (CR), methylene blue (MB) and rhodaming B (RB) under visible light irradiation and dark, respectively. The kinetics and mechanism of removal methylene blue were studied. The results show that NiO/MCM-41 composite has a good removal capacity for organic pollutant MB from the wastewater under the room temperature. Compared with MCM-41 and NiO nanoparticles, 54.2% and 100% higher removal rate were obtained by the NiO/MCM-41 composite.     

Surface heterogeneity effects of activated carbons on the kinetics of paracetamol removal from aqueous solution

The removal of a compound with therapeutic activity (paracetamol) from aqueous solutions using chemically modified activated carbons has been investigated. The chemical nature of the activated carbon material was modified by wet oxidation, so as to study the effect of the carbon surface chemistry and composition on the removal of paracetamol. The surface heterogeneity of the carbon created upon oxidation was found to be a determinant in the adsorption capability of the modified adsorbents, as well as in the rate of paracetamol removal. The experimental kinetic data were fitted to the pseudo-second order and intraparticle diffusion models. The parameters obtained were linked to the textural and chemical features of the activated carbons. After oxidation the wettability of the carbon is enhanced, which favors the transfer of paracetamol molecules to the carbon pores (smaller boundary layer thickness). At the same time the overall adsorption rate and removal efficiency are reduced in the oxidized carbon due to the competitive effect of water molecules.     

Degradation of C.I. Direct Black 168 from aqueous solution by fly ash/H2O2 combining ultrasound

Degradation of C.I. Direct Black 168 from aqueous solution using Fenton-like reactions combining ultrasound was investigated. In the presence of H₂O₂, the effect of the heterogeneous catalysts, such as fly ash, kaolinite or diatomaceous earth on the degradation of Direct Black 168 was observed under ultrasound. The fly ash was the most efficient catalyst. It is apparent that ultrasound can prompt the reaction to take place and give in higher degradation. In the combination of ultrasound and fly ash/H₂O₂, the effect of different system variables namely concentration of the dye, dosage of fly ash, concentration of H₂O₂, pH of solution and the addition of NaCl were studied. 99.0% removal ratio was achieved at initial concentration 100 mg/L, pH 3.0, and dosage of fly ash 2.0 g/L, as well as 2.94 mM H₂O₂. NaCl exhibited only a minor effect on the dye removal.     

Ultrasonic-assisted sol-gel method of preparation of TiO2 nano-particles: characterization, properties and 4-chlorophenol removal application

Nano-size TiO2 photocatalysts were prepared by sol-gel and ultrasonic-assisted sol-gel methods using two different sources of ultrasonicator, i.e., a bath type and tip type. The physicochemical characteristics of the catalysts were investigated by BET, XRD and TEM analyses and the photocatalytic properties of the TiO2 catalysts prepared by three different methods were compared. The intrinsic and extrinsic properties of TiO2, such as the particle size, surface area, pore-volume, pore-diameter, crystallinity as well as anatase, rutile and brookite phase ratios, could be controlled by the ultrasonic-assisted sol-gel method. During this preparation method, the effect of such important operating variables as the ultrasonic irradiation time, power density, the ultrasonic sources (bath-type and tip-type), magnetic stirring during synthesis, initial temperatures and size of the reactors are discussed here. It was found that each of the parameters played a significant role in controlling the properties of the TiO2 nano-particles. Among the three different methods, TiO2 photocatalysts prepared by ultrasonic (tip-US) assisted sol-gel possessed the smallest particle size, highest surface area and highest pore-volume than the catalysts prepared by the other two methods. 4-Chlorophenol was used as a pollutant to observe the photocatalytic degradation ability of the prepared photocatalysts and the TiO2 catalysts prepared by the bath-US ultrasonic-assisted sol-gel method were shown to be the most highly active. This is due to their high surface area and high pore-diameter. This study clearly demonstrates the importance and advantages of ultrasonication in the modification and improvement of the photocatalytic properties of mesoporous nano-size TiO2 particles.     

Sonochemical and photosonochemical degradation of 4-chlorophenol in aqueous media

The degradation of 4-chlorophenol (4-CP) in aqueous media by 516 kHz ultrasonic irradiation was investigated in order to clarify the degradation mechanism. The degradation of concentrated 4-CP solution by means of ultrasound, UV irradiation and their combined application was also studied. The obtained results indicate that *OH radical are the primary reactive species responsible for 4-CP ultrasonic degradation. Very little 4-CP degradation occurs if the sonolysis is carried out in the presence of the *OH radical scavenger tert-butyl alcohol, also indicating that little or no pyrolysis of the compound occurs. The dominant degradation mechanism is the reaction of substrate with *OH radicals at the gas bubble-liquid interface rather than high temperature direct pyrolysis in ultrasonic cavities. This mechanism can explain the lower degradation rate of the ionic form of 4-CP that is partly due to the rapid dissociation of *OH radicals in alkaline solutions. The sonochemical destruction of concentrated 4-CP aqueous solution is obtained with low rate. Coupling photolysis with ultrasound irradiation results in increased efficiency compared to the individual processes operating at common conditions. Interestingly, the photosonochemical decomposition rate constant is greater than the additive rate constants of the two processes. This may be the result of three different oxidative processes direct photochemical action, high frequency sonochemistry and reaction with ozone produced by UV irradiation of air, dissolved in liquid phase because of the geyser effect of ultrasound streaming. Additionally, the photodecomposition, at 254 nm, of hydrogen peroxide produced by ultrasound generating *OH radical can partly explain the destruction enhancement.