A kinetic model for the degradation of benzothiazole by Fe3+-photo-assisted Fenton process in a completely mixed batch reactor

The degradation of benzothiazole in aqueous solution by a photo-assisted Fenton reaction has been studied in a batch reactor in the pH range 2.0–3.2 and for H₂O₂ and Fe(III) concentrations respectively between 1.0×10⁻³–1.5×10⁻¹ and 1.0×10⁻⁶–4.0×10⁻⁶ M.

A kinetic model has been developed to predict the decay of benzothiazole at varying reaction conditions. The use of kinetic constants from the literature in the model allows to simulate the system behavior by taking into account the influence of pH, hydrogen peroxide, Fe(III) and sulfate concentrations and the ionic strength.     

Mechanochemical degradation treatment of TBBPA: A kinetic approach for predicting the degradation rate constant

Persistent organic pollutants (POPs) have been banned from production and use. The brominated flame retardant TBBPA is a type of POP and has been widely used in plastics to enhance their fire resistance. However, because the natural degradation of TBBPA is a difficult process, it is particularly important to propose an appropriate treatment method. Hence, the mechanochemical degradation of TBBPA is a feasible method because it does not require high temperature heating and does not produce secondary pollutants after the reaction is completed. In this study, we performed a series of TBBPA degradation experiments with a planetary ball mill and confirmed the degradation efficiency and the rate under various conditions. Then, we conducted a discrete element method (DEM) simulation to compute the collision energies in the ball mill. By comparing the degradation rate and collision energies, we revealed that the mechanochemical degradation rate of TBBPA can be predicted by a normal collision energy computed by DEM simulation. This kinetic approach enables us to predict the rate constant and consequently, the energy consumption for the mechanochemical treatment. The predictability of these parameters will encourage the further application of mechanochemical reaction in the field of POPs treatment.     

Mass transfer correlation for phenol biodegradation in a fluidized bed bioreactor

Experiments have been carried out in a draft tube fluidized bed bioreactor to study biodegradation of synthetic wastewater containing phenol. The microorganism employed in the study Psuedomonas putida has been immobilized on solid support particles. Studies have been carried out at different feed concentrations of phenol, air flow rates and feed flow rates. The mass transfer coefficient for phenol transfer from bulk phase to the surface of the biofilm on the solid particle has been estimated from observed experimental data using the conservation equations. The mass transfer coefficient was found to be in the range of 0.0726 x 10(-5) to 0.2012 x 10(-5) m s(-1). It was found to increase with increase in feed concentration, air flow rate and feed flow rate. A dimensionless correlation has been developed for the mass transfer coefficient in terms of Sherwood, Reynolds and Schmidt numbers, and the same has been compared with correlations available in literature.     

Performance evaluation of supported ionic liquid membrane for removal of phenol

This work evaluates the performance of ionic liquid in supported liquid membrane (SLM) for the removal of phenol from wastewater. Ionic liquids are organic salts entirely composed of organic cations and either organic or inorganic anions. Due to the fact that the vapor pressure of ionic liquid is not detectable and they are sparingly soluble in most conventional solvents, they can be applied in SLM as the organic phase. In this work, 1-n-alkyl-3-methylimidazolium salts, [C_nMIM]⁺[X]⁻ have been investigated so as to determine an optimal supported ionic liquid membrane. The effect of operational parameters such as pH, stirring speed and the concentration of stripping agent has been studied, and an evaluation of different membrane supports were also carried out. With a minimal amount of the ionic liquid 1-Butyl-3-methylimidazolium hydrogensulfate, 85% phenol removal could be achieved by using polytetrafluoroethylene hydrophobic membrane filter in the SLM.     

Kinetic modelling of aqueous atrazine ozonation processes in a continuous flow bubble contactor

The ozonation of atrazine in different waters (ultrapure and surface waters) has been studied in continuous bubble contactors with kinetic modelling purposes. Three ozonation processes have been considered: ozonation alone and combined with hydrogen peroxide or UV radiation. The kinetic models are based on a molecular and free radical mechanism of reactions, reaction rate and mass transfer data and non-ideal flow analysis models for gas and water phases through the contactors (the tanks in series model and the dispersion model). The models predict well the experimental concentrations of atrazine, dissolved ozone and hydrogen peroxide both at non-steady state and steady state regimes. From both experimental and calculated results, atrazine conversions are observed to be highly dependent on the nature of water where ozonation is carried out. As far as removal of atrazine and oxidation intermediates are concerned, ozone combined with UV radiation resulted in the most effective ozonation process among the three studied.     

Characterization of phenol degradation by Rhizobium sp. CCNWTB 701 isolated from Astragalus chrysopteru in mining tailing region

To screen high strength phenol degrading bacteria, we selected 108 rhizobial strains isolated from nodules of eight wild legumes species in the mining tailing region of Shaanxi province, northwest of China, and cultivated them in a basal salt (BS) medium supplemented with different phenol concentrations as a sole carbon source. The results showed that some of the strains could use phenol as sole carbon source. In order to study the characteristics of phenol degradation, the strain CCNWTB701 isolated from Astragalus chrysopteru was used as well, due to the fact that it was very efficient in phenol degradation. The phenol degradation was around 99.5 and 78.3%, with an initial concentration of 900 and 1000 mg/l phenol in 62 and 66 h, respectively. Kinetic studies indicated that the strain had a high KS (743.1 microM) and an extremely high KSI (10,469 microM) in Haldane's model. The phylogenetic analysis based on 16S rRNA gene sequences showed that CCNWTB701 belonged to the Rhizobium genus, and it was closely related to Rhizobium mongolense and Rhizobium gallicum.     

A kinetic study on the degradation of p-nitroaniline by Fenton oxidation process

A detailed kinetic model was developed for the degradation of p-nitroaniline (PNA) by Fenton oxidation. Batch experiments were carried out to investigate the role of pH, hydrogen peroxide and Fe(2+) levels, PNA concentration and the temperature. The kinetic rate constants, k(ap), for PNA degradation at different reaction conditions were determined. The test results show that the decomposition of PNA proceeded rapidly only at pH value of 3.0. Increasing the dosage of H(2)O(2) and Fe(2+) enhanced the k(ap) of PNA degradation. However, higher levels of H(2)O(2) also inhibited the reaction kinetics. The k(ap) of PNA degradation decreased with the increase of initial PNA concentration, but increased with the increase of temperature. Based on the rate constants obtained at different temperatures, the empirical Arrhenius expression of PNA degradation was derived. The derived activation energy for PNA degradation by Fenton oxidation is 53.96 kJ mol(-1).     

Study the adsorption of phenol from aqueous solution on hydroxyapatite nanopowders

In this study, the hydroxyapatite (HAp) nanopowders prepared by chemical precipitation method were used as the adsorbent, and the potential of HAp nanopowders for phenol adsorption from aqueous solution was studied. The effect of contact time, initial phenol concentration, pH, adsorbent dosage, solution temperature and adsorbent calcining temperature on the phenol adsorption, and the adsorption kinetic, equilibrium and thermodynamic parameters were investigated. The results showed that the HAp nanopowders possessed good adsorption ability to phenol. The adsorption process was fast, and it reached equilibrium in 2h of contact. The initial phenol concentration, pH and the adsorbent calcining temperature played obvious effects on the phenol adsorption capacity onto HAp nanopowders. Increase in the initial phenol concentration could effectively increase the phenol adsorption capacity. At the same time, increase in the pH to high-acidity or to high-alkalinity also resulted in the increase in the phenol adsorption capacity. Increase in the HAp dosage could effectively increase the phenol adsorption percent. However, the higher calcining temperature of HAp nanopowders could obviously decrease the adsorption capacity. The maximum phenol adsorption capacity was obtained as 10.33mg/g for 400mg/L initial phenol concentrations at pH 6.4 and 60 degrees C. The adsorption kinetic and the isotherm studies showed that the pseudo-second-order model and the Freundlich isotherm were the best choices to describe the adsorption behaviors. The thermodynamic parameters suggested that the adsorption of phenol onto HAp was physisorption, spontaneous and endothermic in nature.     

New analytical approximate solution of the generalised temperature integral for kinetic reactions

Simple closed-form expression of the generalised temperature integral in the basic equation to describe kinetic reactions for solid materials in linear heating process is always suitable for use in determining parameters. Many developed solutions only can give high accuracies on the general conditions. A new analytical approximate solution was deduced in this work. The deviations of this solution from the true value are fully analysed. This solution takes advantage in broader application conditions than other known solutions. The application of the new analytical approximate solution in austenite kinetic reaction in this work reinforces that austenite reaction rate is feasible to be given a priori.     

Removal of phenol from aqueous solutions by adsorption onto organomodified Tirebolu bentonite: Equilibrium, kinetic and thermodynamic study

A natural bentonite modified with a cationic surfactant, cetyl trimethylammonium bromide (CTAB), was used as an adsorbent for removal of phenol from aqueous solutions. The natural and modified bentonites (organobentonite) were characterized with some instrumental techniques (FTIR, XRD and SEM). Adsorption studies were performed in a batch system, and the effects of various experimental parameters such as solution pH, contact time, initial phenol concentration, organobentonite concentration, and temperature, etc. were evaluated upon the phenol adsorption onto organobentonite. Maximum phenol removal was observed at pH 9.0. Equilibrium was attained after contact of 1 h only. The adsorption isotherms were described by Langmuir and Freundlich isotherm models, and both model fitted well. The monolayer adsorption capacity of organobentonite was found to be 333 mg g⁻¹. Desorption of phenol from the loaded adsorbent was achieved by using 20% acetone solution. The kinetic studies indicated that the adsorption process was best described by the pseudo-second-order kinetics (R² > 0.99). Thermodynamic parameters including the Gibbs free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) were also calculated. These parameters indicated that adsorption of phenol onto organobentonite was feasible, spontaneous and exothermic in the temperature range of 0–40 °C.     

A kinetic spectrophotometric method for simultaneous determination of phenol and its three derivatives with the aid of artificial neural network

A novel kinetic spectrophotometric method was developed for determination of pyrocatechol, resorcin, hydroquinone and phenol based on their inhibitory effect on the oxidation of Rhodamine B (RhB) in acid medium at pH = 3.0. A linear relationship was observed between the inhibitory effect and the concentrations of the compounds. The absorbance associated with the kinetic reactions was monitored at the maximum wavelength of 557 nm. The effects of different parameters such as pH, concentration of RhB and KBrO₃, and temperature of the reaction were investigated and optimum conditions were established. The linear ranges were 0.22-3.30, 0.108-0.828, 0.36-3.96 and 1.52-19.76 μg mL⁻¹ for pyrocatechol, resorcin, hydroquinone and phenol, respectively, and their corresponding detection limits were 0.15, 0.044, 0.16 and 0.60 μg mL⁻¹. The measured data were processed by several chemometrics methods, such as principal component regression (PCR), partial least squares (PLS) and artificial neural network (ANN), and a set of synthetic mixtures of these compounds was used to verify the established models. It was found that the prediction ability of PLS, PCR and RBF-ANN was similar, however, the RBF-ANN model did perform somewhat better than the other methods. The proposed method was also applied satisfactorily for the simultaneous determination of pyrocatechol, resorcin, hydroquinone and phenol in real water samples.     

Technologies for the removal of phenol from fluid streams: a short review of recent developments

The available technologies for the abatement of phenol from water and gaseous streams are briefly reviewed, and the recent advancements summarized. Separation technologies such as distillation, liquid–liquid extraction with different solvents, adsorption over activated carbons and polymeric and inorganic adsorbents, membrane pervaporation and membrane–solvent extraction, have been discussed. Destruction technologies such as non-catalytic, supercritical and catalytic wet air oxidation, ozonation, non-catalytic, catalytic and enzymatic peroxide wet oxidation, electrochemical and photocatalytic oxidation, supercritical wet gasification, destruction with electron discharges as well as biochemical treatments have been considered. As for the abatement of phenol from gases, condensation, absorption in liquids, adsorption on solids, membrane separation, thermal, catalytic, photocatalytic and biological oxidation have also been considered. The experimental conditions and the performances of the different techniques have been compared.     

Photocatalytic degradation of gaseous benzene over TiO2/Sr2CeO4: kinetic model and degradation mechanisms

Photocatalytic oxidation of benzene in air was carried out over TiO2/Sr2CeO4 catalysts. The prepared photocatalyst was characterized by SBET, UV-vis diffuse reflectance and XPS. TiO2/Sr2CeO4 absorbs much more visible light than TiO2 in the visible light region. The XPS spectrum shows that the binding energy value of Ti 2p3/2 transfers to a lower value. The main purpose was to investigate the kinetic model and degradation mechanisms. The kinetic data matched well with the Langmuir-Hinshelwood (L-H) kinetic model with the limiting rate constant and the adsorption constant in this case were 0.0064 mg l-1 min-1 and 9.2078 l mg-1, respectively. No gas-phase intermediates were detected by direct GC/FID analysis under the conditions despite the high benzene concentration. Ethyl acetate and (3-methyl-oxiran-2-yl)-methanol were two major identified intermediates which were accompanied by butylated hydroxytoluene, 2,6-bis(1,1-dimethylethyl)-4,4-dimethylycyclohe, 2,5-cyclohexadiene-1,4,dione,2,6-bis(1,1-dim). It is plausible that at least one of these less-reactive intermediates caused the deactivation of the photocatalyst. Finally, the photocatalytic oxidation mechanisms were speculated.     

Optimal exponential feeding strategy for dual-substrate biostimulation of phenol degradation using Cupriavidus taiwanensis

The exponential feeding strategy (EFS) of dual substrates (i.e., phenol and glycerol) was applied to optimize the overall performance of phenol degradation by Cupriavidus taiwanensis R186. Addition of a second substrate (e.g., glycerol) could stimulate the phenol biodegradation efficiency of strain R186. Hence, a feasible EFS was developed for fed-batch phenol biodegradation using the dual-substrate biostimulation technique. The phenol degradation kinetics was well characterized with proposed model and response surface analysis. Our findings quantitatively revealed that glycerol could effectively enhance the phenol degradation performance, as the highest phenol degradation efficiency occurred with the supplementation of 0.8–1.2 g L⁻¹ of glycerol. The optimal dual-substrate EFS was identified via contour analysis and kinetic modeling. With the optimal dual-substrate EFS (i.e., a feeding rate constant (α₁ and α₂) of 0.5 and 0.3, respectively), the shortest time (ca. 13.80 h) for phenol degradation was achieved with a specific growth rate of ca. 0.281 h⁻¹.     

Photocatalytic degradation of methyl tert-butyl ether in the gas-phase: a kinetic study

Methyl tert-butyl ether (MTBE) is the basic oxygenated motor fuel additive in Europe and is included in volatile organic compounds (VOCs), which can produce photochemical oxidants. In the present study the gas-phase photocatalytic oxidation (PCO) of MTBE over illuminated titanium dioxide was carried out at ambient temperature in a plug flow reactor. The intermediates detected are mainly tert-butyl formate and acetone, while the final products are CO(2) and water. The system was sensitive to the oxygen concentration, for concentrations up to 15% (v/v). Moisture had a positive effect on the reaction, obtaining an optimum value near 45% relative humidity for 200ppmv MTBE initial concentration. A reaction scheme has been proposed for the interpretation of the experimental results and a kinetic study was conducted, using the Langmuir-Hinshelwood kinetics equation. The MTBE rate constant was 1.545 x 10(-6)Ms(-1)g(cat)(-1) for the reaction without moisture and 2.46 x 10(-6)Ms(-1)g(cat)(-1) for the reaction in the presence of moisture and the adsorption constant was 2.187 x 10(5)M(-1) independent of humidity.     

Oxidation of pesticides by in situ electrogenerated hydrogen peroxide: study for the degradation of 2,4-dichlorophenoxyacetic acid

This paper reports an investigation on the performance of the H2O2 electrogeneration process on a rotating RVC cylinder cathode, and the optimization of the O2 reduction rate relative to cell potential. A study for the simultaneous oxidation of the herbicide 2,4-dichlorophenoxyacetic acid (2,4-D) by the in situ electrogenerated H2O2 is also reported. Experiments were performed in 0.3 M of K2SO4, pH of 10 and 3.5. Oxygen concentration in solution was kept in 25 mg L(-1). Maximum hydrogen peroxide generation rate was reached at -1.6 V versus SCE for both, acidic and alkaline solutions. Then, 100 mg L(-1) of 2,4-D was added to the solution. First order apparent rate constants for 2,4-D degradation ranged from 0.9 to 6.3x10(-5) m s(-1), depending on the catalyst used (UV or UV+Fe(II)). TOC reduction was favored in acidic medium where a decreasing of 69% of the initial concentration was observed in the process catalyzed by UV+Fe(II). This figure was an indication that some of the intermediates derived from 2,4-D decomposition remained in solution, mainly as lighter aliphatic compounds.     

In situ degradation of phenol and promotion of plant growth in contaminated environments by a single Pseudomonas aeruginosa strain

For bioremediation of contaminated environments, a bacterial strain, SZH16, was isolated and found to reduce phenol concentration in a selective medium. Using the reaction vessel containing the soil mixed with phenol and bacteria, we found that the single strain degraded efficiently the phenol level in soil samples. The strain was identified as Pseudomonas aeruginosa on the basis of biochemical tests and by comparison of 16S rDNA sequences, and phosphate solubilization and IAA production were not observed in the strain. Simultaneous examination of the role of strain SZH16 in the plant growth and phenol biodegradation was performed. Results showed that inoculation of the single strain in the phenol-spiked soil resulted in corn growth promotion and in situ phenol degradation and the increase in plant biomass correlated with the decrease in phenol content. Colonization experiments showed that the population of the SZH16 strain remained relatively constant. All these findings indicated that the corn growth promotion might be due to reduction in phytotoxicity, a result of phenol biodegradation by the single strain SZH16. Furthermore, the strain was found to stimulate corn growth and reduce phenol concentration simultaneously in phenol-containing water, and even historically contaminated field soils. It is attractive for environment remediation and agronomic applications.     

Photocatalytic degradation of phenol under visible light using electrospun Ag/TiO2 as a 2D nano-powder: Optimizing calcination temperature and promoter content

Phenol is one of the toxic materials, and releasing it into the water can be quite irritating and harmful to the health of organisms and the environment. In this study, phenol degradation was investigated using Ag/TiO₂ electrospun nanofiber photocatalyst as a 2D nano-powder. Nanofibers have 2 dimensions in the range of nanometers but their length of them are in the range of micrometers. The micrometer size is an advantage for the separation of the photocatalyst from the suspension. Though, nanometer size is suitable for increasing the available surface for the light. The effect of silver content (0.5–15%) as a promoter and the calcination temperature (300–900 °C) was studied on the degradation of phenol over the synthesized nanofiber-based photocatalyst. Photocatalysts were characterized by various techniques including N₂-physisorption, XRD, SEM, EDX, TEM, FTIR, TGA/DSC, TPO, and DRS. The results have indicated that 5% of Ag content on TiO₂ is the best promoter loading in these experiments. Furthermore, the calcination temperature of 450 °C is found to be the optimum value with an optimum rutile fraction of 23.8%. Maximum phenol degradation was 82.65% at pH = 7, catalyst dosage of 1.5 g/L, and phenol concentration of 5 ppm under a low power visible light (18 W).     

Investigation of the catalytic wet peroxide oxidation of phenol over different types of Cu/ZSM-5 catalyst

In this work oxidation of phenol with hydrogen peroxide on Cu/ZSM-5 catalysts was studied. The catalysts samples were prepared by two different methods: by ionic exchange from the protonic form of commercial ZSM-5 zeolite, and by direct hydrothermal synthesis. Characterization of the catalysts extends to X-ray diffraction (XRD), while the adsorption techniques were used for the measurement of the specific surface area. The catalytic tests were carried out in a stainless steel Parr reactor in batch operation mode at the atmospheric pressure and the temperature range from 50 to 80 degrees C. The mass ratio of the active metal component on the zeolite was in the range of 1.62-3.24 wt.%. for catalyst prepared by direct hydrothermal synthesis and 2.23-3.52 wt.% for catalyst prepared by ion exchange method. The initial concentration of phenol and hydrogen peroxide was 0.01 and 0.1 mol dm(-3), respectively. The influence of different methods of Cu/ZSM-5 preparation on their catalytic performance was monitored in terms of phenol conversion and degree of metal leached into aqueous solution.