Kinetics of 2,6-dimethylaniline oxidation by various Fenton processes

The kinetics of 2,6-dimethylaniline degradation by Fenton process, electro-Fenton process and photoelectro-Fenton process was investigated. This study attempted to eliminate the potential interferences from intermediates by making a kinetics comparison of Fenton, electro-Fenton and photoelectro-Fenton methods through use initial rate techniques during the first 10 min of the reaction. Exactly how the initial concentration of 2,6-dimethylaniline, ferrous ions and hydrogen peroxide affects 2,6-dimethylaniline degradation was also examined. Experimental results indicate that the 2,6-dimethylaniline degradation in the photoelectro-Fenton process is superior to the ordinary Fenton and electro-Fenton processes. Additionally, for 100% removal of 1 mM 2,6-dimethylaniline, the supplementation of 1 mM of ferrous ion, 20 mM of hydrogen peroxide, current density at 15.89 A m⁻² and 12 UVA lamps at pH 2 was necessary. The overall rate equations for 2,6-dimethylaniline degradation by Fenton, electro-Fenton and photoelectro-Fenton processes were proposed as well.     

Monitoring of decolorization kinetics of Reactive Brilliant Blue X-BR by online spectrophotometric method in Fenton oxidation process

Online spectrophotometry method is employed to monitor simulated Reactive Brilliant Blue X-BR (RBB X-BR) in aqueous solution in Fenton oxidation process. The effects of initial dosage of FeSO(4) and H(2)O(2), pH value, initial concentration of dye and temperature have been studied. The results show that online spectrophotometric method is a quick, feasible and convenient technique to monitor color removal of RBB X-BR in Fenton process. The optimal dosage of H(2)O(2) and pH is 3.529mM and 3, respectively. The optimal dosage of Fe(2+) for color removal is 0.1618mM. The concentration of initial FeSO(4) against the reaction rate constant (k(ap)) for decolorizing is linear correlation as: k(ap)=0.1354[Fe(2+)](o) (R(2)>0.99). The apparent activation energies of reaction is 25.21kJmol(-1) (R(2)>0.99). The intrinsic reaction rate constant of OH with RBB X-BR in aqueous solution is 7.396x10(10)M(-1)s(-1). The molecule structure of RBB X-BR is decomposed and not mineralized by Fenton's reagent. The main intermediate products are 1,2-diacetylenzene and 2,5-diritrobenzoic acid. The probable mechanism of the decoloration of RBB X-BR is also discussed.     

Chemical oxidation of 2,4-dimethylphenol in soil by heterogeneous Fenton process

Hydrogen peroxide has been used to oxidize a sorbed aromatic contaminant in a loamy sand with 195.9 g kg(-1) of organic carbon by using iron as catalyst at 20 degrees C. The 2,4-dimethylphenol (2,4-DMP) was chosen as pollutant. Because of this soil generates a slightly basic pH in contact to an aqueous phase the solubility of the iron cation was determined in absence and presence of a chelating agent (l-ascorbic acid, l-Asc) and with and without soil. From results, it was found that in presence of soil the iron cation was always adsorbed or precipitaed onto the soil. Therefore, the procedure selected for soil remediation was to add firstly the iron solution used as catalyst and following the hydrogen peroxide solution used as oxidant. As iron cation is sorbed onto the soil before the oxidant reagent is provided a heterogeneous catalytic system results. This modified Fenton runs have been carried out using 0.11 mg(2,4-DMP) g(-1)(soil) and 2.1 mg(Fe) g(-1)(soil). The H(2)O(2)/pollutant weight ratios used were 182 and 364. The results show that H(2)O(2) oxidizes 2,4-DMP producing CO(2) and acetic acid. After 20 min of reaction time a pollutant conversion of 75% and 86% was found, depending on the H(2)O(2) dosage. Moreover, it was found that hydrogen peroxide was heterogeneously decomposed by the soil (due to its organic and/or inorganic components) and its decomposition rate decreases when the iron was previously precipitated-impregnated into the soil.     

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).     

Long-term oxidation kinetics of aluminide coatings on alloy steels by low temperature pack cementation process

The long-term oxidation kinetics of the P92 steel and iron aluminide diffusion coating formed on its surface by the pack cementation process have been investigated at 650 °C over a period of more than 7000 h both in 100% steam and in air under normal one atmospheric pressure by intermittent weight measurement at room temperature. X-ray diffraction (XRD), scanning electron microscopy (SEM) and energy dispersive spectroscopy (EDS) techniques were used to analyse the oxidised surfaces. For the P92 steel substrate, the scale formed by oxidation is largely magnetite (Fe₃O₄) in steam and haematite (Fe₂O₃) in air. Despite this difference in the type of oxide scales formed, it was found that the long-term oxidation kinetics of the P92 steel substrate in both steam and air can be described by a logarithmic time relationship: Δm _t = k _lln(t/t° + 1); the constants k _l and t° were subsequently determined using a closest fit process for oxidations in steam and air. For the coating, the oxide scale formed in both steam and air was Al₂O₃, which provided the long-term oxidation resistance. It was observed that the long-term oxidation kinetics of the coating in both steam and air can be best described by Δm _t = Δm ₀ + k _c t ^1/3; the rate constant k _c of oxidation in steam and air was then determined by the least squares method. For both the P92 steel substrate and coating, the rate of oxidation is faster in steam than in air at 650 °C particularly in the case of the P92 steel substrate.     

Comparison of disperse and reactive dye removals by chemical coagulation and Fenton oxidation

The composition of wastewater from the dyeing and textile processes is highly variable depending on the dyestuff type and typically has high COD and color. This study examined the decolorization of some of the most commonly used disperse and reactive dyestuffs by combination of chemical coagulation and Fenton oxidation. In addition, performances between Fe3+ coagulation and Fenton oxidation of dye solutions were compared by measuring COD and dye removals, distributions of zeta potential, concentration of suspended solid were investigated. Fenton oxidation in combination with Fe3+ coagulation has shown to effectively remove COD and dye. About 90% of COD and 99% of dye removals were obtained at the optimum conditions. Compared to reactive dyes, disperse dyes have lower solubility, higher suspended solids concentrations and lower SCOD/TCOD ratios. The COD and dye removed per unit Fe3+ coagulant added for disperse dye solutions were higher than those for reactive dye solutions. Therefore, the disperse dye solutions are more easily decolorized by chemical coagulation than reactive dye solutions. Conversely, reactive dye solutions have higher applicability of Fenton oxidation than disperse dye solutions due to their higher solubility, lower suspended solids concentrations and higher SCOD/TCOD ratios. The COD and dye removed per Fe2+ Fenton reagent added for reactive dye solutions are respectively higher than those for disperse dye solutions.     

Kinetics of 2,6-dimethylaniline degradation by electro-Fenton process

A new approach for promoting ferric reduction efficiency using a different electrochemical cell and the photoelectro-Fenton process has been developed to degrade organic toxic contaminants. The use of UVA light and electric current as electron donors can efficiently initiate the Fenton reaction. 2,6-Dimethylaniline (2,6-DMA) was the target compound in this study. Effects of initial pH (pH(i)), Fe(2+) loading, H(2)O(2) concentration and current density were determined to test and to validate a kinetic model for the oxidation of organic compound by the electro-Fenton process. Kinetic results show evidence of pseudo-first-order degradation. When reaction pH was higher than 2, amorphous Fe(OH)(3(s)) was generated. Increasing ferrous ion concentration from 1.0 to 1.5 mM increased the hydroxyl radicals and then promote the degradation efficiency of 2,6-DMA. The optimal H(2)O(2) concentration for 2,6-DMA degradation in this study was 25 mM. The degradation of 2,6-DMA was increased with the increase of current density from 3.5 to 10.6 A/m(2). Oxalic acid was the major detected intermediate of 2,6-DMA degradation. The final TOC removal efficiencies were 10%, 15%, 60% and 84% using the electrolysis, Fenton, electro-Fenton and photoelectro-Fenton processes, respectively.     

Decolorization of an azo dye Orange G in aqueous solution by Fenton oxidation process: effect of system parameters and kinetic study

To establish cost-efficient operating conditions for potential application of Fenton oxidation process to treat wastewater containing an azo dye Orange G (OG), some important operating parameters such as pH value of solutions, dosages of H(2)O(2) and Fe(2+), temperature, presence/absence of chloride ion and concentration of the dye, which effect on the decolorization of OG in aqueous solution by Fenton oxidation have been investigated systematically. In addition, the decolorization kinetics of OG was also elucidated based on the experimental data. The results showed that a suitable decolorization condition was selected as initial pH 4.0, H(2)O(2) dosage 1.0 x 10(-2)M and molar ratio of [H(2)O(2)]/[Fe(2+)] 286:1. The decolorization of OG enhanced with the increasing of reaction temperature but decreased as a presence of chloride ion. On the given conditions, for 2.21 x 10(-5) to 1.11 x 10(-4)M of OG, the decolorization efficiencies within 60 min were more than 94.6%. The decolorization kinetics of OG by Fenton oxidation process followed the second-order reaction kinetics, and the apparent activation energy E, was detected to be 34.84 kJ mol(-1). The results can provide fundamental knowledge for the treatment of wastewater containing OG and/or other azo dyes by Fenton oxidation process.     

Degradation of malachite green in aqueous solution by Fenton process

In this study, advanced oxidation process utilizing Fenton's reagent was investigated for degradation of malachite green (MG). The effects of different reaction parameters such as the initial MG concentration, initial pH, the initial hydrogen peroxide concentration, the initial ferrous concentration and the reaction temperature on the oxidative degradation of MG have been investigated. The optimal reacting conditions were experimentally found to be pH 3.40, initial hydrogen peroxide concentration=0.50mM and initial ferrous concentration=0.10mM for initial MG concentration of 20mg/L at 30 degrees C. Under optimal conditions, 99.25% degradation efficiency of dye in aqueous solution was achieved after 60 min of reaction.     

Olive mill wastewater degradation by Fenton oxidation with zero-valent iron and hydrogen peroxide

The degradation of olive mill wastewater (OMW) with hydroxyl radicals generated from zero-valent iron and hydrogen peroxide has been investigated by means of chemical oxygen demand (COD) and phenolic compounds analyses. The effects of the H2O2 dose, the pH and the organic matter concentration have been studied. The optimal experimental conditions were found to have continuous presence of iron metal, acid pH (2.0-4.0), and relatively concentrated hydrogen peroxide (9.5M). Coloration of OMW disappeared and phenolic compound decreased to 50% of initial concentration after 3h reaction time. The application of zero-valent Fe/H2O2 procedure permitted high removal efficiencies of pollutants from olive mill wastewater. The results show that zero-valent Fe/H2O2 could be considered as an effective alternative solution for the treatment of OMW or may be combined with a classical biological process to achieve high quality of effluent water.     

Application of Fenton oxidation to cosmetic wastewaters treatment

The removal of organic matter (TOC and COD) from a cosmetic wastewater by Fenton oxidation treatment has been evaluated. The operating conditions (temperature as well as ferrous ion and hydrogen peroxide dosage) have been optimized. Working at an initial pH equal to 3.0, a Fe(2+) concentration of 200 mg/L and a H(2)O(2) concentration to COD initial weight ratio corresponding to the theoretical stoichiometric value (2.12), a TOC conversion higher than 45% at 25 degrees C and 60% at 50 degrees C was achieved. Application of the Fenton oxidation process allows to reach the COD regional limit for industrial wastewaters discharges to the municipal sewer system. A simple kinetic analysis based on TOC was carried out. A second-order equation describes well the overall kinetics of the process within a wide TOC conversion range covering up to the 80-90% of the maximum achievable conversion.     

Treatment of jean-wash wastewater by combined coagulation, hydrolysis/acidification and Fenton oxidation

Performance of a full-scale combined treatment plant for jean-wash wastewater (JWW) was investigated. The combined process consisted of chemical coagulation, hydrolysis/acidification and Fenton oxidation. Chemical coagulation treatment with polymeric ferric sulfate (PFS)/lime alone proved to be effective in removing the COD (>70%) and part of the color (>50%) from the JWW. Fenton oxidation combined with hydrolysis/acidification as pretreatment offered a noticeable BOD removal efficiency. The average removal efficiencies for COD, BOD, SS, color and aromatic compounds of the combined process were about 95%, 94%, 97%, 95% and 90%, respectively, with the average effluent quality of COD 58 mg/L, BOD 19 mg/L, SS 4 mg/L and color 15(multiple), consistent with the national discharge limits for textile wastewater. The result indicated that the combined procedure could offer an attractive solution for JWW treatment with considerable synergistic advantages.     

Comparative study of oxidation of dye-Reactive Black B by different advanced oxidation processes: Fenton, electro-Fenton and photo-Fenton

This study makes a comparison between photo-Fenton and a novel electro-Fenton called Fered-Fenton to study the mineralization of 10,000 mg/L of dye-Reactive Black B (RBB) aqueous solution, which was chosen as the model dye contaminant. Results indicate that the traditional Fenton process only yields 70% mineralization. This result can be improved by using Fered-Fenton to yield 93% mineralization resulting from the action of ferrous ion regenerated on the cathode. Furthermore, photo-Fenton allows a fast and more complete destruction of dye solutions and as a result of the action of ferrous ion regenerated by UV irradiation yields more than 98% mineralization. In all treatments, the RBB is rapidly decayed to some carboxylic acid intermediates. The major intermediates found are formic acid and oxalic acid. This study finds that formic acid can be completely mineralized by photo-Fenton, but its destruction is problematic using the Fenton method. Oxalic acid is much more difficult to treat than other organic acids. It could get further mineralization with the use of the Fered-Fenton process.     

Kinetic and mechanistic investigations of mesotrione degradation in aqueous medium by Fenton process

In this work, chemical oxidation of mesotrione herbicide by Fenton process in acidic medium (pH 3.5) was investigated. Total disappearance of mesotrione and up to 95% removal of total organic carbon (TOC) were achieved by Fenton's reagent under optimized initial concentrations of hydrogen peroxide (H(2)O(2)) and ferrous iron (Fe(2+)) at pH 3.5. The time-dependent degradation profiles of mesotrione were satisfactorily fitted by first-order kinetics. Competition kinetic model was used to evaluate a rate constant of 8.8(± 0.2) × 10(9)M(-1) s(-1) for the reaction of mesotrione with hydroxyl radicals. Aromatic and aliphatic intermediates of mesotrione oxidation were identified and quantified by high performance liquid chromatography (HPLC). It seems that the degradation of mesotrione by Fenton process begins with the rupture of mesotrione molecule into two moieties: cyclohexane-1,3-dione derivative and 2-nitro-4-methylsulfonylbenzoic acid. Hydroxylation and release of sulfonyl and/or nitro groups from 2-nitro-4-methylsulfonylbenzoic acid lead to the formation of polyhydroxylated benzoic acid derivatives which undergo an oxidative opening of benzene ring into carboxylic acids that end to be transformed into carbon dioxide.     

Treatment of water-based printing ink wastewater by Fenton process combined with coagulation

Attempts were made in this study to examine the efficiency of Fenton process combined with coagulation for treatment of water-based printing ink wastewater. Parameters affecting the Fenton process, such as pH, dosages of Fenton reagents and the settling time, were determined by using jar test experiments. 86.4% of color and 92.4% of chemical oxygen demand (COD) could be removed at pH 4, 50mg/l H(2)O(2), 25mg/l FeSO(4) and 30min settling time. The coagulation using polyaluminium chloride (PAC) and ferrous sulfate (FeSO(4)) was beneficial to improve the Fenton process treated effluent in reducing the flocs settling time, enhancing color and COD removal. The overall color, COD and suspended solids (SS) removal reached 100%, 93.4% and 87.2% under selected conditions, respectively. Thus this study might offer an effective way for wastewater treatment of water-based ink manufacturer and printing corporation.     

Deposition of silica films by the oxidation of silane in oxygen: I: The kinetics and physicochemical model of the process

The kinetics of growth of silica films were studied in a resistance-heated quartz tube reactor over the temperature range 250–600°C under atmospheric pressure in the presence of argon. The concentration of silane was varied from 0.01 to 0.1 mol.% and the ratio [O₂]/[SiH₄] ranged from 5 to 300. The composition of the gaseous mixture was analysed at the outlet of the reactor by infrared spectroscopy.It has been shown that the oxidation of silane starts in the gaseous phase and follows a branched chain reaction. For our ignition limits the following expression was obtained. $\text{[O}{}_2\text{]}\text{[SiH}{}_4\text{]}$= 2.6×10⁵ exp (-$\text{9700}\text{RT}$)Film growth is only observed when silane combustion occurs in the gaseos phase. A physicochemical model of the process is suggested which assumes that at least two intermediate products containing silicon are formed during the chain reaction in the gaseous phase. One of these, P₁, diffuses to the surface and the SiO₂ film results from a heterogeneous reaction. The second product, P₂, is transformed into a white deposit of SiO₂ at the outlet of the reactor.     

Catalyst-free synthesis of silicon nanowires by oxidation and reduction process

A new process has been developed to grow silicon (Si) nanowires (NWs), and their growth mechanisms were explored and discussed. In this process, SiNWs were synthesized by simply oxidizing and then reducing Si wafers in a high temperature furnace. The process involves H₂, in an inert atmosphere, reacts with thermally grown SiO₂ on Si at 1100 °C enhancing the growth of SiNWs directly on Si wafers. High-resolution transmission electron microscopy studies show that the NWs consists of a crystalline core of ~25 nm in diameter and an amorphous oxide shell of ~2 nm in thickness, which was also supported by selected area electron diffraction patterns. The NWs synthesized exhibit a high aspect ratio of ~167 and room temperature phonon confinement effect. This simple and economical process to synthesize crystalline SiNWs opens up a new way for large scale applications.     

Treatment of printed circuit board industrial wastewater by Ferrite process combined with Fenton method

Printed circuit board wastewater typically contains organics and metal ions. The study explored the feasibility of a sequential procedure, FFP (the combination of the Fenton method and the Ferrite process), for treating printed circuit board wastewater, and established the optimum parameters for it. The analytical results showed that the proper pH level was 2 for Fenton oxidation, and the appropriate H₂O₂ dosing type was batch dosing. For the Ferrite process, the suitable Fe/M (Fe is the total dose of Fe²⁺ added to a solution and M is the initial total moles of various metal ions in untreated wastewater) molar ratio was 10 and the sludge met the toxicity characteristic leaching procedure (TCLP) standards. Following FFP treatment, effluent water or sludge easily met Taiwan's standards. Finally, the SEM/EDS test demonstrated that particle sizes of the sludge were approximately 50–80 nm, and the saturation magnetization was 67.5 emu/g.     

Synthesis and kinetics research of ZnS nanoparticles prepared by sonochemical process

Abstract

ZnS nanocrystallites have been successfully prepared by a sonochemical process. The reaction kinetics of the process was also investigated. The as prepared ZnS nanocrystallites were characterised by XRD and TEM. Results show that ZnS nanoparticles can be obtained by sonochemical process using ZnCl₂ and thiacetamide as raw materials. It is found that the as prepared ZnS nanoparticles are hexagonal phase with spherical or spherical-like morphologies. The grain size decreases with increasing ultrasonic irradiation power. Reaction kinetics shows that the weight content of ZnS nanoparticles increases linearly with reaction time at different temperatures. The synthesis activation energy of ZnS nanoparticles is calculated to be 27·80 kJ mol^–1.     

Use of Fenton oxidation to improve the biodegradability of a pharmaceutical wastewater

The applicability of Fenton's oxidation to improve the biodegradability of a pharmaceutical wastewater to be treated biologically was investigated. The wastewater was originated from a factory producing a variety of pharmaceutical chemicals. Treatability studies were conducted under laboratory conditions with all chemicals (having COD varying from 900 to 7000 mg/L) produced in the factory in order to determine the operational conditions to utilize in the full-scale treatment plant. Optimum pH was determined as 3.5 and 7.0 for the first (oxidation) and second stage (coagulation) of the Fenton process, respectively. For all chemicals, COD removal efficiency was highest when the molar ratio of H(2)O(2)/Fe(2+) was 150-250. At H(2)O(2)/Fe(2+) ratio of 155, 0.3M H(2)O(2) and 0.002 M Fe(2+), provided 45-65% COD removal. The wastewater treatment plant that employs Fenton oxidation followed by aerobic degradation in sequencing batch reactors (SBR), built after these treatability studies provided an overall COD removal efficiency of 98%, and compliance with the discharge limits. The efficiency of the Fenton's oxidation was around 45-50% and the efficiency in the SBR system which has two reactors each having a volume of 8m(3) and operated with a total cycle time of 1 day, was around 98%, regarding the COD removal.