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1.
A comparative study of the degradation of Acid Orange 7 (AO 7) aqueous solutions in acidic medium of pH 3.0 by electro-Fenton process using Pt or boron-doped diamond (BDD) anode was reported. The oxidative degradation of AO 7 by electrochemically generated hydroxyl radicals follows a pseudo-first order kinetic with a similar rate constant with BDD or Pt anode. The absolute rate constant of the AO 7 hydroxylation reaction was determined as (1.10+/-0.04)x10(10)M(-1)s(-1) by using the competition kinetic method. The comparative study of TOC measurements during electro-Fenton treatment showed a higher mineralization rate with BDD than Pt anode at the first hours of electrolysis because of the higher oxidizing power of this anode. The electro-Fenton degradation of AO 7 was followed by monitoring the formation and evolution of aromatic intermediates which are oxidized to aliphatic carboxylic acids before mineralization (transformation to CO(2) and inorganic ions, i.e. sulphate, nitrate and ammonium). The follow-up of the solution toxicity evolution shows the formation of intermediates more toxic than AO 7 and the connection between toxicity and aromaticity. A mineralization reaction pathway of AO 7 by electro-Fenton degradation involving all the intermediates identified was proposed.  相似文献   

2.
In this work, the electrochemical degradation of the dye azure B in aqueous solutions was studied by electrochemical advanced oxidation processes (EAOPs), electro-Fenton, and anodic oxidation processes, using Pt/carbon-felt and boron-doped diamond (BDD)/carbon-felt cells with H2O2 electrogeneration. The higher oxidation power of the electro-Fenton (EF) process using BDD anode was demonstrated. The oxidative degradation of azure B by the electrochemically generated hydroxyl radicals (?OH) follows a pseudo-first-order kinetics. The apparent rate constants of the oxidation of azure B by ?OH were measured according to pseudo-first-order kinetic model. The absolute rate constant of azure B hydroxylation reaction was determined by competition kinetics method and found to be 1.19?×?109 M?1 s?1. It was found that the electrochemical degradation of the dye leads to the formation of aromatic by-products which are then oxidized to aliphatic carboxylic acids before their almost mineralization to CO2 and inorganic ions (sulfate, nitrate, and ammonium). The evolution of the TOC removal and time course of short-chain carboxylic acids during treatment were also investigated.  相似文献   

3.
The oxidative degradation of imidacloprid (ICP) has been carried out by electrochemical advanced oxidation processes (EAOPs), anodic oxidation, and electro-Fenton, in which hydroxyl radicals are generated electrocatalytically. Carbon-felt cathode and platinum or boron-doped diamond (BDD) anodes were used in electrolysis cell. To determine optimum operating conditions, the effects of applied current and catalyst concentration were investigated. The decay of ICP during the oxidative degradation was well fitted to pseudo-first-order reaction kinetics and absolute rate constant of the oxidation of ICP by hydroxyl radicals was found to be k abs(ICP)?=?1.23?×?109 L mol?1 s?1. The results showed that both anodic oxidation and electro-Fenton process with BDD anode exhibited high mineralization efficiency reaching 91 and 94 % total organic carbon (TOC) removal at 2 h, respectively. For Pt-EF process, mineralization efficiency was also obtained as 71 %. The degradation products of ICP were identified and a plausible general oxidation mechanism was proposed. Some of the main reaction intermediates such as 6-chloronicotinic acid, 6-chloronicotinaldehyde, and 6-hydroxynicotinic acid were determined by GC-MS analysis. Before complete mineralization, formic, acetic, oxalic, and glyoxylic acids were identified as end-products. The initial chlorine and organic nitrogen present in ICP were found to be converted to inorganic anions Cl?, NO3 ?, and NH4 +.  相似文献   

4.

Introduction

The degradation and mineralization of two triketone (TRK) herbicides, including sulcotrione and mesotrione, by the electro-Fenton process (electro-Fenton using Pt anode (EF-Pt), electro-Fenton with BDD anode (EF-BDD) and anodic oxidation with BDD anode) were investigated in acidic aqueous medium.

Methods

The reactivity of both herbicides toward hydroxyl radicals was found to depend on the electron-withdrawing effect of the aromatic chlorine or nitro substituents. The degradation of sulcotrione and mesotrione obeyed apparent first-order reaction kinetics, and their absolute rate constants with hydroxyl radicals at pH?3.0 were determined by the competitive kinetics method.

Results and discussion

The hydroxylation absolute rate constant (k abs) values of both TRK herbicides ranged from 8.20?×?108 (sulcotrione) to 1.01?×?109 (mesotrione) L?mol?1?s?1, whereas those of the TRK main cyclic or aromatic by-products, namely cyclohexane 1,3-dione , (2-chloro-4-methylsulphonyl) benzoic acid and 4-(methylsulphonyl)-2-nitrobenzoic acid, comprised between 5.90?×?108 and 3.29?×?109?L?mol?1?s?1. The efficiency of mineralization of aqueous solutions of both TRK herbicides was evaluated in terms of total organic carbon removal. Mineralization yields of about 97?C98% were reached in optimal conditions for a 6-h electro-Fenton treatment time.

Conclusions

The mineralization process steps involved the oxidative opening of the aromatic or cyclic TRK by-products, leading to the formation of short-chain carboxylic acids, and, then, of carbon dioxide and inorganic ions.  相似文献   

5.
The electrochemical abatement of the drug ibuprofen (2-(4-isobutylphenyl)propionic acid) from aqueous solution has been carried out by anodic oxidation. The electrolyses have been performed at constant current using a small, undivided cell equipped with a Pt or thin-film boron-doped diamond (BDD) anode and a carbon-felt cathode. The results have shown that ibuprofen has been destroyed under all the conditions tested, following pseudo-first-order kinetics; however, BDD enables higher removal rates than Pt, because the former produces greater quantity of ?OH. Using BDD anode, the pseudo-first-order rate constant increased with applied current and when NaCl replaced Na2SO4 as supporting electrolyte, while it is almost unaffected by ibuprofen concentration. Mineralization of ibuprofen aqueous solutions was followed by total organic carbon (TOC) measurements. After 8 h of electrolysis, TOC removal varied from 91 % to 96 % applying a current in the range of 50–500 mA. The reaction by-products were quantified by chromatographic techniques, and in particular, aliphatic acids (oxalic, glyoxylic, formic, acetic, and pyruvic) have been the main intermediates formed during the electrolyses. The absolute rate constant for the oxidative degradation of ibuprofen have also been determined, by competition kinetic method, as 6.41?×?109 M?1?s?1.  相似文献   

6.
Electrochemical advanced oxidation processes (EAOPs) are environmentally friendly methods based on the destruction of organic pollutants in wastewaters with in situ electrogenerated hydroxyl radical. This species is formed in anodic oxidation (AO) from water oxidation at the anode and in indirect electro-oxidation methods like electro-Fenton (EF) and photoelectro-Fenton (PEF) also from reaction between catalytic Fe2+ and H2O2 continuously produced at the O2-diffusion cathode. The PEF method involves the irradiation of the treated solution with UVA light to enhance the photolysis of organics including Fe(III) complexes. In this work, the oxidation power of such EAOPs to decontaminate synthetic wastewaters of the biocide chloroxylenol (4-chloro-3,5-dimethylphenol) at pH 3.0 is comparatively examined with an undivided electrolytic cell containing a Pt or boron-doped diamond (BDD) anode and a stainless steel or O2-diffusion cathode. The initial chlorine is released as Cl(-) ion, which remains stable in the medium using Pt or is oxidized to Cl2 on BDD. The biocide solutions can be completely decontaminated using AO with a BDD anode, as well as PEF with a Pt or BDD anode. The PEF procedure with a BDD anode is the most powerful method leading to total mineralization in about 300 min, practically independent of current density. When current density rises, the degradation rate of processes increases, but they become less efficient due to the larger enhancement of waste reactions of oxidants. Chloroxylenol is much more rapidly removed in EF and PEF than in AO. 2,6-dimethylhydroquinone, 2,6-dimethyl-p-benzoquinone and 3,5-dimethyl-2-hydroxy-p-benzoquinone are identified as aromatic by-products, and maleic, malonic, pyruvic, acetic and oxalic acids are found as generated carboxylic acids. A general pathway for chloroxylenol mineralization by all EAOPs including the above by-products is proposed.  相似文献   

7.
This study is focused on the effective removal of recalcitrant pollutants hexaclorocyclohexanes (HCHs, isomers α, β, γ, and δ) and chlorobenzenes (CBs) present in a real groundwater coming from a landfill of an old lindane factory. Groundwater is characterized by a total organic carbon (TOC) content of 9 mg L?1, pH0?=?7, conductivity?=?3.7 mS cm?1, high salt concentration (SO42?, HCO3?, Cl?), and ferrous iron in solution. The experiments were performed using a BDD anode and a carbon felt (CF) cathode at the natural groundwater pH and without addition of supporting electrolyte. The complete depletion of the four HCH isomers and a mineralization degree of 90% were reached at 4-h electrolysis with a current intensity of 400 mA, the residual TOC (0.8 mg L?1) corresponding mainly to formic acid. A parallel series reaction pathway was proposed: HCHs and CBs are transformed into chlorinated and hydroxylated intermediates that are rapidly oxidized to non-toxic carboxylic acids and/or mineralized, leading to a rapid decrease in solution pH.  相似文献   

8.
The degradation of 230 mL of a 0.6-mM sulfanilamide solution in 0.05 M Na2SO4 of pH 3.0 has been studied by electro-Fenton process. The electrolytic cell contained either a Pt or boron-doped diamond (BDD) anode and a carbon-felt cathode. Under these conditions, organics are oxidized by hydroxyl radicals formed at the anode surface from water oxidation and in the bulk from Fenton’s reaction between initially added (and then electrochemically regenerated) Fe2+ and cathodically generated H2O2. From the decay of sulfanilamide concentration determined by reversed-phase liquid chromatography, an optimum Fe2+ concentration of 0.20 mM in both cells was found. The drug disappeared more rapidly using BDD than Pt, and, in both cases, it was more quickly removed with raising applied current. Almost total mineralization was achieved using the BDD/carbon-felt cell, whereas the alternative use of Pt anode led to a slightly lower mineralization degree. In both cells, the degradation rate was accelerated at higher current but with the concomitant fall of mineralization current efficiency due to the greater increase in rate of the parasitic reactions of hydroxyl radicals. Reversed-phase liquid chromatography allowed the identification of catechol, resorcinol, hydroquinone, p-benzoquinone, and 1,2,4-trihydroxybenzene as aromatic intermediates, whereas ion exclusion chromatography revealed the formation of malic, maleic, fumaric, acetic, oxalic, formic, and oxamic acids. NH4 +, NO3 ?, and SO4 2? ions were released during the electro-Fenton process. A plausible reaction sequence for sulfanilamide mineralization involving all detected intermediates has been proposed. The toxicity of the solution was assessed from the Vibrio fischeri bacteria luminescence inhibition. Although it acquired its maximum value at short electrolysis time, the solution was completely detoxified at the end of the electro-Fenton treatment, regardless of the anode used.  相似文献   

9.
The degradation of 100ml of solutions with paracetamol (N-(4-hydroxyphenyl)acetamide) up to 1 g l(-1) in the pH range 2.0-12.0 has been studied by anodic oxidation in a cell with a boron-doped diamond (BDD) anode and a graphite cathode, both of 3-cm2 area, by applying a current of 100, 300 and 450 mA between 25 and 45 degrees C. Complete mineralization is always achieved due to the great concentration of hydroxyl radical (*OH) generated at the BDD surface, with release of NH4+ and NO3- ions. The mineralization rate is pH-independent, increases with increasing applied current and temperature, but decreases when drug concentration raises from 315 mg l(-1). Reversed-phase chromatography revealed a similar complex paracetamol decay in acid and alkaline media. Ion-exclusion chromatography allowed the detection of oxalic and oxamic acids as ultimate carboxylic acids. When the same solutions have been comparatively treated with a Pt anode, a quite poor mineralization is found because of the production of much lower *OH concentration. Under these conditions, the degradation rate is enhanced in alkaline medium and polymerization of intermediates is favored in concentrated solutions. Paracetamol can be completely destroyed with Pt and its kinetics follows a pseudo-first-order reaction with a constant rate independent of pH.  相似文献   

10.
This paper reports the degradation of 2,4-DP (2-(2,4-dichlorophenoxy)-propionic acid) solutions of pH 3.0 by environmentally friendly electrochemical methods such as anodic oxidation, electro-Fenton and photoelectro-Fenton with a Pt or boron-doped diamond (BDD) anode. In the two latter techniques an O(2)-diffusion cathode was used and 1.0mM Fe(2+) was added to the solution to give hydroxyl radical (*OH) from Fenton's reaction between Fe(2+) and H(2)O(2) generated at the cathode. All treatments with BDD are viable to decontaminate acidic wastewaters containing 2,4-DP since they give complete mineralization, with loss of chloride ion, at high current due to the great production of oxidant *OH at the BDD surface favoring the destruction of final carboxylic acids. *OH formed from Fenton's reaction destroys more rapidly aromatic products, making the electro-Fenton and photoelectro-Fenton processes much more efficient than anodic oxidation. UVA light in photoelectro-Fenton with BDD has little effect on the degradation rate of pollutants. The comparative procedures with Pt lead to slower decontamination because of the lower oxidizing power of this anode. The effect of current on the degradation rate and efficiency of all methods is studied. The 2,4-DP decay always follows a pseudo-first-order kinetics. Chlorohydroquinone, chloro-p-benzoquinone and maleic, fumaric, malic, lactic, pyruvic, acetic, formic and oxalic acids are detected as products by chromatographic techniques. A general sequence accounting for by the reaction of all these intermediates with the different oxidizing agents is proposed.  相似文献   

11.
Zhao G  Shen S  Li M  Wu M  Cao T  Li D 《Chemosphere》2008,73(9):1407-1413
The research on ultrasound (US) enhanced electrochemical oxidation of Phenol (Ph) on boron-doped diamond (BDD) and Pt electrodes is studied. The enhancement by US on BDD is much greater than for Pt. With the assistance of US, the degradation rate and current efficiency on BDD are increased by 301% and 100%, respectively, while those on Pt are 51% and 49%. The difference of the enhancement on these two electrodes is caused by the fact that mass transport, adsorption amount and electrode reaction affected by US on BDD are different from those of Pt. The kinetics investigation on intermediates formed during electrochemical degradation show that the variety of intermediates produced on BDD is less than for Pt. In the presence of US, on both electrodes, no change occurred to the amounts of the intermediate species. However, time for intermediates to reach the highest concentration is cut down. This effect for degradation of Ph on BDD is more obvious than for Pt. The present research indicates that BDD is suitable for degradation of Ph by US assisted electrochemical oxidation.  相似文献   

12.
The anodic degradation of 1,4-benzoquinone (BQ), one of the most toxic xenobiotic, was investigated by electrochemical oxidation at boron-doped diamond anode. The electrolyses have been performed in a single-compartment flow cell in galvanostatic conditions. The influence of applied current (0.5–2 A), BQ concentration (1–2 g dm?3), temperature (20–45 °C) and flow rate (100–300 dm3 h?1) has been studied. BQ decay kinetic, the evolution of its oxidation intermediates and the mineralization of the aqueous solutions were monitored during the electrolysis by high-performance liquid chromatograph (HPLC) and chemical oxygen demand (COD) measurements. The results obtained show that the use of diamond anode leads to total mineralization of BQ in any experimental conditions due to the production of oxidant hydroxyl radicals electrogenerated from water discharge. The decay kinetics of BQ removal follows a pseudo-first-order reaction, and the rate constant increases with rising current density. The COD removal rate was favoured by increasing of applied current, recirculating flow rate and it is almost unaffected by solution temperature.  相似文献   

13.
Electrochemical oxidation (ELOX) with boron-doped diamond (BDD) anodes was successfully applied to degrade a model aqueous solution of a mixture of commercial naphthenic acids (NAs). The model mixture was prepared resembling the NA and salt composition of oil sands process-affected water (OSPW) as described in the literature. The initial concentration of NAs between 70 and 120 mg/L did not influence the electrooxidation kinetics. However, increasing the applied current density from 20 to 100 A/m2 and the initial chloride concentration from 15 to 70 and 150 mg/L accelerated the rate of NA degradation. At higher chloride concentration, the formation of indirect oxidative species could contribute to the faster oxidation of NAs. Complete chemical oxygen demand removal at an initial NA concentration of 120 mg/L, 70 mg/L of chloride and applied 50 A/m2 of current density was achieved, and 85% mineralization, defined as the decrease of the total organic carbon (TOC) content, was attained. Moreover, after 6 h of treatment and independently on the experimental conditions, the formation of more toxic species, i.e. perchlorate and organochlorinated compounds, was not detected. Finally, the use of ELOX with BDD anodes produced a 7 to 11-fold reduction of toxicity (IC50 towards Vibrio fischeri) after 2 h of treatment.  相似文献   

14.
Scale-up of anodic oxidation system is critical to the practical application of electrochemical treatment in bio-refractory organic wastewater treatment. In this study, the scale-up of electrochemical flow system was investigated by treating petrochemical wastewater using platinized titanium (Ti/Pt) and boron-doped diamond (BDD) anodes. It was demonstrated that flow cell was successfully scaled-up because when it was compared with batch mode (Rocha et al. 2012b), higher performances on organic matter removal were achieved. Under the suitable operating conditions and better anode material, the chemical oxygen demand (COD) of petrochemical wastewater was reduced from 2,746 to 200 mg L?1 within 5 h with an energy consumption of only 56.2 kWh m?3 in the scaled-up BDD anode system. These results demonstrate that anode flow system is very promising in practical bio-refractory organic wastewater treatment.  相似文献   

15.
The anodic oxidation of 1.8l of solutions with mecoprop (2-(4-chloro-2-methylphenoxy)-propionic acid or MCPP) up to 0.64 g l(-1) in Na2SO4 as background electrolyte within the pH range 2.0-12.0 has been studied using a flow plant containing a one-compartment filter-press electrolytic reactor with a boron-doped diamond (BDD) anode and a stainless steel cathode, both of 20-cm2 area. Electrolyses carried out in batch under steady conditions and operating at constant current density between 50 and 150 mA cm(-2) always yield complete mineralization due to the great concentration of hydroxyl radical generated at the BDD anode. The degradation rate is practically independent of pH and Na2SO4 concentration, but it becomes faster with increasing MCPP concentration, current density, temperature and liquid flow rate. The effect of these parameters on current efficiency and energy cost has also been investigated. Generated weak oxidants such as H2O2 and peroxodisulfate ion have little influence on the mineralization process. The kinetics for the herbicide decay follows a pseudo first-order reaction with a higher rate constant when current density increases. Aromatic products such as 4-chloro-o-cresol, 2-methylhydroquinone and 2-methyl-p-benzoquinone, and generated carboxylic acids such as maleic, fumaric, lactic, pyruvic, tartronic, acetic and oxalic, have been identified as intermediates by chromatographic techniques. The initial chlorine is completely released in the form of chloride ion, which is slowly oxidized to Cl2 at the BDD anode. A reaction pathway for MCPP mineralization involving all products detected is proposed.  相似文献   

16.
Diagne M  Oturan N  Oturan MA 《Chemosphere》2007,66(5):841-848
The electro-Fenton process was used to assess the degradation of methyl parathion (MP) in aqueous solutions. This oxidation process allows the production of hydroxyls radicals which react on the organic compounds, leading to their mineralization. Degradation experiments were performed either in perchloric, sulphuric, hydrochloric and nitric acid media under current controlled electrolysis conditions at different pH. The pH effect as well as the nature of the medium (i.e., the nature of the ions present in medium) on the degradation and mineralization efficiency were studied. The mineralization of the initial pollutant was investigated by total organic carbon measurements which show a complete mineralization at pH 3 in perchloric medium. The absolute rate constant of MP hydroxylation reaction was determined as (4.20+/-0.11)x10(9)M(-1)s(-1). Complete degradation of MP and its metabolites occur in less than 45min. Degradation reaction intermediates such as aromatic compounds, carboxylic acids and inorganic ions were identified and a mineralization pathway is proposed.  相似文献   

17.
This paper compares the performance of 2D (plate) and 3D (mesh) boron-doped diamond (BDD) electrodes, fitted into a filter-press reactor, during the electrochemical incineration of indigo textile dye as a model organic compound in chloride medium. The electrolyses were carried out in the FM01-LC reactor at mean fluid velocities between 0.9?≤?u?≤?10.4 and 1.2?≤?u?≤?13.9 cm s?1 for the 2D BDD and the 3D BDD electrodes, respectively, at current densities of 5.63 and 15 mA cm?2. The oxidation of the organic matter was promoted, on the one hand, via the physisorbed hydroxyl radicals (BDD(OH)) formed from water oxidation at the BDD surface and, on the other hand, via active chlorine formed from the oxidation of chloride ions on BDD. The performance of 2D BDD and 3D BDD electrodes in terms of current efficiency, energy consumption, and charge passage during the treatments is discussed.  相似文献   

18.
This paper focuses on the influence of the current density treatment of a concentrated 1-butyl-3-methylimidazolium chloride (BMImCl) solution on an electrochemical reactor with a boron-doped diamond (BDD) anode. The decrease in the total organic carbon (TOC) and the BMImCl concentration demonstrate the capability of BDD in oxidizing ionic liquids (ILs) and further mineralizing (to CO2 and NO3 ?) more rapidly at higher current densities in spite of the reduced current efficiency of the process. Moreover, the presence of Cl? led to the formation of oxychlorinated anions (mostly ClO3 ? and ClO4 ?) and, in combination with the ammonia generated in the cathode from the nitrate reduction, chloramines, more intensely at higher current density. Finally, the analysis of the intermediates formed revealed no apparent influence of the current density on the BMImCl degradation mechanism. The current density presents therefore a complex influence on the IL treatment process that is discussed throughout this paper.  相似文献   

19.
The aim of this study was to assess the degradation and mineralization of hydroquinone (HQ) by the Fenton’s process in a bubble column reactor (BCR). The effect of the main operating variables, namely, air flow rate, effluent volume, hydrogen peroxide (H2O2) concentration, catalyst (Fe2+) dose, initial pH, and temperature, were assessed. For all air flow rates tested, no concentration gradients along the column were noticed, evidencing that a good mixing was reached in the BCR. For the best conditions tested ([H2O2] = 500 mg/L, [Fe2+] = 45 mg/L, T = 24 °C, Q air = 2.5 mL/min, pH = 3.0, and V = 5 L), complete HQ degradation was reached, with ~ 39% of total organic carbon (TOC) removal, and an efficiency of the oxidant use—η H2O2—of 0.39 (ratio between TOC removed per H2O2 consumed normalized by the theoretical stoichiometric value); moreover, a non-toxic effluent was generated. Under these conditions, the intermediates and final oxidation compounds identified and quantified were a few carboxylic acids, namely, maleic, pyruvic, and oxalic. As a strategy to improve the TOC removal, a gradual dosage of the optimal H2O2 concentration was implemented, being obtained ~ 55% of mineralization (with complete HQ degradation). Finally, the matrix effect was evaluated, for which a real wastewater was spiked with 100 mg/L of HQ; no reduction in terms of HQ degradation and mineralization was observed compared to the solution in distilled water.  相似文献   

20.
Photocatalytic degradation of bisphenol A (BPA) in waters and wastewaters in the presence of titanium dioxide (TiO2) was performed under different conditions. Suspensions of the TiO2 were used to compare the degradation efficiency of BPA (20 mg L?1) in batch and compound parabolic collector (CPC) reactors. A TiO2 catalyst supported on glass spheres was prepared (sol–gel method) and used in a CPC solar pilot plant for the photodegradation of BPA (100 μg L?1). The influence of OH·, O2 ·?, and h + on the BPA degradation were evaluated. The radicals OH· and O2 ·? were proved to be the main species involved on BPA photodegradation. Total organic carbon (TOC) and carboxylic acids were determined to evaluate the BPA mineralization during the photodegradation process. Some toxicological effects of BPA and its photoproducts on Eisenia andrei earthworms were evaluated. The results show that the optimal concentration of suspended TiO2 to degrade BPA in batch or CPC reactors was 0.1 g L?1. According to biological tests, the BPA LC50 in 24 h for E. andrei was of 1.7?×?10?2 mg cm?2. The photocatalytic degradation of BPA mediated by TiO2 supported on glass spheres suffered strong influence of the water matrix. On real municipal wastewater treatment plant (MWWTP) secondary effluent, 30 % of BPA remains in solution; nevertheless, the method has the enormous advantage since it eliminates the need of catalyst removal step, reducing the cost of treatment.  相似文献   

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