Electrochemical removal of the insecticide imidacloprid from water on a boron-doped diamond and Ta/PbO<Subscript>2</Subscript> anodes using anodic oxidation process

The removal of pesticides from water is a major environmental concern. This study investigates the electrochemical removal of the insecticide imidacloprid (IMD) from aqueous solutions on a boron-doped diamond (BDD) and Ta/PbO₂ anodes under galvanostatic electrolysis. The influence of operating parameters, such as applied current density (50–100 mA cm^?2), initial chemical oxygen demand COD (0) (281–953 mg L^?1), temperature (25–65 °C) and pH (3.0–10.0) on COD and instantaneous current efficiency (ICE), was studied using the BDD electrode. The degradation efficiency of IMD increased by increasing current density and temperature, but noticeably decreased by the increase of initial pH value and initial concentration of IMD. The COD decay follows a pseudo-first-order kinetic, and the process was under mass transport control. COD removal reaches 90% when using an apparent current density of 100 mA cm^?2, initial COD of 953 mg L^?1, pH of 3.0 and at 25 °C after 4.5 h electrolysis time. Compared with Ta/PbO₂, BDD anode has shown better performance and rapidity in the COD removal using the same electrolysis device.     

Electrochemical oxidation of Basic Blue 3 dye using a diamond anode: evaluation of colour,COD and toxicity removal

BACKGROUND: Textile industries generate considerable amounts of waste‐water, which may contain strong colour, suspended particles, salts, high pH and high chemical oxygen demand (COD) concentration. The disposal of these coloured wastewaters poses a major problem for the industry as well as a threat to the environment. In this study, electrochemical oxidation of Basic Blue 3 (BB3) dye was studied in a bipolar trickle tower (BTT) reactor using Raschig ring shaped boron‐doped diamond (BDD) electrodes in recirculated batch mode. The effects of current density, temperature, flow rate, sodium sulfate concentration (Na₂SO₄) as supporting electrolyte, and initial dye concentration were investigated. RESULTS: The best experimental conditions obtained were as follows: current density 0.875 mA cm^?2, temperature 30 °C, flow rate 109.5 mL min^?1, Na₂SO₄ concentration 0.01 mol L^?1. Under these conditions, 99% colour and 86.7% COD removal were achieved. Toxicity tests were also performed on BB3 solutions under the best experimental conditions. CONCLUSION: Based on these results, the BDD anode was found to be very successful for the simultaneous degradation of BB3 and removal of COD. Additional toxicity test results also showed that electrochemical treatment using a BDD Raschig ring anode in a BTT reactor is an effective way of reducing toxicity as well as removing colour and COD. Copyright © 2010 Society of Chemical Industry     

Electrochemical degradation of anionic surfactants

This study was performed to investigate the electrochemical oxidation of anionic surfactants. In particular, a synthetic solution of sodium dodecyl benzene sulfonate and a real car wash wastewater were treated by galvanostatic electrolysis using a Ti–Ru–Sn ternary oxide and a boron-doped diamond (BDD) anode. Measurements of the Chemical Oxygen Demand (COD) and the concentration of the anionic surfactants were used to follow the oxidation. Using the Ti–Ru–Sn ternary oxide anode, the complete removal of COD and sodium dodecyl benzene sulfonate was obtained only in the presence of chloride ions that act as inorganic mediators. The oxidation rate was almost independent of current density and electrolyte flow rate. In the case of BDD the mineralisation of the sodium dodecyl benzene sulfonate was achieved in all experimental conditions due to reaction with hydroxyl radicals electrogenerated on the diamond surface during electrolysis. The COD removal rate increased with increase in electrolyte flow rate, indicating that the oxidation was mass-transfer controlled. Comparison of the results of the two electrodes showed that chlorine mediated oxidation at the Ti–Ru–Sn ternary oxide anode allowed a faster COD removal of both the synthetic solution and real car wash wastewater.     

Electrochemical oxidation of 1,4‐dioxane at boron‐doped diamond electrode

BACKGROUND: The electrochemical oxidation of 1,4‐dioxane at a boron doped diamond (BDD) surface on a niobium substrate anode was studied because (i) 1,4 dioxane is a resistant contaminant in waste‐waters and ground‐waters which needs to be removed/oxidized and (ii) most of the currently applied techniques for removal/oxidation require chemicals. RESULTS: Results show that in the potential region supporting electrolyte stability 1,4‐dioxane can be oxidized directly. Adhesive products, which cause electrode fouling, are also formed during oxidation in this potential region. The BDD anode can be restored to its initial activity by simple anodic treatment in the potential region of electrolyte decomposition. In this region, oxidation reactions leading to complete oxidation of 1,4‐dioxane, can take place due to electro‐generated hydroxyl radicals. Therefore, dioxane can only be effectively oxidized at these potentials. The effect of current density on the oxidation of 1,4‐dioxane has been investigated. The experimental results have also been compared with a theoretical chemical oxygen demand (COD)–instantaneous current efficiency (ICE) model. At a current density above 32 mA cm^?2, the oxidation process is completely controlled by mass transfer and no intermediates are formed. 92% of the COD can be removed with a total consumption of 7 Ah L^?1. CONCLUSIONS: Results show that dioxane can be effectively and completely oxidized at a BDD anode. Copyright © 2010 Society of Chemical Industry     

Scale-up of B-doped diamond anode system for electrochemical oxidation of phenol simulated wastewater in batch mode

Scale-up of boron-doped diamond (BDD) anode system is critical to the practical application of electrochemical oxidation in bio-refractory organic wastewater treatment. In this study, the scale-up of BDD anode system was investigated on batch-mode electrochemical oxidation of phenol simulated wastewater. It was demonstrated that BDD anode system was successfully scaled up by 121 times without performance deterioration based on the COD and specific energy consumption (E_sp) models in bath mode. The COD removal rate and E_sp for the scaled-up BDD anode system through enlarging the total anode area while keeping similar configuration, remained at the similar level as those before being scaled up, under the same area/volume value, current density, retention time and wastewater characteristics. The COD and E_sp models used to describe the smaller BDD anode system satisfactorily predicted the performance of the scaled-up BDD anode system. Under the suitable operating conditions, the COD of phenol simulated wastewater was reduced from 540 mg l⁻¹ to 130 mg l⁻¹ within 3 h with an E_sp of only 34.76 kWh m⁻³ in the scaled-up BDD anode system. These results demonstrate that BDD anode system is very promising in practical bio-refractory organic wastewater treatment.     

A comparison of electrochemical degradation of phenol on boron doped diamond and lead dioxide anodes

This work compares two electrode materials used to mineralize phenol contained in waste waters. Two disks covered with either boron doped diamond (BDD) or PbO₂ were used as anodes in a one compartment flow cell under the same hydrodynamic conditions. Efficiencies of galvanostatic electrolyses are compared on the basis of measurements of Total Organic Carbon (TOC) and Chemical Oxygen Demand (COD). Galvanostatic electrolyses were monitored by analysis of phenol and of its oxidation derivatives to evaluate the operating time needed for complete elimination of toxic aromatics. The experimental current efficiency is close to the theoretical value for the BDD electrode. Other parameters being equal, phenol species disappeared at the same rate using the two electrode materials but the BDD anode showed better efficiency to eliminate TOC and COD. Moreover, during the electrolysis less intermediates are formed with BDD compared to PbO₂ whatever the current density. A comparison of energy consumption is given based on the criterion of 99% removal of aromatic compounds.     

Biological and electrochemical oxidation of naphthalenesulfonates

A biofilm airlift suspension (BAS) reactor and an undivided flow cell equipped with a boron‐doped diamond (BDD) anode and a stainless‐steel cathode were used to investigate the effects of varying operating conditions on process performance in the biological and electrochemical oxidation of a mixture of naphthalenesulfonates contained in the infiltration water of a contaminated industrial site. The experiments were aimed at evaluating the feasibility of process integration and the criteria for optimization (i.e. how to maximize degradation efficiency with minimum energy consumption) in combined biological and electrochemical oxidation of scarcely biodegradable compounds. Because of high reactor biomass concentration and long biomass retention time, the BAS reactor achieved a high degradation capacity (up to 6.8 kg COD m^?3 d^?1). On the other hand, owing to the recalcitrant character of some of the aromatic sulfonates in the leachate, the overall degradation efficiency did not exceed 70% based on COD measurements. All naphthalene‐mono‐ and ‐disulfonates (except naphthalene‐1,5‐disulfonate) were completely degraded in the BAS reactor, whereas more complex molecules (e.g. naphthalenetrisulfonates) were more recalcitrant to biological oxidation. These compounds were completely mineralized by electrochemical oxidation using a boron‐doped diamond anode. The energy consumption and the time required for the complete mineralization of the infiltration water decreased from 80 kWh m^?3 and 4 h to 61 kWh m^?3 and 3 h for the oxidation of raw and biologically pretreated leachate, respectively. Copyright © 2005 Society of Chemical Industry     

Electrochemical decomplexing and oxidation of organic (chelating) additives in effluents from surface treatment and metal finishing

The electrochemical decomplexing and oxidation of two frequently used complexing agents in surface treatment and metal finishing—EDTA (ethylenediaminetetraacetic acid) and NTA (nitrilotriacetic acid)—and of organic non‐complexing additives used in nickel‐plating baths were the subject of this study. Using a Ti–RuO₂ electrode, a partial indirect oxidation by in‐situ electrochemical generation of chlorine compounds could be achieved for EDTA and NTA. At a boron‐doped diamond (BDD) electrode however, complete decomplexing and high COD (Chemical Oxygen Demand) and TOC (Total Organic Carbon) (up to 95%) removal occurred at an average current density of 2 A dm^?2. It is shown that direct electrochemical oxidation at a BDD electrode resulted in lower energy consumption and higher treatment rates than indirect oxidation at a Ti–RuO₂ electrode. Decomplexing at the BDD electrode occurred at high current efficiencies ranging from 71% to 95% with decomplexing rates in the order of 3.13 mmol (Ah)^?1 and 5.02 mmol (Ah)^?1 for EDTA and NTA respectively. COD removal rates obtained were 0.090 g (Ah)^?1 for EDTA, 0.100 g (Ah)^?1 for NTA and 0.205 g (Ah)^?1 for the nickel‐plating additives. Electrochemical decomplexing and oxidation of common chelating agents can render the subsequent metal precipitation and biological wastewater treatment of surface treatment and metal finishing effluents more efficient. Copyright © 2003 Society of Chemical Industry     

A comparative study on the efficiency of electro-Fenton process in the removal of propham from water

Electro-Fenton process has been widely used in the treatment of organic pollutants lately. Its oxidation efficiency mainly depends on the electrode materials. In this study, boron doped diamond (BDD), carbon sponge (CS) and platinum (Pt) electrodes were used at four different configurations as anode and cathode. The oxidation efficiencies of BDD anode and CS cathode were investigated together for the first time in the electro-Fenton process. Propham was used as the model pollutant. The obtained results indicate that the decay rate of propham and the mineralization rate of propham aqueous solutions were highest in the case of BDD and CS electrodes as expected. The obtained mineralization current efficiency (MCE) value was 81% at 100 mA in the presence of 0.2 mM Fe³⁺ for 30 min electrolysis. The oxidative degradation intermediates of propham showed different accumulation characteristics in all configurations. The oxamic acid resisted to mineralization but it rapidly degraded in the presence of BDD anode.     

Electrochemical process for the treatment of landfill leachate

In this paper, the anodic oxidation of a real leachate from an old municipal solid waste landfill has been studied using an electrolytic flow cell equipped with a lead dioxide (PbO₂) anode and stainless steel as the cathode. The influence of several operation parameters such as (i) the applied current (from 0.5 to 3 A), (ii) liquid flow rate (from 50 to 420 L h⁻¹), (iii) temperature (from 25 to 50 °C), and (iv) pH (from 3.5 to 8.2) on the COD removal rate, current efficiency, and energy consumption has been evaluated. The galvanostatic electrolyses always yielded COD values below the discharge limit (COD <160 mg L⁻¹); the COD removal rate increased with rising applied current, solution pH, and temperature, whereas it remained almost unaffected by the recirculation flow rate. These results indicate that the organic compounds were mainly removed by their indirect oxidation by the active chlorine generated from chlorides oxidation. The specific energy consumption necessary to reduce the organic load to below the disposal limit was 90 kWh m⁻³.     

Electrochemical treatment of wastewaters containing 4‐chlororesorcinol using boron doped diamond anodes

The electrochemical oxidation of aqueous wastes polluted with 4‐chlororesorcinol has been studied on boron‐doped diamond electrodes on acidic medium. The voltammetric results showed that in the potential region where the supporting electrolyte is stable, reactions occur, resulting in the loss of activity due to electrode fouling. Galvanostatic electrolysis study showed that the oxidation of these wastes in single‐compartment electrochemical flow cell with boron doped diamond anodes deal to the complete mineralization of the organics but is no indication of electrode fouling. Resorcinol, 1,2,4‐trihydroxybenzene, benzoquinone, maleic, fumaric, and oxalic acids have been detected as soluble organics and chlorides (Cl^?) and hypochlorites (ClO^?) as mineral products during the electrolysis of 4‐chlororesorcinol. The electrochemical oxidation of 4‐chlororesorcinol consists of a sequence of steps: Release of Cl and/or hydroxylation of the aromatic ring; formation of quinonic compounds; oxidative opening of aromatic ring to form carboxylic acids; and oxidation of carboxylic acids to carbon dioxide. Both, direct oxidation at boron doped diamond surface and mediated oxidation by powerful oxidants electrogenerated from electrolyte oxidation at anode surface are involved in these stages.     

BDD anodic oxidation as tertiary wastewater treatment for the removal of emerging micro‐pollutants,pathogens and organic matter

This work reports for the first time the removal of 17α‐ethynylestradiol (EE2), a synthetic estrogen hormone, from secondary treated effluents by electrochemical oxidation. Experiments were conducted in a single compartment reactor comprising a boron‐doped diamond (BDD) anode and a zirconium cathode. EE2, in the range 100–800 µg L^?1, was spiked in the post‐chlorination effluent of a municipal treatment plant and oxidized at 0.9–2.6 mA cm^?2 current density. Complete degradation of 100 µg L^?1 EE2 was achieved in 7 min at 2.1 mA cm^?2 and inherent conditions, while the addition of 0.1 mol L^?1 NaCl achieved removal in just a few seconds. The process was then tested in the pre‐chlorination effluent at 2.1 mA cm^?2 and inherent conditions; complete E. coli killing and EE2 removal occurred in just 1.5 and 3.5 min, respectively, while overall estrogenicity (assessed by the YES assay) and residual organic matter (in terms of chemical oxygen demand (COD)) decreased by 50% and 85% after 30 min, respectively. These results clearly show the potential of BBD electrochemical oxidation to serve as an efficient tertiary wastewater treatment. Copyright © 2011 Society of Chemical Industry     

Electrochemical waste water treatment: Electrooxidation of acetaminophen

Oxidation of acetaminophen at boron-doped diamond (BDD) and at Ti/SnO₂ anodes in a plug-flow divided electrochemical reactor led to electrochemical combustion, whereas at Ti/IrO₂ benzoquinone was the exclusive product except at very long electrolysis times. The difference is explicable in terms of the different mechanisms of oxidation: direct oxidation at the anode for Ti/IrO₂ vs. indirect oxidation involving electrogenerated hydroxyl radicals at BDD and Ti/SnO₂. At BDD, at which the efficiency of degradation of acetaminophen was greatest, the rate of electrolysis at constant concentration was linearly dependent on the current, and at constant current linearly dependent on the concentration. Current efficiencies for mineralization up to 26% were achieved without optimization of the cell design.     

Effects of ultrasound on electrochemical oxidation mechanisms of p-substituted phenols at BDD and PbO2 anodes

The effects of low-frequency (40 kHz) ultrasound are investigated with regard to the effectiveness and mechanisms of electrochemical oxidation of p-substituted phenols (p-nitrophenol, p-hydroxybenzaldehyde, phenol, p-cresol, and p-methoxyphenol) at BDD (boron-doped diamond) and PbO₂ anodes. Although ultrasound improved the disappearance rates of p-substituted phenols at both the BDD and PbO₂ anodes, the degree of enhancement varied according to the type of p-substituted phenol and type of anode under consideration. At the BDD anode, the %Increase values were in the range 73-83% for p-substituted phenol disappearance and in the range 60-70% for COD removal. However, at the PbO₂ anode, the corresponding %Increase values were in the range 50-70% for disappearance of p-substituted phenols and only 5-25% for COD removal, much lower values than obtained at the BDD anode. Further investigations on the influence of ultrasound on the electrochemical oxidation mechanisms at BDD and PbO₂ anodes revealed that the different increase extent were due to the specialized electrochemical oxidation mechanisms at these two anodes. The hydroxyl radicals were mainly free at the BDD electrodes with a larger reaction zone, but adsorbed at the PbO₂ electrodes with a smaller reaction zone. Therefore, the enhancement due to ultrasound was greater at the BDD anode than at the PbO₂ anode.     

Treatment of textile dye wastewater by using an electrochemical bipolar disc stack reactor

Textile dye house wastewater from a reactive dye processing unit was treated by using an electrochemical oxidation technique. The experiments were carried out in an electrochemical bipolar disc reactor using RuO₂ coated on titanium as anode and titanium as cathode. The sodium chloride present in the effluent was used as supporting electrolyte. Operating parameters such as current density, reservoir hold‐up and electrolysis time were studied for maximum Chemical Oxygen Demand (COD) reduction and other relevant parameters such as current efficiency and power consumption per kg of COD removal were calculated. The higher flow rate and lower reservoir hold‐up resulted in improved COD removal. The applied current density was also found to significantly influence the reduction of COD. A suitable mathematical model is also proposed to illustrate the relationship between the basic parameters. Pseudo mass transfer coefficients were also evaluated for different experimental conditions. Copyright © 2004 Society of Chemical Industry     

Treatment of Fenton‐refractory olive oil mill wastes by electrochemical oxidation with boron‐doped diamond anodes

In this work, the electrochemical oxidation of an actual industrial waste with conductive diamond anodes has been studied. The wastewater is the effluent of a wastewater treatment plant consisting of a Fenton reactor followed by a settler and a sand filter, in which the wastes generated in an olive oil mill are treated. These wastes contain a residual chemical oxygen demand of nearly 700 mg dm^?3 which cannot be further oxidized with the Fenton process. The electrolyses were carried out under galvanostatic conditions, using a bench‐scale plant equipped with a single‐compartment electrochemical flow cell. Boron‐doped diamond (BDD) and stainless steel (AISI 304) were use as anode and cathode of the cell, respectively. The complete mineralization of the waste was obtained with high current efficiencies limited only by mass transport processes. This confirms that besides the hydroxyl radical‐mediated oxidation that occurs in the Fenton process, the electrochemical oxidation with conductive diamond electrodes combines other important oxidation processes such as direct electro‐oxidation on the BDD surface and oxidation mediated by other electrochemically formed compounds generated in this electrode. Copyright © 2006 Society of Chemical Industry     

High power generation with simultaneous COD removal using a circulating column microbial fuel cell

BACKGROUND: A circulating column microbial fuel cell (MFC) with Cu anode and Au? Cu air cathode was used for power generation and chemical oxygen demand (COD) removal from synthetic wastewater. The column was operated in repeated‐fed batch mode using acclimated anaerobic sludge. The contents of the column MFC were circulated while the feed wastewater was fed to the reactor in fed‐batch mode. Effects of feed COD concentration and COD loading rate on voltage difference, power density and percentage COD removal were investigated. RESULTS: The highest voltage difference (650 mV), power density (40 W m^?2) were obtained with a feed COD of 6400 mg L^?1, yielding 45% COD removal with a COD loading rate of nearly 90 mg h^?1. Low COD loadings (<90 mg h^?1) caused substrate limitations, and high loadings (>90 mg h^?1) resulted in inhibition of COD removal and power generation. The highest percentage COD removal (50%) was obtained with feed COD content of 10.35 g L^?1 or a COD loading rate of 145 mg h^?1. CONCLUSION: The power densities obtained with the circulating column MFC were considerably higher than those reported in the literature due to elimination of mass transfer limitations by the high circulation rates, proximity of electrodes and small anode surface area used in this study. Further improvements may be possible with optimization of the operating parameters. Copyright © 2009 Society of Chemical Industry     

ELECTROCHEMICAL RECOVERY OF CHLORINE AND HYDROGEN FROM HYDROGEN CHLORIDE BY-PRODUCT PRODUCED IN THE PETROCHEMICAL INDUSTRY

Simultaneous production of hydrogen as an energy carrier and chlorine as a valuable chemical from recycled hydrogen chloride was investigated employing a lab-scale membrane electrolysis setup. The effects of various process parameters including current density (1–4 kA m^?2), cell temperature (45°–75°C), flow rate of hydrochloric acid feed (200–500 mL min^?1), and concentration of acid (18–21 wt.%) on the cell voltage and chlorine current efficiency (ChCE) were studied. The Taguchi design of experiments (L₁₆ array) was employed to design the minimum number of experiments necessary to fully study the process. A filter press type cell of 10 cm² surface area comprising a DSA anode, an alloy of predominantly nickel cathode and Nafion 115 membrane, was used. It was observed that increasing anolyte flow rate, anolyte concentration, or cell temperature caused a decrease in cell voltage and an increase in ChCE, while increasing current density linearly increased cell voltage and decreased ChCE.     

Kinetic modelling of the electrochemical mineralization of organic pollutants for wastewater treatment

The electrochemical mineralization of organic pollutants is a new technology for treatment of dilute wastewater (COD < 5 g L⁻¹). In this method, use of the electrical energy can produce complete oxidation of pollutants on high oxidation power anodes. An ideal anode for this type of treatment is a boron-doped diamond electrode (BDD) characterized by a high reactivity towards oxidation of organics. In the present work kinetic aspects of organic mineralization is discussed. The proposed theoretical kinetic model on boron-doped diamond anodes is in excellent agreement with experimental results. In addition economic aspects of electrochemical organic mineralization are reported.     

Advanced oxidation of cork‐processing wastewater using Fenton's reagent: kinetics and stoichiometry

This work evaluates Fenton oxidation for the removal of organic matter (COD) from cork‐processing wastewater. The experimental variables studied were the dosages of iron salts and hydrogen peroxide. The COD removal ranged from 17% to 79%, depending on the reagent dose, and the stoichiometric reaction coefficient varied from 0.08 to 0.43 g COD (g H₂O₂)^?1 (which implies an efficiency in the use of hydrogen peroxide varying from 17% to 92%). In a study of the process kinetics, based on the initial rates method, the COD elimination rate was maximum when the molar ratio [H₂O₂]_o:[Fe²⁺]_o was equal to 10. Under these experimental conditions, the initial oxidation rate was 50.5 mg COD dm^?3 s^?1 with a rate of consumption of hydrogen peroxide of 140 mg H₂O₂ dm^?3 s^?1, implying an efficiency in the use of the hydrogen peroxide at the initial time of 77%. The total amount of organic matter removed by Fenton oxidation was increased by spreading the H₂O₂ and ferrous salt reagent over several fractions by 15% for two‐fractions and by 21% for three‐fractions. Copyright © 2004 Society of Chemical Industry