The electrochemical oxidation of aqueous phenol at a glassy carbon electrode

The electrooxidation of phenol is of interest as a model compound for the treatment of aqueous organic wastes. The effect of voltage, concentration and temperature on the electrochemical oxidation of acidic dilute aqueous solutions of phenol was studied. Electrolysis was carried out by recirculating phenol solutions through a flow-by electrochemical reactor employing a reticulated glassy carbon anode. Concentrations of phenol and some breakdown products were monitored using HPLC analysis. Increased voltage was found to shift the product distribution to favour more oxidized products but also to increase electrode corrosion and decrease current efficiency. Higher phenol concentrations (over the range of 5-20 mmol/L) showed a shift in product distribution to favour less oxidized, mostly insoluble products. Elevated temperatures (about 50°C and higher) showed a marked ability to reduce electrode passivation and increase the phenol oxidation rate.     

Electrochemical conversion of phenolic wastewater on carbon electrodes in the presence of NaCl

The electrochemical conversion of highly concentrated synthetic phenolic wastewater was studied on carbon electrodes in a batch electrochemical reactor. The effects of reaction temperature, electrolyte concentration, current density and initial phenol concentration on phenol conversion were elucidated. The wastewater was synthetically prepared and used in reactions carried out generally at 25 °C with an initial phenol concentration of 3500 mg dm^?3. Although current density increased, phenol conversion% and initial phenol conversion rate did not increase correspondingly above 35 °C and an electrolyte concentration of 90 g dm^?3. As the voltage values applied were increased, the increasing current density resulted in fast phenol conversion. Kinetic investigations denoted that overall phenol destruction kinetics was of zero order with an activation energy of 10.9 kJ mol^?1. Under appropriate conditions, phenol was completely converted within 15 min for an initial phenol concentration of 98 mg dm^?3 while 8 h was required to gain 95% conversion using 4698 mg dm^?3. Solid polymeric materials were produced at initial phenol concentrations above 500 mg dm^?3 using the appropriate current density. In the reaction medium, only mono‐, di‐ and tri‐substituted chlorophenols were formed and 100% of all species were either oxidised or contributed to the formation of a polymeric structure. Almost all of the phenol loaded to the reactor was converted into non‐passivating polymeric products, denoting a safe and easy method for the separation of phenol. © 2001 Society of Chemical Industry     

Electrochemical polymerisation of phenol in aqueous solution on a Ta/PbO<Subscript>2</Subscript> anode

This paper deals with the treatment of aqueous phenol solutions using an electrochemical technique. Phenol can be partly eliminated from aqueous solution by electrochemically initiated polymerisation. Galvanostatic electrolyses of phenol solutions at concentration up to 0.1 mol dm⁻³ were carried out on a Ta/PbO₂ anode. The polymers formed are insoluble in acidic medium but soluble in alkaline. These polymers were filtered and then dissolved in aqueous solution of sodium hydroxide (1 mol dm⁻³). The polymers formed were quantified by total organic carbon (TOC) measurement. It was found that the conversion of phenol into polymers increases as a function of initial concentration, anodic current density, temperature, and solution pH. The percentage of phenol polymerised can reach 15%.     

Combined adsorption and electrochemical processes for the treatment of acidic aqueous phenol wastes

This paper describes a combined adsorption/electrochemical reaction device for the treatment of acidic aqueous phenol wastes. The system works in batch mode. In each operation cycle there are two stages: (i) treatment of waste, in which the organic matter contained in the waste is removed from the aqueous solution and (ii) activated carbon regeneration, in which adsorbed organics are removed from the system and converted into carbon dioxide. The system leads to successful treatment of these wastes and transforms the organics contained in the waste into carbon dioxide and electrocoagulated solids. The granular activated carbon (GAC) bed of the system achieves rapid removal of the organics, with treatment time shorter than those reported for conventional electrochemical treatments. The regeneration of the GAC is achieved by electrochemical means and efficiencies close to 80% are obtained. The energy consumption of this system is similar to those reported for other electrochemical technologies used to treat aqueous wastes.     

电化学降解废水中酚的研究

在氯盐电解质中用电化学方法处理含酚废水，研究了盐的种类、浓度、温度、电流密度、苯酚初始浓度、阴阳极转换频率分别对苯酚去除率、ClO^-浓度及其电流效率的影响当Na2SO4的浓度为0．2mol／L、NaCl的浓度为0．1mol／L、苯酚初始浓度为200mg／L、电流密度为0．04A／cm^2、温度为35℃、pH=12．5、阴阳极转换频率5min／次及反应时间200min的条件下，苯酚的去除率为100％，COD去除率为5％。     

Electrochemical treatment of diluted cyanide aqueous wastes

The electrochemical oxidation of diluted cyanide aqueous wastes has been studied in a single compartment electrochemical flow cell. It has been determined that the anode material influences greatly the process's performance. Boron doped diamond and PbO₂ anodes can oxidize these wastes in the presence of both sulfate or chloride anions. On the contrary, dimensional stable anodes cannot oxidize cyanide in sulfate‐containing wastewaters, and require the presence of chloride ions. The oxidation of cyanides leads to the formation of cyanate in a first step, and later to the formation of carbon dioxide and nitrogen. There is a net consumption of hydroxyl ions during the process. Energy consumptions in the range 20–70 kWh m^?3 are required to decrease the initial pollutant load by 70–80%. Global current efficiencies in the range 3–8% are obtained. These low current efficiencies are justified by the low cyanide concentrations that the wastes used in this work contain. Copyright © 2005 Society of Chemical Industry     

Electrochemical oxidation of several chlorophenols on diamond electrodes: Part II. Influence of waste characteristics and operating conditions

The electrochemical treatment of wastes containing several chlorophenols (4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol) using boron-doped diamond electrodes is described. Both direct and indirect processes are involved in the oxidation of the organics, indirect processes being mediated by oxidising agents (such as hypochlorite or peroxodisulphate) generated on the surface of the anode. The influence of the waste characteristics (initial concentration, pH and supporting media) is reported. The presence of reversible redox reagents, like the sulphate/peroxodisulphate redox couple, plays an important role in determining the global oxidation rate. Hypochlorite formation depends only on the organochlorinated compound and not on the presence of other reversible redox reagents in the waste. Alkaline pH favours the accumulation of carboxylic acid intermediates since, under these conditions, the oxidation rate of such compounds is low. The influence of the operating conditions (temperature and current density) is also discussed. The results show that high temperatures improve the rate of the mediated reactions and that high current density values decrease the efficiency of the direct electrochemical processes.     

Comparative Study of Electrocoagulation and Electrooxidation Processes for the Degradation of Ellagic Acid From Aqueous Solution

A comparative study of electrocoagulation and electrooxidation processes for the degradation of ellagic acid from aqueous solution was carried out. For the electrocoagulation process, metallic iron was used as electrodes whereas graphite and RuO₂/IrO₂/TaO₂ coated titanium electrodes were used for the electrooxidation processes. The effect of the process variables such as initial pH, concentration of the supporting electrolyte, applied current density, electrolysis time, and anode materials on COD removal were systematically examined and discussed. Maximum COD removal of 93% was obtained at optimum conditions by electrocoagultion using an iron electrode. The ellagic acid was degraded completely by electrooxidation using graphite electrodes under the optimum conditions. During electrooxidation, the chloride ion concentration was estimated and the effect of the Cl^? ion was discussed. The finding of this study shows that an increase in the applied current density, NaCl concentration, and electrolysis time enhanced the COD removal efficiency. The UV–Vis spectra analysis confirms the degradation of ellagic acid from aqueous solution.     

Electrochemical oxidation of several chlorophenols on diamond electrodes Part I. Reaction mechanism

The electrochemical oxidation of 4-chlorophenol, 2,4-dichlorophenol and 2,4,6-trichlorophenol aqueous wastes using boron-doped diamond electrodes was studied. This treatment led to complete mineralization of the wastes regardless of the operating conditions. A simple mechanistic model is consistent with the voltammetric and electrolysis results. According to this model, the electrochemical treatment of chlorophenol aqueous wastes involves the anodic and cathodic release of chlorine followed by the formation of non-chlorinated aromatic intermediates. Subsequent cleavage of the aromatic ring gives rise to non-chlorinated carboxylic acids. Chlorine atoms arising from the hydrodehalogenation of the chlorophenols are converted into more oxidized molecules at the anode. These molecules react with unsaturated C₄ carboxylic acid to finally yield trichloroacetic acid through a haloform reaction. The non-chlorinated organic acids are ultimately oxidized to carbon dioxide and the trichloroacetic acid into carbon dioxide and volatile organo-chlorinated molecules. Both direct and mediated electrochemical oxidation processes are involved in the electrochemical treatment of chlorophenols.     

Anodic oxidation of phenol for waste water treatment

The electrochemical oxidation of phenol for waste water treatment applications was investigated on lead dioxide packedbed anodes. Cells were operated in both batch and continuous modes with feed streams up to 1100 mg/l phenol dissolved in aqueous solutions of Na₂SO₄ and H₂SO₄ or NaOH. All the phenol in solution could be readily oxidized but complete total organic carbon (T.O.C.) removal was more difficult. The percent phenol oxidized increased with increasing current density, and decreased as initial phenol concentration, electrolyte flow rate, pH and anode particle size were increased. Results are compared to simple mathematical models.     

Anodic oxidation of phenol for waste water treatment

The electrochemical oxidation of phenol for waste water treatment applications was investigated on lead dioxide packed-bed anodes. Cells were operated in both batch and continuous modes with feed streams up to 1100 nig/1 phenol dissolved in aqueous solutions of Na₂SO₄ and H₂SO₄ or NaOH. All the phenol in solution could be readily oxidized but complete total organic carbon (T.O.C.) removal was more difficult. The percent phenol oxidized increased with increasing current density, and decreased as initial phenol concentration, electrolyte flow rate, pH and anode particle size were increased. Results are compared to simple mathematical models.     

在不分隔的反应器中原位电生成活性氯氧化降解蒽醌染料

The purpose of this paper was to investigate the possibility of treating C. I. Reactive Blue 19 wastewater by electrochemical oxidation via electrogenerated active chlorine, using metallic oxide coatings （dimensional stable anode, DSA） as anode. The electrolysis for the simulated wastewater was conducted at a constant current. Absorbances at 592 nm and 255 nm were measured to follow the decolorization of the dye and the degradatin of its aromatic ring. After 4 h of electrolysis under the experimental conditions： current density of 15 A·m^-2, 0.2 mol·L^-1 NaCl, 0.1 mol·L^-1 Na2SO4, 0.1 mmol·L^-1 dye, initial pH=6.4 and T=30℃, 100% decolorization of the dye and about 45% degradation of its aromatic ring were achieved, while no obvious change of total organic carbon was observed. The experimental results suggest that the decolorization of the dye and degradation of its aromatic ring were directly affected by current density, temperature, concentrations of the dye and sodium chloride, while slightly affected by initial pH and sodium sulfate concentration; the decolorization of the dye and degradation of its aromatic ring followed pseudo-first-order kinetics; and indirect electrooxidation, using electrogenerated active chlorine, predominated in the electrochemical oxidation.     

Electrochemical oxidation of Crystal Violet in the presence of hydrogen peroxide

BACKGROUND: The combination of electrochemical oxidation using a Ti/RuO₂? IrO₂ anode with hydrogen peroxide has been used for the degradation of Crystal Violet. The effect of major parameters such as initial pH, hydrogen peroxide concentration, current density, electrolyte concentration and hydroxyl radical scavenger on the decolorisation was investigated. RESULTS: The decolorisation rate increased with initial pH and hydrogen peroxide concentration, but decreased with electrolyte and radical scavenger concentration. The decolorisation rate increased with current density, but the increase became insignificant after current density exceeded 47.6 mA cm^?2. On the other hand, hydrogen peroxide decomposition rate increased with initial pH and current density, but decreased with electrolyte and radical scavenger concentration. The amount of hydrogen peroxide decomposed during 30 min reaction increased linearly with hydrogen peroxide dosage. The main intermediates were separated and identified by gas chromatography–mass spectrometry (GC–MS) technique and a plausible degradation pathway of Crystal Violet was proposed. At neutral pH, the electrochemical process in the presence of hydrogen peroxide was more efficient than that in the presence of Fenton's reagent (electro‐Fenton process). CONCLUSION: The anodic oxidation process could decolorise Crystal Violet effectively when hydrogen peroxide was present. Almost complete decolorisation was achieved after 30 min reaction under the conditions 2.43 mmol L^?1 hydrogen peroxide, 47.6 mA cm^?2 current density and pH₀ 7, while 62% COD removal efficiency was obtained when the reaction time was prolonged to 90 min. Copyright © 2010 Society of Chemical Industry     

自制氧化铅电极降解苯酚的试验研究

以钛片为基底,Sn O2+Sb2O5为中间层,自制氧化铅电极用于苯酚的电化学降解。试验结果表明,自制电极具有良好的苯酚去除效果:在室温为15℃,电极间距为15 mm,电流密度为16 m A/cm2,苯酚溶液p H为6.3,导电介质Na2SO4浓度为0.25 mol/L时,电解300 m L初始质量浓度为100 mg/L的苯酚,4 h后去除率可达91.89%。研究降解过程中苯酚初始浓度、p H、导电介质、电流密度、电极间距等因素对苯酚降解过程的影响。在此基础上对苯酚降解影响较大的初始浓度、p H、电流密度3个因素优化,通过响应曲面分析交互影响和单因素影响,结果表明,三者交互影响不大,苯酚初始浓度影响最大,p H影响最小,与单因素影响分析结果吻合。     

Electrolysis of progesterone with conductive‐diamond electrodes

BACKGROUND: Progesterone is considered an endocrine disruptor chemical. It can be found in industrial discharges, municipal wastewaters, and, in some instances, even in treated effluents at the level of ng dm^?3. RESULTS: Conductive diamond electrolysis can be used to remove progesterone from aqueous solutions. Increases in current density lead to less efficient processes, indicating mass transfer control of the process rate. Occurrence of chlorides in the electrolytic media favors the depletion of progesterone compared with sulphates, although it does not affect the mineralization rate. Independently of the solubilizing agent used, the process behaves similarly during a first stage of the electrolysis (at the four ranges of pollutant concentration studied). However, in a second stage, the rate changes abruptly due to reduced action of hydroxyl radicals in methanol media. CONCLUSIONS: Progesterone can be removed efficiently by conductive diamond electrolysis from aqueous solutions within the range of initial concentrations 10^?2 to 10² mg dm^?3. The process efficiency increases with the current density. Removal rate does not depend on the nature of the electrolyte, but this parameter affects the intermediates formed during the experiment. When pure methanol is used as solubilizing agent, only direct electro‐oxidation takes place. Copyright © 2012 Society of Chemical Industry     

Removal of sulfamethoxazole from waters and wastewaters by conductive‐diamond electrochemical oxidation

BACKGROUND: Sulfamethoxazole (SMX, used as a model bacteriostatic antibiotic) is persistent to conventional biological treatments of wastewaters. In this work, conductive‐diamond electrochemical oxidation (CDEO) was found to be an effective technology for its removal from the effluents of conventional wastewater treatment plants. RESULTS: The use of CDEO has been evaluated for the removal of the antibiotic SMX from water and wastewaters. The results show that CDEO can reduce the concentration of this organic pollutant to values below 0.1 µg dm^?3. The variation of the SMX concentration during electrolysis shows a complex shape with a plateau zone that increases in size with the initial concentration of SMX. This complex trend is not observed in the changes of TOC, which seems to indicate that the CDEO of SMX solutions does not lead directly to the generation of carbon dioxide as a final product. A tentative reaction pathway has been proposed based on a thorough analysis of the reaction mixture, in which the main intermediate products were identified. The use of liquid chromatography time‐of‐flight mass spectrometry (LC‐TOFMS) allowed the identification of nine organic intermediates (with M_w 98, 108, 172, 173, 197, 203, 227, 269 and 287) during the electrolysis and the concentration of these compounds depends on the initial SMX concentration and on the current density applied. CONCLUSIONS: CDEO is able to reduce the concentration of the organic pollutant below 0.1 mg dm^?3. SMX removal is faster than that of TOC. This fact indicates the formation of reaction intermediates. Analytical techniques show that nine reaction intermediates are generated in the system, and that their concentration depends on the initial SMX concentration and on the current density used. Copyright © 2012 Society of Chemical Industry     

Veratric acid treatment by anodic oxidation with BDD anode

BACKGROUND: Veratric acid (VA, 3,4‐dimethoxy‐benzoic acid) is representative of the polyphenolic type compounds present in olive mill wastewater (OMW). Given the bactericide factor, the inhibitor character and the anti bacteriological activity of this compound, traditional biological digestion cannot be applied and therefore new technologies, such as electrochemical oxidation using a boron‐doped diamond (BDD) anode have to be considered to avoid its accumulation in the environment. RESULTS: The electrochemical oxidation of aqueous solutions containing 1 mmol L^?1 VA has been investigated using a filter‐press reactor with a BDD anode during galvanostatic electrolysis. The influence of several operating parameters, such as applied current density, temperature, flow‐rate and supporting electrolyte concentration and type has been investigated. The experimental results showed that under the experimental conditions used the oxidation of VA was under mass‐transfer control and VA was completely degraded by the reaction with hydroxyl radicals electrogenerated at the BDD surface. The chemical oxygen demand (COD) decay kinetic followed a pseudo‐first‐order reaction and the apparent rate constant increased with flow rate and temperature. Under optimal experimental conditions of flow‐rate (300 L h^?1), temperature (35 °C) and current density (10 mA cm^?2), 99.5% of COD was removed during 2 h electrolysis, with 16.4 kWh m^?3 energy consumption. CONCLUSIONS: This study suggests that anodic oxidation with a BDD electrode is an excellent method for the treatment of effluents contaminated with VA and related polyphenols. Copyright © 2011 Society of Chemical Industry     

Electrochemical degradation of 17β-estradiol (E2) at boron-doped diamond (Si/BDD) thin film electrode

Electrochemical degradation of aqueous solutions containing 17β-estradiol (E2), concentrations range of 250-750 μg dm⁻³, has been extensively studied using boron-doped diamond (BDD) anode with a working solution volume of 250 ml under galvanostatic control. Cyclic voltammetric experiments were performed to examine the redox response of E2 as a function of cycle number. The effect of operating variables such as initial concentration of E2, applied current density, supporting medium (Na₂SO₄, NaNO₃, and NaCl) and initial pH of the electrolyte (pH 2-10) were systematically examined and discussed. Electrolysis at high anodic potential causes complex oxidation of E2 that leads to form the final sole product as CO₂. A pseudo first-order kinetics for E2 decay was found against varying applied current density. Also, kinetic analysis suggests that electrooxidation reaction of E2 undergo the control of applied current density. It was observed that electrolyte pH and supporting medium have a vital role on E2 degradation. From a comparison study with other anode materials such as platinum (Pt) and glassy carbon (GC), the superiority of the BDD anode was proved. Total organic carbon results have shown that almost complete mineralization could be accomplished at higher applied current density with specific electrical charge 22.5 × 10⁻² A h dm⁻³. Mineralization current efficiency was comparatively lower with increasing applied current density.     

Electrochemical oxidation of the increasingly used disinfectant benzalkonium chloride

Benzalkonium chloride (BAC) is a key ingredient in many cleaning and disinfectant products due to it being an effective antiviral and biocidal agent. Because of its prolific use, especially following the recent global COVID pandemic, increased levels of BAC have been found in the environment, in particular, in wastewater, where it has negative impacts due to its toxicity. This necessitates an effective treatment for BAC in wastewater to reduce its toxicity. In this work, electrochemical oxidation of BAC on a boron-doped diamond anode was studied to successfully remove BAC. The electrochemical measurements performed at different current densities confirmed that BAC was completely oxidized within 20 min of treatment at 50 mA/cm². However, chemical oxygen demand (COD) measurements showed that around 50% of the initial BAC was completely mineralized after 1 h of degradation at 50 mA/cm², while the remaining electrooxidation of BAC resulted in the production of transformation products.     

Electrochemical treatment of Remazol Brilliant Blue on a boron-doped diamond electrode

A detailed study on the electrochemical oxidation of aqueous solutions of Remazol Brilliant Blue Reactive on a boron-doped diamond electrode is presented. Electrolyses, conducted under galvanostatic conditions, were monitored evaluating the removal of colour, chemical oxygen demand and total organic carbon.The influence of the supporting electrolyte, current density, initial dye concentration, temperature and pH is discussed.Colour removal was found to be dependent mostly on the chloride concentration suggesting the involvement of electrogenerated active chlorine in the reaction of discolouration. Rate constants calculated from colour decay versus time revealed a zero order reaction up to 150 mg L⁻¹ in dye.The degradation efficiency was directly related to the dye concentration thus indicating that oxidation and mineralisation occurred under mass transfer control.Using 0.01 M chloride, under mild operating conditions of pH, temperature and current density, the treatment proposed enabled to achieve complete discolouration and total mineralisation of Remazol Brilliant Blue solution in a range from 50 to 150 mg L⁻¹.