Use of electrochemical technology to increase the quality of the effluents of bio-oxidation processes. A case studied

In this work, it has been studied the use of conductive-diamond electrochemical oxidation (CDEO) as a refining technology to assure the quality of the effluents of door manufacturing processes (DMP). To do this, the raw effluents of these factories have been treated by a combination of physicochemical, biological and CDEO treatments. CDEO was found to be a feasible alternative to the refinement of a wooden DMP waste. It can successfully decrease the organic load of the effluents of the biological oxidation with low energy requirements. In addition, in case of incidents in the biological process, CDEO can treat successfully the effluents of the coagulation process. The effluents of the biological treatment have also been treated by CDEO in order to check the possible use of electrochemical technology to increase the biodegradability of the effluents and their possible recycle to the biological treatment. Unfortunately, electrochemical technology was found to be not adequate to increase the biodegradability of the effluents of a biological treatment. The hard oxidation conditions generated during CDEO do not lead to the accumulation of intermediates but to the almost direct formation of carbon dioxide. Lowering the current density or changing the electrodes can not enhance the biodegradability of the effluents of an electrochemical cell.     

High efficiencies in the electrochemical oxidation of an anthraquinonic dye with conductive-diamond anodes

Oxidation of anthraquinonic dye Acid Blue 62 by electrolysis with conductive-diamond electrodes is studied in this work. COD, TOC, and color have been selected to monitor the degradation of the molecule as a function of several operating inputs (current density, pH, temperature, and NaCl concentration). Results show that the electrochemical oxidation of this model of large molecules follows a first order kinetics in all the conditions assessed, and it does not depend on the pH and temperature. The occurrence of chloride ions in wastewaters increases the rate of color and COD removal as a consequence of the mediated oxidation promoted by the chlorinated oxidizing species. However, chloride occurrence does not have an influence on the mineralization rate. First-order kinetic-constants for color depletion (attack to chromophores groups), oxidation (COD removal), and mineralization (TOC removal) were found to depend on the current density and to increase significantly with its value. A single model was proposed to explain these changes in terms of the mediated oxidation processes. Rate of mineralization remained very close to that expected for a purely mass transfer-controlled process. This was explained assuming that mediated oxidation does not have a significant influence on the mineralization in spite it has some effect on intermediate oxidation stages. The efficiency of the oxidation was found to depend mainly on the concentration of COD being negligible the effect of the other inputs assessed except for the occurrence of chloride ions. Opposite, the efficiency of mineralization depends on concentration of TOC and current density and it did not depend on the chloride occurrence. This observation was found to have an important influence on the power required to remove a given percentage of the initial TOC or COD. To decrease COD efficiently, the occurrence of chloride in the solution is very important, while to remove TOC efficiently, it is more important to work at low current densities and chloride effect is negligible. Energy consumption could be decreased by folds using the proper conditions.     

吸附-电化学氧化耦合处理对氯苯酚废水及动力学

以毡状活性炭纤维为阳极,不锈钢为阴极,吸附-电化学氧化耦合降解对氯苯酚废水进行了研究。考察了吸附或耦合电化学氧化过程、电流密度、支持电解质硫酸钠浓度和活性炭纤维重复使用对废水COD去除率的影响,结果表明,采用吸附-电化学氧化耦合方法,当电流密度7.6 mA/cm2支持电解质（硫酸钠）浓度为1 g/L,处理时间为180 min,4-CP废水COD去除率可达97.09%。毡状活性炭纤维对4-CP的静态吸附过程符合Langmiu吸附等温方程。建立了吸附-电化学氧化COD去除动力学模型,动力学模型参数表明,对于COD的去除,电化学氧化作用比吸附作用大。     

Advanced oxidation processes for the treatment of olive-oil mills wastewater

In this work, the treatment of an actual industrial waste with three advanced oxidation processes (AOP) has been studied: conductive-diamond electrooxidation (CDEO), ozonation and Fenton oxidation. The wastewater comes from olive-oil mills (OMW) and contains a COD of nearly 3000 mg dm(-3). CDEO allowed achieving the complete mineralization of the waste with high current efficiencies. Likewise, both ozonation and Fenton oxidation were able to treat the wastes, but they obtained very different results in terms of efficiency and mineralization. The accumulation of oxidation-refractory compounds as final products excludes the use of ozonation and Fenton oxidation as a sole treatment technology. This confirms that besides the hydroxyl-radical mediated oxidation, CDEO combines other important oxidation processes such as the direct electro-oxidation on the diamond surface and the oxidation mediated by other electrochemically formed compounds generated on this electrode.     

Degradation of tetracycline at a boron-doped diamond anode: influence of initial pH,applied current intensity and electrolyte

The anodic oxidation of tetracycline was performed in an up-flow reactor, operating in batch mode with recirculation, using as anode a boron-doped diamond electrode. The influence on the degradation rate of solution initial pH (2 to 12), applied current intensity (25 to 300 A m^?2) and type of electrolyte (sodium sulphate or sodium chloride) were investigated. For the assays run at equal current density, with sodium sulphate as electrolyte, the solution’s initial pH of 2 presented the highest absorbance and chemical oxygen demand removals. Regarding the influence of current density, for equal charge passed, the organic load removal rate decreased with the increase in applied current. When sodium sulphate was used as an electrolyte, high-performance liquid chromatography (HPLC) results have shown an almost complete removal of tetracycline after a 2-h assay. HPLC results have also shown the presence of oxamic acid as one of the intermediates of tetracycline anodic oxidation. The complete removal of tetracycline was much faster in the presence of chloride ions that promoted the complete degradation of this antibiotic in 30 min. However, in the presence of chloride ions, the tetracycline mineralization is slower, as observed by the lower organic carbon removal rate when compared to that of the tetracycline degradation in the presence of sulphate.     

光电催化氧化法降解藻毒素MCLR

使用DSA阳极,对光电催化氧化降解藻毒素MCLR的效能及其影响因素进行了研究。结果表明,电极表面的TiO2在光催化氧化降解MCLR的过程中发挥了明显的光催化作用。在光降解、电催化氧化、光催化氧化和光电催化氧化4个过程中,光电催化氧化对MCLR和TOC的去除率最高,分别可达100%和13%,并且光电催化氧化的去除率大于光催化氧化和电催化氧化之和,表明后两者的耦合过程产生了一定的协同作用。辐照光源和电流密度存在最佳匹配条件,分别为UVC辐照、电流密度10 mA/cm2和UVA辐照、电流密度1.0 mA/cm2,此条件下光电协同作用最显著。在光电催化氧化过程中,随极板间距增大而出现的去除率下降取决于电催化过程,而不是光催化过程;光电催化氧化MCLR的去除率随其初始浓度增加而减小。     

Treatment of Basic Red 29 dye solution using iron-aluminum electrode pairs by electrocoagulation and electro-Fenton methods

The aim of this study is the treatment of Basic Red 29 (BR29) dye solution using hybrid iron-aluminum electrodes by electrocoagulation and electro-Fenton methods. The effect of current density, initial pH, supporting electrolyte, H₂O₂, and initial dye concentration on dye removal efficiency was investigated, and the best experimental conditions were obtained. Time-coarse variation of UV-Vis spectra and toxicity and chemical oxygen demand (COD) removal were also examined at the best experimental conditions. Both systems were found very successful for the removal of BR29 dye. The removal efficiency of >95 % for BR29 dye solution was reached easily in a short time. At the best experimental conditions, for the initial BR29 concentration of 100 mg/L, >95 % BR29 dye and 71.43 % COD removal were obtained after 20 and 40 min of electrolysis, respectively. Additionally, toxicity results for electro-Fenton treatment of 100 mg/L BR29 were also very promising. According to the results obtained, although electro-Fenton is more effective, both systems can be used successfully to treat textile wastewater including dyes.     

Electrochemical combustion of herbicide mecoprop in aqueous medium using a flow reactor with a boron-doped diamond anode

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.     

电催化氧化技术处理制革综合废水

选择DSA电极中的钛基掺硼金钢石膜电极(Ti/BDD),用于制革综合废水的电催化氧化处理研究,考察了在不同的电流密度、电压、电解质、pH值和电解时间等因素对COD去除率和电流效率的影响。结果表明,控制电流密度为30mA/cm2,电压为8.0 V,电解质(NaCl)浓度为2.0 g/L,pH为4.0,电催化氧化处理2 h后,废水的COD和NH4+-N的去除率分别达到了83.6%和90.3%,BOD/COD为0.45,比能耗为35.34 kWh/kg COD,电流效率为37%。     

生物膜氧化沟污水处理性能的研究

生物膜氧化沟是在普通氧化沟内放置合适填料，使之成为活性污泥法与生物膜法相结合的混合污水处理工艺。本研究通过清水试验，选择出了生物膜氧人诉合适填料及其安装方式，并同时比较了生物膜氧化沟和普通氧化沟的传质效果，水流阻力、水力混合特性。通过污水试验，确定了生物膜氧化沟的填料最佳填充率。并比较了生物膜氧化沟和普通氧化沟的去除ＣＯＤ、ＳＳ、ＴＮ效率及两者的污泥性能。     

Electrocatalytic oxidation of methyl tert-butyl ether (MTBE) in aqueous solution at a nickel electrode

This study utilized the electrocatalytic characteristics of nickel electrode to perform degradation of methyl tert-butyl ether (MTBE) in aqueous solution. Lab experiments were conducted in a spiltless bath type cell equipped with a nickel electrode as working electrode, a platinum wire as counter electrode, and an Ag/AgCl electrode as reference electrode. Effects of controlled potential, supporting electrolyte, and solution pH on the efficiency of MTBE removal were examined under the control of the constant-potential conditions. Experiment results showed that the optimum electrolytic condition was operated at 0.35 V in a 1M KOH electrolyte solution, and the initial 20 mgl(-1) MTBE was reduced by 73% within 180 min under the optimum control. As using 1M Na2SO4 and 1M KCl as electrolyte, the efficiency of MTBE removal dropped to 60% and 50% under the similar controls. Comparing with various pH controls, the strong basic condition is favorable for electrocatalytic oxidation of MTBE in the Ni-electrolytic system. The efficiency of MTBE removal showed a rising trend with increasing initial pH of the solution. The formation of a redox NiOOH/Ni(OH)2 layer on the anode surface, which was observed on the SEM image, can explain that nickel plays a mediator role on improving electrocatalytic oxidation of MTBE at 0.35 V in a strong basic condition. The by-products of MTBE degradation were identified as acetone and CO(2) by GC/MS, and the distributions of carbon atoms in acetone, CO2, and MTBE were found 22%, 51%, and 27% through the optimum control of electrochemical oxidation.     

Electrochemical degradation of p-substituted phenols of industrial interest on Pt electrodes. Attempt of a structure-reactivity relationship assessment

The electrochemical oxidation of p-substituted phenols, with both electron donor (OH- and NH2-) and electron withdrawing groups (NO2-, COOH-, and halogens), on Pt anodes using sodium sulfate as support electrolyte has been studied. It was found that, except for p-halogen phenols, compounds with electron donor substituents are easier to remove and their initial rates of degradation are correlated to the octanol-water partitioning coefficient (log Poct) and the Hammett's constant. Degradation of all of our starting compounds produced the same intermediates, therefore, a general pathway of reaction is proposed. Additionally, the influence of pH, temperature, electrolyte concentration and current density on the initial and total degradation of p-chlorophenol was also investigated.     

钯修饰碳纳米管电极电催化氧化三氯生

采用钯修饰多壁碳纳米管(MWCNTs)电极电催化氧化降解三氯生,考察了极板间距、电流密度、离子强度、pH、初始浓度和电解时间对三氯生去除效率的影响,并探讨了其反应动力学。结果表明:钯修饰多壁碳纳米管(MWCNTs)电极电催化氧化降解三氯生的最佳条件为:三氯生初始浓度为50 mg/L,电流密度约为10 mA/cm2,极板间距为1 cm,pH为11,电解质Na2SO4浓度为1 000 mg/L。此条件下,反应时间为3 h时三氯生的去除率可达到99%以上,三氯生的降解为零级反应。     

Electrochemical oxidation of herbicide bifenox acid in aqueous medium using diamond thin film electrode

The electrochemical oxidation of bifenox acid was studied at a boron-doped diamond thin film by cyclic voltammetry and galvanostatic electrolysis. The course of the electrolysis was monitored by measurement of chemical oxygen demand (COD) and by gas chromatography/mass spectrometry (GC / MS) analysis. It was found that exhaustive electrolysis leads to degradation and, ultimately, to mineralization of the starting herbicide. The degradation intermediates were identified showing that the oxidation process begins with the fragmentation of the molecule followed by reactions involving the hydroxyl radical, which is generated by the discharge of water. The study of the effect of current density and concentration showed that the degradation efficiency increases with decreasing current densities and increasing concentrations. The whole results were interpreted in a mechanistic scheme involving two oxidation pathways, the first is a direct oxidation at the electrode and the second uses hydroxyl radical as mediator of the oxidation. Finally, a kinetic study based on spectrophotometric measurements showed that the degradation process is pseudo first order.     

哌啶清洁生产工艺条件的研究

研究了有机电催化还原的方法生产哌啶的清洁生产工艺,探讨了电极种类、吡啶初始浓度、电流密度、电解质溶液浓度及添加剂的加入等条件对哌啶的收率和电流效率的影响。结果表明,采用RaneyNi板式电极,吡啶初始浓度为0．2～0．3mol／L,电流密度为20-80A／dm^2,常温下在0．5mol／L的NaOH水溶液中进行电还原反应,可获得90％以上的哌啶收率和80％以上电流效率。该清洁生产工艺具有产率高、纯度高,生产条件温和,节能高效等优点。     

电化学方法用于酸性红B模拟废水脱色试验研究

本文研究了两种电极材料 (SnO2 Ti和RuO2 Ti)对酸性红B模拟废水的脱色效果 ,考察了不同 pH、电流密度(j)及外加电解质 (Na2 SO4/NaCl)对处理过程的影响。结果表明 ,两种电极材料都能对酸性红B染料废水进行有效脱色 ,主要是Cl-在电解过程中的间接氧化作用 ,同时也包括电极表面的直接氧化作用。     

Degradation of clofibric acid in acidic aqueous medium by electro-Fenton and photoelectro-Fenton

Acidic aqueous solutions of clofibric acid (2-(4-chlorophenoxy)-2-methylpropionic acid), the bioactive metabolite of various lipid-regulating drugs, have been degraded by indirect electrooxidation methods such as electro-Fenton and photoelectro-Fenton with Fe(2+) as catalyst using an undivided electrolytic cell with a Pt anode and an O(2)-diffusion cathode able to electrogenerate H(2)O(2). At pH 3.0 about 80% of mineralization is achieved with the electro-Fenton method due to the efficient production of oxidant hydroxyl radical from Fenton's reaction between Fe(2+) and H(2)O(2), but stable Fe(3+) complexes are formed. The photoelectro-Fenton method favors the photodecomposition of these species under UVA irradiation, reaching more than 96% of decontamination. The mineralization current efficiency increases with rising metabolite concentration up to saturation and with decreasing current density. The photoelectro-Fenton method is then viable for treating acidic wastewaters containing this pollutant. Comparative degradation by anodic oxidation (without Fe(2+)) yields poor decontamination. Chloride ion is released during all degradation processes. The decay kinetics of clofibric acid always follows a pseudo-first-order reaction, with a similar rate constant in electro-Fenton and photoelectro-Fenton that increases with rising current density, but decreases at greater metabolite concentration. 4-Chlorophenol, 4-chlorocatechol, 4-chlororesorcinol, hydroquinone, p-benzoquinone and 1,2,4-benzenetriol, along with carboxylic acids such as 2-hydroxyisobutyric, tartronic, maleic, fumaric, formic and oxalic, are detected as intermediates. The ultimate product is oxalic acid, which forms very stable Fe(3+)-oxalato complexes under electro-Fenton conditions. These complexes are efficiently photodecarboxylated in photoelectro-Fenton under the action of UVA light.     

Electrochemical removal of synthetic textile dyes from aqueous solutions using Ti/Pt anode: role of dye structure

In this work, the efficiency of electrochemical oxidation (EO) was investigated for removing a dye mixture containing Novacron Yellow (NY) and Remazol Red (RR) in aqueous solutions using platinum supported on titanium (Ti/Pt) as anode. Different current densities (20, 40 and 60 mA cm^?2) and temperatures (25, 40 and 60 °C) were studied during electrochemical treatment. After that, the EO of each of these dyes was separately investigated. The EO of each of these dyes was performed, varying only the current density and keeping the same temperature (25 °C). The elimination of colour was monitored by UV-visible spectroscopy, and the degradation of organic compounds was analysed by means of chemical oxygen demand (COD). Data obtained from the analysis of the dye mixture showed that the EO process was effective in colour removal, in which more than 90 % was removed. In the case of COD removal, the application of a current density greater than 40 mA cm^?2 favoured the oxygen evolution reaction, and no complete oxidation was achieved. Regarding the analysis of individual anodic oxidation dyes, it was appreciated that the data for the NY were very close to the results obtained for the oxidation of the dye mixture while the RR dye achieved higher colour removal but lower COD elimination. These results suggest that the oxidation efficiency is dependent on the nature of the organic molecule, and it was confirmed by the intermediates identified. Figure

Chemical structures of a NY and b RR     

Removal of copper from water by electrocoagulation process—effect of alternating current (AC) and direct current (DC)

Purpose and aim

In general, direct current (DC) is used in an electrocoagulation processes. In this case, an impermeable oxide layer may form on the cathode as well as corrosion formation on the anode due to oxidation. This prevents the effective current transfer between the anode and cathode, so the efficiency of electrocoagulation processes declines. These disadvantages of DC have been diminished by adopting alternating current (AC) in electrocoagulation processes. The main objective of this study is to investigate the effects of AC and DC on the removal of copper from water using magnesium alloy as anode and cathode.

Materials and methods

Magnesium alloy of size 2.0 dm² was used as anode and as cathode. To optimize the maximum removal efficiency, different parameters like effect of initial concentration, effect of temperature, pH, and effect of current density were studied. Copper adsorbed magnesium hydroxide coagulant was characterized by SEM, EDAX, XRD, and FTIR.

Results

The results showed that the optimum removal efficiency of copper is 97.8 and 97.2 % with an energy consumption of 0.634 and 0.996 kWh/m³ at a current density of 0.025 A/dm², pH of 7.0 for AC and DC, respectively. The adsorption of copper is preferably fitting the Langmuir adsorption isotherm for both AC and DC respectively. The adsorption process follows the second-order kinetics model with good correlation. Temperature studies showed that adsorption was endothermic and spontaneous in nature.

Conclusions

The magnesium hydroxide generated in the cell removes the copper present in the water, reducing the copper concentration to less than 1 mg/L, making it safe for drinking. The results of the scale-up study show that the process was technologically feasible.     

含中间层的DSA电极电催化氧化硝基苯废水的研究

为了提高难降解有机废水的可生化性，以及更高效地去除废水中的特征污染物，同时避免二次污染，利用自制的含锡锑中间层的钌钯氧化物涂层电极对有机废水中的硝基苯进行处理，并利用SEM、XRD等方法对电极中间层、表层进行微观表征。微观测试表明，基体、中间层、表层之间结合力较强，有利于增强电极寿命；水处理实验表明，电催化氧化反应体系适合高浓度有机废水的处理，由于该反应体系需要外加电解质加强传质，这在实际运用中为废水中盐度的处理提供了一种新的途径，当电流密度为20 mA/cm²、电解质浓度为10 g/L、pH=5、极板间距=2 cm时，电催化氧化体系对硝基苯具有较高的去除效率。