José M. Aquino

Electrochemical degradation of a real textile effluent using boron-doped diamond or β-PbO2 as anode

Constant current electrolyses are carried out in a filter-press reactor using a boron-doped diamond (Nb/BDD) or a Ti-Pt/β-PbO(2) anode, varying current density (j) and temperature. The degradation of the real textile effluent is followed by its decolorization and chemical oxygen demand (COD) abatement. The effect of adding NaCl (1.5 g L(-1)) on the degradation of the effluent is also investigated. The Nb/BDD anode yields much higher decolorization (attaining the DFZ limit) and COD-abatement rates than the Ti-Pt/β-PbO(2) anode, at any experimental condition. The best conditions are j = 5 mA cm(-2) and 55 °C, for the systems optimized hydrodynamic conditions. The addition of chloride ions significantly increases the decolorization rate; thus a decrease of more than 90% of the effluent relative absorbance is attained using an applied electric charge per unit volume of the electrolyzed effluent (Q(ap)) of only about 2 kA h m(-3). Practically total abatement of the effluent COD is attained with the Nb/BDD anode using a Q(ap) value of only 7 kA h m(-3), with an energy consumption of about 30 kW h m(-3). This result allows to conclude that the Nb/BDD electrode might be an excellent option for the remediation of textile effluents.

Electrochemical degradation of the reactive red 141 dye on a β-PbO2 anode assessed by the response surface methodology

The electrochemical degradation of the Reactive Red 141 dye using a filter-press reactor with a β-PbO2 anode was investigated through the application of the response surface methodology. The charge required for 90% decolorization (Q90) and the chemical oxygen demand removal percentage after 30 min electrolysis (COD30) were used to model the system. The investigated independent variables were the current density, pH, NaCl concentration, and temperature. Low values of Q90 (0.2-0.3 A h L-1) were obtained at acidic conditions (pH 1-3) and high concentrations of NaCl (1.0-2.0 g L-1), when Cl2 and HOCl are the predominant oxidant species. The best values of COD30 were obtained at high current densities and acidic to neutral conditions (pH 5-7); however, the consequent energy consumption makes the process not economically feasible under these conditions. For strongly acidic solutions, specific energy consumptions associated to Q90 as low as 0.79 kW h m-3 were attained.

A comparison of electrodeposited Ti/β-PbO2 and Ti-Pt/β-PbO2 anodes in the electrochemical degradation of the direct yellow 86 dye

The electrochemical performance of electrodeposited Ti/β-PbO2 and Ti-Pt/β-PbO2 anodes was galvanostatically evaluated (batch mode, 50 mA cm-2) to degrade the Direct Yellow 86 dye (100 or 200 mg L-1 in 0.1 mol L-1 Na2SO4 + 1.5 g L-1 NaCl), investigating the effect of pH and temperature. Similar results were obtained for both electrodes and the best conditions for removal of color and chemical oxygen demand are pH 7 and 40 °C, when 90% decolorization is attained by passing a charge of only ~0.13 A h L-1 and total mineralization is achieved with expenditure of ~5 kW h m-3.

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.

Localized Corrosion Susceptibility of Supermartensitic Stainless Steel in Welded Joints

Abstract Supermartensitic stainless steels is known for its better weld-ability and corrosion resistance compared to the conventional martensitic, mainly due to its lower carbon content. This enables the production of welded joints with superior resistance to hydrogen embrittlement and to sensitization, particularly in the heat-affected zone. These characteristics can be optimized with the production of weldments using high-power density processes, such as electron beam welding. This process creates a narrow heat-affected zone with a high thermal gradient, which makes it less susceptible to precipitation, particularly to chromium carbides. Thus, its pitting potential is improved.

INFLUENCE OF CHLORIDE-MEDIATED OXIDATION ON THE ELECTROCHEMICAL DEGRADATION OF THE DIRECT BLACK 22 DYE USING BORON-DOPED DIAMOND AND β-PbO2 ANODES

The Direct Black 22 dye was electrooxidized at 30 mA cm-2 in a flow cell using a BDD or β-PbO2 anode, varying pH (3, 7, 11), temperature (10, 25, 45 °C), and [NaCl] (0 or 1.5 g L-1). In the presence of NaCl, decolorization rates were similar for all conditions investigated, but much higher than predicted through a theoretical model assuming mass-transport control; similar behavior was observed for COD removal (at pH 7, 25 °C), independently of the anode. With no NaCl, COD removals were also higher than predicted with a theoretical model, which suggests the existence of distinct dye degradation pathways.

Anodic behaviour of supermartensitic stainless steel weldments

Abstract The corrosion resistance evaluation was carried out in a supermartensitic stainless steel weldment through anodic polarisation curves and through corrosion rate measurements in an acidic medium. The electrochemical measurements were carried out separately in the base metal samples, the heat affected zone and the weld metal of electron beam weldments. An improvement was found in the corrosion resistance from the base metal to the weld metal.

Efeito do revenido na resistência à corrosão dos aços inoxidáveis supermartensíticos

Supermartensitic stainless steels have been used in the oil and gas industry for onshore and offshore tubing applications, due to their good mechanical properties, weldability and excellent corrosion resistance. They are hardened by quenching heat treatment, and to improve their toughness, are submitted to tempering. During the tempering, some phase precipitation occurs, which depending on the time and temperature parameters, produces some undesired changes in the steel properties. The aim of this research was to study the microstructure and the corrosion resistance of supermartensitic stainless steel in quenched and different tempered conditions (550°C, 600°C and 650°C). At the microstructure of the 650°C tempered sample was observed the formation of austenite and precipitates of chromium, like Cr3C2 and Cr7C3.The polarization curves indicated that the heat treatment influences the anodic behavior, changing the passive region and the passive film characteristics. The tempering changes the corrosion resistance, decreasing the degree of sensitization when increasing the temperature from 550°C to 650°C, this occurs due to the recovery of the chromium impoverished zones.

Intergranular and Pitting Corrosion Susceptibilities of a Supermartensitic Stainless Steel Weldment

Abstract Degree of sensitization and pitting corrosion potential of a supermartensitic stainless steel weldment were measured and compared. An improvement in the degree of sensitization and in the ...

The effect of the supporting electrolyte on the electrooxidation of enrofloxacin using a flow cell with a BDD anode: Kinetics and follow-up of oxidation intermediates and antimicrobial activity

The role of the supporting electrolyte - SE (Na2SO4; NaCl; Na2CO3; NaNO3; Na3PO4 - 0.1 M ionic strength) in the galvanostatic (10 mA cm-2) electrochemical degradation of the fluoroquinolone antibiotic enrofloxacin (ENRO; 100 mg L-1) using a filter-press flow cell with a boron-doped diamond anode was investigated (flow rate, solution volume, and temperature were kept fixed at 420 L h-1, 1.0 L, and 25 °C, respectively). The electrochemical degradation performance with the different SEs was assessed by following up [ENRO], total organic carbon concentration (TOC), oxidation intermediates (detected by LC and LC-QqTOF), and antimicrobial activity towards Escherichia coli as the electrolyses progressed. With NaCl as SE, complete removal of ENRO was attained ∼10 times faster than with the other salts. The determination of terminal oxidation intermediates (short-chain carboxylic acids) produced during the electrolyses allowed concluding that their nature and number is indeed affected by the salt used as SE, most probably due to distinct electrogenerated oxidants. With NaCl, the antimicrobial activity of the electrolyzed solution decreased gradually (to ∼20%) from 8 to 16 h of electrolysis due to the cleavage of the fluoroquinolone structure. On the other hand, with Na2SO4, Na2CO3 and NaNO3 as SEs the growth of Escherichia coli cells was observed only after ∼14 h, whereas it was completely inhibited with Na3PO4. Clearly, the electrooxidation and mineralization of ENRO is strongly affected by the SEs used, which determine the degradation mechanism and, consequently, the removal rates of the solutions organic load and antimicrobial activity.