Pilot-scale electrochemical advanced oxidation (EAOP) system for the treatment of Ni-EDTA-containing wastewater.

Electrochemical advanced oxidation processes (EAOP) have shown great potential for the abatement of complexed heavy metals, such as metal-EDTA complexes, in recent studies. While removal of metal-EDTA complexes has been extensively examined in bench-scale reactors, much less attention has been given to the efficacy of this process at larger scale. In this study, we utilize a 72 L pilot-scale continuous flow system comprised of six serpentine flow channels and 90 pairs of flow-through electrodes for the degradation of Ni-EDTA complexes and removal of Ni from solution. The influence of a range of key operating parameters including flow rate, current density and initial Ni-EDTA concentration on rate and extent of Ni-EDTA degradation and Ni removal were examined. Our results showed that at a feed flow rate of 36 L h-1, current density of 5 mA cm-2 and initial Ni-EDTA concentration of 1 mM, the pilot-scale system achieved 74 % total Ni removal, 78 % total EDTA removal and 40 % TOC removal with energy consumption of 13.6 kWh m-3 order-1 and energy efficiency of 7.9 g kWh-1 for total Ni removal. A mechanistically-based kinetic model, which was developed in our previous bench-scale study, provides a satisfactory description of the experimental results obtained in the pilot-scale unit. Long term operation of the pilot-scale unit resulted in corrosion of PbO2 anode along with inorganic scaling as well as organic fouling on the PbO2 surface resulting in an obvious decline in Ni-EDTA degradation. Overall, the results of this study suggest that large scale anodic oxidation of wastewaters containing metal-organic complexes is an effective means of degrading organic ligands thereby enabling removal of the metal at the cathode. However, additional efforts are required to enhance the durability of the anode material and reduce material costs and energy consumption.

Electrochemical treatment of wastewaters containing metal-organic complexes: A one-step approach for efficient metal complex decomposition and selective metal recovery.

Metal-organic complexes, especially those of ethylenediaminetetraacetic acid (EDTA) with metals such as copper (Cu) and nickel (Ni) (denoted here as Cu-EDTA and Ni-EDTA), are common contaminants in wastewaters from chemical and plating industries. In this study, a multi-electrode (ME) system using a two-chamber reactor and two pairs of electrodes is proposed for simultaneous electrochemical oxidation of a wastewater containing both Cu-EDTA and Ni-EDTA complexes as well as separation and selective recovery of Cu and Ni onto two different cathodes via electrodeposition. Our results demonstrate that the ME system successfully achieved 90% EDTA removal, 99% solid Cu recovery at the Cu recovery cathode and 56% Ni recovery (33.3% on the Ni recovery cathode and 22.6% in the solution) after a four-hour operation. The system further achieved 85.5% Ni recovery after consecutive five cycles of operation for 20 h. While Cu removal was mainly driven by the direct reduction of EDTA-complexed Cu(II) at the cathode, oxidation of EDTA within the Ni-EDTA complex at the anode was a prerequisite for Ni removal. The oxidation of metal-bound EDTA and free EDTA was driven by •OH and direct electron transfer on the PbO2 anode surface and graphite anode, respectively. We further show that ME system performs well for all pH conditions, treatment of real wastewaters as well as wastewaters containing other metals ions (Cr and Zn) along with Cu/Ni. The separation efficiency of Cu and Ni is dependent on applied electrode potential as well as nature and concentration of binding ligand present with comparatively lower separation efficiency achieved in the presence of weaker binding capacity and/or at lower ligand concentration and lower applied electrode potential. As such, some optimization of electrode potential is required depending on the nature/concentration of ligands in the wastewaters. Overall, this study provides new insights into the design and operation of EAOP technology for effective organic abatement and metal recovery from wastewaters containing mixtures of various metal-organic complexes.

Electrochemical Removal of Metal-Organic Complexes in Metal Plating Wastewater: A Comparative Study of Cu-EDTA and Ni-EDTA Removal Mechanisms.

Cu and Ni complexes with ethylenediaminetetraacetic acid (Cu/Ni-EDTA), which are commonly present in metal plating industry wastewaters, pose a serious threat to both the environment and human health due to their high toxicity and low biodegradability. In this study, the treatment of solutions containing either or both Cu-EDTA and Ni-EDTA using an electrochemical process is investigated under both oxidizing and reducing electrolysis conditions. Our results indicate that Cu-EDTA is decomplexed as a result of the cathodic reduction of Cu(II) with subsequent electrodeposition of Cu(0) at the cathode when the cathode potential is more negative than the reduction potential of Cu-EDTA to Cu(0). In contrast, the very negative reduction potential of Ni-EDTA to Ni(0) renders the direct reduction of EDTA-complexed Ni(II) at the cathode unimportant. The removal of Ni during the electrolysis process mainly occurs via anodic oxidation of EDTA in Ni-EDTA, with the resulting formation of low-molecular-weight organic acids and the release of Ni2+, which is subsequently deposited as Ni0 on the cathode. A kinetic model incorporating the key reactions occurring in the electrolysis process has been developed, which satisfactorily describes EDTA, Cu, Ni, and TOC removal. Overall, this study improves our understanding of the mechanism of removal of heavy metals from solution during the electrochemical advanced oxidation of metal plating wastewaters.

Characterizing fluorescence fingerprints of different types of metal plating wastewater by fluorescence excitation-emission matrix.

To prevent the illegal discharge of metal plating wastewater (MPW), it is necessary to explore a monitoring method that could achieve the identification of MPW in natural water bodies. Fluorescence excitation-emission matrix-parallel factor (EEM-PARAFAC) analysis might be a promising tool for the detection of MPW. However, before conducting the practical monitoring, the apparent fluorescence features of different kinds of MPW must be first understood. In this study, six types of MPW (576 samples) from ten metal plating plants were collected and their fluorescence fingerprints (FFs) were characterized by EEM-PARAFAC analysis. Results showed that pretreatment wastewater (PTW), copper-contained electroplating wastewater (Cu-EPW), nickel-contained electroplating wastewater (Ni-EPW), copper-contained electroless wastewater (Cu-ELW), nickel-contained electroless wastewater (Ni-ELW), and metal plating effluent (MPE) presented one, three, one, one, two, and three types of FFs, respectively. Among them, three individual fluorescent components were identified in Ni-EPW and two were decomposed in other kinds of MPW. Owing to the discrepancies of production processes, electroplating additives, wastewater treatment techniques, and management levels, different metal plating plants owned different FFs. By spectral comparison, the tyrosine-like components in PTW and Ni-ELW might derived from some phenolic and benzenesulfonic acidic compounds. Fluorescent component similarity analysis indicated that EEM-PARAFAC technique could distinguish the raw and treated MPW. This study not only constructed the first FF database for MPW, but also provided valuable guidance for their practical monitoring in aquatic environment.

Hybrid ceramic membrane reactor combined with fluidized adsorbents and scouring agents for hazardous metal-plating wastewater treatment.

In this study, a ceramic membrane consisting of aluminum oxide in the support and active layer with a surface pore size of 0.1 µm was applied with a real hazardous metal-plating wastewater. Alumina membrane was submerged directly into a fluidized membrane reactor specially designed for fluidizing the granular activated carbon (GAC) particles along membrane surface by recirculating a bulk wastewater through the reactor to improve fouling control and removal efficiency of contaminants. Zeolite particle which has the similar size to the GAC was also tested to compare membrane performance. Neutralizing a wastewater pH resulted in the agglomeration of particulate and colloidal materials, leading to the significant deposit of the fouling layer on membrane surface. The external fouling layer formed on membrane surface enhanced the removal efficiency of the heavy metal ions due to its role as secondary membrane. In addition to the fouling control by mechanical scouring actions, fluidizing the GAC particles on membrane was more beneficial to improve organic removal efficiency than zeolite. The increase in GAC dosage from 10 to 30 v/v% did not result in any beneficial effect on both fouling reduction and organic removal efficiency.

Evaluation of the chelating performance of biopolyelectrolyte green complexes (NIBPEGCs) for wastewater treatment from the metal finishing industry.

In this paper nonstoichiometric interbiopolyelectrolyte green complexes (NIBPEGCs) were prepared using chitosan (Ch), alginate (AG) and poly(acrylic acid)(PAA). They are proposed as innovative formulations (polyelectrolytes and chelating agents) suitable for the elimination heavy metals contained in wastewater. This application may represent an integral solution for industries rejecting solid and aqueous metallic materials; however, it has not been previously reported. NIBPEGCs physicochemical performance was evaluated based on pH, particle size, surface charge, isoelectric point, dose, coagulation-flocculation kinetics and chemical affinity with seven metal ions. The experimental results showed that NIBPEGCs composed by AG/Ch and PAA/Chitosan have all the three complementary functions: chemical affinity, electrostatic interaction and particle entrapment anticipating more simple operation units to remove heavy metals. Complexes of AG/Ch (negative) were higher performance in removing heavy metals, with a dose window (150-180mg/L), lower dose of 410mg/L PAA/Ch (negative). Investigation of chelating performances of NIBPEGCs show that the efficiency of metal removal is: Ca˃Cr˃Cu˃Pb˃Ni˃Zn˃Cd. Transmittance vs time profiles, metals and zeta potential analysis showed that chelation capacity is the crucial factor to ensure metallic species removal, followed by physical entrapment of the metallic colloids. Integrating all presented results allow to sustain the development of excellent metals removal formulations.

Removal of copper, nickel and chromium mixtures from metal plating wastewater by adsorption with modified carbon foam.

In this study, the characterizations and adsorption efficiencies for chromium, copper and nickel were evaluated using manufacture-grade Fe2O3-carbon foam. SEM, XRD, XRF and BET analyses were performed to determine the characteristics of the material. Various pore sizes (12-420 µm) and iron contents (3.62%) were found on the surface of the Fe2O3-carbon foam. Fe2O3-carbon foam was found to have excellent adsorption efficiency compared to carbon foam for mixed solutions of cationic and anionic heavy metals. The adsorption capacities for chromium, copper and nickel were 6.7, 3.8 and 6.4 mg/g, respectively, which were obtained using a dual exponential adsorption model. In experiments with varying dosages of the Fe2O3 powder, no notable differences were observed in the removal efficiency. In a fixed-bed column test, Fe2O3-carbon foam achieved adsorption capacities for chromium, copper and nickel of 33.0, 12.0 and 9.5 mg/g, respectively, after 104 h. Based on these results, Fe2O3-carbon foam was observed to be a promising material for treatment of plating wastewater.