Recovery of Ni(II) from real electroplating wastewater using fixed-bed resin adsorption and subsequent electrodeposition

Resin adsorption and subsequent electrodeposition were used for nickel recovery. Treated wastewater can meet the Electroplating Pollutant Discharge Standard. The spent resin is completely regenerated by 3 BV of 4% HCl solution. 95.6% of nickel in concentrated eluent was recovered by electrodeposition. Effective recovery of high-value heavy metals from electroplating wastewater is of great significance, but recovering nickel ions from real electroplating wastewater as nickel sheet has not been reported. In this study, the pilot-scale fixed-bed resin adsorption was conducted to recover Ni(II) ions from real nickel plating wastewater, and then the concentrated Ni(II) ions in the regenerated solution were reduced to nickel sheet via electrodeposition. A commercial cation-exchange resin was selected and the optimal resin adsorption and regeneration conditions were investigated. The resin exhibited an adsorption capacity of 63 mg/g for Ni(II) ions, and the average amount of treated water was 84.6 bed volumes (BV) in the pilot-scale experiments. After the adsorption by two ion-exchange resin columns in series and one chelating resin column, the concentrations of Ni(II) in the treated wastewater were below 0.1 mg/L. After the regeneration of the spent resin using 3 BV of 4% (w/w) HCl solution, 1.5 BV of concentrated neutral nickel solution (>30 g/L) was obtained and used in the subsequent electrodeposition process. Using the aeration method, alkali and water required in resin activation process were greatly reduced to 2 BV and 3 BV, respectively. Under the optimal electrodeposition conditions, 95.6% of Ni(II) in desorption eluent could be recovered as the elemental nickel on the cathode. The total treatment cost for the resin adsorption and regeneration as well as the electrodeposition was calculated.     

Preparation and characterization of a novel blue-TiO2/PbO2-carbon nanotube electrode and its application for degradation of phenol

In this study, we fabricated a blue-TiO₂/PbO₂-carbon nanotube (CNT) electrode in which blue TiO₂ nanotube arrays (blue-TNA) served as the substrate for PbO₂-CNT eletrodeposition. Scanning electron microscope (SEM) showed compact surface structure of the electrode. The β-PbO₂ crystal structure was detected by X-ray diffraction (XRD). The distribution of Pb, O, C, and Na elements on the electrode surface have been confirmed by X-ray photoelectron spectroscopy (XPS). Blue-TiO₂/PbO₂-CNT electrode had higher response current (213.12 mA), larger active surface area and lower charge transfer resistance (2.22 Ω/cm²) than conventional TiO₂/PbO₂-CNT electrode. The influences of current density, initial phenol concentration, initial solution pH, and Na₂SO₄ concentration on the electrochemical oxidation of phenol have been analyzed. The results showed that the 100 mg/L phenol could be destroyed completely after 210 min, and chemical oxygen demand (COD) removal rate was 89.3% within 240 min. Additionally, the electrode showed long actual lifetime (5468.80 hr) and low energy consumption (0.08 kWh/gCOD). A phenol degradation mechanism was proposed by analyzing the intermediate products with high-performance liquid chromatography-mass spectrometry (HPLC-MS). Importantly, the blue-TiO₂/PbO₂-CNT electrode exhibited superior stability and high degradation efficiency after 15 times reuse, demonstrating its promising application potential on phenol-containing wastewater treatment.     

Electro-oxidation of Ni (II)-citrate complexes at BDD electrode and simultaneous recovery of metallic nickel by electrodeposition

The simultaneous electro-oxidation of Ni (II)-citrate and electrodeposition recovery of nickel metal were attempted in a combined electro-oxidation-electrodeposition reactor with a boron-doped diamond (BDD) anode and a polished titanium cathode. Effects of initial nickel citrate concentration, current density, initial pH, electrode spacing, electrolyte type, and initial electrolyte dosage on electrochemical performance were examined. The efficiencies of Ni (II)-citrate removal and nickel metal recovery were determined to be 100% and over 72%, respectively, under the optimized conditions (10 mA/cm², pH 4.09, 80 mmol/L Na₂SO₄, initial Ni (II)-citrate concentration of 75 mg/L, electrode spacing of 1 cm, and 180 min of electrolysis). Energy consumption increased with increased current density, and the energy consumption was 0.032 kWh/L at a current density of 10 mA/cm² (pH 6.58). The deposits at the cathode were characterized by scanning electron microscopy (SEM), energy-dispersive spectrometry (EDS), X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS). These characterization results indicated that the purity of metallic nickel in cathodic deposition was over 95%. The electrochemical system exhibited a prospective approach to oxidize metal complexes and recover metallic nickel.     

Removing and recycling mercury from scrubbing solution produced in wet nonferrous metal smelting flue gas purification process

Wet purification technology for nonferrous metal smelting flue gas is important for mercury removal; however, this technology produces a large amounts of spent scrubbing solution that contain mercury. The mercury in these scrubbing solutions pose a great threat to the environment. Therefore, this research provides a novel strategy for removing and recycling mercury from the scrubbing solution, which is significant for decreasing mercury pollution while also allowing for the safe disposal of wastewater and a stable supply of mercury resources. Some critical parameters for the electrochemical reduction of mercury were studied in detail. Additionally, the electrodeposition dynamics and electroreduction mechanism for mercury were evaluated. Results suggested that over 92.4% of mercury could be removed from the scrubbing solution in the form of a Hg-Cu alloy under optimal conditions within 150 min and with a current efficiency of approximately 75%. Additionally, mercury electrodeposition was a quasi-reversible process, and the controlled step was the mass transport of the reactant. A pre-conversion step from Hg(Tu)₄²⁺ to Hg(Tu)₃²⁺ before mercury electroreduction was necessary. Then, the formed Hg(Tu)₃²⁺ on the cathode surface gained electrons step by step. After electrodeposition, the mercury in the spent cathode could be recycled by thermal desorption. The results of the electrochemical reduction of mercury and subsequent recycling provides a practical and easy-to-adopt alternative for recycling mercury resources and decreasing mercury contamination.     

Ni-Fe/泡沫镍催化还原体系脱氯工艺参数的优化及表征

以泡沫镍做载体,采用电沉积法制备出镍/铁/泡沫镍双金属催化还原剂,并对目标污染物氯乙酸进行了脱氯研究,分析了催化还原剂在制备过程中沉积液浓度、电流密度对催化活性的影响,采用扫描电子显微镜对双金属体系表征以观察所制备的催化还原剂的表面形貌,可以观察到采用电沉积制备的Ni/Fe-泡沫镍双金属还原剂在基体泡沫镍上分布均匀、密集、呈针状结构,在一定电流密度下,沉积60 min的情况下无团聚现象。研究表明,本研究所制备的镍-铁/泡沫镍双金属催化还原剂对氯乙酸具有良好的脱氯效果。     

Electrocatalytic reduction of nitrate using Pd-Cu modified carbon nanotube membranes

● Pd-Cu modified CNT membranes were prepared successfully by electrodeposition method. ● The deposition voltage and deposition time were optimized for Pd-Cu co-deposition. ● NO₃⁻-N was removed efficiently from water by Pd-Cu modified CNT membranes. ● The presence of dissolved oxygen did not affect the nitrate reduction performance. ● Mass transfer rate was promoted significantly with the increase in membrane flux. Excessive nitrate in water is harmful to the ecological environment and human health. Electrocatalytic reduction is a promising technology for nitrate removal. Herein, a Pd-Cu modified carbon nanotube membrane was fabricated with an electrodeposition method and used to reduce nitrate in a flow-through electrochemical reactor. The optimal potential and duration for codeposition of Pd and Cu were −0.7 V and 5 min, respectively, according to linear scan voltammetry results. The membrane obtained with a Pd:Cu ratio of 1:1 exhibited a relatively high nitrate removal efficiency and N₂ selectivity. Nitrate was almost completely reduced (~99 %) by the membrane at potentials lower than −1.2 V. However, −0.8 V was the optimal potential for nitrate reduction in terms of both nitrate removal efficiency and product selectivity. The nitrate removal efficiency was 56.2 %, and the N₂ selectivity was 23.8 % for the Pd:Cu=1:1 membrane operated at −0.8 V. Nitrate removal was enhanced under acidic conditions, while N₂ selectivity was decreased. The concentrations of Cl⁻ ions and dissolved oxygen showed little effect on nitrate reduction. The mass transfer rate constant was greatly improved by 6.6 times from 1.14 × 10⁻³ m/h at a membrane flux of 1 L/(m²·h) to 8.71 × 10⁻³ m/h at a membrane flux of 15 L/(m²·h), which resulted in a significant increase in the nitrate removal rate from 13.6 to 133.5 mg/(m²·h). These findings show that the Pd-Cu modified CNT membrane is an efficient material for nitrate reduction.