Enhanced removal of Pb from electrolytic manganese anode slime and preparation of chemical MnO2.

Electrolytic manganese anode slime (EMAS) is produced during the production of electrolytic manganese metal. In this study, a method based on vacuum carbothermal reduction was used for Pb removal in EMAS. A Pb-removal efficiency of 99.85% and MnO purity in EMAS of 97.34 wt.% were obtained for a reduction temperature of 950°C and a carbon mass ratio of 10% for a holding time of 100 min. The dense structure of the EMAS was destroyed, a large number of multidimensional pores and cracks were formed, and the Pb-containing compound was reduced to elemental Pb by the vacuum carbothermal reduction. A recovery efficiency for chemical MnO2 of 36.6% was obtained via preparation from Pb-removed EMAS through the 'roasting-pickling disproportionation' process, with an acid washing time of 100 min, acid washing temperature of 70°C, H2SO4 concentration of 0.8 mol·L-1, liquid-solid mass ratio of 7 mL·g-1, calcination temperature of 60°C and calcination time of 2.5 h. Moreover, the crystal form of the prepared chemical MnO2 was found to be basically the same as that of electrolytic MnO2, and its specific surface area, micropore volume and discharge capacity were all higher than that of electrolytic MnO2. This study provides a new method for Pb removal and recycling for EMAS.HighlightsVacuum carbothermal reduction method was used for Pb removal in EMAS.The removal efficiency of Pb was 99.85%.Chemical MnO2 with excellent discharge performance was prepared using treated EMAS.This study provides a new method for EMAS resource utilization.

Highly Active Manganese Oxide from Electrolytic Manganese Anode Slime for Efficient Removal of Antibiotics Induced by Dissociation of Peroxymonosulfate.

In this paper, high-activity manganese oxide was prepared from electrolytic manganese anode slime to realize the efficient removal of antibiotics. The effects of sulfuric acid concentration, ethanol dosage, liquid-solid ratio, leaching temperature and leaching time on the leaching of manganese from electrolytic manganese anode slime were systematically studied. Under the optimal conditions, the leaching rate of manganese reached 88.74%. In addition, a Mn3O4 catalyst was synthesized and used to activate hydrogen persulfate (PMS) to degrade tetracycline hydrochloride (TCH). The synthesized Mn3O4 was characterized by XRD, XPS, Raman, SEM and HRTEM. As a result, the prepared Mn3O4 is spherical, with high purity and crystallinity. The catalytic activity of Mn3O4 for PMS to degrade TCH was increased to 82.11%. In addition, after four cycles, the performance remained at 78.5%, showing excellent stability and recyclability. In addition, O2- and 1O2 are the main active species in the degradation reaction. The activity of Mn3O4 is attributed to it containing Mn(II) and Mn(III) at the same time, which can quickly realize the transformation of high-valence and low-valence manganese, promote the transfer of electrons and realize the degradation of organic pollutants.

Immobilizing arsenic-enriched wastewater from utilization of crude antimony oxides as scorodite using a novel multivalent iron source.

Arsenic-enriched wastewater (A-EW) is a hypertoxic sewage from the utilization of crude antimony oxides in lead anode slime metallurgy. In traditional methods, the H+ accumulation inhibits the arsenic immobilization during scorodite synthesis. In this study, a novel multivalent iron source comprised of Fe(OH)3 and FeSO4·7H2O was proposed to resolve the adverse effects of pH fluctuation during immobilizing A-EW as scorodite. Various approaches, such as scanning electron microscopy and X-ray photoelectron spectroscopy, were applied to characterize the synthesized scorodite. This work was divided into two parts. In thermodynamics, HnAsO4(3-n)- (n = 1, 2, 3) and Fe(OH)n(3-n)+ (n = 0, 1, 2, 3) can feasibly coprecipitate as scorodite according to their △rGm,Tθ ranged from -111.10 kJ mol-1 to -33.53 kJ mol-1. In experimental research, A-EW was immobilized as scorodite by optimizing conditions as initial pH = 2.0, molar ratio of Fe to As = 1.2, molar ratio of Fe(II) to Fe(III) = 4:6, arsenic concentration = 40 g/L, and temperature = 95 °C. The arsenic precipitation ratio is 99.60%, and the micromorphology of synthesized scorodite presents a regular octahedron having size of 5-10 µm. The low leachability of As (0.41 mg/L) in toxicity characteristic leaching procedure (TCLP) confirmed that the prepared scorodite is nonhazardous. The solution pH is stable at 2.0 as the H+ depletion (0.5660 mol) by Fe(OH)3 dissolution and Fe2+ oxidization balanced with that (0.5657 mol) generated from As(V)-Fe(III) coprecipitation. In general, the A-EW was effectively immobilized by proposed multivalent iron source, and can be potentially applied to safely dispose other industrial effluents, such as high arsenic leachates and arsenic-bearing waste acid from nonferrous metallurgy.

Size effect of γ-MnO2 precoated anode on lead-containing pollutant reduction and its controllable fabrication in industrial-scale for zinc electrowinning.

Lead (Pb) is the most widely used anode in zinc (Zn) electrowinning and other metallurgical industries. The resource loss and environmental pollution caused by Pb anode corrosion are urgent problems to be solved. A γ-MnO2 precoated anode was prepared successfully to reduce the Pb-containing pollutant. The size effects with its controllable preparation on an industrial scale were studied. Severe nonuniform distribution of γ-MnO2 film was observed with curbing the reduction of anode slime only 68%, when anode size increased from lab to industry. Nonuniform rate (R) and average thickness (d) were found to be the key indicators to determine the film structure distribution and their performance differences, which were random and difficult to be controlled in scale-up size. However, a controllable industrial γ-MnO2 precoated anodes (IMPA) fabricated through optimized current density (J0) and electrodeposition time (t) in our developed film-forming system. Then, the long-term performances of two IMPA with different indicators (IMPA-1: R = 34%, d = 108 µm, IMPA-2: R = 23%, d = 55 µm) were compared with the industrial typical Pb-based anode (ITPA). Of the three different anodes, the optimized IMPA-2 displayed the best performance. Within 24 d of electrowinning cycle, the corrosion inhibition effect and the anode slime reduction rate for IMPA-2 improved by 56% and 30% than IMPA-1, and improved by 100% and 91% than ITPA. Furthermore, the mechanism analysis of size effect change showed that R of IMPA was contributed to the local gas holdup distribution along the anode. Controlled size effect of uniform oxide film will have a future application prospect for the sustainability of industry, which provides an important cleaner production of Zn electrowinning and related hydrometallurgy industries.

Comparison of Life Cycle Environmental Impact between Two Processes for Silver Separation from Copper Anode Slime.

The cost of silver separation is lowered when ammonia and hydrazine hydrate are replaced with sodium thiosulfate and sodium dithionite in the process of extracting of metallic silver from copper anode slime. The overall environmental impact of two types of copper silver separation processes from anode slime has been analyzed\using the LCA method. Through the subdivision analysis, we found the raw materials or emission items that should be improved first. The following conclusions are drawn: (1) The life cycle environmental impact of the sodium thiosulfate process is much lower than the existing process; (2) The resource and environmental impacts of the sodium thiosulfate method are mainly in the fields of climate change, photochemical smog, and ionizing radiation, exceeding two-thirds of the impact on all of the resources and environment; (3) In terms of input and output items, the main impact of the new process on the resources and the environment is concentrated on the use of sodium hydroxide, accounting for 33.98% of the total equivalent, followed by sodium thiosulfate and sodium carbonate, respectively. These input-output items are the key fields that need attention in future technology improvement.

Thermochemical Route for Extraction and Recycling of Critical, Strategic and High-Value Elements from By-Products and End-of-Life Materials, Part II: Processing in Presence of Halogenated Atmosphere.

During the treatment of copper anode slime (CAS) under an air atmosphere, several aspects of the interactions of its main components (CuAgSe, Cu2-xSeyS1-y, Ag3AuSe2) with oxygen were described in Part I. As a comparative and complementary study, this work deals with the thermal behavior of CAS under air in the presence of polyvinyl chloride (PVC) between 195 and 770 °C. The preliminary thermal treatment of an e-waste sample containing brominated substances was also performed. The reaction products were systematically analyzed by scanning electron microscopy through energy-dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD) to investigate the thermal behaviors of the studied samples in a halogenated medium. At low temperatures, the copper, silver and selenium compounds of the CAS reacted with the HCl, issued from PVC degradation, leading to the formation of their respective chlorides. Bromides of valuable metals (Cu, Pb, Sn…) were synthesized during the e-waste treatment at 500 °C and they were distributed between the solid residue and gaseous phase. The data obtained give an insight into the reactivity of several metals towards halogenated substances, which may be valuable information for conducting the extraction and recycling of targeted elements from industrial by-products and end-of-life materials by a thermochemical route.

Thermochemical Route for Extraction and Recycling of Critical, Strategic and High Value Elements from By-Products and End-of-Life Materials, Part I: Treatment of a Copper By-Product in Air Atmosphere.

Development of our modern society requests a number of critical and strategic elements (platinum group metals, In, Ga, Ge…) and high value added elements (Au, Ag, Se, Te, Ni…) which are often concentrated in by-products during the extraction of base metals (Cu, Pb, Zn…). Further, recycling of end-of-life materials employed in high technology, renewable energy and transport by conventional extractive processes also leads to the concentration of such chemical elements and their compounds in metallurgical by-products and/or co-products. One of these materials, copper anode slime (CAS), derived from a copper electrolytic refining factory, was used for this study. The sample was subjected to isothermal treatment from 225 to 770 °C under air atmosphere and the reaction products were systematically analyzed by scanning electron microscopy through energy dispersive spectroscopy (SEM-EDS) and X-ray diffraction (XRD) to investigate the thermal behavior of the treated sample. The main components of the anode slime (CuAgSe, Cu2-xSeyS1-y, Ag3AuSe2) react with oxygen, producing mostly copper and selenium oxides as well as Ag-Au alloys as final products at temperatures higher than 500 °C. Selenium dioxide (SeO2) is volatilized and recovered in pure state by cooling the gaseous phase, whilst copper(II) oxide, silver, gold and tellurium remain in the treatment residue.

Influence of Mn2+ ions on the corrosion mechanism of lead-based anodes and the generation of heavy metal anode slime in zinc sulfate electrolyte.

The influence of Mn2+ ions on the generation of heavy metal anode slime during zinc electrolysis industry was extensively investigated using several electrochemical methods, electron microscope technologies, and particle size analysis. Results showed that the Mn2+ could obviously promote oxygen evolution reaction (OER) and thereby weaken oxidation efficiency of Mn2+ (ηMnO2) and dissolution of Pb2+. The significant improvement in kinetic parameters for OER was found in electrolytes of 1 and 3 g/L Mn2+, but became unstable as the Mn2+ concentration increased to 10 g/L. This result was correlated with much different properties of oxide layers that its changes of microstructure are involved in, since it confirmed that the positive role of compact oxide layers in contributing to high corrosion resistance and activity for OER, but excessive Mn2+, resulted in its micromorphology of overthickness and instability. Such differences resulted from the effect of the Mn2+ concentration fluctuation on kinetic rates of the nucleation growth process. The formation and adsorption of intermediate MnO2-OHads identified as the controlled step for Mn2+ catalyzing OER was also recommended. The generation mechanism of anode slime was found to be changed in essence due to varying Mn2+ concentrations. In electrolyte of 1 g/L Mn2+, results revealed that the root cause of excessive small suspended anode slime (around 20 µm) was the change of the initial pathway of Mn2+ electro-oxidation, whereas, it showed great improvement in the settling performance as the Mn2+ concentration was increased to 10 g/L. Considering the potential of optimizing Mn2+ concentrations as a cleaner approach to control anode slime, deepening the understanding of the impact mechanism of Mn2+ can provide new insights into intervention in the generation of anode slime.

Direct separation of arsenic and antimony oxides by high-temperature filtration with porous FeAl intermetallic.

A temperature-controlled selective filtration technology for synchronous removal of arsenic and recovery of antimony from the fume produced from reduction smelting process of lead anode slimes was proposed. The chromium (Cr) alloyed FeAl intermetallic with an asymmetric pore structure was developed as the high-temperature filter material after evaluating its corrosive resistance, structural stability and mechanical properties. The results showed that porous FeAl alloyed with 20wt.% Cr had a long term stability in a high-temperature sulfide-bearing environment. The separation of arsenic and antimony trioxides was realized principally based on their disparate saturated vapor pressures at specific temperature ranges and the asymmetric membrane of FeAl filter elements with a mean pore size of 1.8µm. Pilot-scale filtration tests showed that the direct separation of arsenic and antimony can be achieved by a one-step or two-step filtration process. A higher removal percentage of arsenic can reach 92.24% at the expense of 6∼7% loss of antimony in the two-step filtration process at 500∼550°C and 300∼400°C. The FeAl filters had still good permeable and mechanical properties with 1041h of uninterrupted service, which indicates the feasibility of this high-temperature filtration technology.

Ultra fast ultrasound-assisted decopperization from copper anode slime.

An ultra fast decopperization method from the anode slime has been developed based on the ultrasound-assisted leaching. The effects of parameters such as ultrasound power, leaching time, sulfuric acid concentration and liquid/solid ratio were investigated. Under optimum conditions, the concentration of Cu in residue was only 2.64%. The removal efficiency increases considerably and the decopperization time was significantly shortened comparing with conventional method (>10%, 24h). Se and Te have not been detected in lixivium, indicating the selective leaching of Cu. In addition, the mineralogical characteristics of the untreated anode slime and the residues after ultrasound-assisted decopperization are investigated. The results revealed that the increasing of decopperization efficiency was attributed to the change of the phase composition and the morphology and size of samples during ultrasound-assisted decopperization.