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Electrolytic metal manganese wastewater (EMMW) is industrial wastewater produced in the process of producing electrolytic metal manganese, which contains Mn2+ and NH4+–N pollutants.

Electrolytic manganese metal residue (EMMR) harmless treatment has always lacked a low-cost and quick processing technology. In this study, surfactants, namely tetradecyl trimethylammonium chloride (TTC), sodium dodecyl benzene sulfonate (SDBS), sodium lignin sulfonate (SLS), and octadecyl trimethylammonium chloride (OTC), were used in the solidification of Mn2+ and removal of NH4+-N from electrolytic manganese metal residue (EMMR). The Mn2+ and NH4+-N concentrations under different reaction conditions, Mn2+ solidification and NH4+-N removal mechanisms, and leaching behavior were studied. The results revealed that the surfactants could enhance the Mn2+ solidification and NH4+-N removal from EMMR, and the order of enhancement was as follows: TTC ＞ SDBS ＞ OTC ＞ SLS. The NH4+-N and Mn2+ concentrations were 12.3 and 0.05 mg/L with the use of 60.0 mg/kg TTC under optimum conditions (solid-liquid ratio of 1.5:1, EMMR to BRM mass ratio of 100:8, temperature of 20 ℃, and reaction duration of 12 h), which met the integrated wastewater discharge standard (GB8978-1996). Mn2+ was mainly solidified as Mn(OH)2, MnOOH and MnSiO3, and NH4+-N in EMMR was mostly removed in the form of ammonia. The results of this study could provide a new idea for cost-effective EMMR harmless treatment.

Electrolytic manganese anode slime (EMAS) contains many Mn resources, and efficient Mn leaching is the key to realizing its high-value utilization. In this study, the effects of Fe2+ concentration,...

Waste printed circuit boards (WPCBs) are considered as the most complicated and valuable component among e-waste. Slurry electrolysis can separate and recover metals from the extremely complex WPCBs. To promote its industrial application, a 5000 mL scale experiment was conducted to confirm industrial feasibility. Those results showed that copper and total metal recovery rates were 94.5 % and 75.2 % under the optimized conditions (30 g/L WPCBs, 10 g/L CuSO4·5H2O, 30 g/L NaCl, 190 g/L H2SO4, 30 g/L H2O2, 298 K temperature, 250 r/min stirring speed, 300 A/m2 and 8 h). The copper purity was 92.9 %, and SEM-EDS analyses indicated the main dendritic metals recovered were copper and lead. USEtox toxicity potential evaluation results demonstrated human toxicity and ecotoxicity of WPCBs sharply decreased after treatment. A cost analysis of this process indicated that the $ 1.0 cost was partially offset by the $ 1.9 return from 1 kg WPCBs. Thus, slurry electrolysis has a promising industrial future for e-waste recycling/utilization.

About 80 % of zinc is produced by “roasting-leaching-purifying-electrodeposition”. Lead-silver and jarosite residues are generated during this process, posing a serious threat to the ecosystem and environment since it contains a lot of heavy metals such as Pb. To better understand metal mobility and toxicity of these two zinc hydrothermal residues, it was analyzed by standard leaching toxicity procedures, bioavailability test and sequential extraction procedures. The results showed that the main phases of lead-silver and jarosite residues are KFe3(SO4)2(OH)6, CaSO4·2H2O, PbSO4, Fe3O4 and ZnFe2O4. These two residues contain a high content of Fe, Pb and Zn and also a significant amount of precious metals, such as Ag and In, showing a great resource potential. Meanwhile, lead-silver and jarosite residues are classified as hazardous waste both in China and the USA since their toxicity leaching concentration of Cd, Pb and Se exceeds the threshold of 1, 5 and 1 ppm. Metals contained in these two residues could easily be released to the environment, especially Cd, Pb and Zn, though metals are mainly in the form of residual, higher than 85 %. In addition, lead-silver and jarosite residues also show a significant biohazardous potential since EDTA and DTPA extractable Zn, Pb, Mn, Cd, Cu and As of these two residues are considerably high. All these results could help the zinc manufactories, governments and also the recycling companies better understand the risk of zinc hydrometallurgical residues and urge them to hind this harm to the ecosystem, and most importantly the human being itself.

Waste printed circuit boards (WPCBs) contain valuable material resources and hazardous substances, thereby posing a challenge for sustainable resource recovery and environmental protection initiatives. Overcoming this challenge will require mapping the toxic footprint of WPCBs to specific materials and substances used in manufacturing electronic components (ECs). Therefore, this work collected 50 EC specimens from WPCBs in five ubiquitous consumer products, such as television, refrigerator, air conditioner, washing machine and computer. The work extracted and analyzed metal contents and used leachability assessments based on tests adopted by the regulatory policies from China and the United States. The work found that copper and iron are the most abundant constituents in ECs, with concentrations ranging 5.90-796.62g/kg and 0-831.53g/kg, respectively; whereas abundance of precious metal content is in the order of silver>gold>palladium>platinum, with silver concentration ranging 15-5290mg/kg. The content of marginally-regulated toxic substance arsenic ranged 0-9700mg/kg; whereas fully regulated toxic metals such as chromium, lead and mercury did not exceed the thresholds set by China and US standards. The work found new toxic threats from arsenic and selenium leached from 20 of 50 ECs exceeding regulatory standards. These results will aid manufacturers and recyclers in protecting workers' health and environmental quality from arsenic and selenium pollution, and should initiate discussion about regulating these toxic components as part of a comprehensive program to reduce the toxic footprint of electronic products.

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.% was 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 Pd-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 Pd-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, liquid-solid mass ratio of 7 mL/g, 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 Pd removal and recycling for EMAS.

Waste electrical and electronic equipment (WEEE), also called electronic waste or e-waste, the core of “urban mining”, is attracting more and more attention to its pollution control and circular recycling. Hence, we defined WEEE, preliminarily discussed its history in China and pointed out that China has made great achievements in WEEE circular reutilization and pollution control. Meanwhile, we analyzed the four levels of circular WEEE recycling: repair, reuse and remanufacture, waste-to-materials, waste-to-products and waste-to-energy, and also put forward questions during this process. Moving forward, WEEE management will turn to intelligent management targeted on hazardous waste and other pollution, not merely the guidelines. Meanwhile, WEEE technology will transfer to value-added and automated reutilization, not just simple dismantling.

Electrolytic manganese residue (EMR) contains high concentrations of NH

Phosphogypsum (PG) contains plenty of PO43− and F− and some heavy metals. Phosphorus ore flotation tailing (POFT) mainly consists of dolomite (CaMg(CO3)2) and calcium fluophosphate (Ca5(PO4)3F). Traditional methods of POFT and PG storage could seriously damage the ecological environment. In this study, an innovative method for simultaneous stabilization/solidification (S/S) of PG and POFT was studied. The effects of PG and POFT mass ratio, S/S pH, solid-liquid ratio and temperature on the concentrations of PO43− and F− in the leaching solution as well as the characteristics of POFT and PG were studied. Meanwhile, the simultaneous S/S mechanisms of PG and POFT and leaching test were investigated. The results showed that the concentrations of F− and PO43− in the leaching solution were 6.0 mg/L and 4.0 mg/L, respectively, when the mass ratio of PG and POFT was 1:1 and the initial pH was 8.0 after being solidified for 30 days. F− and PO43− were mainly stabilized as (Ca, Mg, Zn)F2 and (Ca, Mg, Zn)3(PO4)2, respectively. Leaching test results showed that PO43− was reduced from 508.0 mg/L to 4.0 mg/L, and the concentrations of all the measured heavy metals and F− were within the permitted level for the GB8978-1996 after 30 days S/S.

Waste printed circuit boards (WPCBs) are usually dismantled, crushed, and sorted to WPCB metal-enriched scraps, still containing an amount of non-metallic materials. This research used slurry electrolysis to refine these WPCB metal-enriched scraps and to examine if a standard ionic liquid, [MIm]HSO4, can replace H2SO4 in the system. The impact of the refinement process on metal migration and transformation is discussed in detail. The results demonstrated that metals in WPCB metal-enriched scraps could be successfully refined using slurry electrolysis, and [MIm]HSO4 can be used to replace H2SO4 in the system. When 80% of H2SO4 was replaced by [MIm]HSO4 (electrolyte of 200 mL, 30 g/L CuSO4·5H2O, 60 g/L NaCl, 130 g/L H2SO4, and 1.624 A for 4 h), the total metal recovery rate is 85%, and the purity, current efficiency, and particle size of cathode metal powder were 89%, 52%, and 3.77 μm, respectively. Moreover, the microstructure of the cathode metal powder was dendritic in the H2SO4-CuSO4-NaCl slurry electrolysis system, whereas at an 80% [MIm]HSO4 substitution rate slurry electrolysis system, the cathode metal powder was irregular and accumulated as small-sized spherical particles. Thus, replacing inorganic leaching solvents with ionic liquids may provide a potential choice for the resources in WPCB metal-enriched scraps.

Electrolytic manganese residue (EMR) contains large quantities of manganese (Mn2+) and ammonia nitrogen (NH4+-N). Phosphogypsum (PG) contains plenty of phosphate (PO43−), fluorine (F−) and some heavy metals. Separate storage of EMR and PG could seriously damage the ecological environment. In this study, synergistic stabilization/solidification (S/S) of EMR and PG was studied. The effects of EMR:PG mass ratio, S/S pH, solid-liquid ratio and temperature on the concentrations of NH4+-N, PO43−, Mn2+ and F− in the leaching solution, and the characteristics of EMR and PG were studied. Meanwhile, the synergistic S/S mechanisms of EMR and PG, and leaching test were investigated. The results showed that the concentrations of F−, PO43−, NH4+-N and Mn2+ in the leaching solution were 4.5 mg/L, 13.6 mg/L, 55.5 mg/L and 0.8 mg/L, respectively, when the mass ratio of EMR to PG was 1:2 and the pH was 9.0 adjusted by MgO after 20 days S/S. Manganese was mainly solidified as Mn3(PO4)2·7H2O and Mn(OH)2, and ammonia nitrogen was mainly stabilized as struvite; fluorine was mainly stabilized as (Mn, Ca, Mg)F2, and phosphate was mainly solidified as (Mn, Ca, Mg)3(PO4)2 and (Mn, Ca, Mg)HPO4. The leaching test results showed that PO43− and NH4+-N were reduced to 13.6 mg/L and 55.5 mg/L, respectively, and the concentrations of all the measured heavy metals and F− were within the permitted level for the GB8978-1996 after 20 days S/S.

Electrolytic metal manganese residue leachate (EMMRL) was produced from long-term deposition of electrolytic metal manganese residue. EMMRL contains huge amount of manganese and ammonia nitrogen which could seriously damage the ecological environment. In this study, a chemical equilibrium model-Visual MINTEQ was used to simultaneously optimize removal of manganese and ammonia nitrogen from EMMRL with chemical precipitation methods. In the laboratory experiment, the effect of different N: P ratios and pH were investigated, and the characterization of the precipitates was characterized by X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and scanning electron microscope (SEM). The results showed that over 99.9% manganese and 96.2% ammonia nitrogen were simultaneously removed, respectively, when molar ratio of N:P was 1:1.15 at pH 9.5. Moreover, the experimental results corresponded well with the model outputs with respect to ammonia nitrogen and manganese removal. Manganese was mainly removed in the form of MnHPO4·3H2O and manganite, and ammonia nitrogen was mainly removed in the form of struvite. Economic evaluation indicated the chemical precipitation methods can be applied in the factory when the price of precipitation was higher than 0.295 $/kg.

A comparative investigation of hydroxide precipitation, sulfide precipitation, carbonate precipitation and the struvite formation process for removing manganese and ammonia nitrogen from electrolytic metal manganese residue leachate (EMMRL) was investigated. Chemical equilibrium model-Visual MINTEQ was applied to simulate the chemical reactions and optimize chemical dosages in manganese and ammonia nitrogen removal. Phase transition, morphology, and valence state of the precipitates were characterized by X-ray diffraction (XRD), Scanning electron microscopy (SEM), Fourier transform infrared spectroscopy (FT-IR), and X-ray Photoelectron Spectroscopy (XPS). Results indicated that carbonate precipitation prior to the other two methods for removal of manganese and ammonia nitrogen. The removal efficiency of manganese was 99.9%, when molar ratio of C to Mn was 1.1:1 at pH 9.5, and manganese was removed in the form of MnCO3. When molar ratio of P to N was 1.1:1 at pH 9.5, the removal efficiency of ammonia nitrogen was 97.4%, and ammonia nitrogen was removed in the form of struvite. Economic evaluation reveals that the treatment cost was 9.316 $ m−3 when carbonate and phosphate was used to remove manganese and ammonia nitrogen from EMMRL.

Electrolytic manganese residue (EMR) is a solid waste generated in the process of producing electrolytic metal manganese and contains a lot of manganese and ammonia nitrogen. In this study, electrokinetic remediation (EK) of manganese and ammonia nitrogen from EMR were carried out by using pulse electric field (PE) in different agents, and sodium dodecyl benzene sulfonate (SDBS), citric acid (CA) and ethylene diamine tetraacetic acid (EDTA) were used as enhancement agents. The removal behavior of ammonia nitrogen and manganese under direct current field (DC) and PE, and the relationship between manganese fractionation and transport behavior, as well as the energy consumption were investigated. The results demonstrated that the removal efficiency of ammonia nitrogen and manganese using PE were higher than DC. SDBS, EDTA and CA could enhance electroosmosis and electromigration, and the sequence of enhancement agent effects were CA, SDBS, EDTA, distilled water. The highest removal efficiency of manganese and ammonia nitrogen were 94.74% and 88.20%, and the effective removal amount of manganese and ammonia nitrogen was 23.93 and 1.48 mg·wh−1, when CA and SDBS+CA was used as the enhancement agents, respectively. Moreover, electromigration was the main removal mechanism of manganese and ammonia nitrogen in the EK process.

Metal mobility and toxicity of the municipal solid waste incineration (MSWI) fly ash from different seasons in Beijing were studied using leaching toxicity procedures, sequential extraction procedures, and bioavailability procedures. The X-ray diffraction results showed that MSWI fly ash contained CaSO4, CaCO3, and KCl. The Pb, Zn, and Cd contents of MSWI fly ash were high, especially during autumn, being 42, 77, and 1260 times higher than that of their soil backgrounds, respectively. Leaching toxicity experiments showed that MSWI fly ash is hazardous, since Pb exceeded the maximum threshold (5 mg/L). The main alkali metal ions and anions, heavy metals total content, leaching concentration, chemical speciation, and bioavailability varied seasonally. The Pb and Zn leaching concentrations in summer and autumn were higher than that of the other two seasons. Sequential extraction procedures indicated that Pb, Zn, and Cd showed extremely high metal mobility, i.e., the residual states of Pb and Cd in spring were 5.83% and 1.21%, respectively, and that of Zn in autumn was 10.68%. These results will help industries, governments, and the public better understand the risk of MSWI fly ash and will urge them to pay more attention to preventing harm to the ecosystem and human beings.

Superfine copper particles could be directly prepared from waste printed circuit boards by slurry electrolysis. Meanwhile, copper fractal growth could be observed. To better understand this phenomenon, the factors that affect copper dendrites in a point-cathode system were discussed in detail. These results showed that the fractal degree of copper dendrites increased as the increase of applied voltage and the decrease of copper sulfate and gelatin concentrations. Sodium lauryl sulfate and hydrochloric acid concentrations could not significantly impact the fractal degree of copper dendrites, while gelatin concentration could. The minimum copper fractal dimension was 1.069 when gelatin and copper sulfate concentration was 120 mg/L and 0.1 mol/L, respectively with an applied voltage of 11 V. Moreover, the results diffusion-limited aggregation model demonstrated that particle translational speed, particle numbers and binding probability significantly affected copper dendrite patterns. The scanning electron microscopy results indicated that the three additives greatly affected the refinement of the copper crystal. These findings contribute to enrich the theoretical study on metals recovery from e-waste by slurry electrolysis.

Electrolytic manganese residue (EMR) has become a barrier to the sustainable development of the electrolytic metallic manganese (EMM) industry. EMR has a great potential to harm local ecosystems and human health, due to it contains high concentrations of soluble pollutant, especially NH4+ and Mn2+, and also the possible dam break risk because of its huge storage. There seems to be not a mature and stable industrial solution for EMR, though a lot of researches have been done in this area. Hence, by fully considering the EMM ecosystem, we analyzed the characteristics and eco-environmental impact of EMR, highlighted state-of-the-art technologies for EMR reduction, pretreatment, and reuse; indicated the factors that block EMR treatment and disposal; and proposed plausible and feasible suggestions to solve this problem. We hope that the results of this review could help solve the problem of EMR and thus promote the sustainable development of EMM industry.

Copper is a nonferrous metal closely connected to humans. Approximately 40% of copper is produced by reclaimed copper smelting (RCS). Reclaimed copper smelting fly ash and smelting slag are generated during the RCS process, posing a serious threat to the ecosystem and environment as they contain many heavy metals, such as Cu and Zn. In this study, the metal mobility and toxicity of RCS fly ash and smelting slag were analyzed using standard leaching toxicity procedures, sequential extraction procedures, and bioavailability tests. The results showed that the main phases of RCS fly ash were Cu2(OH)3Cl, FeCl2·2H2O, CuS2, C, CuO, Cu, Ca2SiO4, ZnClO42, Zn(OH)2·0.5H2O, and KFeCl3, and those for smelting slag were SiO2, CaCO3, SiS2, CaAl2Si2O8·4H2O, Cu4O3, CuO, ZnO, NiSO4·6H2O, AlPO4, and Na3Mn(PO4)(CO)3. These two slags contain high contents of Cu, Zn and Fe and trace amounts of heavy metals, such as Ba, Be, Cd, Cr, Ni, As, Pb, Au, Se and Sb. RCS fly ash is classified as hazardous waste in both China and the USA as the toxic leaching concentrations of Pb and Cd exceed the thresholds of 5 and 1 mg L−1. Cu and Zn contained in these two slags can easily be released into the environment, although the residual fraction of Cu and Zn was found to be higher than 65%. Additionally, RCS fly ash and smelting slag also show significant biohazardous potential as the EDTA- and DTPA-extractable Zn, Cu and Se of these two residues are considerably high. The results described above could provide reclaimed copper smelting companies and governments with a better understanding of the risk of RCS fly ash and smelting slag, urging them to stop the slag from harming ecosystems and humans.

In this study, electric field and ball milling were used to leach Mn2+ from low-grade pyrolusite (LGP). The effects of current density, reaction time, reaction temperature, ball-to-powder weight ratio, and ball milling time on the leaching efficiency of Mn2+ from LGP as well as the leaching mechanism were systematically studied. The results showed that the combined use of electric field and ball milling enhanced the leaching of Mn2+ from LGP. The leaching efficiency of Mn2+ reached 97.79% under the optimum conditions of LGP-to-pyrite mass ratio of 1:0.18, current density of 30 mA/cm2, LGP-to-H2SO4 mass ratio of 1:0.4, liquid-to-solid ratio of 5:1, ball-to-powder weight ratio of 1:1, ball milling time of 2 h, temperature of 80 °C, and leaching duration of 120 min. This value was 25.95% higher than that attained without ball milling and 41.45% higher than that attained when neither ball milling nor electric field was employed. Pyrite was fully oxidized to generate additional SO42− and Fe3+, and was further hydrolyzed to form jarosite (KFe3(SO4)2(OH)6) and hydronium jarosite (Fe3(SO4)2(OH)5·2H2O) via ball milling and electric field application. Moreover, the electric field changed the surface charge distribution of the mineral particles and promoted collisions between them as well as the collapse of the crystal lattice, further improving the leaching efficiency of Mn2+ from LGP. This study provided a new method for leaching Mn from LGP.

Electrolytic manganese residue (EMR) is a solid waste remained in filters after using sulfuric acid to leaching manganese carbonate ore. EMR contains high concentration of soluble manganese (Mn

The objectives of this study were to investigate the adsorption and transfer behaviors of phenanthrene (PHE) and bisphenol A (BPA) in purple paddy soils amended with dissolved organic matter (DOM) derived from rice and canola straw in the West Sichuan Plain of China. In the pristine soil, PHE was preferentially adsorbed on both pristine clayey (L) and sandy (T) paddy soils than BPA, indicating that the retention/adsorption by soils is closely dependent on the chemical properties of organic pollutants (OPs). The noticeably higher adsorption of PHE and BPA on smaller size fraction of the soils (L2 and T2) were observed, possibly due to their higher surface areas and higher content in organic matters with higher aromaticity and hydrophobicity in this soil fraction. The DOMs derived from rice (RDOM) and canola (CDOM) straws possessed remarkable differences in E2/E3 and SUV254 measurements, which reflected that their chemical composition might be different. When CDOM was introduced in the studied soil T1, adsorption of BPA was doubled, but the augment in adsorption was much less impressive with RDOM, showing the nature of derived DOM played an important role. The study also demonstrated that in the fine fraction of clayey soil (L2), the retention of a same OP (PHE) was remarkably dropped when CDOM or RDOM was introduced, whereas in a sandy soil of the same size fraction (T2), the phenomenon was the opposite, suggesting a potential risk that, in certain types of soil, the introduction of straw derived DOMs may enhance the mobility of some OPs. The humification time of straw seems not to affect the adsorptions of OPs in most studied systems. Adsorption kinetics of PHE and BPA in the adsorption systems with derived DOMs were well fitted to the two-step first-order model with radj2 values of 0.994-0.998. Results of this study will provide further comprehensive fundamental data for risk assessment and control of organic pollutants (OPs) in farmland ecosystems.

In industrial electrolytic manganese metal process, the energy consumption closely related to the electrolysis of cathode and anode. The effect of Cl- concentration on electrochemical oscillation a...

In this study, a new electrochemical method was used to simultaneously efficient removal of Mn

Solidification/stabilization (S/S) is an option for the treatment of electrolytic manganese residue (EMR). Basic burning raw material (BRM) could successfully solidify/stabilize EMR, though heavy metals S/S mechanism and long-term stability remain unclear. Herein, Mn

Completely separating and recovering metals and nonmetals from waste printed circuit boards (WPCBs) is key to e-waste recycling. Here we proposed a novel approach, slurry or suspension electrolysis, to separate metals and nonmetals from WPCBs. The factors that impact the separation rate during the slurry electrolysis were discussed in detail. The results indicate that CuSO4·5H2O, NaCl, H2SO4, WPCBs dosage, current and time could impact metals separating from WPCBs. Increasing NaCl and H2SO4 concentration and extending electrolysis time could effectively increase the metal and nonmetal separation rate, while increasing WPCBs dosage and current have negative impacts on the metal and nonmetal separation rate. Slurry electrolysis could directly and completely separate and recover metals from WPCBs with a separation rate up to 97.79% under the conditions of 3 g WPCBs dosage in 100 mL electrolyte, 30 g/L CuSO4·5H2O, 40 g/L NaCl, 150 g/L H2SO4, 0.5 A and 9 h. The separated micro-metal powders are mainly Cu, about 86.6%, without any nonmetal powders. Copper recovered is dendritic, with a copper recovery rate up to nearly 99%. Thus, slurry electrolysis shows a prospective future in e-waste reutilization, providing a way to enrich metals for all kinds of urban mines.