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The large amount of wastewater containing various pollutants generated during the tungsten beneficiation process has become a bottleneck for the sustainable development of tungsten mining enterprises. Typical pollutants mainly include suspended solids (SSs), silicate ions, metal ions, and residual organic reagents. The direct discharge of untreated tungsten beneficiation wastewater can cause serious harm to the ecological environment, while recycling can significantly affect flotation indicators. In this paper, the sources and characteristics of typical pollutants were analyzed, and various purification techniques were outlined, including coagulation, adsorption, chemical precipitation, oxidation, and biological treatment methods. Among these techniques, coagulation is particularly effective for the removal of SSs, while adsorption and chemical precipitation are recommended for the removal of soluble ions. For residual organic reagents, oxidation methods have demonstrated high treatment efficiencies. The mainstream methods for wastewater recycling were summarized, including centralized recycling, as well as internal recycling at certain stages. For tungsten beneficiation such a complex process, where the quality of wastewater varies greatly between different stages, it is suitable to recycle the wastewater after appropriate treatment at a specific stage. Furthermore, this study provided a perspective on the future directions of tungsten beneficiation wastewater treatment, serving as a reference for related research and industrial practices.

Abstract In recent years, the development of lithium-ion batteries (LIBs) with high energy density has become one of the important research directions to fulfill the needs of electric vehicles and smart grid technologies. Nowadays, traditional LIBs have reached their limits in terms of capacity, cycle life, and stability, necessitating their further improvement and development of alternative materials with remarkably enhanced properties. A nitrogen-containing carbon nanotube (N-CNT) host for bimetallic sulfide (NiCo2S4) is proposed in this study as an anode with attractive electrochemical performance for LIBs. The prepared NiCo2S4/N-CNT nanocomposite exhibited improved cycling stability, rate performance, and an excellent reversible capacity of 623.0 mAh g–1 after 100 cycles at 0.1 A g–1 and maintained a high capacity and cycling stability at 0.5 A g–1. The excellent electrochemical performance of the composite can be attributed to the unique porous structure, which can effectively enhance the diffusivity of Li ions while mitigating the volume expansion during the charge–discharge processes.

A new kind of sulfide precipitant, namely, slow release sulfide precipitant (SRSP), was developed and prepared first to realize the selective recovery of copper from an acid leaching solution. The experimental results indicated that SRSP as a precipitant could selectively and efficiently recover copper and the high purity of copper sulfide slag with a Cu grade of 48.16%, and a Cu recovery rate of 97.84% could be obtained. Moreover, copper in leaching solution could be recovered more efficiently and selectively by SRSP compared with Na2S. The results of H2S gas release, chemical reaction energy calculation, and SEM image analyses illustrated that realizing the selective recovery of copper mainly depended on the ions of S2− and HS− produced by the dissolution of SRSP. Moreover, the concentrations of S2− and HS− should always be kept at a low level in the process of selective recovery of copper; this is the biggest difference from the traditional precipitant and the key to preventing the escape of H2S gas in the copper recovery process. More pivotally, SRSP provides an alternative sulfide precipitant for the selective recovery of copper from the acid leaching solution of copper smelting dust.

Abstract The practical application of lithium/sulfur (Li/S) batteries is hindered by the migration of soluble polysulfides (Li2S n , 4 ≤ n ≤ 8) from cathode to anode, leading to poor electrochemical stability of the cell. To address this issue, in the present study, a TiO2/porous carbon (TiO2/PC) composite-coated Celgard 2400 separator was successfully fabricated and used as a polysulfide barrier for the Li/S battery. In TiO2/PC, the highly conductive PC with three-dimensional ordered porous structure physically constrains polysulfides and at the same time serves as an additional upper current collector. On the other hand, the TiO2 on the surface of PC chemically adsorbed polysulfides during the charge/discharge process. Due to the physical and chemical adsorption properties of TiO2/PC composite coating layer, an initial discharge capacity of 926 mAh g−1 at 0.1 C and a low fading rate (75% retention after 150 cycles) were achieved. Moreover, in the rate capability test, the discharge capacity for the TiO2/PC-modified Li/S battery was recovered to 728 mAh g−1 at 0.1 C after high-rate cycling and remained ~ 88% of the initial reversible capacity.

Liquid–solid fluidized beds have a wide range of applications in metallurgical processing, mineral processing, extraction, and wastewater treatment. Great interest on their flow stability and heterogeneous fluidization behaviors has been aroused in research. In this study, various fluidization experiments were performed by adjusting the operating conditions of particle size, particle density, and liquid superficial velocity. For each case, the steady state of liquid–solid fluidization was obtained, and the bed expansion height and pressure drop characteristics were analyzed. The time evolution of pressure drop at different bed heights can truly reflect the liquid–solid heterogeneous fluidization behaviors that are determined by operating conditions. With the increase in superficial liquid velocity, three typical fluidization stages were observed. Accordingly, the flow resistance coefficient was obtained based on the experimental data of bed expansion height and pressure drop. The flow resistance coefficient experiences a decrease with the increase in the modified particle Reynolds number and densimetric Froude number.

Chlorine is generated during iron ore sintering, mostly in the form of alkali chlorides and primarily accumulates in sintering dust, which must be removed before reusing. In this study, an in-situ monitor leaching system based was designed to detect chloride ion water leaching behaviors in real-time and improve the understanding of chlorine dissolution kinetic behaviors in water. Various parameters, including water leaching temperature, solid/liquid ratio, stirring speed, particle size and surfactant addition have been studied. Meanwhile their chlorine dissolution data exhibited a good fit to Stumm’s kinetic models. The results of kinetics analysis and transition state theory calculation on apparent activation energy demonstrated that the dissolution process was controlled by diffusion at low S/L ratio, while changed to be controlled by surface chemical reaction as the S/L ratio increased. Furthermore, increasing both temperature and stirring speed improved the chlorine removal speed. Moreover, reducing the particle size and adding 0.2% nonionic surfactant Triton X-100 reduced the surface energy and accelerated surface chemical reaction, which were also beneficial for removing chlorine from sintering dust. In addition, the SEM-EDS examination inferred that the existence of laurionite (PbOHCl) limited the chlorine dissolution rate to less than 97%, while beneficiation or hydrometallurgy treatment was needed to further remove chlorine.

In this study, a Eulerian-Eulerian liquid-solid two-phase flow model combined with kinetic theory of granular flow was established to study the hydrodynamic characteristics and fluidization behaviors of coarse coal particles in a 3D liquid-solid fluidized bed. First, grid independence analysis was conducted to select the appropriate grid model parameters. Then, the developed computational fluid dynamics (CFD) model was validated by comparing the experimental data and simulation results in terms of the expansion degree of low-density fine particles and high-density coarse particles at different superficial liquid velocities. The simulation results agreed well with the experimental data, thus validating the proposed CFD mathematical model. The effects of particle size and particle density on the homogeneous or heterogeneous fluidization behaviors were investigated. The simulation results indicate that low-density fine particles are easily fluidized, exhibiting a certain range of homogeneous expansion behaviors. For the large and heavy particles, inhomogeneity may occur throughout the bed, including water voids and velocity fluctuations.

Previous studies have shown that Pb-BHA complexes (lead complexes of benzohydroxamic acid) have better collecting ability and can be used in flotation experiments with BHA acting as a collector and lead ions acting as activators. However, the structures of Pb-BHA complexes adsorbed on a mineral surface remain unclear. In this work, the adsorption behavior of Pb-BHA complexes on the scheelite surface was studied by flotation experiments and adsorption capacity measurements, and the structures of the adsorbed Pb-BHA complexes were determined using X-ray photoelectron spectroscopy (XPS) and time-of-flight secondary ion mass spectrometry (TOF-SIMS). The adsorption capacity results showed that more BHA was adsorbed on the scheelite surface in Pb-BHA flotation, and the XPS and TOF-SIMS analysis showed that the species of Pb-BHA complexes adsorbed on the scheelite surface were similar in activation flotation and Pb-BHA flotation. Therefore, the different contents of the complexes on the scheelite surface were responsible for the flotation behavior. XPS and TOF-SIMS showed that BHA combined with lead ions to form complexes with different structures, such as five- and four-membered ring structures. Structure fragment inference based on the measurements indicated that lead ions formed monomer complexes with two BHAs, and that lead hydroxide polymers with a certain degree of polymerization bonded with oxygen atoms in the complexes. The Pb-BHA complexes combine with oxygen atoms on the scheelite surface to form an adsorbate, rendering the surface hydrophobic.

A three-dimensionally ordered macroporous ZnO (3DOM ZnO) framework was synthesized by a template method to serve as a sulfur host for lithium–sulfur batteries. The unique 3DOM structure along with an increased active surface area promotes faster and better electrolyte penetration accelerating ion/mass transfer. Moreover, ZnO as a polar metal oxide has a strong adsorption capacity for polysulfides, which makes the 3DOM ZnO framework an ideal immobilization agent and catalyst to inhibit the polysulfides shuttle effect and promote the redox reactions kinetics. As a result of the stated advantages, the S/3DOM ZnO composite delivered a high initial capacity of 1110 mAh g−1 and maintained a capacity of 991 mAh g−1 after 100 cycles at 0.2 C as a cathode in a lithium–sulfur battery. Even at a high C-rate of 3 C, the S/3DOM ZnO composite still provided a high capacity of 651 mAh g−1, as well as a high areal capacity (4.47 mAh cm−2) under high loading (5 mg cm−2).

Previous studies have proved that the lead complexes of benzohydroxamic acid (Pb–BHA) are effective collectors of scheelite flotations; however, the separation of scheelite from calcite needs depressants with high selectivity. In this study, we reported a novel depressant for calcite minerals, and Pb–BHA served as the collector of scheelite. The flotation behavior of polyaspartic acid (PASP) in a scheelite and calcite flotation that uses Pb–BHA was determined via flotation experiments. Furthermore, the selective adsorption of PASP on the mineral surfaces and the effect of PASP on the adsorption of Pb–BHA on the mineral surfaces were investigated through zeta potential measurements, X-ray photoelectron spectroscopy (XPS), crystal chemistry calculations, and Fourier transform infrared spectroscopy (FTIR) measurements. Thus, PASP demonstrated high selectivity in both scheelite and calcite and contributed to the successful separation of scheelite from calcite. PASP exhibited a higher adsorption capacity and stronger chemisorption with the active sites of calcium atoms on the calcite surface. The crystal chemistry calculations indicated that the distance of the PASP functional groups matched with the calcium distance of a calcite mineral surface, which can be attributed to the selectivity of PASP. Furthermore, the adsorption of PASP impeded the adsorption of Pb–BHA on the calcite surfaces, whereas the opposite was the case for scheelite. The mutually reinforcing selectivity of PASP and Pb–BHA considerably contributes to the efficient flotation separation of scheelite from calcite.

A Mg-1.32Bi-0.72Ca (BX11) alloy having bimodal grain structure was successfully prepared by a novel processing route of combining extrusion and three-pass caliber rolling. The first extruded and then caliber-rolled (E-CRed) alloy demonstrates a necklace-like grain structure with ultrafine grains formed around the microscale deformed grains, which is remarkably different from the uniform microstructure of the as-extruded alloy. In addition, the E-CRed BX11 alloy exhibits strong basal texture which is mainly original from the microscale deformed grains. Furthermore, the E-CRed BX11 alloy demonstrates excellent comprehensive mechanical properties, with an ultra-high yield strength of 351 MPa and a good elongation to failure of 13.2%. The significant strength improvement can be mainly attributed to the significant grain refinement and much stronger basal texture compared with the as-extruded sample.

An exceptionally high-strength rare-earth-free Mg−8Al−3Bi (AB83) alloy was successfully fabricated via extrusion and caliber rolling. After three-pass caliber rolling, the homogenous microstructure of the as-extruded AB83 alloy was changed to a necklace-like bimodal structure consisting of ultra-fine dynamic recrystallized (DRXed) grains and microscale deformed grains. Additionally, both Mg17Al12 and Mg3Bi2 nanoprecipitates, undissolved microscale Mg17Al12, and Mg3Bi2 particles were dispersed in the matrix of caliber-rolled (CRed) AB83 alloy. The CRed AB83 sample demonstrated a slightly weakened basal texture, compared with that of the as-extruded sample. Consequently, CRed AB83 showed a tensile yield strength of 398 MPa, an ultimate tensile strength of 429 MPa, and an elongation of 11.8%. The superior mechanical properties of the caliber-rolled alloy were mainly originated from the combined effects of the necklace-like bimodal microstructure containing ultra-fine DRXed grains, the homogeneously distributed nanoprecipitates and microscale particles, as well as the slightly modified basal texture.

An AZ80 alloy with ultra-high strength and good ductility has been successfully prepared by a novel processing route of combining extrusion and caliber rolling. The caliber rolled (CRed) AZ80 alloy has a necklace grain structure with ultrafine dynamic recrystallized (DRXed) grains formed around the micro-scale deformed grains, which is remarkably different from the uniform microstructure of as-extruded sample free from caliber rolling. In addition, both the deformed region and the DRXed part in CRed AZ80 alloy exhibit more random basal texture than that of the as-extruded sample. Furthermore, the CRed AZ80 alloy demonstrates an excellent comprehensive mechanical property with the ultimate tensile strength of 446MPa and elongation of 13%, respectively. These good mechanical properties of CRed AZ80 alloy can be attributed to the synthetic effects of necklace bimodal microstructure containing ultra-fine grains, profuse Mg17Al12 precipitates, and the modified texture.

In order to further separate the concentrate containing galena and jamesonite before undergoing hydrometallurgical process, flotation experiment was performed on the basis of mineralogical analysis. And the adsorption mechanisms of collector H on galena and jamesonite were also studied by FT-IR spectra analysis and molecular dynamics (MD) simulation. The flotation result shows that the efficient separation can be achieved with H as selective collector. Galena concentrated with Pb grade of 72.09% and Pb recovery of 50.96% was obtained, and jamesonite concentrated with Sb grade and recovery of 10.89% and 76.67% respectively was obtained as well. Infrared spectrum analysis indicates that collector H can adsorb on the surface of galena and react with Pb2+ to generate hydrophobic salt, while no evident adsorption phenomenon was observed on the surface of jamesonite. The MD simulation and calculation results demonstrate that adsorption energy of collector H on galena and jamesonite surface is −872.74 kJ/mol and −500.538 kJ/mol, respectively, which means collector H is easier to adsorb on the surface of galena than that of jamesonite. Keywords: Mixed concentration, Galena, Jamesonite, Flotation, Molecular dynamic simulation, Adsorption energy

Red mud (RM) is an industrial waste produced in large amounts during alumina extraction from bauxite. Its disposal generates serious environmental pollution due to high alkalinity. Therefore, a strategy for the effective utilization of RM must be developed. For instance, RM may be transformed into useful products, such as adsorbents. Given its high concentrations of aluminum oxides, iron oxides, titanium oxides, silica oxides, and hydroxides, RM may be developed as a cheap adsorbent for the removal of various ions from aqueous solution and soils (e.g., metal and non-metal ions, phenolic compounds, and dyes) and waste gas purification (sulfide and carbide). This review summarizes the background, properties, and applications of RM as an adsorbent. Proper approaches of removing metal and non-metal elements from wastewater are also systematically reviewed and compared. Emphasis is placed on the surface modification of RM to obtain high adsorption. Finally, the scope for future research in this area for RM is discussed in depth.

The flotation separation of scheelite from calcite is problematic, where sodium silicate modified by polyvalent metal ions has shown some advantages for selective depression. In this study, an Al-Na2SiO3 polymer was used as the depressant for the flotation separation of scheelite from calcite using a lead complex of benzohydroxamic acid (Pb-BHA) as the collector. Furthermore, a number of measurements were conducted to investigate the structure of the Al-Na2SiO3 polymer and its adsorption behavior with Pb-BHA complexes on the mineral surface. Flotation experiments indicated that the Al-Na2SiO3 polymer shows good selectivity for the flotation separation of scheelite from calcite at pH 8, where the optimum ratio of sodium silicate to aluminum sulfate was 2:1. Fourier-Transform Infrared (FTIR) and solution chemical analyses revealed that aluminum hydroxide complexes and the hydroxy moiety of silicic acid are able to self-assemble via condensation affording an Al-Na2SiO3 polymer, i.e., a composite aluminosilicate polymer. The zeta potential measurements and adsorption capacity measurements indicated that, upon adsorption of the Al-Na2SiO3 polymer and Pb-BHA complexes on the mineral surface, the Al-Na2SiO3 polymer had less influence on the adsorption of Pb-BHA complexes on the scheelite surface, while the opposite was true for calcite. Therefore, more Pb-BHA complexes and fewer Al-Na2SiO3 polymers were deposited on the scheelite surface, while fewer Pb-BHA complexes and more Al-Na2SiO3 polymers were adsorbed on the calcite surface. The selective separation of scheelite from calcite was attributed to the cooperative selectivity of the Pb-BHA complexes and Al-Na2SiO3 polymer.

Pb⁻BHA complexes have been shown to be selective for the separation of tungsten and cassiterite minerals from calcium minerals. These minerals could be enriched synchronously to some extent using Pb⁻BHA complexes flotation. However, it is difficult to further improve the quality and recovery of the scheelite, wolframite, and cassiterite concentrate due to their different behavior in flotation, such as flotation rate and sensitivities to depressants. Moreover, the super fine particles create some challenges for the cleaning flotation process. In this study, advanced gravity separators for super fine particles were introduced for the cleaning process based on the slight difference in the specific gravity of scheelite, wolframite, and cassiterite. The new process featured pre-enrichment using Pb⁻BHA flotation, and upgrading using gravity separation, taking into account both the similarities and differences in floatability and density of the different minerals. The grades of WO3 and Sn in the concentrate of the new process reached to 61% and 2.89%, respectively, and the recovery of Sn was significantly improved. In addition, gravity separation is highly efficient, cost effective, and chemical-free, which is environmentally friendly. This study has proven that physical separation can be used for the purification of flotation products and provide some solutions for separation problems of complex refractory ores, which has, up until now, been rarely reported in the literature and/or applied in mineral processing.

Hydrogen peroxide (H2O2) is a strong oxidizer that causes non-selective oxidation of sulfide minerals, and its influence on bismuth sulfide ores is not well-documented. In this study, H2O2 was proposed as an alternative bismuthinite depressant, and its effect on a Mo-Bi-containing ore was intensively investigated by batch flotation tests. Results showed that the addition of H2O2 significantly destabilized the froth phase, thus decreasing the solids and water recovery. The recovery of bismuth in molybdenum concentrate was dramatically decreased to 4.64% by H2O2 compared with that in the absence of H2O2 (i.e., 50.14%). The modified first-order kinetic model demonstrated that the flotation rate of molybdenite slightly declined after H2O2 addition, whereas that of bismuthinite was drastically reduced from 0.30 min−1 to 0.08 min−1 under the same condition. Simulation revealed that H2O2 affected the floatability of both molybdenite and bismuthinite but resulted in more detrimental effect to bismuthinite. Hence, H2O2 has the potential to act as an effective depressant in bismuth sulfide ore flotation.

Novel collector lead(II)-benzohydroxamic acid (Pb(II)–BHA) complexes in aqueous solution were characterized by using experimental approaches, including Ultraviolet-visible (UV-Vis) spectroscopy and electrospray ionization-mass spectrometry (ESI-MS), as well as first-principle density functional theory (DFT) calculations with consideration for solvation effects. The Job plot delineated that a single coordinated Pb(BHA)+ should be formed first, and that the higher coordination number complexes can be formed subsequently. Moreover, the Pb(II)–BHA species can aggregate with each other to form complicated structures, such as Pb(BHA)2 or highly complicated complexes. ESI-MS results validated the existence of Pb-(BHA)n=1,2 under different solution pH values. Further, the first-principles calculations suggested that Pb(BHA)+ should be the most stable structure, and the Pb atom in Pb(BHA)+ will act as an active site to attack nucleophiles. These findings are meaningful to further illustrate the adsorption mechanism of Pb(II)–BHA complexes, and are helpful for developing new reagents in mineral processing.

A portion of dodecyl amine (DDA) in a muscovite flotation system was replaced with alcohols with different carbon-chain lengths. These alcohols included octanol (OCT); decanol (DEC); dodecanol (DOD); and tetradecanol (TER). The muscovite adsorption behavior of the mixed DDA and alcohol systems were investigated through zeta potential; contact angle; and adsorption quantity tests. Single-mineral flotation tests showed that the muscovite-collecting power of the mixed DDA/alcohol (OCT, DEC, or DOD) system was stronger than that of the pure DDA system. The muscovite-collecting power of the collector systems decreased in the following order: DDA/DEC > DDA/OCT > DDA/DEC > DDA > DDA/TER. Zeta potential and contact angle analysis indicated that when combined with DDA; alcohols physically adsorbed on the surfaces of muscovite. This behavior improved the hydrophobicity of muscovite. Furthermore, adsorption analysis revealed that synergy between DDA and alcohol enhanced the adsorption of alcohol on muscovite. DDA has a dominant role in synergistic adsorption; whereas alcohol has a supporting role. Among all tested alcohols; DDA and DOD exhibit the highest synergetic adsorption effect because of their similar carbon-chain lengths. This similarity promotes the formation of a compact adsorption layer on the muscovite surface.