Lithium-ion batteries(LIBs)containing graphite as anode material and LiCoO_(2),LiMn_(2)O_(4),and LiNi_(x)Mn_(y)Co_(z)O_(2) as cathode materials are the most used worldwide because of their high energy density,capacita...Lithium-ion batteries(LIBs)containing graphite as anode material and LiCoO_(2),LiMn_(2)O_(4),and LiNi_(x)Mn_(y)Co_(z)O_(2) as cathode materials are the most used worldwide because of their high energy density,capacitance,durability,and safety.However,such widespread use implies the generation of large amounts of electronic waste.It is estimated that more than 11 million ton of LIBs waste will have been generated by 2030.Battery recycling can contribute to minimizing environmental contamination and reducing production costs through the recovery of high-value raw materials such as lithium,cobalt,and nickel.The most common processes used to recycle spent LIBs are pyrometallurgical,biometallurgical,and hydrometallurgical.Given the current scenario,it is necessary to develop environmentally friendly methods to recycle batteries and synthesize materials with multiple technological applications.This study presents a review of industrial and laboratory processes for recycling spent LIBs and producing materials that can be used in new batteries,energy storage devices,electrochemical sensors,and photocatalytic reactions.展开更多
The precipitation of Fe_(3)O_(4)particles and the accompanied formation of Fe_(3)O_(4)-wrapped copper structure are the main obstacles to copper recovery from the molten slag during the pyrometallurgical smelting of c...The precipitation of Fe_(3)O_(4)particles and the accompanied formation of Fe_(3)O_(4)-wrapped copper structure are the main obstacles to copper recovery from the molten slag during the pyrometallurgical smelting of copper concentrates.Herein,the commercial powdery pyrite or anthracite is replaced with pyrite-anthracite pellets as the reductants to remove a large amount of Fe_(3)O_(4)particles in the molten slag,resulting in a deep fracture in the Fe_(3)O_(4)-wrapped copper microstructure and the full exposure of the copper matte cores.When 1wt%composite pellet is used as the reductant,the copper matte droplets are enlarged greatly from 25μm to a size observable by the naked eye,with the copper content being enriched remarkably from 1.2wt%to 4.5wt%.Density functional theory calculation results imply that the formation of the Fe_(3)O_(4)-wrapped copper structure is due to the preferential adhesion of Cu_(2)S on the Fe_(3)O_(4)particles.X-ray photoelectron spectroscopy,Fourier transform infrared spectrometer(FTIR),and Raman spectroscopy results all reveal that the high-efficiency conver-sion of Fe_(3)O_(4)to FeO can decrease the volume fraction of the solid phase and promote the depolymerization of silicate network structure.As a consequence,the settling of copper matte droplets is enhanced due to the lowered slag viscosity,contributing to the high efficiency of copper-slag separation for copper recovery.The results provide new insights into the enhanced in-situ enrichment of copper from mol-ten slag.展开更多
Spent hydrogenation catalysts are important secondary resources due to richness in the valuable metals of Ni,Mo and V.Recovery of valuable metals from spent catalysts has high economic value and environmental benefits...Spent hydrogenation catalysts are important secondary resources due to richness in the valuable metals of Ni,Mo and V.Recovery of valuable metals from spent catalysts has high economic value and environmental benefits since they are hazardous wastes as well.Traditional recycling processes including hydrometallurgical leaching and soda roasting-leaching have disadvantages such as generating large amounts of wastewater,long process,and low recovery efficiency of valuable metals.Thus,this paper proposed synergistic enrichment of Ni,Mo and V via pyrometallurgical reduction at 1400-1500℃.The melting temperature and viscosity of slag were reduced through slag designing by software FactSage 7.1.The phase diagram of Al_(2)O_(3)-Cap-SiO_(2)-Na_(2)O-B_(2)O_(3)was drawn,and low-temperature region(≤1300℃)was selected as target slag composition.Ni,Mo,and V can be collaborative captured and recovered through the mutual solubility at molten state.Increasing the melting temperature and the amount of CaO,Na_(2)O and C were conducive to improving the metals recovery rates.The kilogram-scale experiments were carried out,and the recovery efficiencies of Ni,Mo and V were 98.3%,95.3%and 97.9%under optimized conditions:at 1500℃,with the basicity of 1.0,13.1 wt%SiO_(2),7.0 wt%B_(2)O_(3),7.7 wt%Na_(2)O and 20.0wt%C.The distribution behavior of valuable metals was clarified by investigating the melting process of slag and the reduction in valuable metals.Ni was preferentially reduced and acted as a capturing agent,which captured other metals to form NiMoV alloys.展开更多
Slag is waste from pyrometallurgical processing, usually stored in stacks or warehouses around or near smelters. Slag research has focused on potential environmental problems associated with slag weathering or process...Slag is waste from pyrometallurgical processing, usually stored in stacks or warehouses around or near smelters. Slag research has focused on potential environmental problems associated with slag weathering or processing for secondary metal recovery and/or other uses (construction, landscaping, etc.). Located in northern Mexico, the city of Chihuahua has a mining history that dates back to the eighteenth century. A lead smelter located southeast of Chihuahua City;closed in 1997, leaving behind a large pile of slag. In this study, a chemical analysis of smelter slag was carried out. The tailings contain Zn (15 - 35 wt%), Pb (0.5 - 4 wt%), As (0.6 wt%), Sn (888 ppb) and Hg (170 ppb). XRD identified several minerals such as hardystonite (Ca<sub>2</sub>ZnSi<sub>2</sub>O<sub>7</sub>), melanotekite (), kentrolite () and sphalerite (ZnS) in the glass. Major elements are present in phases such as monticellite (CaMgSiO<sub>4</sub>), kirschsteinite (CaFe<sup>2+</sup>SiO<sub>4</sub>), hedenbergite (CaFe<sup>2+</sup>Si<sub>2</sub>O<sub>6</sub>), babingtonite (Fe<sub>2</sub>Si<sub>3</sub>O<sub>9</sub>), magnetite (Fe<sub>3</sub>O<sub>4</sub>), and calcite (CaCO<sub>3</sub>). Whether the goal is reuse, recycling or remediation, research into the properties of slag and its environmental and health impacts (on vulnerable exposed populations) should continue to be relevant.展开更多
Stainless steel pickling sludge (SSPS), generated from the lime neutralization process of spent pickling liquor, is classified as a hazardous waste consisting of abundant metals like Fe, Cr and Ni, and other elements ...Stainless steel pickling sludge (SSPS), generated from the lime neutralization process of spent pickling liquor, is classified as a hazardous waste consisting of abundant metals like Fe, Cr and Ni, and other elements like F, S and Na, etc. Rather than a common disposal in landfill, recovering these metals and other valuable components from SSPS can not only create economic benefits, but also eliminate its adverse impacts on human health and the environment. A review of the formation mechanism and basic properties of SSPS was made, and the technical features, advantages and limitations of a series of pyrometallurgical treatment processes were summarized. Based on these, the main challenges for recycling of SSPS through the existing techniques are demonstrated. The traditional pelletizing/sintering-blast furnace process can only be used as a partial solution. Direct use of SSPS as flux in an argon-oxygen decarburization converter or electric arc furnace is a promising way, but low S sludges are preferred. The STAR process shows excellent recovery for metals, but it also has a low tolerance to the S and F contents in SSPS. And theINMETCO process is highly flexible in treatment of various wastes, whereas it exhibits relatively low Cr recovery and produces poor-quality pig iron. In addition, the feasibility of the rotary kiln-electric furnace, solid -state reduction of chromite and reduction-magnetic separation processes requires further studies. An urgent task at present is to develop a system for scientific classification and separate collection of SSPS in terms of chemical composition, notably S and F contents.展开更多
Hydrodesulfurization(HDS)catalysts are widely used in petrochemical industries,playing a crucial role in desulfurization process to get high-quality oil.The generation of Al-based spent HDS catalyst is estimated to be...Hydrodesulfurization(HDS)catalysts are widely used in petrochemical industries,playing a crucial role in desulfurization process to get high-quality oil.The generation of Al-based spent HDS catalyst is estimated to be 1.2×105 tons per year around the world.The spent HDS catalysts have been regarded as an important secondary resource due to their abundant output,considerable metal value,and regeneration potential;however,if improperly handled,it would severely pollute the environment due to high content of heavy metals.Thus,the recovery of valuable metals from spent HDS catalysts is of great importance from both resource utilization and environmental protection points of view.In this work,recent advances in the spent HDS catalyst treatment technologies have been reviewed,focusing on the recovery of valuable transition metals and environmental impacts.Finally,typical commercial processes have been discussed,providing in-depth information for peer researchers to facilitate their future research work in designing more effective and environmentally friendly recycling processes.展开更多
The quality of semi-products of platinum metals and alloys, produced by way of plastic working, essentially depends on or, in many cases, is completely determined by the quality of ingots. Plastic working does not mak...The quality of semi-products of platinum metals and alloys, produced by way of plastic working, essentially depends on or, in many cases, is completely determined by the quality of ingots. Plastic working does not make it possible to eliminate or localize metallurgical defects. In many cases it promotes the occurence thereof. Low-rate casting with directional crystallization can ensure the production of dense ingots free of non-metallic inclusions, shrinkage and gas weakness, with observance of certain temperature/rate modes. After comparative tests of vertical and horizontal molds, preference has been given to horizontal water-cooled molds, allowing to cast all alloys in the conditions of directional crystallization.展开更多
基金the Brazilian Federal Agency for Support and Evaluation of Graduate Education(CAPES)the Brazilian National Council for Scientific and Technological Development(CNPq,306239/2019-1)for their financial support。
文摘Lithium-ion batteries(LIBs)containing graphite as anode material and LiCoO_(2),LiMn_(2)O_(4),and LiNi_(x)Mn_(y)Co_(z)O_(2) as cathode materials are the most used worldwide because of their high energy density,capacitance,durability,and safety.However,such widespread use implies the generation of large amounts of electronic waste.It is estimated that more than 11 million ton of LIBs waste will have been generated by 2030.Battery recycling can contribute to minimizing environmental contamination and reducing production costs through the recovery of high-value raw materials such as lithium,cobalt,and nickel.The most common processes used to recycle spent LIBs are pyrometallurgical,biometallurgical,and hydrometallurgical.Given the current scenario,it is necessary to develop environmentally friendly methods to recycle batteries and synthesize materials with multiple technological applications.This study presents a review of industrial and laboratory processes for recycling spent LIBs and producing materials that can be used in new batteries,energy storage devices,electrochemical sensors,and photocatalytic reactions.
基金supported by the National Natural Science Foundation of China(No.52274349)the National Key Basic Research and Development Program of China(No.2022YFC3900801)+1 种基金the Fujian Province University-Industry Cooperation Research Program,China(No.2023H6007)the Fujian Province Natural Science Foundation,China(No.2023J05024).
文摘The precipitation of Fe_(3)O_(4)particles and the accompanied formation of Fe_(3)O_(4)-wrapped copper structure are the main obstacles to copper recovery from the molten slag during the pyrometallurgical smelting of copper concentrates.Herein,the commercial powdery pyrite or anthracite is replaced with pyrite-anthracite pellets as the reductants to remove a large amount of Fe_(3)O_(4)particles in the molten slag,resulting in a deep fracture in the Fe_(3)O_(4)-wrapped copper microstructure and the full exposure of the copper matte cores.When 1wt%composite pellet is used as the reductant,the copper matte droplets are enlarged greatly from 25μm to a size observable by the naked eye,with the copper content being enriched remarkably from 1.2wt%to 4.5wt%.Density functional theory calculation results imply that the formation of the Fe_(3)O_(4)-wrapped copper structure is due to the preferential adhesion of Cu_(2)S on the Fe_(3)O_(4)particles.X-ray photoelectron spectroscopy,Fourier transform infrared spectrometer(FTIR),and Raman spectroscopy results all reveal that the high-efficiency conver-sion of Fe_(3)O_(4)to FeO can decrease the volume fraction of the solid phase and promote the depolymerization of silicate network structure.As a consequence,the settling of copper matte droplets is enhanced due to the lowered slag viscosity,contributing to the high efficiency of copper-slag separation for copper recovery.The results provide new insights into the enhanced in-situ enrichment of copper from mol-ten slag.
基金financially supported by the National Natural Science Foundation of China(Nos.U2002212,52204412 and 52102058)the National Key R&D Program of China(Nos.2019YFC1907101,2019YFC1907103 and 2021YFC1910504)+3 种基金the Key R&D Program of Ningxia Hui Autonomous Region(No.2021BEG01003)Guangdong Basic and Applied Basic Research Foundation(No.2020A1515110408)Foshan Science and Technology Innovation Special Foundation(No.BK21BE002)the Fundamental Research Funds for the Central Universities(Nos.FRFTP-20-031A1 and FRF-BD-20-24A)。
文摘Spent hydrogenation catalysts are important secondary resources due to richness in the valuable metals of Ni,Mo and V.Recovery of valuable metals from spent catalysts has high economic value and environmental benefits since they are hazardous wastes as well.Traditional recycling processes including hydrometallurgical leaching and soda roasting-leaching have disadvantages such as generating large amounts of wastewater,long process,and low recovery efficiency of valuable metals.Thus,this paper proposed synergistic enrichment of Ni,Mo and V via pyrometallurgical reduction at 1400-1500℃.The melting temperature and viscosity of slag were reduced through slag designing by software FactSage 7.1.The phase diagram of Al_(2)O_(3)-Cap-SiO_(2)-Na_(2)O-B_(2)O_(3)was drawn,and low-temperature region(≤1300℃)was selected as target slag composition.Ni,Mo,and V can be collaborative captured and recovered through the mutual solubility at molten state.Increasing the melting temperature and the amount of CaO,Na_(2)O and C were conducive to improving the metals recovery rates.The kilogram-scale experiments were carried out,and the recovery efficiencies of Ni,Mo and V were 98.3%,95.3%and 97.9%under optimized conditions:at 1500℃,with the basicity of 1.0,13.1 wt%SiO_(2),7.0 wt%B_(2)O_(3),7.7 wt%Na_(2)O and 20.0wt%C.The distribution behavior of valuable metals was clarified by investigating the melting process of slag and the reduction in valuable metals.Ni was preferentially reduced and acted as a capturing agent,which captured other metals to form NiMoV alloys.
文摘Slag is waste from pyrometallurgical processing, usually stored in stacks or warehouses around or near smelters. Slag research has focused on potential environmental problems associated with slag weathering or processing for secondary metal recovery and/or other uses (construction, landscaping, etc.). Located in northern Mexico, the city of Chihuahua has a mining history that dates back to the eighteenth century. A lead smelter located southeast of Chihuahua City;closed in 1997, leaving behind a large pile of slag. In this study, a chemical analysis of smelter slag was carried out. The tailings contain Zn (15 - 35 wt%), Pb (0.5 - 4 wt%), As (0.6 wt%), Sn (888 ppb) and Hg (170 ppb). XRD identified several minerals such as hardystonite (Ca<sub>2</sub>ZnSi<sub>2</sub>O<sub>7</sub>), melanotekite (), kentrolite () and sphalerite (ZnS) in the glass. Major elements are present in phases such as monticellite (CaMgSiO<sub>4</sub>), kirschsteinite (CaFe<sup>2+</sup>SiO<sub>4</sub>), hedenbergite (CaFe<sup>2+</sup>Si<sub>2</sub>O<sub>6</sub>), babingtonite (Fe<sub>2</sub>Si<sub>3</sub>O<sub>9</sub>), magnetite (Fe<sub>3</sub>O<sub>4</sub>), and calcite (CaCO<sub>3</sub>). Whether the goal is reuse, recycling or remediation, research into the properties of slag and its environmental and health impacts (on vulnerable exposed populations) should continue to be relevant.
基金the financial supports from the National Natural Science Foundation of China(Nos.51574281 and 51574189)the National Torch Program of China(No.2011GH561685)Hunan Provincial Co-innovation Center for Clean and Efficient Utilization of Strategic Metal Mineral Resources.
文摘Stainless steel pickling sludge (SSPS), generated from the lime neutralization process of spent pickling liquor, is classified as a hazardous waste consisting of abundant metals like Fe, Cr and Ni, and other elements like F, S and Na, etc. Rather than a common disposal in landfill, recovering these metals and other valuable components from SSPS can not only create economic benefits, but also eliminate its adverse impacts on human health and the environment. A review of the formation mechanism and basic properties of SSPS was made, and the technical features, advantages and limitations of a series of pyrometallurgical treatment processes were summarized. Based on these, the main challenges for recycling of SSPS through the existing techniques are demonstrated. The traditional pelletizing/sintering-blast furnace process can only be used as a partial solution. Direct use of SSPS as flux in an argon-oxygen decarburization converter or electric arc furnace is a promising way, but low S sludges are preferred. The STAR process shows excellent recovery for metals, but it also has a low tolerance to the S and F contents in SSPS. And theINMETCO process is highly flexible in treatment of various wastes, whereas it exhibits relatively low Cr recovery and produces poor-quality pig iron. In addition, the feasibility of the rotary kiln-electric furnace, solid -state reduction of chromite and reduction-magnetic separation processes requires further studies. An urgent task at present is to develop a system for scientific classification and separate collection of SSPS in terms of chemical composition, notably S and F contents.
基金financially supported by National Key Research and Development Program of China(Grant No.2020YFC1909703)S&T Program of Hebei(Grant Nos.20373808D and 206Z4401G)+1 种基金Fangchenggang Key R&D Program Grant No.AB20014008National Natural Science Foundation of China(Grant No.52074256)
文摘Hydrodesulfurization(HDS)catalysts are widely used in petrochemical industries,playing a crucial role in desulfurization process to get high-quality oil.The generation of Al-based spent HDS catalyst is estimated to be 1.2×105 tons per year around the world.The spent HDS catalysts have been regarded as an important secondary resource due to their abundant output,considerable metal value,and regeneration potential;however,if improperly handled,it would severely pollute the environment due to high content of heavy metals.Thus,the recovery of valuable metals from spent HDS catalysts is of great importance from both resource utilization and environmental protection points of view.In this work,recent advances in the spent HDS catalyst treatment technologies have been reviewed,focusing on the recovery of valuable transition metals and environmental impacts.Finally,typical commercial processes have been discussed,providing in-depth information for peer researchers to facilitate their future research work in designing more effective and environmentally friendly recycling processes.
文摘The quality of semi-products of platinum metals and alloys, produced by way of plastic working, essentially depends on or, in many cases, is completely determined by the quality of ingots. Plastic working does not make it possible to eliminate or localize metallurgical defects. In many cases it promotes the occurence thereof. Low-rate casting with directional crystallization can ensure the production of dense ingots free of non-metallic inclusions, shrinkage and gas weakness, with observance of certain temperature/rate modes. After comparative tests of vertical and horizontal molds, preference has been given to horizontal water-cooled molds, allowing to cast all alloys in the conditions of directional crystallization.
