Solvent extraction,a separation and purification technology,is crucial in critical metal metallurgy.Organic solvents commonly used in solvent extraction exhibit disadvantages,such as high volatility,high toxicity,and ...Solvent extraction,a separation and purification technology,is crucial in critical metal metallurgy.Organic solvents commonly used in solvent extraction exhibit disadvantages,such as high volatility,high toxicity,and flammability,causing a spectrum of hazards to human health and environmental safety.Neoteric solvents have been recognized as potential alternatives to these harmful organic solvents.In the past two decades,several neoteric solvents have been proposed,including ionic liquids(ILs)and deep eutectic solvents(DESs).DESs have gradually become the focus of green solvents owing to several advantages,namely,low toxicity,degradability,and low cost.In this critical review,their classification,formation mechanisms,preparation methods,characterization technologies,and special physicochemical properties based on the most recent advancements in research have been systematically described.Subsequently,the major separation and purification applications of DESs in critical metal metallurgy were comprehensively summarized.Finally,future opportunities and challenges of DESs were explored in the current research area.In conclusion,this review provides valuable insights for improving our overall understanding of DESs,and it holds important potential for expanding separation and purification applications in critical metal metallurgy.展开更多
Rare metals including Lithium(Li),Beryllium(Be),Rubidium(Rb),Cesium(Cs),Zirconium(Zr),Hafnium(Hf),Niobium(Nb),Tantalum(Ta),Tungsten(W)and Tin(Sn)are important critical mineral resources.In China,rare metal mineral dep...Rare metals including Lithium(Li),Beryllium(Be),Rubidium(Rb),Cesium(Cs),Zirconium(Zr),Hafnium(Hf),Niobium(Nb),Tantalum(Ta),Tungsten(W)and Tin(Sn)are important critical mineral resources.In China,rare metal mineral deposits are spatially distributed mainly in the Altay and Southern Great Xingán Range regions in the Central Asian orogenic belt;in the Middle Qilian,South Qinling and East Qinling mountains regions in the Qilian-Qinling-Dabie orogenic belt;in the Western Sichuan and Bailongshan-Dahongliutan regions in the Kunlun-Songpan-Garze orogenic belt,and in the Northeastern Jiangxi,Northwestern Jiangxi,and Southern Hunan regions in South China.Major ore-forming epochs include Indosinian(mostly 200-240 Ma,in particular in western China)and the Yanshanian(mostly 120-160 Ma,in particular in South China).In addition,Bayan Obo,Inner Mongolia,northeastern China,with a complex formation history,hosts the largest REE and Nb deposits in China.There are six major rare metal mineral deposit types in China:Highly fractionated granite;Pegmatite;Alkaline granite;Carbonatite and alkaline rock;Volcanic;and Hydrothermal types.Two further types,namely the Leptynite type and Breccia pipe type,have recently been discovered in China,and are represented by the Yushishan Nb-Ta-(Zr-Hf-REE)and the Weilasituo Li-Rb-Sn-W-Zn-Pb deposits.Several most important controlling factors for rare metal mineral deposits are discussed,including geochemical behaviors and sources of the rare metals,highly evolved magmatic fractionation,and structural controls such as the metamorphic core complex setting,with a revised conceptual model for the latter.展开更多
Exploitable or potentially exploitable deposits of critical metals,such as rare-earth(REE)and high-field-strength elements(HFSE),are commonly associated with alkaline or peralkaline igneous rocks.However,the origin,tr...Exploitable or potentially exploitable deposits of critical metals,such as rare-earth(REE)and high-field-strength elements(HFSE),are commonly associated with alkaline or peralkaline igneous rocks.However,the origin,transport and concentration of these metals in peralkaline systems remains poorly understood.This study presents the results of a mineralogical and geochemical investigation of the Na-metasomatism of alkali amphiboles and clinopyroxenes from a barren peralkaline granite pluton in NE China,to assess the remobilization and redistribution of REE and HFSE during magmatic-hydrothermal evolution.Alkali amphiboles and aegirine-augites from the peralkaline granites show evolutionary trends from sodic-calcic to sodic compositions,with increasing REE and HFSE concentrations as a function of increasing Na-index[Na^(#),defined as molar Na/(Na+Ca)ratios].The Na-amphiboles(i.e.,arfvedsonite)and aegirine-augites can be subsequently altered,or breakdown,to form hydrothermal aegirine during late-or post-magmatic alteration.Representative compositions analyzed by insitu LA-ICPMS show that the primary aegirine-augites have high and variable REE(2194-3627 ppm)and HFSE(4194-16,862 ppm)contents,suggesting that these critical metals can be scavenged by alkali amphiboles and aegirine-augites.Compared to the primary aegirine-augites,the presentative early replacement aegirine(Aeg-I,Na^(#)=0.91-0.94)has notably lower REE(1484-1972)and HFSE(4351-5621)contents.In contrast,the late hydrothermal aegirine(Aeg-II,Na^(#)=0.92-0.96)has significantly lower REE(317-456 ppm)and HFSE(6.44-72.2 ppm)contents.Given that the increasing Na^(#)from aegirine-augites to hydrothermal aegirines likely resulted from Na-metasomatism,a scavenging-release model can explain the remobilization of REE and HFSE in peralkaline granitic systems.The scavenging and release of REE and HFSE by Na-metasomatism provides key insights into the genesis of globally significant REE and HFSE deposits.The high Na-index of the hydrothermal aegirine might be useful as a geochemical indicator in the exploration for these critical-metals.展开更多
Separation and purification of critical metal ions such as rare-earth elements (REEs), scandium and niobium from their minerals is difficult and often deter- mines if extraction is economically and environmentally f...Separation and purification of critical metal ions such as rare-earth elements (REEs), scandium and niobium from their minerals is difficult and often deter- mines if extraction is economically and environmentally feasible. Solvent extraction is a commonly used metal-ion separation process, usually favored because of its sim- plicity, speed and wide scope, which is why it is often employed for separating trace metals from their minerals. However, the types of solvents widely used for the recovery of metal ions have adverse environmental impact. Alternatives to solvent extraction have been explored and advances in separation technologies have shown commer- cial establishment of liquid membranes as an alternative to conventional solvent extraction for the recovery of metals and other valuable materials. Liquid membrane transport incorporates solvent extraction and membrane separation in one continuously operating system. Both methods con- ventionally use solvents that are harmful to the environ- ment, however, the introduction of ionic liquids (ILs) over the last decade is set to minimize the environmental impact of both solvent extraction and liquid membrane separation processes. ILs are a family of organic molten salts with low or negligible vapour pressure which may be formed below 100 ~C. Such liquids are also highly thermally stable and less toxic. Their ionic structure makes them thermody- namically favorable solvents for the extraction of metallic ions. The main aim of this article is to review the current achievements in the separation of REE, scandium, niobium and vanadium from their minerals, using ILs in eithersolvent extraction or liquid membrane processes. The mechanism of separation using ILs is discussed and the engineering constraints to their application are identified.展开更多
Serrated flows are known as repeated yielding of bulk metallic glasses(BMGs)during plastic deformation under different loading conditions,which are associated with the operation of shear banding.According to the sta...Serrated flows are known as repeated yielding of bulk metallic glasses(BMGs)during plastic deformation under different loading conditions,which are associated with the operation of shear banding.According to the statistics of some parameters,the shear avalanches can display a self-organized critical state,suggesting a large ductility of BMGs.The emergence of the self-organized criticality(SOC)behavior in different BMGs is due to the temperature,strain rate,and chemical compositions.The SOC behavior is accompanied with the following phenomena:the interactions occur in the shear bands;the incubation time is longer than the relaxation time;the time interval is lacking of typical time scale;and the spatial or temporal parameters should display apower-law distribution.展开更多
Carbon neutrality requires systematic transformations of both energy and metal systems.These transformations are not isolated but rather interlinked and interdependent,such that trade-offs between different strategies...Carbon neutrality requires systematic transformations of both energy and metal systems.These transformations are not isolated but rather interlinked and interdependent,such that trade-offs between different strategies exist.Herein,we explore the critical interlinkages between energy and metal systems and further propose a circular metal-energy nexus to advance global coordinated actions towards a carbon-neutral future.展开更多
Coal,coal measure gas,coal conversion to oil and gas,and coal-based new materials are reliable guarantees for stable energy supply and economic and social development in China.The coal-dominated resource endowment and...Coal,coal measure gas,coal conversion to oil and gas,and coal-based new materials are reliable guarantees for stable energy supply and economic and social development in China.The coal-dominated resource endowment and the economic and social development stage determine the irreplaceable position of coal resources in the energy system.Coal measure resources,including aggregated or dispersed solids,liquid and gaseous multitype energies,and metal as well as nonmetallic minerals,are the products of multisphere interaction and metallogenetic materials generation,migration,and accumulation.Coal measures record rich deep-time geological information of transitional and terrestrial peat bogs,which is a crucial carrier to reveal ecosystem evolution,significant organic carbon sequestration,atmospheric O_(2)/CO_(2)variation,and wildfire events.Coal measure evolution is accompanied by the migration and transformation of various materials during diagenesis-metamorphism,forming differentiated coal compositions besides properties and various mineral resources in its adjacent strata.The enrichment condition,occurrence state,and separation potential are the premise for level-by-level use and efficient development of coal measure resources.Coal measure metallogeny is based on the metallogenic system of multiple energy and mineral resources in coal measures and their environmental effects.Fully understanding coal measure metallogeny is beneficial for promoting the coal transition from fuel to raw materials and strengthening its attribute of multiple mineral resources.The metallogeny comprises various aspects,including:(1)the symbiosis mechanism,co-exploration and co-mining conditions of various resources;(2)the source-sink system of ore-forming materials;(3)the differential carbon accumulation and hydrogen enrichment effect;(4)organic(coal and hydrocarbon)and inorganic(mineral)interactions;and(5)combination of minerals naturally enrichment during the metallogenic process and artificial enrichment during the ore processing process.The coal measure metallogeny belongs to the geoscience disciplines,and studies the types,formation,distribution,enrichment mechanisms,evaluation methods,and development strategies of resources related to coal measures.The key scientific problems include geological records related to mineral enrichment processes,metallogenic mechanisms,resource distribution,occurrence evaluation,and accurate development.Developing coal measure metallogeny is significant in improving the critical mineral metallogenic theory,revealing various deep-time earth systems and realizing the national energy transformation and high-quality development.展开更多
The upper Permian Heshan Formation in Pingguo,Guangxi,China,is strongly enriched in lithium(Li)and niobium(Nb).The lower bauxite layer contains 0.02–0.04 wt.%Nb_(2)O_(5)(averaging 0.035 wt.%),and the overlying clay r...The upper Permian Heshan Formation in Pingguo,Guangxi,China,is strongly enriched in lithium(Li)and niobium(Nb).The lower bauxite layer contains 0.02–0.04 wt.%Nb_(2)O_(5)(averaging 0.035 wt.%),and the overlying clay rock layer contains 0.06–1.05 wt.%Li_(2)O(averaging 0.44 wt.%),both of which exceed the cut-off grades for independent Li and Nb deposits and are therefore highly prospective.In this study,a preliminary discussion of the genesis of the Li and Nb enrichment is presented to serve as a reference for the investigation,evaluation,and prospecting for clay-and sedimentary-type Li and Nb ores in other regions.The preliminary conclusions are that:(1)The bauxite ore contains abundant anatase,which positively correlates with the whole-rock concentrations of TiO_(2) and Nb,indicating that the Nb is hosted mainly in the anatase;(2)the cookeite content in the clay rock positively correlates with the whole-rock Li concentration,indicating that cookeite is the main carrier mineral of Li,and its genesis can be attributed to reactions between clay minerals(e.g.,pyrophyllite and illite)and Li-Mg-rich underground brine or pore water and groundwater in coastal areas;and(3)provenance analysis of immobile elements(Al,Ti,Nb,Ta,Zr,Hf,and rare earth elements)suggests distinct sources for the Nb-rich bauxite and the overlying Li-rich clay rocks,with the bauxite and Nb originating largely from alkaline felsic rocks in the Emeishan Large Igneous Province,and the clay rocks being derived from peraluminous or moderately fractionated felsic rocks associated with Permian Paleo-Tethyan magmatic arcs.展开更多
基金financially supported by the Original Exploration Project of the National Natural Science Foundation of China(No.52150079)the National Natural Science Foundation of China(Nos.U22A20130,U2004215,and 51974280)+1 种基金the Natural Science Foundation of Henan Province of China(No.232300421196)the Project of Zhongyuan Critical Metals Laboratory of China(Nos.GJJSGFYQ202304,GJJSGFJQ202306,GJJSGFYQ202323,GJJSGFYQ202308,and GJJSGFYQ202307)。
文摘Solvent extraction,a separation and purification technology,is crucial in critical metal metallurgy.Organic solvents commonly used in solvent extraction exhibit disadvantages,such as high volatility,high toxicity,and flammability,causing a spectrum of hazards to human health and environmental safety.Neoteric solvents have been recognized as potential alternatives to these harmful organic solvents.In the past two decades,several neoteric solvents have been proposed,including ionic liquids(ILs)and deep eutectic solvents(DESs).DESs have gradually become the focus of green solvents owing to several advantages,namely,low toxicity,degradability,and low cost.In this critical review,their classification,formation mechanisms,preparation methods,characterization technologies,and special physicochemical properties based on the most recent advancements in research have been systematically described.Subsequently,the major separation and purification applications of DESs in critical metal metallurgy were comprehensively summarized.Finally,future opportunities and challenges of DESs were explored in the current research area.In conclusion,this review provides valuable insights for improving our overall understanding of DESs,and it holds important potential for expanding separation and purification applications in critical metal metallurgy.
基金financially supported by the National Key R&D Program of China(grant no.2017YFC0602405)the National Natural Science Foundation of China(grant no.42030811)。
文摘Rare metals including Lithium(Li),Beryllium(Be),Rubidium(Rb),Cesium(Cs),Zirconium(Zr),Hafnium(Hf),Niobium(Nb),Tantalum(Ta),Tungsten(W)and Tin(Sn)are important critical mineral resources.In China,rare metal mineral deposits are spatially distributed mainly in the Altay and Southern Great Xingán Range regions in the Central Asian orogenic belt;in the Middle Qilian,South Qinling and East Qinling mountains regions in the Qilian-Qinling-Dabie orogenic belt;in the Western Sichuan and Bailongshan-Dahongliutan regions in the Kunlun-Songpan-Garze orogenic belt,and in the Northeastern Jiangxi,Northwestern Jiangxi,and Southern Hunan regions in South China.Major ore-forming epochs include Indosinian(mostly 200-240 Ma,in particular in western China)and the Yanshanian(mostly 120-160 Ma,in particular in South China).In addition,Bayan Obo,Inner Mongolia,northeastern China,with a complex formation history,hosts the largest REE and Nb deposits in China.There are six major rare metal mineral deposit types in China:Highly fractionated granite;Pegmatite;Alkaline granite;Carbonatite and alkaline rock;Volcanic;and Hydrothermal types.Two further types,namely the Leptynite type and Breccia pipe type,have recently been discovered in China,and are represented by the Yushishan Nb-Ta-(Zr-Hf-REE)and the Weilasituo Li-Rb-Sn-W-Zn-Pb deposits.Several most important controlling factors for rare metal mineral deposits are discussed,including geochemical behaviors and sources of the rare metals,highly evolved magmatic fractionation,and structural controls such as the metamorphic core complex setting,with a revised conceptual model for the latter.
基金financially supported by the National Natural Science Foundation of China(42122023 and 41930424)Key Research Program of the Innovation Academy for Earth Science,CAS(IGGCAS201901)+1 种基金Youth Innovation Promotion Association CAS(Y2021095)the Science and Technology Planning Project of Guangdong Province,China(2020B1212060055).
文摘Exploitable or potentially exploitable deposits of critical metals,such as rare-earth(REE)and high-field-strength elements(HFSE),are commonly associated with alkaline or peralkaline igneous rocks.However,the origin,transport and concentration of these metals in peralkaline systems remains poorly understood.This study presents the results of a mineralogical and geochemical investigation of the Na-metasomatism of alkali amphiboles and clinopyroxenes from a barren peralkaline granite pluton in NE China,to assess the remobilization and redistribution of REE and HFSE during magmatic-hydrothermal evolution.Alkali amphiboles and aegirine-augites from the peralkaline granites show evolutionary trends from sodic-calcic to sodic compositions,with increasing REE and HFSE concentrations as a function of increasing Na-index[Na^(#),defined as molar Na/(Na+Ca)ratios].The Na-amphiboles(i.e.,arfvedsonite)and aegirine-augites can be subsequently altered,or breakdown,to form hydrothermal aegirine during late-or post-magmatic alteration.Representative compositions analyzed by insitu LA-ICPMS show that the primary aegirine-augites have high and variable REE(2194-3627 ppm)and HFSE(4194-16,862 ppm)contents,suggesting that these critical metals can be scavenged by alkali amphiboles and aegirine-augites.Compared to the primary aegirine-augites,the presentative early replacement aegirine(Aeg-I,Na^(#)=0.91-0.94)has notably lower REE(1484-1972)and HFSE(4351-5621)contents.In contrast,the late hydrothermal aegirine(Aeg-II,Na^(#)=0.92-0.96)has significantly lower REE(317-456 ppm)and HFSE(6.44-72.2 ppm)contents.Given that the increasing Na^(#)from aegirine-augites to hydrothermal aegirines likely resulted from Na-metasomatism,a scavenging-release model can explain the remobilization of REE and HFSE in peralkaline granitic systems.The scavenging and release of REE and HFSE by Na-metasomatism provides key insights into the genesis of globally significant REE and HFSE deposits.The high Na-index of the hydrothermal aegirine might be useful as a geochemical indicator in the exploration for these critical-metals.
文摘Separation and purification of critical metal ions such as rare-earth elements (REEs), scandium and niobium from their minerals is difficult and often deter- mines if extraction is economically and environmentally feasible. Solvent extraction is a commonly used metal-ion separation process, usually favored because of its sim- plicity, speed and wide scope, which is why it is often employed for separating trace metals from their minerals. However, the types of solvents widely used for the recovery of metal ions have adverse environmental impact. Alternatives to solvent extraction have been explored and advances in separation technologies have shown commer- cial establishment of liquid membranes as an alternative to conventional solvent extraction for the recovery of metals and other valuable materials. Liquid membrane transport incorporates solvent extraction and membrane separation in one continuously operating system. Both methods con- ventionally use solvents that are harmful to the environ- ment, however, the introduction of ionic liquids (ILs) over the last decade is set to minimize the environmental impact of both solvent extraction and liquid membrane separation processes. ILs are a family of organic molten salts with low or negligible vapour pressure which may be formed below 100 ~C. Such liquids are also highly thermally stable and less toxic. Their ionic structure makes them thermody- namically favorable solvents for the extraction of metallic ions. The main aim of this article is to review the current achievements in the separation of REE, scandium, niobium and vanadium from their minerals, using ILs in eithersolvent extraction or liquid membrane processes. The mechanism of separation using ILs is discussed and the engineering constraints to their application are identified.
基金Item Sponsored by National Natural Science Foundation of China(51371122)Program for the Innovative Talents of Higher Learning Institutions of Shanxi of China(2013)The Youth Natural Science Foundation of Shanxi Province of China(2015021005)
文摘Serrated flows are known as repeated yielding of bulk metallic glasses(BMGs)during plastic deformation under different loading conditions,which are associated with the operation of shear banding.According to the statistics of some parameters,the shear avalanches can display a self-organized critical state,suggesting a large ductility of BMGs.The emergence of the self-organized criticality(SOC)behavior in different BMGs is due to the temperature,strain rate,and chemical compositions.The SOC behavior is accompanied with the following phenomena:the interactions occur in the shear bands;the incubation time is longer than the relaxation time;the time interval is lacking of typical time scale;and the spatial or temporal parameters should display apower-law distribution.
基金This study is supported by the National Natural Science Foundation of China(Grants No.71904182,41871204,and 71961147003)P.W.acknowledges support from the CAST Young Elite Scientist Sponsorship Program.
文摘Carbon neutrality requires systematic transformations of both energy and metal systems.These transformations are not isolated but rather interlinked and interdependent,such that trade-offs between different strategies exist.Herein,we explore the critical interlinkages between energy and metal systems and further propose a circular metal-energy nexus to advance global coordinated actions towards a carbon-neutral future.
基金supported by the National Natural Science Foundation of China(Grant Nos.42072194&U1910205)。
文摘Coal,coal measure gas,coal conversion to oil and gas,and coal-based new materials are reliable guarantees for stable energy supply and economic and social development in China.The coal-dominated resource endowment and the economic and social development stage determine the irreplaceable position of coal resources in the energy system.Coal measure resources,including aggregated or dispersed solids,liquid and gaseous multitype energies,and metal as well as nonmetallic minerals,are the products of multisphere interaction and metallogenetic materials generation,migration,and accumulation.Coal measures record rich deep-time geological information of transitional and terrestrial peat bogs,which is a crucial carrier to reveal ecosystem evolution,significant organic carbon sequestration,atmospheric O_(2)/CO_(2)variation,and wildfire events.Coal measure evolution is accompanied by the migration and transformation of various materials during diagenesis-metamorphism,forming differentiated coal compositions besides properties and various mineral resources in its adjacent strata.The enrichment condition,occurrence state,and separation potential are the premise for level-by-level use and efficient development of coal measure resources.Coal measure metallogeny is based on the metallogenic system of multiple energy and mineral resources in coal measures and their environmental effects.Fully understanding coal measure metallogeny is beneficial for promoting the coal transition from fuel to raw materials and strengthening its attribute of multiple mineral resources.The metallogeny comprises various aspects,including:(1)the symbiosis mechanism,co-exploration and co-mining conditions of various resources;(2)the source-sink system of ore-forming materials;(3)the differential carbon accumulation and hydrogen enrichment effect;(4)organic(coal and hydrocarbon)and inorganic(mineral)interactions;and(5)combination of minerals naturally enrichment during the metallogenic process and artificial enrichment during the ore processing process.The coal measure metallogeny belongs to the geoscience disciplines,and studies the types,formation,distribution,enrichment mechanisms,evaluation methods,and development strategies of resources related to coal measures.The key scientific problems include geological records related to mineral enrichment processes,metallogenic mechanisms,resource distribution,occurrence evaluation,and accurate development.Developing coal measure metallogeny is significant in improving the critical mineral metallogenic theory,revealing various deep-time earth systems and realizing the national energy transformation and high-quality development.
基金supported by the National Key R&D Program of China(Grant No.2017YFC0602500)the National Natural Science Foundation of China(Grant Nos.92062107,41703052 and 41903038)+1 种基金the Key Research Program of the Institute of Geology&Geophysics,CAS(Grant No.IGGCAS-201902)the Key Research Program of the Chinese Academy of Sciences(Grant No.ZDRWZS-2020-4-1)。
文摘The upper Permian Heshan Formation in Pingguo,Guangxi,China,is strongly enriched in lithium(Li)and niobium(Nb).The lower bauxite layer contains 0.02–0.04 wt.%Nb_(2)O_(5)(averaging 0.035 wt.%),and the overlying clay rock layer contains 0.06–1.05 wt.%Li_(2)O(averaging 0.44 wt.%),both of which exceed the cut-off grades for independent Li and Nb deposits and are therefore highly prospective.In this study,a preliminary discussion of the genesis of the Li and Nb enrichment is presented to serve as a reference for the investigation,evaluation,and prospecting for clay-and sedimentary-type Li and Nb ores in other regions.The preliminary conclusions are that:(1)The bauxite ore contains abundant anatase,which positively correlates with the whole-rock concentrations of TiO_(2) and Nb,indicating that the Nb is hosted mainly in the anatase;(2)the cookeite content in the clay rock positively correlates with the whole-rock Li concentration,indicating that cookeite is the main carrier mineral of Li,and its genesis can be attributed to reactions between clay minerals(e.g.,pyrophyllite and illite)and Li-Mg-rich underground brine or pore water and groundwater in coastal areas;and(3)provenance analysis of immobile elements(Al,Ti,Nb,Ta,Zr,Hf,and rare earth elements)suggests distinct sources for the Nb-rich bauxite and the overlying Li-rich clay rocks,with the bauxite and Nb originating largely from alkaline felsic rocks in the Emeishan Large Igneous Province,and the clay rocks being derived from peraluminous or moderately fractionated felsic rocks associated with Permian Paleo-Tethyan magmatic arcs.