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Advances in Recovery and Utilization Technologies for Strategic Indium Resources
Liu Hui;Liu Fei;Sun Qing;Guo Xiaokun;Zhou Zhonghua;Zhang Shaobo;Chen Hao;Indium is a critical and irreplaceable metal raw material for strategic emerging industries,including advanced displays,semiconductor lighting,photovoltaics,and high-frequency electronics.However,indium is characterized by an extremely low crustal abundance and a complex paragenetic occurrence in polymetallic ores,and low overall recovery due to the highly disseminated and low-grade nature of the resources.Secondary resources,especially waste indium tin oxide(ITO) targets and liquid crystal display(LCD) panels,offer a promising urban mine with low global recycling rate.The supply-demand imbalance poses a significant risk to the indium supply chain,driving urgent demand for advanced recovery technologies.This review systematically covers the entire technological chain from pretreatment to purification.In leaching,oxidative pressure leaching,reductive leaching with PbS or organic acids,and ultrasonic assistance effectively break down refractory zinc ferrite and sulfide matrices,achieving extraction rates above 94%.For separation and enrichment,solvent extraction remains the dominant industrial route.Acidic organophosphorus extractants such as P204 and P507 are widely employed,but they suffer from strong affinity toward Fe3+,leading to co-extraction,and require high acid concentrations for stripping.Amine-based extractants like N503 and ionic liquids offer milder stripping conditions,while macrocyclic crown ethers,exemplified by benzo-18-crown-6,provide exceptional selectivity through size-matching and ionpair recognition,achieving complete extraction within minutes.Solid-phase adsorption has emerged as a greener alternative,with a wide spectrum of materials,including phosphorylated carbons,functionalized polymers,metal and organic frameworks,covalent organic frameworks,biomass derivatives,and ion-imprinted polymers,demonstrating adsorption capacities up to 474 mg/g and high selectivity over competing ions.Electrochemical recovery,including conventional electrowinning from sulfate/chloride baths and molten salt electrolysis,enables direct metal deposition and even one-step production of 5N-grade indium; the use of ionic liquid electrolytes effectively suppresses hydrogen evolution,improving current efficiency.Pyrometallurgical routes such as sulfation roasting,chlorination volatilization,and reductive roasting provide alternative processing options for specific secondary wastes,achieving recovery rates exceeding 98% under optimized conditions.For ultra-high purity indium,vacuum distillation effectively removes volatile impurities like Cd,Zn,Tl,and Pb,while zone refining exploits differences in solid-liquid distribution coefficients to eliminate Fe,Cu,Ni,and other elements; combined vacuum distillation and zone refining have successfully produced 7N5 grade indium,with machine-learning-assisted optimization further accelerating parameter tuning.Future efforts should concentrate on designing greener separation materials,integrating short-process recovery systems,implementing intelligent process control,and scaling up highend indium-based products,yet the overarching goal remains to bridge laboratory innovations to industrial practice for sustainable indium utilization.This comprehensive review aims to provide theoretical guidance and technical references for the sustainable and efficient utilization of strategic indium resources.
Preparation Technologies and Application Progress of High-Purity Antimony
Tan Renjie;Tian Qinghua;Xin Yuntao;Xu Zhipeng;High-purity antimony(Sb) is reviewed as a key raw material for antimonide semiconductors,infrared detectors,thermoelectric materials,phase-change memory,antimony-based thin-film optoelectronic materials,two-dimensional antimony materials,and high-purity alloys.The review aims to clarify the relationships among feedstock type,purification route,difficult-to-remove impurities,product purity,and application requirements,and to summarize the main technical factors controlling the stable preparation of 5N–7N antimony.Reported processes were classified into compound conversion,metallic antimony refining,electrolytic refining,vacuum distillation,and zone refining.Compound-conversion routes generally use SbCl5,Sb_2O3,SbCl3,or industrial antimony as intermediates and involve chlorination,distillation or rectification,hydrolysis,dechlorination,hydrogen reduction,and further zone refining when necessary.These routes show good selectivity for arsenic removal because antimony chlorides and impurity chlorides differ in boiling point,vapor pressure,and hydrolysis behavior,but the use of HCl,Cl2,and H2 require corrosion-resistant equipment,sealed operation,and tail-gas treatment.Metallic antimony routes usually start from 3N–4N refined antimony and use vacuum distillation,fuming refining,alkaline refining,zone refining,or Czochralski purification.They are suitable for ingot preparation and avoid complicated chlorination steps,but they require high initial purity,stable vacuum systems,clean crucibles and condensers,and strict control of As,Pb,and Bi.Electrolytic refining shows advantages in low operating temperature and process continuity,while the accumulation,co-deposition,and entrainment of As,Bi,Pb,and Cu in electrolyte and cathode products still limite long-term stability.Vacuum distillation is identified as the central physical purification step linking front-end refining and terminal zone refining.According to saturated vapor pressure and condensation behavior,impurities in antimony are divided into highly volatile impurities such as Zn,As,Na,and Mg,low-volatility impurities such as Fe,Cu,Ni,Mn,Au,and Al,and near-volatility impurities such as Pb,Bi,and part of As.Two-step vacuum distillation separates the pre-removal of volatile impurities from the main evaporation and condensation of Sb.Under 50 Pa,630 ℃,and 60 min in the first step and 1–10 Pa,655 ℃,and 30 min in the second step,industrial antimony is purified to 99.998%(4N8).Multi-zone vacuum distillation and selective condensation further improve impurity control by collecting products from different condensation zones.At 632 ℃ in the main zone,500 ℃ in the auxiliary zone,3 h,and 3.5 mPa,antimony with purity higher than 99.999% is obtained.After secondary selective condensation,As,Bi,and Pb in the middle condensate decrease to 0.12,0.49,and 0.04 mg/kg,respectively,and the purity reaches 99.99992%.Zone refining is suitable for terminal purification of 6N–7N antimony because impurities with distribution coefficients far from unity can be enriched at the ingot end; however,As is difficult to remove by zone refining alone.Application analysis shows that high-purity antimony evaluation has shifted from nominal purity to coordinated control of key impurities,product form,and batch stability.InSb,GaSb,AlSb,and InAs/GaSb type-Ⅱ superlattices require strict control of electrically active and volatile impurities,whereas Sb_2Se3,Sb_2S3,Sb_2Te3,phase-change materials,and two-dimensional antimony materials are more sensitive to oxygen,alkali metals,halogens,transition metals,and residues introduced during purification and handling.The review indicates that high-purity antimony preparation requires staged impurity removal rather than a single purification operation.Future development should focus on vacuum distillation-zone refining coupling,multi-temperature condensation,impurity capture,electrolyte purification,clean equipment materials,stable scale-up of vacuum equipment,and applicationoriented impurity specifications for semiconductor,infrared,thermoelectric,photovoltaic,and two-dimensional material uses.
Research Progress on Resource Recovery and Utilization of Copper-containing Etching Waste Liquor from Printed Circuit Board Manufacturing
Gao Yu;Wang Qinmeng;Song Jiangke;Wang Songsong;Lin Guoliang;Quan Wencan;The etching process used in printed circuit board(PCB) manufacturing generates large quantities of copper-containing spent etching solutions.The safe treatment and disposal of these waste solutions,together with the efficient recovery of valuable metals,are urgent requirements for global sustainable development.This review analyzes the sources,compositions,and copper speciation characteristics of copper-containing spent etching solutions.Particular attention is given to the reaction mechanisms,key operating parameters,copper recovery performance,and residual-liquor management associated with chemical precipitation,cementation,solvent extraction,liquid-membrane separation,electrochemical treatment,and chemical oxidative regeneration.Recent advances in the preparation of high-value-added copper-based products are also summarized.The available resourcerecovery technologies are comparatively evaluated in terms of applicable waste-solution types,major products,technological maturity,process advantages,principal limitations,residual-liquor destinations,and prospects for industrial implementation.The economic feasibility and application potential of producing different copper-based products are further analyzed.Finally,in view of current industrial practices and technological development needs,the following future research directions are proposed.First,databases for actual spent etching solutions should be established,and component migration mechanisms should be clarified.Waste solutions should be classified according to acidic or alkaline systems,the Cu+/Cu2+ ratio,Cl~- or total ammonia concentration,impurity loading,and organic content.The valence-state transformation and decomplexation behavior of copper-chloride and copperammonia complexes,as well as the migration of Fe,Ni,Zn,Pb,Cr,As,Cd,and other impurities during precipitation,extraction,electrowinning,and crystallization,should be elucidated to establish relationships among wastesolution composition,process selection,and product quality.Second,the synergistic treatment and short-process closed-loop utilization of multiple copper-containing waste streams generated during PCB production should be promoted.Copper-containing spent etching solutions,electroplating wastewater,copper-clad laminate offcuts,PCB frame scraps,waste printed circuit boards,and other copper-bearing materials should be managed in an integrated manner.Process coupling and continuous integration should be advanced for routes such as precipitation–residual copper removal–ammonium salt recovery–water reuse,extraction–stripping–electrowinning or crystallization,and electrochemical regeneration–selective copper bleeding.Meanwhile,the coordinated control of organic matter and impurities such as Fe,Ni,Zn,Pb,and Sn should be strengthened to reduce reagent consumption and treatment costs and to achieve the closed-loop recovery of copper,ammonium salts,and water.Third,an integrated technoeconomic–environmental assessment and hierarchical collaborative utilization system should be developed.Using the treatment of a unit quantity of waste solution or the recovery of a unit quantity of copper as the functional unit,resource recovery,reagent and energy consumption,product qualification rate,generation of residual liquor and solid waste,economic benefits,carbon emissions,and other indicators should be comprehensively evaluated.Based on these assessments,an industrial model featuring "priority for on-site closed-loop recycling,supplementary centralized treatment in industrial parks,graded feedstock processing,and product-oriented utilization" should be established.Low-impurity waste solutions should preferentially be converted into electroplating-grade copper sulfate,active copper oxide,or high-purity copper for reuse in PCB production,while quality and environmental standards for regenerated etchants,copper-based products,and by-product salts should be further improved.
Research Progress on Resin Adsorption Technology in Wet Phosphoric Acid Purification
Bao Shenxu;Yang Xun;Chen Bo;Xin Chunfu;Kuang Buxiao;Hubei Three Gorges Laboratory;Wet-process phosphoric acid,because of its high compatibility with the sulfuric acid decomposition of phosphate rock,accounts for approximately 90% of global phosphoric acid production.An intrinsic drawback of this process is that during sulfuric acid digestion,all associated metal cations,heavy metals,anions,and organic matter are carried into the phosphoric acid liquor,generating a complex impurity matrix containing Fe3+,Al3+,Mg2+,Cd2+,As3+,SO42-,F~-,and various organic compounds.Strategic emerging industries such as new energy and electronic information raise purity requirements for high-grade phosphoric acid and phosphates from percentage levels to mg/kg or μg/kg levels,shifting the purification objective from rough removal to deep refining.Resin adsorption technology,with its designable functional groups,tunable selectivity,and high purification depth,attracts increasing research attention.This review summarizes recent progress in resin adsorption for purifying wet-process phosphoric acid and constructs an analytical framework covering novel resin material development,deeper understanding of adsorption mechanisms,and industrial bottlenecks.Supported ionic liquid resins,in which ionic liquids were immobilized onto porous resins via chemical grafting,achieves high phosphate selectivity through a synergistic mechanism combining anion exchange and hydrogen-bonding complexation; phosphate adsorption capacities reach 307–333 mg/g and the separation factor for Mg2+ exceeds 600.Functionalized chelating resins,by introducing multidentate groups such as amino and phosphonic acid groups into the polymer backbone,enhance recognition for Cd2+ and Fe3+; however,this high selectivity is often accompanied by lower adsorption capacity and slow kinetics,making them more suitable as polishing units.Macroporous adsorption resins show potential to replace activated carbon in organic tail-gas treatment and achieves solvent recovery rates above 99% under optimized conditions.Regarding adsorption mechanisms,the review distinguish two process orientations: the impurity-removal route,which relies on ion exchange and chelation to selectively remove impurity ions,and the enrichment route,which involves anion exchange combined with hydrogen-bonding/coordination synergy to selectively capture phosphate species.Thermodynamic studies indicate that the adsorption is spontaneous,endothermic,and accompanied by an entropy increase.Kinetic analyses generally show that chemical adsorption is the rate-controlling step.Although preliminary studies had reported selectivity coefficients for various metal ions,quantitative prediction under multicomponent coexistence remains a theoretical weak point.Industrialization is still in its infancy,constrained by high material and regeneration costs,a lack of long-term stability data for resins in strong acid and high-temperature environments,and immature scale-up engineering.Future efforts are recommended to focus on developing highperformance and low-cost resins,elucidating competitive adsorption mechanisms and theoretical modeling,developing green and efficient regeneration technologies,applying artificial intelligence-assisted material screening and process optimization,using in-situ characterization for mechanistic studies,and advancing process integration and industrial demonstrations to accelerate translation from laboratory research to industrial application.
Recent Development in Nickel and Cobalt Recovery Technologies from Laterite
LIU Da-xing (Beijing General Research Institute of Mining and Metallurgy , Beijing 100044, China)Laterite deposits and relevant metallurgical processes were introduced in this paper The recent deve lopment of hydrometallurgy processes for laterite and its impact on nickel and cobalt industry were reviewed
Principles and Technologies for Remediation of Heavy Metal Contaminated Soil
ZHANG Yi-shuo;ZHOU Zhong-kui;YANG Shun-jing;LI Rui;LI Long-xiang;LI Jing-yu;FAN Xiao-lei;Heavy metal pollution can lead to changes in ecological structure, function, and physicochemical properties of soil, greatly reduce crop yields, harm ecological environment and human health, and has become one of the major global environmental pollutants in the world.In order to repair soil heavy metal pollution, several soil remediation technologies have been developed.The principles, advantages and disadvantages, applicability and technical feasibility of various remediation technologies were discussed.The combined remediation technologies should be the key research direction of concern for solving soil heavy metal pollution problem in the future.
Status and Development of Gold Extraction from Refractory Gold Ore
SUN Liu-gen;YUAN Chao-xin;WANG Yun;SUN Yan-wen;CHANG Yao-chao;XU Xiao-hui;DU Qi-ping;LIU Yong-tao;Beijing General Research Institute of Mining & Metallurgy;Processing mechanism,latest research and application status of refractory gold concentrate by cyanidation and non-cyanidation were briefly introduced.Advantages and disadvantages of each method were analyzed.The development direction of processing refractory gold ore was proposed.
Study on De-Arsenic from Dust of Flash Smelting Furnace
LIANG Yong1,LI Liang-xing1,LIAO Chun-fa1,SHI Yu-chen2(1.School of Material and Chemical Engineering,Jiangxi University of Science & Technology,Ganzhou,Jiangxi 341000,China;2.China Railway Resources Group Co.,Ltd,Beijing 100039,China)The de-arsenic from the dust of copper flash smelting furnace applying the pyrometallurgical method is studied.The effect of temperature,roasting time and coke additive on de-arsenic is investigated using the orthogonal experiment.The results indicate that de-arsenic rate is above 80% and the recovery of copper is above 95% under the conditions of 1 100 ℃ roasting temperature,1 h roasting time and 12% coke additive.
Status and Development of Antimony Metallurgy Technology in China
WANG Cheng yan, QIU Ding fan, JIANG Pei hai (Beijing General Research Institute of Mining & Metallurgy, Beijing 100044, China)Jamesonite, the major mineral of antimony in Guangxi province of China, is very difficult to be treated For treating it, many institutes of China have studied a lot of new hydrometallurgy technology in recently year Sixprocesses have been introduced in this paper The Slurry Electrolysis technology is introduced in focal point
Principles and Technologies for Remediation of Heavy Metal Contaminated Soil
ZHANG Yi-shuo;ZHOU Zhong-kui;YANG Shun-jing;LI Rui;LI Long-xiang;LI Jing-yu;FAN Xiao-lei;Heavy metal pollution can lead to changes in ecological structure, function, and physicochemical properties of soil, greatly reduce crop yields, harm ecological environment and human health, and has become one of the major global environmental pollutants in the world.In order to repair soil heavy metal pollution, several soil remediation technologies have been developed.The principles, advantages and disadvantages, applicability and technical feasibility of various remediation technologies were discussed.The combined remediation technologies should be the key research direction of concern for solving soil heavy metal pollution problem in the future.
Review on Recycling Technology of Retired LiFePO4 Batteries
WANG Meng;ZHANG Jia-liang;CHEN Yong-qiang;WANG Cheng-yan;In recent years, the new energy vehicles and energy storage fields develop rapidly in China.The usage of lithium iron phosphate battery rises sharply.In the future, a large number of retired lithium iron phosphate batteries will be generated, the recycling of which will not only alleviate the problem of lithium resource shortage in China but also reduce the environmental pollution caused by fluorinated electrolyte.The research on recycling of retired lithium iron phosphate batteries in recent years was reviewed, including lithium battery pretreatment, repair technologies for spent lithium iron phosphate cathode material, hydrometallurgical recovery, selective lithium extraction method, and recovery of lithium extraction tailing, etc.The latest research results of each technology were summarized.The advantages and disadvantages of each process were analyzed from the aspects of economics of the process, recovery rate and environmental impact and other aspects.The future development direction of recycling technology of retired lithium iron phosphate batteries was prospected.
Research Progress in Recycling Technology of Cathode Materials for Spent Lithium Iron Phosphate Batteries
WU De-you;LIU Zhi-qiang;RAO Shuai;ZHANG Kui-fang;Guangdong Research Institute of Rare Metal;With rapid development of new energy vehicles,a large number of waste batteries will be generated after retirement of LiFePO4 power batteries.It will pollute environment and waste metal resources if they are not disposed of in time.Recycling technology progress of spent LiFePO4 cathode materials in recent years was introduced,including hydrometallurgical recovery of valuable metals,repair and regeneration of spent LiFePO4 and decomposition and resynthesis of LiFePO4,etc.Advantages and disadvantages of different recycling methods were pointed out.Development direction of spent LiFePO4 batteries recycling technology was prospected.
Carbon Emission Accounting Method and Strategy Analysis under the Background of Double Carbon: Taking Copper and Aluminum Industry as an Example
WANG Wei;WU Jing-jing;GE Ya-ping;LI Qi-ke;As a major carbon emitter in the non-ferrous metals industry, its task of carbon reduction and emission reduction is of great significance.On the basis of expounding the methods and steps of carbon emission accounting, combined with copper and aluminum industries, taking copper smelting enterprises A and electrolytic aluminum plants B as examples, the carbon emissions of copper and aluminum enterprises were calculated respectively.The results show that annual carbon emission of copper smelting enterprises A is 162 kt, and annual carbon emission of electrolytic aluminum enterprises B is 4 140.7 kt.Under the dual carbon strategic goal(carbon peak and carbon neutralization),carbon reduction and emission reduction strategies such as new energy industry upgrading and capacity structure transfer in the field of copper and aluminum are put forward.
Development Status and Trend of Flue Gas Desulfuration in China
LIANG Dong-dong;LI Da-jiang;GUO Chi-hao;SUN Liu-gen;CHANG Yao-chao;HUANG Hai-hui;Beijing General Research Institute of Mining and Metallurgy;Application,research development,and principle and characteristics of flue gas desulfurization technology were summarized.New desulfurization technologies already put forward were described.The desulphurization technology development in China was prospected.The development of desulfurization technologies feasible for industrial production in China was put forwarded.
