DE19781673T1 - Rückgewinnung von Wertmetallgehalten - Google Patents

Rückgewinnung von Wertmetallgehalten

Info

Publication number
DE19781673T1
DE19781673T1 DE1997181673 DE19781673T DE19781673T1 DE 19781673 T1 DE19781673 T1 DE 19781673T1 DE 1997181673 DE1997181673 DE 1997181673 DE 19781673 T DE19781673 T DE 19781673T DE 19781673 T1 DE19781673 T1 DE 19781673T1
Authority
DE
Germany
Prior art keywords
recovery
valuable metal
metal contents
contents
valuable
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
DE1997181673
Other languages
English (en)
Inventor
Patrick M Brown
Robert A Hard
Donna D Harbuck
Gordon K Green
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Cabot Corp
US Department of the Interior
Original Assignee
Cabot Corp
US Department of the Interior
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Cabot Corp, US Department of the Interior filed Critical Cabot Corp
Publication of DE19781673T1 publication Critical patent/DE19781673T1/de
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/20—Obtaining niobium, tantalum or vanadium
    • C22B34/24—Obtaining niobium or tantalum
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/04—Extraction of metal compounds from ores or concentrates by wet processes by leaching
    • C22B3/06—Extraction of metal compounds from ores or concentrates by wet processes by leaching in inorganic acid solutions, e.g. with acids generated in situ; in inorganic salt solutions other than ammonium salt solutions
    • C22B3/08—Sulfuric acid, other sulfurated acids or salts thereof
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B3/00—Extraction of metal compounds from ores or concentrates by wet processes
    • C22B3/20—Treatment or purification of solutions, e.g. obtained by leaching
    • C22B3/26—Treatment or purification of solutions, e.g. obtained by leaching by liquid-liquid extraction using organic compounds
    • C22B3/28—Amines
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B34/00—Obtaining refractory metals
    • C22B34/10—Obtaining titanium, zirconium or hafnium
    • C22B34/14—Obtaining zirconium or hafnium
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02—Obtaining thorium, uranium, or other actinides
    • C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
    • C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
    • C22B60/0221—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching
    • C22B60/0226—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using acidic solutions or liquors
    • C22B60/0234—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes by leaching using acidic solutions or liquors sulfurated ion as active agent
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02—Obtaining thorium, uranium, or other actinides
    • C22B60/0204—Obtaining thorium, uranium, or other actinides obtaining uranium
    • C22B60/0217—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes
    • C22B60/0252—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries
    • C22B60/026—Obtaining thorium, uranium, or other actinides obtaining uranium by wet processes treatment or purification of solutions or of liquors or of slurries liquid-liquid extraction with or without dissolution in organic solvents
    • C—CHEMISTRY; METALLURGY
    • C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22B—PRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B60/00—Obtaining metals of atomic number 87 or higher, i.e. radioactive metals
    • C22B60/02—Obtaining thorium, uranium, or other actinides
    • C22B60/0291—Obtaining thorium, uranium, or other actinides obtaining thorium
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00—Technologies related to metal processing
    • Y02P10/20—Recycling

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Geology (AREA)
  • Environmental & Geological Engineering (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Inorganic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
DE1997181673 1996-03-26 1997-03-14 Rückgewinnung von Wertmetallgehalten Withdrawn DE19781673T1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US08/621,631 US7282187B1 (en) 1996-03-26 1996-03-26 Recovery of metal values
PCT/US1997/004089 WO1997036011A1 (en) 1996-03-26 1997-03-14 Recovery of metal values

Publications (1)

Publication Number Publication Date
DE19781673T1 true DE19781673T1 (de) 1999-04-29

Family

ID=24490955

Family Applications (1)

Application Number Title Priority Date Filing Date
DE1997181673 Withdrawn DE19781673T1 (de) 1996-03-26 1997-03-14 Rückgewinnung von Wertmetallgehalten

Country Status (8)

Country Link
US (1) US7282187B1 (de)
JP (1) JP4267698B2 (de)
CN (1) CN1068061C (de)
AU (1) AU2581897A (de)
BR (1) BR9708259A (de)
DE (1) DE19781673T1 (de)
RU (1) RU2203335C2 (de)
WO (1) WO1997036011A1 (de)

Families Citing this family (44)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5787332A (en) * 1996-09-26 1998-07-28 Fansteel Inc. Process for recovering tantalum and/or niobium compounds from composites containing a variety of metal compounds
US6241800B1 (en) * 1999-09-02 2001-06-05 Westinghouse Electric Company Llc Acid fluxes for metal reclamation from contaminated solids
BRPI0500778B1 (pt) * 2005-02-03 2014-07-29 Krupinite Corp Ltd Beneficiamento químico de matéria-prima contendo Tântalo-Nióbio
FR2904888B1 (fr) * 2006-08-11 2008-12-19 Cezus Cie Europ Du Zirconium S Methode de stabilisation du radium dans les effluents radiferes.
CN101842504B (zh) 2007-05-21 2012-11-14 奥贝特铝业有限公司 从铝土矿石中提取铝和铁的工艺
CN102312094B (zh) * 2010-07-07 2013-03-20 核工业北京地质研究院 一种从含铀的铌钽浸出尾渣中提取铀的方法
FR2970265B1 (fr) * 2011-01-06 2013-02-08 Areva Nc Mise en solution et recuperation d'au moins un element nb, ta et d'au moins un autre element u, terres rares a partir de minerais et concentres
RU2588960C2 (ru) 2011-03-18 2016-07-10 Орбит Элюминэ Инк. Способы извлечения редкоземельных элементов из алюминийсодержащих материалов
US9410227B2 (en) 2011-05-04 2016-08-09 Orbite Technologies Inc. Processes for recovering rare earth elements from various ores
WO2012162817A1 (en) 2011-06-03 2012-12-06 Orbite Aluminae Inc. Methods for preparing hematite
BR112014006275A2 (pt) 2011-09-16 2017-04-11 Orbite Aluminae Inc processos de preparação de alumina e de vários outros produtos
EP2802675B1 (de) 2012-01-10 2020-03-11 Orbite Aluminae Inc. Verfahren zur behandlung von rotschlamm
AU2013203808B2 (en) 2012-03-29 2016-07-28 Aem Technologies Inc. Processes for treating fly ashes
BR112015000626A2 (pt) 2012-07-12 2017-06-27 Orbite Aluminae Inc processos para preparação de óxido de titânio e outros produtos variados
DE102012214057A1 (de) * 2012-08-08 2014-02-13 Siemens Aktiengesellschaft Verfahren und Vorrichtung zur Gewinnung mindestens eines Wertmetalloxids
BR112015006536A2 (pt) 2012-09-26 2017-08-08 Orbite Aluminae Inc processos para preparar alumina e cloreto de magnésio por lixiviação com hcl de vários materiais.
US9534274B2 (en) 2012-11-14 2017-01-03 Orbite Technologies Inc. Methods for purifying aluminium ions
CN103305708B (zh) * 2013-07-05 2014-10-08 南昌航空大学 一种反萃取分离有机相中钪和钍的方法
CN103468980B (zh) * 2013-08-15 2016-04-13 中国恩菲工程技术有限公司 一种红土镍矿提取钪的方法
US10030286B1 (en) 2013-11-13 2018-07-24 Ii-Vi Incorporated Method of direct solvent extraction of rare earth metals from an aqueous acid-leached ore slurry
JP5954350B2 (ja) * 2014-01-31 2016-07-20 住友金属鉱山株式会社 スカンジウム回収方法
JP6319362B2 (ja) * 2014-01-31 2018-05-09 住友金属鉱山株式会社 スカンジウム回収方法
JP6194867B2 (ja) * 2014-09-10 2017-09-13 信越化学工業株式会社 抽出分離方法
WO2016058007A2 (en) * 2014-10-10 2016-04-14 Rare Element Resources, Ltd. Processing for the extraction of rare earth elements
AU2015351446B2 (en) * 2014-11-26 2018-08-02 Sumitomo Metal Mining Co., Ltd. Method for recovering high-purity scandium
US10808296B2 (en) 2015-10-30 2020-10-20 Ii-Vi Delaware, Inc. Selective recovery of rare earth metals from an acidic slurry or acidic solution
US10933410B2 (en) 2015-10-30 2021-03-02 Ii-Vi Delaware, Inc. Composite extractant-enhanced polymer resin, method of making the same, and its usage for extraction of valuable metal(s)
JP6409796B2 (ja) 2016-02-23 2018-10-24 住友金属鉱山株式会社 スカンジウムの回収方法
IT201600101809A1 (it) * 2016-10-11 2018-04-11 Ecotec Gestione Impianti S R L Procedimento per la preparazione di un concentrato contenente metalli, metalli rari e terre rare da residui generati nella filiera di produzione dell’allumina tramite il processo Bayer, o da materiali di composizione chimica similare, e affinamento del concentrato così ottenibile.
WO2018097001A1 (ja) * 2016-11-24 2018-05-31 住友金属鉱山株式会社 スカンジウムの精製方法
JP6922478B2 (ja) * 2016-11-24 2021-08-18 住友金属鉱山株式会社 スカンジウムの精製方法
CN106676291A (zh) * 2016-12-28 2017-05-17 核工业北京化工冶金研究院 一种从矿石中综合回收铀铌钽的方法
CN107475542B (zh) * 2017-07-17 2021-03-16 中国恩菲工程技术有限公司 处理稀土精矿的方法
DE102018102026A1 (de) 2018-01-30 2019-08-01 Duesenfeld Gmbh Verfahren zum Verwerten von Lithium-Batterien
CN109837400B (zh) * 2018-11-14 2021-08-06 中国地质科学院郑州矿产综合利用研究所 一种从富铌渣中提取稀土和铌的方法
CN110961248B (zh) * 2019-11-29 2022-03-04 南华大学 一种含钪铀矿中分离钪、铀的方法
JP7463182B2 (ja) 2020-04-22 2024-04-08 Ｊｘ金属株式会社 レアメタルの回収方法
JP7463180B2 (ja) 2020-04-22 2024-04-08 Ｊｘ金属株式会社 レアメタルの回収方法
CN112133905B (zh) * 2020-09-24 2021-12-17 江西普瑞美新材料科技有限公司 一种高镍三元前驱体及其制备方法
CN112553480A (zh) * 2020-10-10 2021-03-26 吕梁学院 一种赤泥中锆的回收方法
WO2022077055A1 (en) * 2020-10-12 2022-04-21 Australian Nuclear Science And Technology Organisation Process for extracting zirconium
CN114262798B (zh) * 2021-12-27 2023-11-14 河南荣佳钪钒科技有限公司 一种从氯化法钛白体系渣中回收二氧化钍的方法
WO2024030853A2 (en) * 2022-08-01 2024-02-08 Niocorp Developments Ltd. Processes and methods for recovering rare earth elements and scandium from acidic solutions
CN115807157A (zh) * 2022-11-04 2023-03-17 核工业北京化工冶金研究院 一种铀铍矿高效浸出除氟方法

Family Cites Families (45)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2767047A (en) 1953-10-20 1956-10-16 Harley A Wilhelm Process of separating tantalum and niobium values from each other
US2962372A (en) 1958-01-17 1960-11-29 Union Carbide Corp Columbium and tantalum separation
US2953453A (en) 1958-06-20 1960-09-20 Nat Distillers Chem Corp Recovery of columbium values
US3117833A (en) 1958-09-25 1964-01-14 Fansteel Metallurgical Corp Process of purifying and separating columbium and tantalum values from each other
US3300297A (en) 1964-05-26 1967-01-24 Kawecki Chemical Company Beneficiation of tantalum- and columbium-bearing tin slags
US3658511A (en) 1969-12-22 1972-04-25 Kawecki Berylco Ind Upgrading the tantalum and columbium contents of oxidic metallurgical products
US3712939A (en) 1971-03-29 1973-01-23 Union Carbide Corp Method for recovering tantalum and/or columbium
DE2435427A1 (de) 1974-07-23 1976-02-05 Starck Hermann C Fa Verfahren zur verarbeitung von tantalniob-haltigen schlacken und rueckstaenden
US4155982A (en) 1974-10-09 1979-05-22 Wyoming Mineral Corporation In situ carbonate leaching and recovery of uranium from ore deposits
US4233278A (en) 1978-03-24 1980-11-11 Davy Powergas Inc. Process for purifying crude phosphoric acid
US4164417A (en) 1978-04-28 1979-08-14 Kawecki Berylco Industries, Inc. Process for recovery of niobium values for use in preparing niobium alloy products
US4234555A (en) 1978-06-29 1980-11-18 The United States Of America As Represented By The United States Department Of Energy Removal of uranium from aqueous HF solutions
US4278640A (en) 1979-03-19 1981-07-14 International Minerals & Chemical Corporation Method for solvent extraction of metallic mineral values from acidic solutions
DE2927835A1 (de) 1979-07-10 1981-06-04 Hermann C. Starck Berlin, 1000 Berlin Verfahren zur rueckgewinnung von fluorwasserstoffsaeure und deponierfaehigen rueckstaenden bei der verarbeitung niob- und/oder tantal-haltiger rohstoffe
US4320093A (en) 1979-11-13 1982-03-16 Bohumil Volesky Separation of uranium by biosorption
US4293528A (en) 1979-11-19 1981-10-06 Mobil Oil Corporation Yellowcake processing in uranium recovery
JPS56114831A (en) 1980-02-15 1981-09-09 Toshiba Corp Recovery of tantalum from scrap containing tantalum
US4446116A (en) 1981-04-02 1984-05-01 Hermann C. Starck Bertin Process for recovering niobium and/or tantalum compounds from such ores further containing complexes of uranium, thorium, titanium and/or rare earth metals
US4451438A (en) 1982-03-26 1984-05-29 Herman C. Starck Berlin Process for recovering niobium and/or tantalum metal compounds from such ores further containing complexes of uranium, thorium, titanium and/or rare earth metals
US4477416A (en) 1982-09-27 1984-10-16 Union Carbide Corporation Salt roasting of vanadium ore in the presence of carbon
US4412861A (en) 1982-10-27 1983-11-01 Kreuzmann Alvin B Method for the recovery of uranium values from uranium tetrafluoride
JPS5983730A (ja) * 1982-11-05 1984-05-15 Agency Of Ind Science & Technol 微量金属イオンの回収方法
US4743271A (en) 1983-02-17 1988-05-10 Williams Technologies, Inc. Process for producing a clean hydrocarbon fuel
US4536034A (en) 1983-04-14 1985-08-20 Mobil Oil Corporation Method for immobilizing contaminants in previously leached ores
US4695290A (en) 1983-07-26 1987-09-22 Integrated Carbons Corporation Integrated coal cleaning process with mixed acid regeneration
US4663130A (en) 1983-11-14 1987-05-05 Cabot Corporation Process for dissolving tantalum/columbium materials containing alkali metal impurities
US4654200A (en) 1984-06-01 1987-03-31 Inderjit Nirdosh Processes for extracting radium from uranium mill tailings
JPS61146717A (ja) 1984-12-18 1986-07-04 Sumitomo Chem Co Ltd タンタルの精製方法
US4753033A (en) 1985-03-24 1988-06-28 Williams Technologies, Inc. Process for producing a clean hydrocarbon fuel from high calcium coal
US4624703A (en) * 1986-01-24 1986-11-25 Gte Products Corporation Recovery of tungsten, scandium, iron, and manganese values from tungsten bearing material
US4718996A (en) 1986-01-24 1988-01-12 Gte Products Corporation Recovery of tungsten, scandium, iron, and manganese values from tungsten bearing material
JPS62235218A (ja) * 1986-04-04 1987-10-15 Unitika Ltd ウランおよびフツ酸の分離回収法
US4808384A (en) 1986-06-23 1989-02-28 Gte Products Corporation Recovery of tungsten, scandium, iron, and manganese from tungsten bearing material
US4765909A (en) * 1987-04-23 1988-08-23 Gte Laboratories Incorporated Ion exchange method for separation of scandium and thorium
BR8703766A (pt) 1987-07-20 1989-01-31 Mamore Mineracao E Metalurgica Processo para a abertura de minerios
US4778663A (en) 1987-08-27 1988-10-18 American Cyanamid Company Uranium recovery from wet process phosphoric acid unsymmetrical phosphine oxides
US5023059A (en) * 1988-11-02 1991-06-11 Bielecki Edwin J Recovery of metal values and hydrofluoric acid from tantalum and columbium waste sludge
US5015447A (en) * 1989-07-18 1991-05-14 Alcan International Limited Recovery of rare earth elements from sulphurous acid solution by solvent extraction
US5084253A (en) 1989-11-13 1992-01-28 Nuclear Metals, Inc. Method of removing niobium from uranium-niobium alloy
DE4021207A1 (de) 1990-07-03 1992-01-16 Starck Hermann C Fa Verfahren zur gewinnung und trennung von tantal und niob
US5384105A (en) 1992-05-29 1995-01-24 Eco Tek, Inc. Metal and fluorine values recovery from mineral ore treatment
US5273725A (en) 1992-05-29 1993-12-28 Eco Tek, Inc. Metal and fluorine values recovery from mineral ore treatment
US5531970A (en) * 1992-05-29 1996-07-02 Advanced Recovery Systems, Inc. Metal and fluorine values recovery from mineral ore treatment
US5437848A (en) 1992-07-10 1995-08-01 Cabot Corporation Recovery of metal values from process residues
US5492680A (en) * 1994-08-04 1996-02-20 The United States Of America As Represented By The Secretary Of The Interior Separation of scandium from tantalum residue using fractional liquid-liquid extraction

Also Published As

Publication number Publication date
WO1997036011A1 (en) 1997-10-02
RU2203335C2 (ru) 2003-04-27
JP4267698B2 (ja) 2009-05-27
CN1219978A (zh) 1999-06-16
BR9708259A (pt) 2001-09-11
US7282187B1 (en) 2007-10-16
CN1068061C (zh) 2001-07-04
AU2581897A (en) 1997-10-17
JP2000507308A (ja) 2000-06-13

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