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WO2011126375A1 - Extraction d'éléments à partir de minéraux à teneur en carbonates - Google Patents

Extraction d'éléments à partir de minéraux à teneur en carbonates Download PDF

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Publication number
WO2011126375A1
WO2011126375A1 PCT/NO2010/000129 NO2010000129W WO2011126375A1 WO 2011126375 A1 WO2011126375 A1 WO 2011126375A1 NO 2010000129 W NO2010000129 W NO 2010000129W WO 2011126375 A1 WO2011126375 A1 WO 2011126375A1
Authority
WO
WIPO (PCT)
Prior art keywords
alkaline
mineral
particles
carbonates
elements
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.)
Ceased
Application number
PCT/NO2010/000129
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English (en)
Inventor
Dag Øistein ERIKSEN
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Primusinterpares As
Original Assignee
Primusinterpares As
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 Primusinterpares As filed Critical Primusinterpares As
Priority to PCT/NO2010/000129 priority Critical patent/WO2011126375A1/fr
Publication of WO2011126375A1 publication Critical patent/WO2011126375A1/fr
Priority to NO20121127A priority patent/NO20121127A1/no
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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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
    • C22B59/00—Obtaining rare earth metals
    • 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
    • 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

Definitions

  • This invention relates to a method for extraction of elements from carbonate- containing minerals with limited use of mineral acid and small discharges of C0 2 .
  • Carbonate minerals comprise among others calcite (CaC0 3 ), dolomite
  • CaMg(C0 3 ) 2 CaMg(C0 3 ) 2
  • ankerite Ca(Fe,Mg,Mn)(C0 3 )2
  • These minerals often also contain other elements, e.g. rare earth elements, in lower abundances than the main elements listed. They may also be found in matrixes together with abrasive minerals like hematite.
  • These elements may be extracted by dissolving the carbonate containing mineral in a mineral acid to form an aqueous solution of the elements, and then recovering the element of interest by use of hydrometallurgical method.
  • SX processes are usually run in continuous mode where the aqueous and organic phases are moving counter-currently.
  • mixer-settlers are usually employed, but also columns with mixing and separation sections are used.
  • Each mixer-settler represents one separation stage, but equilibrium may not have to be achieved in each stage.
  • An SX process may contain 100 stages or more.
  • SX processes are known to sustain high loads and being robust in operation conditions.
  • Various kinds of mixers and settlers and their combinations have been developed. The need of the specific process will determine what kind of mixer and settler to be chosen as well as the number of stages.
  • IX processes are most often based on an aqueous phase percolating through a column packed with a non-dissolvable resin. To avoid clogging of the resin the liquid must be free of solid particles. Also, precipitation or gas emission in the column must be avoided. There are several modes of operation, but most industrial IX processes are semi-continuous. There is one true continuous IX-technology, the CAC - Continuous Annular Chromatograph. The concept of this device is to transform the time used in traditional
  • the simulated moving bed is a semi-continuous mode with the advantage that the column can be very long. This method is used in very difficult separations where a huge number of theoretical plates are needed, i.e. very long column. SMB is particularly suited for affinity chromatography.
  • IX indium tetrachloride
  • SX the term "theoretical plate" is used as there is a continuous separation along the column in contrast to SX where each stage is a physical unit. This also implies that it is better to use IX when high purity products are desired as the pure part of the exiting peak can be removed, while for SX all from the final stage must be used.
  • solvent extraction agents may be absorbed into inert, porous polymer supports in the form of particles.
  • impregnated resins behave like other kind of IX-resins without any loss of extractant [4].
  • extractant there are a huge number of selective extractants are available also for the high purity separations.
  • this kind of resins requires the same absence of solids in the feed solution.
  • the main objective of the invention is to provide a cost effective method for extracting elements from carbonate containing minerals.
  • a further objective of the invention is to provide a method which minimises the use of mineral acid.
  • the invention is based on the realisation that the when C0 2 is injected into water, there is formed a weak acid, carbonic acid, which will dissolve carbonates of alkaline and alkaline earth elements in the form of bicarbonates, but generally not carbonates of elements other than the alkaline and alkaline earth elements, such as for instance Group IV elements, rare earth elements and other.
  • Carbonates from these elements will often remain as a solid carbonate phase in the weak acid solution formed by carbonic acid.
  • the general reaction for dissolving the carbonates in the case of a divalent metal may be written:
  • the injection of C0 2 may be employed in a closed cycle process where the rare earth carbonates are separated from the major fraction of the carbonate mineral without using the relatively expensive mineral acid.
  • the main objective of the invention may be obtained by a method as follows:
  • the present invention relates to method for extracting elements from carbonate containing minerals, where the method comprises:
  • particles we mean relatively small bits of crushed mineral rock.
  • the mean particle diameter should typically be about 0.5 mm, but any other mean particle diameters may also be applied.
  • the invention will function with almost any mean particle diameter, but smaller diameters will favour the reaction kinetics of the dissolution reactions.
  • Hydrometallurgical methods for selectively precipitating rare earth elements from the dissolution made in step 7) of the method according to first aspect of the invention are well known to a skilled person. There is no need for describing such methods.
  • any suitable hydrometallurgical method may be applied since the inventive feature of the first aspect is the use of carbonic acid to selectively dissolve the alkaline and alkaline earth carbonates and thus allow use of liquid-solid separation techniques for separating out the non-dissolvable remaining are earth carbonates of the mineral.
  • the method may for example also be applied for extracting Group 4 elements - Ti, Zr, Hf, which will have great value and can be dissolved by using much less acid compared to dissolving the whole mineral.
  • the method according to the first aspect of the invention solves the problem of excessive use of mineral acid since the mineral acid is not used to solve the major fraction of the carbonate mineral, but only the carbonates of interest.
  • the method obtains another benefit in that it consumes C0 2 .
  • the method becomes C0 2 negative and may be employed to extract C0 2 from other C0 2 -forming processes.
  • the method according to the invention may be made C0 2 -neutral by including a precipitation step of the alkaline bicarbonates as solid carbonates with capture and reuse of the C0 2 in step 3).
  • the invention relates to a method for extracting elements from carbonate containing minerals, where the method comprises:
  • step 7) increase the pH of the liquid phase from step 4) by adding a base until the alkaline and alkaline earth elements are precipitated as solid carbonates,
  • step 9) separating the precipitated carbonates from step 8) and discharge them.
  • the precipitation of the alkaline and alkaline earth metals may be given as reaction II above in the case of a divalent metal, but in reverse.
  • the discharge of the precipitated carbonates may be in a waste disposal.
  • the invention may be used for forming a valuable product, precipitated calcium carbonate (PCC).
  • PCC precipitated calcium carbonate
  • This may be obtained by including a separation step in step 6) for selectively precipitating the calcium carbonate.
  • PCC precipitated calcium carbonate
  • Fen is the site where the main Norwegian thorium deposits are found.
  • the thorium minerals at Fen are known to be oxide and silicate, but experience obtained in the 1980's indicates that some is also abundant in carbonate rock.
  • the Fen area has been surveyed for rare earth elements (REE), in particular scandium, and the total REE-containing rock, "rodberg and rauhaugitt” (hematite containing dolomite-calcite and ankerite ferrocarbonatite) were estimated to 400 million tonnes with an average REE content of 0.9 % REO (rare earth oxide, Ln 2 0 3 ).
  • REE rare earth elements
  • Table 1 gives content of REE in one typical sample of Rodberg
  • Table 2 indicates concentration of selected elements in hydrochloric leachates.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Geology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Environmental & Geological Engineering (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Geochemistry & Mineralogy (AREA)
  • Manufacture And Refinement Of Metals (AREA)

Abstract

Cette invention concerne un procédé d'extraction d'éléments à partir de minéraux à teneur en carbonates avec utilisation limitée d'acide minéral et de faibles décharges de CO2. Le procédé consiste à broyer le minéral en particules, à immerger le minéral broyé dans l'eau, à injecter du CO2 dans l'eau jusqu'à ce que les carbonates alcalins et alcalino-terreux soient dissous, à séparer les particules solides restantes de la phase liquide, à décharger la phase liquide et à immerger les particules solides restantes dans l'eau et ajouter un acide minéral jusqu'à ce que les particules soient dissoutes, à séparer et faire précipiter les éléments ioniques des terres rares en tant qu'oxydes à l'aide de procédés hydrométallurgiques classiques.
PCT/NO2010/000129 2010-04-07 2010-04-07 Extraction d'éléments à partir de minéraux à teneur en carbonates Ceased WO2011126375A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/NO2010/000129 WO2011126375A1 (fr) 2010-04-07 2010-04-07 Extraction d'éléments à partir de minéraux à teneur en carbonates
NO20121127A NO20121127A1 (no) 2010-04-07 2012-10-05 Ekstraksjon av grunnstoffer fra karbonatholdige mineraler

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
PCT/NO2010/000129 WO2011126375A1 (fr) 2010-04-07 2010-04-07 Extraction d'éléments à partir de minéraux à teneur en carbonates

Publications (1)

Publication Number Publication Date
WO2011126375A1 true WO2011126375A1 (fr) 2011-10-13

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Country Status (2)

Country Link
NO (1) NO20121127A1 (fr)
WO (1) WO2011126375A1 (fr)

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109022767A (zh) * 2018-09-28 2018-12-18 中国恩菲工程技术有限公司 稀土沉淀装置和稀土沉淀方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3159452A (en) * 1960-02-19 1964-12-01 Gulf Research Development Co Process for recovering thorium and rare earth values
US5034201A (en) * 1989-09-20 1991-07-23 Rhone-Poulenc Chimie Recovery of rare earth values from gypsum
GB2464733A (en) * 2008-10-24 2010-04-28 Primus Inter Pares As A method of extracting rare earth elements from carbonate-containing minerals

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3159452A (en) * 1960-02-19 1964-12-01 Gulf Research Development Co Process for recovering thorium and rare earth values
US5034201A (en) * 1989-09-20 1991-07-23 Rhone-Poulenc Chimie Recovery of rare earth values from gypsum
GB2464733A (en) * 2008-10-24 2010-04-28 Primus Inter Pares As A method of extracting rare earth elements from carbonate-containing minerals

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
ANDERSEN, T., SECONDARY PROCESSES IN CARBONATITES: PETROLOGY OF "RØDBERG" (HEMATITE-CALCITE-DOLOMITE CARBONATITE) IN FEN CENTRAL COMPLEX, TELEMARK (SOUTH NORWAY) LITHOS, vol. 17, 1984, pages 227 - 245
BYERS, CHARLES H.; WILLIAMS, DAVID F.: "Efficient recovery oflanthanides by continuous ion exchange", INDUSTRIAL & ENGINEERING CHEMISTRY RESEARCH, vol. 35, no. 4, 1996, pages 993 - 998
CARTA, GIORGIO; DECARLI; JOSEPH P., II; BYERS, CHARLES H.; SISSON, WARREN G.: "Separation of metals by continuous annular chromatography with step elution", CHEMICAL ENGINEERING COMMUNICATIONS, vol. 79, 1989, pages 207 - 27
CHI R ET AL: "Preparation of enriched cerium oxide from bastnasite with hydrochloric acid by two-step leaching", METALLURGICAL AND MATERIALS TRANSACTIONS B, SPRINGER-VERLAG, NEW YORK, vol. 37, no. 2, 1 April 2006 (2006-04-01), pages 155 - 160, XP019697838, ISSN: 1543-1916 *
NAVRATIL, J. D.; MURPHY, A.; SUN, D.: "Mixed solvent extraction-annular chromatographic systems for f-element separation and purification", PROCESS METALLURGY, 1992, pages 1151 - 1156
WAKUI, Y.; MATSUNAGA, H.; SUZUKI, T.M.: "Distribution of Rare Earth Elements between (2-Ethylhexyl Hydrogen 2-Ethylhexylphosphonate)-Impregnated Resin and Acid Aqueous solution", ANALYTICAL SCIENCES, vol. 4, 1988, pages 325 - 327

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN109022767A (zh) * 2018-09-28 2018-12-18 中国恩菲工程技术有限公司 稀土沉淀装置和稀土沉淀方法

Also Published As

Publication number Publication date
NO20121127A1 (no) 2012-10-05

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