WO1989008723A1 - Recovery of lithium from a lithium bearing silicate ore - Google Patents

Recovery of lithium from a lithium bearing silicate ore Download PDF

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Publication number
WO1989008723A1
WO1989008723A1 PCT/GB1989/000235 GB8900235W WO8908723A1 WO 1989008723 A1 WO1989008723 A1 WO 1989008723A1 GB 8900235 W GB8900235 W GB 8900235W WO 8908723 A1 WO8908723 A1 WO 8908723A1
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WO
WIPO (PCT)
Prior art keywords
lithium
alkali metal
process according
chloride
recovery
Prior art date
Application number
PCT/GB1989/000235
Other languages
French (fr)
Inventor
Derek John Fray
Paramjit Mahi
Original Assignee
The British Petroleum Company Plc
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 The British Petroleum Company Plc filed Critical The British Petroleum Company Plc
Publication of WO1989008723A1 publication Critical patent/WO1989008723A1/en

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Classifications

    • CCHEMISTRY; METALLURGY
    • C22METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
    • C22BPRODUCTION AND REFINING OF METALS; PRETREATMENT OF RAW MATERIALS
    • C22B26/00Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10Obtaining alkali metals
    • C22B26/12Obtaining lithium
    • YGENERAL 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
    • Y02TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02PCLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P10/00Technologies related to metal processing
    • Y02P10/20Recycling

Definitions

  • the present invention relates to the recovery of lithium containing ores and more particularly to the recovery of lithium from lithium bearing silicate ores.
  • the product from the reactor is a solid containing potassium spodumene and there is too much residual potassium chloride present for the solid to be fed directly to electrolysis cells for recovery of metallic lithium.
  • the salts are leached from the reactor solid and the lithium subsequently precipitated as lithium carbonate by the addition of sodium carbonate and then presumably the lithium carbonate is reacted with hydrochloric acid to form lithium chloride.
  • This entails the consumption of sodium carbonate and hydrochloric acid and the discarding of the resultant waste solution.
  • the present invention involves less reactant consumption and may enable recycling of the salt to the reactor after the extraction of the lithium.
  • a process for the recovery of lithium from a lithium bearing silicate ore comprising the steps of (a) mixing a concentrate of the lithium bearing silicate ore with an alkali metal chloride at a mole ratio of 1 to 7 of lithium ion to alkali metal ion, (b) heating the mixture at a temperature of 900 to 1300*C, and (c) grinding the residue with water-free ethanol to thereby selectively remove the lithium ion.
  • the lithium ion (in the form of lithium chloride) may then be separated from the ethanol by, say, evaporation and the ethanol recycled to the grinding stage.
  • the solids coated with ethanol may then be further dried e.g. in a fluidised bed at 100'C and the ethanol also recycled. High purity lithium may then be obtained by a conventional molten salt electrolytic process.
  • the lithium bearing silicate ore is preferably spodumene of formula Li2 ⁇ .AI2O3.4Si ⁇ 2-
  • the alkali metal chloride may be either a single salt such as potassium chloride or a mixture of alkali metal chlorides. In the case where the alkali metal is potassium chloride, it is preferred that the ratio of concentrate to potassium chloride has a mole ratio of about 1:2.5 (Li + :K + ).
  • the temperature of the process is preferably 950*C to 1200*C at atmospheric pressure and elevated pressures may also be used.
  • the reaction time of step (b) may vary from about 10 minutes to 3 hours.
  • the lithium bearing silicate ore (spodumene) is ground to a suitable particle size in a ball mill 1 and mixed with an alkali metal chloride in a solids mixer 2.
  • the mixture is passed to a rotary kiln 3 and subjected to heat treatment at about llOO'C.
  • a typical time period for the heat treatment is from 15 to 60 minutes.
  • the alkali metal chloride is usually potassium or sodium chloride but may also be a mixture of chlorides.
  • the solid reacted mixture was then passed to a rotary cooler 4 at about 50*C and thence ground in a ball mill 5.
  • the ground solid reacted mixture was then passed to an ethanol leach system for treatment with water free ethanol.
  • the system comprises three stirred baths 6 arranged in series, the slurry passing through the baths successively.
  • the product from the final bath consists of two streams, a solution stream of lithium salt (chloride) dissolved in ethanol and a solids stream (wet with ethanol).
  • the solution stream of lithium chloride in ethanol is passed to a spray drying system 7 in which the ethanol is evaporated off and recovered for subsequent re-use in the process.
  • the resultant lithium chloride solids are then passed to an electrolysis cell 8 to produce the lithium metal.
  • the ethanol wet solids stream is dried (the evaporated ethanol being subsequently re-used) and subjected to a water leach process in the stirred vessel 9 to recover dry potassium chloride for subsequent re-use in the process from the waste silicate solids using filter 10, crystalliser 11 and dryer 12.
  • the drawing shows a schematic flowsheet for the recovery of lithium metal from a spodumene concentrate.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Environmental & Geological Engineering (AREA)
  • General Life Sciences & Earth Sciences (AREA)
  • Geology (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Metallurgy (AREA)
  • Organic Chemistry (AREA)
  • Manufacture And Refinement Of Metals (AREA)
  • Electrolytic Production Of Non-Metals, Compounds, Apparatuses Therefor (AREA)
  • Silicates, Zeolites, And Molecular Sieves (AREA)

Abstract

Process for the recovery of lithium from a lithium bearing silicate ore in which a concentrate of the lithium bearing silicate ore is mixed with an alkali metal chloride at a mole ratio of 1 to 7 of lithium ion to alkali metal ion. The mixture is heated at a temperature of 900 to 1300°C and the residue is ground with water free ethanol to thereby selectively remove the lithium ion.

Description

RECOVERY OF LITHIUM FROM A LITHIUM BEARING SILICATE ORE
The present invention relates to the recovery of lithium containing ores and more particularly to the recovery of lithium from lithium bearing silicate ores.
A number of processes have been proposed for the recovery of lithium from ores. For example, treatment of the ore with a strong acid to dissolve the lithium. However, recovery of the lithium values in a pure state is rendered difficult by the co-dissolution of other metals in the ore such as aluminium or iron which acts as contaminants. It is known (US 2893828) to recover lithium from lithium bearing silicates such as spodumene by mixing with an alkali metal halide such as potassium chloride and a refractory material such as silica and heating at a temperature between about 980*C and 1100'C until substantially all of the lithium has been converted to lithium chloride. The lithium chloride is then extracted from the residue by water leaching.
In the process of US 2893838 the product from the reactor is a solid containing potassium spodumene and there is too much residual potassium chloride present for the solid to be fed directly to electrolysis cells for recovery of metallic lithium. In US 2893828 the salts are leached from the reactor solid and the lithium subsequently precipitated as lithium carbonate by the addition of sodium carbonate and then presumably the lithium carbonate is reacted with hydrochloric acid to form lithium chloride. This entails the consumption of sodium carbonate and hydrochloric acid and the discarding of the resultant waste solution. The present invention involves less reactant consumption and may enable recycling of the salt to the reactor after the extraction of the lithium. Thus according to the present invention there is provided a process for the recovery of lithium from a lithium bearing silicate ore comprising the steps of (a) mixing a concentrate of the lithium bearing silicate ore with an alkali metal chloride at a mole ratio of 1 to 7 of lithium ion to alkali metal ion, (b) heating the mixture at a temperature of 900 to 1300*C, and (c) grinding the residue with water-free ethanol to thereby selectively remove the lithium ion.
The lithium ion (in the form of lithium chloride) may then be separated from the ethanol by, say, evaporation and the ethanol recycled to the grinding stage. The solids coated with ethanol may then be further dried e.g. in a fluidised bed at 100'C and the ethanol also recycled. High purity lithium may then be obtained by a conventional molten salt electrolytic process.
The lithium bearing silicate ore is preferably spodumene of formula Li2θ.AI2O3.4Siθ2- The alkali metal chloride may be either a single salt such as potassium chloride or a mixture of alkali metal chlorides. In the case where the alkali metal is potassium chloride, it is preferred that the ratio of concentrate to potassium chloride has a mole ratio of about 1:2.5 (Li+:K+). The temperature of the process is preferably 950*C to 1200*C at atmospheric pressure and elevated pressures may also be used. The reaction time of step (b) may vary from about 10 minutes to 3 hours.
In an embodiment of the present process, by use of potassium chloride only in the reactor ion exchange step, on cooling the potassium chloride and lithium chloride form a simple eutectic whereas the presence of sodium chloride allows the formation of a sodium chloride/lithium chloride compound. It is therefore much more straightforward to leach lithium chloride from a discrete phase, as in a eutectic, than from a compound. The invention will now be described by way of example only and with reference to the accompanying drawing.
The lithium bearing silicate ore (spodumene) is ground to a suitable particle size in a ball mill 1 and mixed with an alkali metal chloride in a solids mixer 2. The mixture is passed to a rotary kiln 3 and subjected to heat treatment at about llOO'C. A typical time period for the heat treatment is from 15 to 60 minutes. The alkali metal chloride is usually potassium or sodium chloride but may also be a mixture of chlorides. The solid reacted mixture was then passed to a rotary cooler 4 at about 50*C and thence ground in a ball mill 5.
The ground solid reacted mixture was then passed to an ethanol leach system for treatment with water free ethanol. The system comprises three stirred baths 6 arranged in series, the slurry passing through the baths successively. The product from the final bath consists of two streams, a solution stream of lithium salt (chloride) dissolved in ethanol and a solids stream (wet with ethanol).
The solution stream of lithium chloride in ethanol is passed to a spray drying system 7 in which the ethanol is evaporated off and recovered for subsequent re-use in the process. The resultant lithium chloride solids are then passed to an electrolysis cell 8 to produce the lithium metal.
The ethanol wet solids stream is dried (the evaporated ethanol being subsequently re-used) and subjected to a water leach process in the stirred vessel 9 to recover dry potassium chloride for subsequent re-use in the process from the waste silicate solids using filter 10, crystalliser 11 and dryer 12.
The drawing shows a schematic flowsheet for the recovery of lithium metal from a spodumene concentrate.

Claims

Claims:
1. A process for the recovery of lithium from a lithium bearing silicate ore comprising the steps of (a) mixing a concentrate of the lithium bearing silicate ore with an alkali metal chloride at a mole ratio of 1 to 7 of lithium ion to alkali metal ion, (b) heating the mixture at a temperature of 900 to 1300*C, and (c) grinding the residue with water-free ethanol to thereby selectively remove the lithium ion.
2. A process according to claim 1 in which the lithium bearing silicate ore is spodumene.
3. A process according to claim 1 or claim 2 in which the alkali metal chloride is in the form of a single or a mixture of alkali metal chloride.
4. A process according to any of claims 1 to 3 in which the alkali metal chloride is potassium chloride and the ratio of concentrate to potassium chloride has a mole ratio of about 1:2.5 (Li+:K+).
5. A process according to any of the preceding claims in which the temperature is from 950*C to 1200*C.
6. A process according to any of the preceding claims in which the reaction time of step (b) is from 10 minutes to 3 hours.
7. A process according to any of the preceding claims in which high purity lithium is obtained from the lithium ion by a molten salt electrolyic process.
8. Lithium whenever produced by a process according to any of the preceding claims.
PCT/GB1989/000235 1988-03-17 1989-03-09 Recovery of lithium from a lithium bearing silicate ore WO1989008723A1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB8806334 1988-03-17
GB8806334A GB8806334D0 (en) 1988-03-17 1988-03-17 Recovery process

Publications (1)

Publication Number Publication Date
WO1989008723A1 true WO1989008723A1 (en) 1989-09-21

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PCT/GB1989/000235 WO1989008723A1 (en) 1988-03-17 1989-03-09 Recovery of lithium from a lithium bearing silicate ore

Country Status (4)

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AU (1) AU3355389A (en)
GB (1) GB8806334D0 (en)
WO (1) WO1989008723A1 (en)
ZW (1) ZW3689A1 (en)

Cited By (26)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2299253C2 (en) * 2005-09-26 2007-05-20 Открытое акционерное общество "Новосибирский завод химконцентратов" Method of extraction of lithium from the mixture of the lepidolite and spodumene concentrates
RU2319756C2 (en) * 2005-12-22 2008-03-20 Открытое акционерное общество "Новосибирский завод химконцентратов" Method used for extraction of lithium from the mixture of lithium concentrates
RU2319755C2 (en) * 2005-12-22 2008-03-20 Открытое акционерное общество "Новосибирский завод химконцентратов" Method used for extraction of lithium out of the lepidolithium concentrate
RU2347829C2 (en) * 2007-12-17 2009-02-27 Федеральное государственное образовательное учреждение высшего профессионального образования "Государственный технологический университет "Московский институт стали и сплавов" Method of producing lithium hydroxide out of spodumene concentrate
RU2347828C2 (en) * 2007-12-17 2009-02-27 Федеральное государственное образовательное учреждение высшего профессионального образования "Государственный технологический университет "Московский институт стали и сплавов" Method of processing spodumene concentrate
RU2347830C2 (en) * 2007-12-17 2009-02-27 Федеральное государственное образовательное учреждение высшего профессионального образования "Государственный технологический университет "Московский институт стали и сплавов" Method of processing spodumene concentrates
RU2352659C2 (en) * 2008-02-06 2009-04-20 Федеральное государственное образовательное учреждение высшего профессионального образования "Государственный технологический университет "Московский институт стали и сплавов" Extraction method of lithium from mixture of lepidolite and spodumene concentrates
RU2352658C2 (en) * 2008-02-06 2009-04-20 Федеральное государственное образовательное учреждение высшего профессионального образования "Государственный технологический университет "Московский институт стали и сплавов" Method of receiving lithium-bearing alumina from spodumene concentrate
RU2354727C2 (en) * 2008-02-05 2009-05-10 Государственное общеобразовательное учреждение высшего профессионального образования "Уральский государственный технический университет-УПИ" Method of berillium extraction from raw mineral material
RU2356963C2 (en) * 2008-02-05 2009-05-27 Государственное образовательное учреждение высшего профессионального образования "Уральский государственный технический университет-УПИ" Extraction method of beryllium from beryllium-bearing spodumene concentrate
RU2356961C2 (en) * 2008-02-05 2009-05-27 Государственное общеобразовательное учреждение высшего профессионального образования "Уральский государственный технический университет-УПИ" Method of lithium extraction from mineral raw materials
RU2360017C2 (en) * 2007-10-04 2009-06-27 Открытое акционерное общество "Ведущий научно-исследовательский институт химической технологии" (ОАО "ВНИИХТ") METHOD OF CONCENTRATED SOLUTIONS OF LITHIUM SULFATE RECEIVING FROM CONCENTRATE OF β-SPODUMENE
RU2360986C2 (en) * 2007-09-21 2009-07-10 Открытое акционерное общество "Ведущий научно-исследовательский институт химической технологии" (ОАО "ВНИИХТ") TREATMENT METHOD OF CONCENTRATE OF β-SPODUMENE
RU2361939C2 (en) * 2008-02-29 2009-07-20 Институт геологии и минералогии Сибирского отделения РАН PROCESSING METHOD OF CONCENTRATE β-SPODUMENE
RU2371492C2 (en) * 2008-02-05 2009-10-27 Государственное общеобразовательное учреждение высшего профессионального образования "Уральский государственный технический университет-УПИ" Extraction method of lithium from spodumene-containing beryllium concentrate
RU2390571C1 (en) * 2008-09-15 2010-05-27 Институт химии твердого тела и механохимии Сибирского отделения Российской Академии наук Статус государственного учреждения (ИХТТМ СО РАН) Procedure for complex processing crude spodumene ore for production of lithium products and cements
CN101892394B (en) * 2009-12-18 2013-07-24 中南大学 Method and device for extracting lithium from lithium mica
RU2531019C1 (en) * 2013-09-16 2014-10-20 Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина Mix material for extraction of lithium from lithium concentrates mix
RU2546952C1 (en) * 2013-12-03 2015-04-10 Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Уральский федеральный университет имеми первого Президента России Б.Н. Ельцина" Method of working of lithium concentrates mixture
RU2547052C1 (en) * 2013-12-09 2015-04-10 Федеральное государственное автономное образовательное учреждение высшего профессионального образования "Уральский федеральный университет имени первого Президента России Б.Н. Ельцина Method of lithium concentrate processing
RU2547366C2 (en) * 2013-02-25 2015-04-10 Акционерное общество "Ульбинский металлургический завод" Method of processing beryllium fluorite-containing concentrates
RU2624749C2 (en) * 2015-12-01 2017-07-06 Федеральное государственное автономное образовательное учреждение высшего образования "Национальный исследовательский Томский политехнический университет" Method of obtaining beryllium oxide and beryllium metal
RU2646296C1 (en) * 2017-05-02 2018-03-02 Федеральное государственное автономное образовательное учреждение высшего образования Уральский федеральный университет имени первого Президента России Б.Н. Ельцина Lepidolithic concentrate processing method
RU2663021C1 (en) * 2017-07-17 2018-08-01 Акционерное общество "Ведущий научно-исследовательский институт химической технологии" Method of lithuania extraction from sphodumene
WO2020257074A1 (en) * 2019-06-21 2020-12-24 Xerion Advanced Battery Corp. Methods for extracting lithium from spodumene
KR20210080058A (en) * 2019-12-20 2021-06-30 주식회사 포스코 Method of extracting lithium from lithium-containing ore

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GB269878A (en) * 1926-04-22 1927-09-08 Metallbank & Metallurg Ges Ag Process of treating lithium-containing silicates by means of neutral alkali salts
US2893828A (en) * 1954-08-09 1959-07-07 Int Minerals & Chem Corp Lithium values recovery process
US3268290A (en) * 1963-11-04 1966-08-23 Dow Chemical Co Recovery of lithium chloride from mixtures of other salts and metals
EP0250342A1 (en) * 1986-06-18 1987-12-23 Pechiney Process for recovering aluminium and lithium from metallic scrap
JPS63140096A (en) * 1986-12-02 1988-06-11 Sumitomo Light Metal Ind Ltd Manufacturing method for high-purity metallic lithium

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB269878A (en) * 1926-04-22 1927-09-08 Metallbank & Metallurg Ges Ag Process of treating lithium-containing silicates by means of neutral alkali salts
US2893828A (en) * 1954-08-09 1959-07-07 Int Minerals & Chem Corp Lithium values recovery process
US3268290A (en) * 1963-11-04 1966-08-23 Dow Chemical Co Recovery of lithium chloride from mixtures of other salts and metals
EP0250342A1 (en) * 1986-06-18 1987-12-23 Pechiney Process for recovering aluminium and lithium from metallic scrap
JPS63140096A (en) * 1986-12-02 1988-06-11 Sumitomo Light Metal Ind Ltd Manufacturing method for high-purity metallic lithium

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Title
Patent Abstracts of Japan, vol. 12, no. 398 (C-538)(3245), 21 October 1988, & JP-A-63140096 (SUMITOMO LIGHT METAL IND. LTD) 11 Juni 1988 *

Cited By (28)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2299253C2 (en) * 2005-09-26 2007-05-20 Открытое акционерное общество "Новосибирский завод химконцентратов" Method of extraction of lithium from the mixture of the lepidolite and spodumene concentrates
RU2319756C2 (en) * 2005-12-22 2008-03-20 Открытое акционерное общество "Новосибирский завод химконцентратов" Method used for extraction of lithium from the mixture of lithium concentrates
RU2319755C2 (en) * 2005-12-22 2008-03-20 Открытое акционерное общество "Новосибирский завод химконцентратов" Method used for extraction of lithium out of the lepidolithium concentrate
RU2360986C2 (en) * 2007-09-21 2009-07-10 Открытое акционерное общество "Ведущий научно-исследовательский институт химической технологии" (ОАО "ВНИИХТ") TREATMENT METHOD OF CONCENTRATE OF β-SPODUMENE
RU2360017C2 (en) * 2007-10-04 2009-06-27 Открытое акционерное общество "Ведущий научно-исследовательский институт химической технологии" (ОАО "ВНИИХТ") METHOD OF CONCENTRATED SOLUTIONS OF LITHIUM SULFATE RECEIVING FROM CONCENTRATE OF β-SPODUMENE
RU2347829C2 (en) * 2007-12-17 2009-02-27 Федеральное государственное образовательное учреждение высшего профессионального образования "Государственный технологический университет "Московский институт стали и сплавов" Method of producing lithium hydroxide out of spodumene concentrate
RU2347828C2 (en) * 2007-12-17 2009-02-27 Федеральное государственное образовательное учреждение высшего профессионального образования "Государственный технологический университет "Московский институт стали и сплавов" Method of processing spodumene concentrate
RU2347830C2 (en) * 2007-12-17 2009-02-27 Федеральное государственное образовательное учреждение высшего профессионального образования "Государственный технологический университет "Московский институт стали и сплавов" Method of processing spodumene concentrates
RU2371492C2 (en) * 2008-02-05 2009-10-27 Государственное общеобразовательное учреждение высшего профессионального образования "Уральский государственный технический университет-УПИ" Extraction method of lithium from spodumene-containing beryllium concentrate
RU2354727C2 (en) * 2008-02-05 2009-05-10 Государственное общеобразовательное учреждение высшего профессионального образования "Уральский государственный технический университет-УПИ" Method of berillium extraction from raw mineral material
RU2356963C2 (en) * 2008-02-05 2009-05-27 Государственное образовательное учреждение высшего профессионального образования "Уральский государственный технический университет-УПИ" Extraction method of beryllium from beryllium-bearing spodumene concentrate
RU2356961C2 (en) * 2008-02-05 2009-05-27 Государственное общеобразовательное учреждение высшего профессионального образования "Уральский государственный технический университет-УПИ" Method of lithium extraction from mineral raw materials
RU2352658C2 (en) * 2008-02-06 2009-04-20 Федеральное государственное образовательное учреждение высшего профессионального образования "Государственный технологический университет "Московский институт стали и сплавов" Method of receiving lithium-bearing alumina from spodumene concentrate
RU2352659C2 (en) * 2008-02-06 2009-04-20 Федеральное государственное образовательное учреждение высшего профессионального образования "Государственный технологический университет "Московский институт стали и сплавов" Extraction method of lithium from mixture of lepidolite and spodumene concentrates
RU2361939C2 (en) * 2008-02-29 2009-07-20 Институт геологии и минералогии Сибирского отделения РАН PROCESSING METHOD OF CONCENTRATE β-SPODUMENE
RU2390571C1 (en) * 2008-09-15 2010-05-27 Институт химии твердого тела и механохимии Сибирского отделения Российской Академии наук Статус государственного учреждения (ИХТТМ СО РАН) Procedure for complex processing crude spodumene ore for production of lithium products and cements
CN101892394B (en) * 2009-12-18 2013-07-24 中南大学 Method and device for extracting lithium from lithium mica
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