WO2023275345A2 - Processes for the recovery and reuse of sulphate reagents from leach liquors derived from lithium micas - Google Patents

Processes for the recovery and reuse of sulphate reagents from leach liquors derived from lithium micas Download PDF

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Publication number
WO2023275345A2
WO2023275345A2 PCT/EP2022/068229 EP2022068229W WO2023275345A2 WO 2023275345 A2 WO2023275345 A2 WO 2023275345A2 EP 2022068229 W EP2022068229 W EP 2022068229W WO 2023275345 A2 WO2023275345 A2 WO 2023275345A2
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Prior art keywords
lithium
leach liquor
mica
salt
glauber salt
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PCT/EP2022/068229
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French (fr)
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WO2023275345A3 (en
Inventor
Roderick SMITH
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British Lithium Limited
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Publication of WO2023275345A3 publication Critical patent/WO2023275345A3/en

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    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • C22B1/06—Sulfating roasting
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D15/00—Lithium compounds
    • C01D15/06—Sulfates; Sulfites
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
    • C01B33/00—Silicon; Compounds thereof
    • C01B33/20—Silicates
    • C01B33/36—Silicates having base-exchange properties but not having molecular sieve properties
    • C01B33/38—Layered base-exchange silicates, e.g. clays, micas or alkali metal silicates of kenyaite or magadiite type
    • C01B33/42—Micas ; Interstratified clay-mica products
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01D—COMPOUNDS OF ALKALI METALS, i.e. LITHIUM, SODIUM, POTASSIUM, RUBIDIUM, CAESIUM, OR FRANCIUM
    • C01D5/00—Sulfates or sulfites of sodium, potassium or alkali metals in general
    • C01D5/16—Purification
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/02—Roasting processes
    • 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
    • C22B26/00—Obtaining alkali, alkaline earth metals or magnesium
    • C22B26/10—Obtaining alkali metals
    • C22B26/12—Obtaining lithium
    • 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
    • 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
    • C22B1/00—Preliminary treatment of ores or scrap
    • C22B1/14—Agglomerating; Briquetting; Binding; Granulating
    • C22B1/24—Binding; Briquetting ; Granulating
    • C22B1/2406—Binding; Briquetting ; Granulating pelletizing
    • 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

  • the present invention relates to processes for the recovery of Glauber salt from a leach liquor derived from aqueous leaching of lithium-mica minerals after calcining in the presence of sulphate salts to produce a water-soluble lithium.
  • the processes of the present invention can be used to achieve >95% recovery of Glauber Salt for reuse as a calcining reagent.
  • Lithium micas present an important source of lithium that is likely to grow in significance as the demand for lithium is expected to increase considerably in light of a worldwide effort to reduce carbon emissions.
  • Lithium is predominantly used to make battery chemicals. It can be extracted from brines, and from hard rock deposits containing spodumene. The former involves pumping and evaporation of vast quantities of water to extract and concentrate brines before impurity removal to produce a final lithium salt product.
  • Spodumene a lithium-bearing pyroxene mineral, is mined from hard rock deposits and typically requires calcining (also known as roasting) and acid leaching to produce a lithium-enriched solution or pregnant leach solution that is then purified to obtain a final lithium salt product.
  • lithium in mica can also present potentially economic deposits. These occur within granites in Europe and elsewhere, which also contain gangue minerals, principally quartz and feldspar. However, lithium is currently not extracted commercially from lithium-mica and so to exploit these deposits commercially there is a need to develop environmentally sustainable and economic methods for extraction of lithium salts of acceptable quality from these micas.
  • Lithium-mica minerals such as zinnwaldite (KLiFeAI(AISi 3 )Oio(OH,F) 2 ; potassium lithium iron aluminium silicate hydroxide fluoride) and lepidolite (KLhAISUOioiCHF ) are tri-octahedral mica minerals that exist in a solid solution series whose end members are siderophyllite (KFe 2 AI(Al 2 Si 2 0io)(F,OH) 2 ; potassium iron aluminium silicate hydroxide fluoride) and polylithionite (KLi 2 AI(Si 4 0io)(F,OH) 2 ;potassium lithium aluminium silicate hydroxide fluoride).
  • KFeAI(AISi 3 )Oio(OH,F) 2 potassium lithium iron aluminium silicate hydroxide fluoride
  • lepidolite KLhAISUOioiCHF
  • LiAI(Si 2 C> 6 ) lithium aluminium inosilicate
  • the lithium content of pure zinnwaldite is 1.59% by mass, compared to 3.73% for spodumene.
  • Calcining of lithium mica in the presence of sulphate ions such as those contained in sodium or calcium sulphate provides a means of rendering the lithium contained in the minerals water soluble through a solid-state reaction.
  • An aqueous leaching step after the calcining brings the lithium and other mobilised species, including the sulphates, alkalis and earth alkalis into solution in the form of aqueous cations.
  • these impurities need removing from the pregnant leach solution as part of impurity removal steps to facilitate purification of lithium to a saleable quality of lithium salt.
  • disposal of the sulphate ions would be a wasteful and environmentally unsustainable practice as well as being detrimental to the economics of the lithium refining process.
  • the present invention relates to a method of recovery and recycling of reagents to abate the environmental impact and improve the economics of the purification of lithium leach solutions.
  • lithium-mica rich ores or concentrates The major sources of commercially mined lithium are from brine solutions (principally in South America) and spodumene containing ores (principally in Western Australia). Currently, there is no commercial production of lithium from lithium-mica rich ores or concentrates.
  • Sulphate salts including lithium sulphate
  • lithium sulphate are readily soluble and therefore provide a clear route towards producing a lithium-enriched leach liquor. This requires calcining of lithium mica at a temperature above 800° C in the presence of a salt of sulphate such as sodium sulphate or calcium sulphate (which is also known as gypsum, for example anhydrous gypsum). Following leaching of the calcined product, a lithium-containing leach liquor is produced that also contains sodium ions/calcium ions and sulphate ions in solution.
  • a salt of sulphate such as sodium sulphate or calcium sulphate (which is also known as gypsum, for example anhydrous gypsum).
  • Glauber salt sodium sulphate decahydrate precipitated (in particular crystallised) and recycled from a liquor derived from the leaching of calcined lithium mica-material containing feed by cooling of said calcined- leach liquor.
  • a process A1 for recovering Glauber salt from a leach liquor derived from the leaching of calcined lithium mica-material comprising: calcining a lithium mica-material containing feed in the presence of a sulphate salt (for example sodium sulphate or calcium sulphate) and at least one of: lime and/or calcium carbonate to provide a calcined lithium mica-material containing feed; aqueous leaching of the calcined lithium mica-material containing feed at a solids percentage in the slurry of between 5% and 40%, operating at atmospheric pressure and at temperatures between 5°C and 95°C to generate leached, calcined lithium mica-material and a leach liquor; cooling the leach liquor to a predetermined temperature to cause Glauber salt to precipitate to generate lithium-enriched leach liquor; and recovery of the Glauber salt.
  • a sulphate salt for example sodium sulphate or calcium sulphate
  • lime and/or calcium carbonate to provide a calcined lithium mica-material
  • a process A2 for providing a Glauber salt from a liquor derived from the leaching of calcined lithium mica-material containing feed comprising: exposing a lithium mica-material containing feed with a Li grade in excess of 1% Li to heat (i.e.
  • calcining in the presence of sodium sulphate and at least one of: lime and/or calcium carbonate to provide a calcined lithium mica-material containing feed; aqueous leaching of the calcined lithium mica-material containing feed at a solids percentage in the slurry between 5% and 40%, operating at atmospheric pressure and at temperatures between 5°C and 95°C to generate leached calcined lithium mica-material and a leach liquor; cooling the leach liquor to a predetermined temperature to cause Glauber salt to precipitate to generate lithium-enriched leach liquor; and recovery of the Glauber salt by filtration at a temperature below 33°C.
  • the leach liquor following the leaching step contains dissolved lithium ions, and other ions such as sodium ions, calcium ions and/or sulphate ions.
  • the leach liquor is enriched in lithium following the precipitation of the Glauber salt.
  • a process B1 for recovering Glauber salt from a leach liquor derived from the leaching of calcined lithium mica- material comprising: calcining a lithium mica-material containing feed in the presence of a sulphate salt and at least one of: lime and/or calcium carbonate to provide a calcined lithium mica-material containing feed; aqueous leaching of the calcined lithium mica-material containing feed at a solids percentage in the slurry of between 5% and 40%, operating at atmospheric pressure and at temperatures between 5°C and 95°C to generate leached, calcined lithium mica-material and a leach liquor; adding one or more hydroxide salt(s) and/or carbonate salt(s) to the leach liquor to cause the precipitation of lithium, which is then removed from the leach liquor; cooling the leach liquor to a predetermined temperature to cause Glauber salt to precipitate; and recovery of the Glauber salt.
  • a process Cl for recovering Glauber salt from a leach liquor derived from the leaching of calcined lithium mica- material comprising: recovering Glauber salt from a leach liquor using process Al, A2 or B1 as herein described; and reintroducing the recovered Glauber salt into the step of exposing the lithium mica material to heat (i.e. calcining).
  • the recovered Glauber salt is mixed with the calcining feed in the first steps of processes Al, A2 or Bl, thereby reusing the Glauber salt in the calcining process.
  • This provides the advantage of reducing the quantity of waste material, and reducing the amount of calcining feed materials that are required. Furthermore, lithium that is lost to the Glauber salt precipitation is also recovered, thereby increasing overall lithium recovery.
  • the Glauber salt may precipitate in crystalline form, in which case the precipitation can be referred to as "crystallisation”.
  • the calcining step preferably comprises heating lithium mica material in the presence of sodium sulphate (which may comprise recovered Glauber salt), for example to a temperature between 750 and 850 °C at a residence time in the hot zone of less than 50 minutes and under an oxidising atmosphere.
  • sodium sulphate which may comprise recovered Glauber salt
  • a higher temperature range of between 800 and 1100 °C is preferred.
  • the feed in the calcining step also contains at least one of: lime and/or calcium carbonate.
  • Lime in the context of the present invention contains calcium oxide and/or calcium hydroxide.
  • the feed in the calcining step also contains one of calcium hydroxide and calcium carbonate.
  • the Glauber salt is preferably sodium sulphate decahydrate.
  • the cooling step may comprise cooling the leach liquor to a temperature of less than 33 °C, for example to a temperature of less than 10 °C, to achieve a high yield of Glauber salt for recycling as a reagent in the calcining step.
  • the precipitation of the Glauber salt may further comprise the addition of a seeding material to provide nucleation points to achieve a high yield of Glauber salt for recycling as a reagent.
  • the seeding material may comprise one or more of: calcium sulphate seed crystals and/or sodium sulphate seed crystals and/or potassium sulphate seed crystals and/or magnesium sulphate seed crystals.
  • the concentration (by weight) of lithium in leach liquor following precipitation of the Glauber salt is increased by 40%, for example by 50%, by 60%, by 65% or by 70%. In one embodiment, the concentration (by weight) of lithium in leach liquor following precipitation of the Glauber salt is increased by 63%.
  • the processes of the invention may further comprise the addition of one or more hydroxide salt(s) and/or carbonate salt(s) to the leach liquor.
  • the one or more hydroxide salt(s) and/or carbonate salt(s) may be included in the process ahead of crystallisation of the Glauber salt to facilitate removal of impurities from the leach liquor.
  • the impurities may include, but are not limited to, one or more of: iron, titanium, magnesium and potassium.
  • the hydroxide salt(s) and/or carbonate salt(s) are selected to preferentially cause precipitation of the impurity ions (e.g. one or more of: iron, titanium, magnesium and potassium) ratherthan the lithium ions.
  • this step is separate to step of adding one or more hydroxide salt(s) and/or carbonate salt(s) to the leach liquor to cause the precipitation of lithium.
  • the removal of impurities can be carried out at any suitable point in the process following the aqueous leaching.
  • the lithium mica-material containing feed is a milled, preferably a milled and beneficiated, feed stream.
  • the lithium mica-material containingfeed is not a powder.
  • the lithium mica-material containing feed is ground to P80 ⁇ 250 micron up to P80 ⁇ 350 micron and the mica concentrate is deslimed at 20 microns to remove "powder".
  • a coarser grind uses far less energy for grinding than a fine grind (i.e. a powder).
  • the lithium mica-material containing feed may be provided or formed from igneous rock.
  • the precipitation of lithium is suitably achieved by adding a carbonate such as sodium carbonate to the leach liquor, to cause precipitation of lithium carbonate.
  • the precipitated lithium (suitably in the form of lithium carbonate) can be removed from the leach liquor by any suitable means, for example by filtration.
  • the igneous rock may have been formed during the Variscan Orogeny.
  • the igneous rock may form for example be a felsic intrusive rock such as a granite intrusion part of the Cornubian batholith, the Bohemian Batholiths, the Moldanubian Plutonic Complex or the Central French Massif.
  • the lithium mica-material containing feed is preferably derived from naturally deposited lithium-mica-bearing sediments or anthropogenically generated waste streams or lithium- mica bearing storage dams derived from naturally deposited lithium-mica-bearing rock or sediments.
  • FIG. 1 is a schematic illustration of the Glauber salt crystallisation process according to one embodiment of the present invention.
  • Figure 2 shows an example embodiment of a precipitation apparatus used for precipitation of Glauber salt from a leach liquor derived from calcined lithium mica-material containing feed.
  • the calcining process is carried out at a temperature between 750 and 850 °C (particularly when sodium sulphate is used in the calcining step). According to another embodiment, the calcining process is carried out at a temperature between 800 and 1100 °C (particularly when calcium sulphate is used in the calcining step). Suitably, the calcining is carried out under atmospheric pressure.
  • the aqueous leaching of the calcined lithium mica-material containing feed is carried out using water which has not had the pH modified.
  • the use of acid in the present leaching process is not required.
  • the leach liquor or lithium- enriched leach liquor that forms the feed to the Glauber salt crystallisation stage of the process may contain between 0.1 and 45g/l of lithium (Li). It is however to be understood that the feed may contain any suitable lithium concentrations, for example between 1 and 20 g/l, preferably between 5 and 20 g/l.
  • the leach liquor or lithium enriched leach liquor is suitably placed within a precipitation tank for precipitation (in particular crystallisation) and subsequent recovery of the Glauber salt.
  • the leach liquor or lithium-enriched leach liquor may be cooled to a temperature between - 10 ° C and 33 °C, for example between -10 °C and 5 °C, for example between -5 °C and 5 °C to achieve crystallisation of the Glauber salt. Crystallisation of the Glauber salt may occur unaided in the presence of cooling, or with the aid of addition of seed crystals to the leach liquor or lithium-enriched leach liquor.
  • the seed crystals may be added batch-wise or at a steady addition rate to the leach liquor or lithium-enriched leach liquor.
  • the seed crystals may be one or more of: sodium sulphate, calcium sulphate or another sulphate salt, or any combination thereof.
  • the seed crystals may have any suitable particle size distribution to facilitate or aid crystallisation of the Glauber salt.
  • the seed crystals may for example have a dimension of less than 1mm.
  • the seed crystals may for example have a dimension of more than 10pm.
  • the seed crystals have a dimension which is in the range of between 10pm and 1 mm, preferably between 0.1 pm and 1 mm.
  • the seed crystals may be added at any suitable concentration to the leach liquor or lithium- enriched leach liquor. Preferably, the seed crystals are added at less than 0.01 to 1% m/m.
  • Cooling of the precipitation tank may be achieved through one or more of: immersed chilling elements, a jacketed tank system (as shown in Figure 2) or by placing in a cooled environment.
  • the leach liquor or lithium-enriched leach liquor within the precipitation tank may be unagitated during precipitation/crystallisation of the Glauber salt.
  • the lithium enriched leach liquor within the precipitation tank may be gently stirred by agitator and/or vibration.
  • the leach liquor or lithium-enriched leach liquor may be left for at least 0.1 hr to obtain a predetermined amount of Glauber salt.
  • the leach liquor or lithium- enriched leach liquor may be left for up to 24hrs to obtain a predetermined amount of Glauber salt.
  • the process may further comprise an impurity removal step.
  • the impurity removal step reduces and/or eliminates contamination of the leach liquor or lithium-enriched leach liquor through the addition of one or more impurity removal agents.
  • Impurity removal agent(s) such as sodium carbonate combined with one or more of calcium carbonate and/or calcium hydroxide may be added to the leach liquor or lithium-enriched leach liquor, prior to crystallisation/precipitation of the Glauber salt. Addition of these impurity removal agents is done at 1 - 3 % m/m for sodium carbonate and 0.01 - 0.1% m/m for calcium carbonate and/or calcium hydroxide.
  • the Glauber salt may be recovered from the leach liquor or lithium-enriched leach liquor by vacuum or pressure filtration solution.
  • the temperature is preferably maintained below 33 °C to prevent melting of the Glauber salt.
  • the Glauber salt After recovery of the Glauber salt, the Glauber salt is heated to evaporate waters of crystallisation.
  • the recovery amount is defined as the molar quantity of Glauber salt recovered as a percentage of the molar quantity of the amount of sodium sulphate used in the calcining process.
  • the Glauber salt may then be reused as a reagent in the calcining process of lithium mica.
  • This reuse further involves the dewatering of Glauber salt to a temperature between 33 °C and 105 °C to melt the crystals and evaporate waters of hydration.
  • the resultant powder or slurry is mixed with fresh Li mica-containing feed that has not been calcined, additional sodium sulphate, and one or more of calcium hydroxide or calcium carbonate for the calcination process.
  • this mixing step may be done on a powder basis ahead of the calcining step.
  • this step may include pelletisation of the sodium sulphate and other reagents with the fresh Li mica-containing feed ahead of the calcining step.
  • the recovered Glauber salt is added to a mixture containing lithium mica-material (typically in the presence of additional sodium sulphate, or in the presence of calcium sulphate) and heated for up to 50 minutes at a temperature above 800 °C before being leached to produce a leach liquor that contains lithium also contains a large quantity of sodium sulphate and/or calcium sulphate in solution as described hereinabove.
  • Glauber Salt An additional advantage of the recovery and reuse process for Glauber Salt is that any Li lost to the Glauber Salt is re-introduced as a calcining reagent along with the sodium sulphate derived from dehydration of the Glauber Salt.
  • the present invention therefore provides an economical and efficient process for the recovery of Glauber salt from a leach liquor or lithium-enriched leach liquor. Furthermore, the present invention provides an improved, environmentally friendly process, for calcining lithium containing mica-material using recovered Glauber salt.
  • a purified Li leach liquor is derived from calcining of fresh Li mica-containing feed in the presence of sodium sulphate and one of calcium hydroxide and calcium carbonate.
  • This sodium sulphate is added to the fresh Li mica-containing feed at a ratio of 0.7:1 sodium sulphate/Li-mica containing feed on a mass basis, equating to the addition of 906.8 moles of sodium sulphate to a calcining feed batch mass of 183.9kg.
  • the resultant filtered and purified Li-containing leach liquor is cooled to a temperature between -5°C and 5°C, sufficiently cold to crystalise out the sodium sulphate in the form of Glauber salt but still warm enough to prevent formation of ice in this leach liquor.
  • This crystallisation process yields a slurry containing a mixture of solid Glauber salt crystals and a leach liquor which is further enriched in Li due to waters of hydration being incorporated into the Glauber salt.
  • This slurry is transferred to a filtration unit where the Glauber salt crystals are separated from the Li-enriched leach liquor to allow dehydration of the former and further refining to recover lithium into a saleable form from the latter.
  • This filtration step is carried out with the slurry temperature maintained at a temperature below 33°C to prevent melting of the Glauber salt crystals.
  • the crystallisation process in the presented example takes 618.6 moles of sodium sulphate out of solution and increases the Li concentration in the leach liquor from 82.4g/l Li to 133.9g/l Li.
  • the yield of sodium sulphate contained in the Glauber salt as a percentage of the feed that went into the calcining process in this example is 68.2%.
  • the solids from the filtration process are heated to a temperature of 60°C to gently evaporate the water of hydration contained in the Glauber salt. This process may be carried out till all water is evaporated and dehydrated sodium sulphate is left for re-use in the calcining process, mixed in as a powder.
  • a small quantity of water may be left behind in the sodium sulphate and Glauber salt mixture to aid binding together of the sodium sulphate/Glauber salt/Li mica/calcium carbonate and/or calcium hydroxide mixture.

Abstract

The present invention relates to processes for recovering Glauber salt from a leach liquor derived from the leaching of calcined lithium mica material. An exemplary process comprises calcining a lithium mica-material containing feed in the presence of a sulphate salt and at least one of: lime and/or calcium carbonate to provide a calcined lithium mica-material containing feed. The feed is then subjected to aqueous leaching at a solids percentage in the slurry of between 5% and 40%, operating at atmospheric pressure and at temperatures between 5°C and 95°C to generate leached, calcined lithium mica-material and a leach liquor. The leach liquor is then cooled to a predetermined temperature to cause Glauber salt to precipitate to generate lithium-enriched leach liquor; and recovery of the Glauber salt. The Glauber salt is then suitably reintroduced into the calcining step.

Description

PROCESSES FOR THE RECOVERY AND REUSE OF SULPHATE REAGENTS FROM LEACH
LIQUORS DERIVED FROM LITHIUM MICAS
The present invention relates to processes for the recovery of Glauber salt from a leach liquor derived from aqueous leaching of lithium-mica minerals after calcining in the presence of sulphate salts to produce a water-soluble lithium. The processes of the present invention can be used to achieve >95% recovery of Glauber Salt for reuse as a calcining reagent.
BACKGROUND OF INVENTION
Lithium micas present an important source of lithium that is likely to grow in significance as the demand for lithium is expected to increase considerably in light of a worldwide effort to reduce carbon emissions.
Lithium is predominantly used to make battery chemicals. It can be extracted from brines, and from hard rock deposits containing spodumene. The former involves pumping and evaporation of vast quantities of water to extract and concentrate brines before impurity removal to produce a final lithium salt product. Spodumene, a lithium-bearing pyroxene mineral, is mined from hard rock deposits and typically requires calcining (also known as roasting) and acid leaching to produce a lithium-enriched solution or pregnant leach solution that is then purified to obtain a final lithium salt product.
Alongside spodumene, lithium in mica can also present potentially economic deposits. These occur within granites in Europe and elsewhere, which also contain gangue minerals, principally quartz and feldspar. However, lithium is currently not extracted commercially from lithium-mica and so to exploit these deposits commercially there is a need to develop environmentally sustainable and economic methods for extraction of lithium salts of acceptable quality from these micas.
Lithium-mica minerals such as zinnwaldite (KLiFeAI(AISi3)Oio(OH,F)2; potassium lithium iron aluminium silicate hydroxide fluoride) and lepidolite (KLhAISUOioiCHF ) are tri-octahedral mica minerals that exist in a solid solution series whose end members are siderophyllite (KFe2AI(Al2Si20io)(F,OH)2; potassium iron aluminium silicate hydroxide fluoride) and polylithionite (KLi2AI(Si40io)(F,OH)2;potassium lithium aluminium silicate hydroxide fluoride). They contain a wider range of elements than spodumene LiAI(Si2C>6) (lithium aluminium inosilicate) and, consequently, they are less rich in lithium. For instance, the lithium content of pure zinnwaldite is 1.59% by mass, compared to 3.73% for spodumene.
Given the disadvantages of lithium-mica minerals of lower grade and higher mineral complexity compared to spodumene there is a need for a refining process for leach solutions derived from lithium-mica minerals with improved lithium recovery efficiency, with fewer processing steps, improved specificity for a particular ore, at lower cost and lower environmental impact. There is also a need for a beneficiation process which does not require the use of environmentally damaging reagents or processes.
Calcining of lithium mica in the presence of sulphate ions such as those contained in sodium or calcium sulphate provides a means of rendering the lithium contained in the minerals water soluble through a solid-state reaction. An aqueous leaching step after the calcining brings the lithium and other mobilised species, including the sulphates, alkalis and earth alkalis into solution in the form of aqueous cations. Subsequently, these impurities need removing from the pregnant leach solution as part of impurity removal steps to facilitate purification of lithium to a saleable quality of lithium salt. At this stage, disposal of the sulphate ions would be a wasteful and environmentally unsustainable practice as well as being detrimental to the economics of the lithium refining process. The present invention relates to a method of recovery and recycling of reagents to abate the environmental impact and improve the economics of the purification of lithium leach solutions.
The major sources of commercially mined lithium are from brine solutions (principally in South America) and spodumene containing ores (principally in Western Australia). Currently, there is no commercial production of lithium from lithium-mica rich ores or concentrates.
Leaching of mica using sulphuric acid at elevated temperatures, either at atmospheric pressure or in an autoclave or other device to increase pressure, is well described but does not rely on calcium sulphate or sodium sulphate. This process, whilst avoiding the need for calcining, utilises vast quantities of sulphuric acid that will need appropriate arrangements for environmentally friendly disposal.
Sulphate salts, including lithium sulphate, are readily soluble and therefore provide a clear route towards producing a lithium-enriched leach liquor. This requires calcining of lithium mica at a temperature above 800° C in the presence of a salt of sulphate such as sodium sulphate or calcium sulphate (which is also known as gypsum, for example anhydrous gypsum). Following leaching of the calcined product, a lithium-containing leach liquor is produced that also contains sodium ions/calcium ions and sulphate ions in solution.
Recovery and reuse of sodium sulphate, particularly in the form of Glauber salt (sodium sulphate decahydrate) could provide an important advance to make the overall sulphate calcining - aqueous leaching process more environmentally friendly and economically viable. From a review of other known methods, recoveries of sodium sulphate, in particular Glauber salt in the region of that achieved in the presented invention is not documented in literature. SUMMARY OF INVENTION
According to a first aspect of the invention, there is provided a Glauber salt (sodium sulphate decahydrate) precipitated (in particular crystallised) and recycled from a liquor derived from the leaching of calcined lithium mica-material containing feed by cooling of said calcined- leach liquor. According to a second aspect of the invention, there is provided a process A1 for recovering Glauber salt from a leach liquor derived from the leaching of calcined lithium mica-material comprising: calcining a lithium mica-material containing feed in the presence of a sulphate salt (for example sodium sulphate or calcium sulphate) and at least one of: lime and/or calcium carbonate to provide a calcined lithium mica-material containing feed; aqueous leaching of the calcined lithium mica-material containing feed at a solids percentage in the slurry of between 5% and 40%, operating at atmospheric pressure and at temperatures between 5°C and 95°C to generate leached, calcined lithium mica-material and a leach liquor; cooling the leach liquor to a predetermined temperature to cause Glauber salt to precipitate to generate lithium-enriched leach liquor; and recovery of the Glauber salt. According to a third aspect of the invention, there is provided a process A2 for providing a Glauber salt from a liquor derived from the leaching of calcined lithium mica-material containing feed, the process comprising: exposing a lithium mica-material containing feed with a Li grade in excess of 1% Li to heat (i.e. calcining) in the presence of sodium sulphate and at least one of: lime and/or calcium carbonate to provide a calcined lithium mica-material containing feed; aqueous leaching of the calcined lithium mica-material containing feed at a solids percentage in the slurry between 5% and 40%, operating at atmospheric pressure and at temperatures between 5°C and 95°C to generate leached calcined lithium mica-material and a leach liquor; cooling the leach liquor to a predetermined temperature to cause Glauber salt to precipitate to generate lithium-enriched leach liquor; and recovery of the Glauber salt by filtration at a temperature below 33°C.
In both processes A1 and A2, the leach liquor following the leaching step contains dissolved lithium ions, and other ions such as sodium ions, calcium ions and/or sulphate ions. The leach liquor is enriched in lithium following the precipitation of the Glauber salt.
According to a fourth aspect of the present invention, there is provided a process B1 for recovering Glauber salt from a leach liquor derived from the leaching of calcined lithium mica- material comprising: calcining a lithium mica-material containing feed in the presence of a sulphate salt and at least one of: lime and/or calcium carbonate to provide a calcined lithium mica-material containing feed; aqueous leaching of the calcined lithium mica-material containing feed at a solids percentage in the slurry of between 5% and 40%, operating at atmospheric pressure and at temperatures between 5°C and 95°C to generate leached, calcined lithium mica-material and a leach liquor; adding one or more hydroxide salt(s) and/or carbonate salt(s) to the leach liquor to cause the precipitation of lithium, which is then removed from the leach liquor; cooling the leach liquor to a predetermined temperature to cause Glauber salt to precipitate; and recovery of the Glauber salt.
According to a fifth aspect of the present invention, there is provided a process Cl for recovering Glauber salt from a leach liquor derived from the leaching of calcined lithium mica- material comprising: recovering Glauber salt from a leach liquor using process Al, A2 or B1 as herein described; and reintroducing the recovered Glauber salt into the step of exposing the lithium mica material to heat (i.e. calcining).
In process Cl the recovered Glauber salt is mixed with the calcining feed in the first steps of processes Al, A2 or Bl, thereby reusing the Glauber salt in the calcining process. This provides the advantage of reducing the quantity of waste material, and reducing the amount of calcining feed materials that are required. Furthermore, lithium that is lost to the Glauber salt precipitation is also recovered, thereby increasing overall lithium recovery.
In all of the above aspects, the Glauber salt may precipitate in crystalline form, in which case the precipitation can be referred to as "crystallisation".
The calcining step preferably comprises heating lithium mica material in the presence of sodium sulphate (which may comprise recovered Glauber salt), for example to a temperature between 750 and 850 °C at a residence time in the hot zone of less than 50 minutes and under an oxidising atmosphere. When calcium sulphate is used in the calcining step, a higher temperature range of between 800 and 1100 °C is preferred.
The feed in the calcining step also contains at least one of: lime and/or calcium carbonate. Lime in the context of the present invention contains calcium oxide and/or calcium hydroxide. In one embodiment, the feed in the calcining step also contains one of calcium hydroxide and calcium carbonate.
The Glauber salt is preferably sodium sulphate decahydrate. The cooling step may comprise cooling the leach liquor to a temperature of less than 33 °C, for example to a temperature of less than 10 °C, to achieve a high yield of Glauber salt for recycling as a reagent in the calcining step.
The precipitation of the Glauber salt may further comprise the addition of a seeding material to provide nucleation points to achieve a high yield of Glauber salt for recycling as a reagent. The seeding material may comprise one or more of: calcium sulphate seed crystals and/or sodium sulphate seed crystals and/or potassium sulphate seed crystals and/or magnesium sulphate seed crystals.
In processes A1 and A2, when the Glauber salt is precipitated (and suitably crystallised) out of the leach liquor, the remaining leach liquor is advantageously further enriched in Li due to waters of hydration being incorporated into the precipitated Glauber salt. In one embodiment, the concentration (by weight) of lithium in leach liquor following precipitation of the Glauber salt is increased by 40%, for example by 50%, by 60%, by 65% or by 70%. In one embodiment, the concentration (by weight) of lithium in leach liquor following precipitation of the Glauber salt is increased by 63%.
The processes of the invention may further comprise the addition of one or more hydroxide salt(s) and/or carbonate salt(s) to the leach liquor. The one or more hydroxide salt(s) and/or carbonate salt(s) may be included in the process ahead of crystallisation of the Glauber salt to facilitate removal of impurities from the leach liquor. The impurities may include, but are not limited to, one or more of: iron, titanium, magnesium and potassium. Suitably, the hydroxide salt(s) and/or carbonate salt(s) are selected to preferentially cause precipitation of the impurity ions (e.g. one or more of: iron, titanium, magnesium and potassium) ratherthan the lithium ions. Thus, for process Bl, this step is separate to step of adding one or more hydroxide salt(s) and/or carbonate salt(s) to the leach liquor to cause the precipitation of lithium. The removal of impurities can be carried out at any suitable point in the process following the aqueous leaching.
Preferably, the lithium mica-material containing feed is a milled, preferably a milled and beneficiated, feed stream. Suitably, the lithium mica-material containingfeed is not a powder. Typically, the lithium mica-material containing feed is ground to P80 < 250 micron up to P80 < 350 micron and the mica concentrate is deslimed at 20 microns to remove "powder". A coarser grind uses far less energy for grinding than a fine grind (i.e. a powder).
The lithium mica-material containing feed may be provided or formed from igneous rock.
In process Bl, the precipitation of lithium is suitably achieved by adding a carbonate such as sodium carbonate to the leach liquor, to cause precipitation of lithium carbonate. The precipitated lithium (suitably in the form of lithium carbonate) can be removed from the leach liquor by any suitable means, for example by filtration.
The igneous rock may have been formed during the Variscan Orogeny. The igneous rock may form for example be a felsic intrusive rock such as a granite intrusion part of the Cornubian batholith, the Bohemian Batholiths, the Moldanubian Plutonic Complex or the Central French Massif.
The lithium mica-material containing feed is preferably derived from naturally deposited lithium-mica-bearing sediments or anthropogenically generated waste streams or lithium- mica bearing storage dams derived from naturally deposited lithium-mica-bearing rock or sediments.
Embodiments of the present invention will now be described in further detail in relation to the accompanying Figures:
BRIEF DESCRIPTION OF FIGURES
Figure 1 is a schematic illustration of the Glauber salt crystallisation process according to one embodiment of the present invention; and
Figure 2 shows an example embodiment of a precipitation apparatus used for precipitation of Glauber salt from a leach liquor derived from calcined lithium mica-material containing feed.
DETAILED DESCRIPTION
According to one embodiment, the calcining process is carried out at a temperature between 750 and 850 °C (particularly when sodium sulphate is used in the calcining step). According to another embodiment, the calcining process is carried out at a temperature between 800 and 1100 °C (particularly when calcium sulphate is used in the calcining step). Suitably, the calcining is carried out under atmospheric pressure.
The aqueous leaching of the calcined lithium mica-material containing feed is carried out using water which has not had the pH modified. Thus, unlike certain prior art leaching processes, the use of acid in the present leaching process is not required.
According to one embodiment of the processes of the invention, the leach liquor or lithium- enriched leach liquor that forms the feed to the Glauber salt crystallisation stage of the process may contain between 0.1 and 45g/l of lithium (Li). It is however to be understood that the feed may contain any suitable lithium concentrations, for example between 1 and 20 g/l, preferably between 5 and 20 g/l.
The leach liquor or lithium enriched leach liquor is suitably placed within a precipitation tank for precipitation (in particular crystallisation) and subsequent recovery of the Glauber salt.
The leach liquor or lithium-enriched leach liquor may be cooled to a temperature between - 10 ° C and 33 °C, for example between -10 °C and 5 °C, for example between -5 °C and 5 °C to achieve crystallisation of the Glauber salt. Crystallisation of the Glauber salt may occur unaided in the presence of cooling, or with the aid of addition of seed crystals to the leach liquor or lithium-enriched leach liquor. The seed crystals may be added batch-wise or at a steady addition rate to the leach liquor or lithium-enriched leach liquor.
The seed crystals may be one or more of: sodium sulphate, calcium sulphate or another sulphate salt, or any combination thereof.
The seed crystals may have any suitable particle size distribution to facilitate or aid crystallisation of the Glauber salt. The seed crystals may for example have a dimension of less than 1mm. The seed crystals may for example have a dimension of more than 10pm. Preferably, the seed crystals have a dimension which is in the range of between 10pm and 1 mm, preferably between 0.1 pm and 1 mm.
The seed crystals may be added at any suitable concentration to the leach liquor or lithium- enriched leach liquor. Preferably, the seed crystals are added at less than 0.01 to 1% m/m.
Cooling of the precipitation tank may be achieved through one or more of: immersed chilling elements, a jacketed tank system (as shown in Figure 2) or by placing in a cooled environment. The leach liquor or lithium-enriched leach liquor within the precipitation tank may be unagitated during precipitation/crystallisation of the Glauber salt. In one embodiment, the lithium enriched leach liquor within the precipitation tank may be gently stirred by agitator and/or vibration. During crystallisation/precipitation of the Glauber salt, the leach liquor or lithium-enriched leach liquor may be left for at least 0.1 hr to obtain a predetermined amount of Glauber salt. Preferably, a period of during crystallisation/precipitation, the leach liquor or lithium- enriched leach liquor may be left for up to 24hrs to obtain a predetermined amount of Glauber salt. The process may further comprise an impurity removal step. The impurity removal step reduces and/or eliminates contamination of the leach liquor or lithium-enriched leach liquor through the addition of one or more impurity removal agents.
Impurity removal agent(s) such as sodium carbonate combined with one or more of calcium carbonate and/or calcium hydroxide may be added to the leach liquor or lithium-enriched leach liquor, prior to crystallisation/precipitation of the Glauber salt. Addition of these impurity removal agents is done at 1 - 3 % m/m for sodium carbonate and 0.01 - 0.1% m/m for calcium carbonate and/or calcium hydroxide.
The Glauber salt may be recovered from the leach liquor or lithium-enriched leach liquor by vacuum or pressure filtration solution. The temperature is preferably maintained below 33 °C to prevent melting of the Glauber salt.
After recovery of the Glauber salt, the Glauber salt is heated to evaporate waters of crystallisation.
Preferably, over 65% amount of Glauber salt is recovered where the recovery amount is defined as the molar quantity of Glauber salt recovered as a percentage of the molar quantity of the amount of sodium sulphate used in the calcining process.
The Glauber salt may then be reused as a reagent in the calcining process of lithium mica. This reuse further involves the dewatering of Glauber salt to a temperature between 33 °C and 105 °C to melt the crystals and evaporate waters of hydration. Following partial to complete dehydration of the Glauber salt to return it to pure sodium sulphate, the resultant powder or slurry is mixed with fresh Li mica-containing feed that has not been calcined, additional sodium sulphate, and one or more of calcium hydroxide or calcium carbonate for the calcination process. Preferably, this mixing step may be done on a powder basis ahead of the calcining step. Preferably, this step may include pelletisation of the sodium sulphate and other reagents with the fresh Li mica-containing feed ahead of the calcining step.
The recovered Glauber salt is added to a mixture containing lithium mica-material (typically in the presence of additional sodium sulphate, or in the presence of calcium sulphate) and heated for up to 50 minutes at a temperature above 800 °C before being leached to produce a leach liquor that contains lithium also contains a large quantity of sodium sulphate and/or calcium sulphate in solution as described hereinabove.
An additional advantage of the recovery and reuse process for Glauber Salt is that any Li lost to the Glauber Salt is re-introduced as a calcining reagent along with the sodium sulphate derived from dehydration of the Glauber Salt.
The present invention therefore provides an economical and efficient process for the recovery of Glauber salt from a leach liquor or lithium-enriched leach liquor. Furthermore, the present invention provides an improved, environmentally friendly process, for calcining lithium containing mica-material using recovered Glauber salt.
EXAMPLE
In the presented example (which is representative of processes Al, A2 and Cl) a purified Li leach liquor is derived from calcining of fresh Li mica-containing feed in the presence of sodium sulphate and one of calcium hydroxide and calcium carbonate. This sodium sulphate is added to the fresh Li mica-containing feed at a ratio of 0.7:1 sodium sulphate/Li-mica containing feed on a mass basis, equating to the addition of 906.8 moles of sodium sulphate to a calcining feed batch mass of 183.9kg. After calcining, leaching and impurity removal, the resultant filtered and purified Li-containing leach liquor is cooled to a temperature between -5°C and 5°C, sufficiently cold to crystalise out the sodium sulphate in the form of Glauber salt but still warm enough to prevent formation of ice in this leach liquor. This crystallisation process yields a slurry containing a mixture of solid Glauber salt crystals and a leach liquor which is further enriched in Li due to waters of hydration being incorporated into the Glauber salt. This slurry is transferred to a filtration unit where the Glauber salt crystals are separated from the Li-enriched leach liquor to allow dehydration of the former and further refining to recover lithium into a saleable form from the latter. This filtration step is carried out with the slurry temperature maintained at a temperature below 33°C to prevent melting of the Glauber salt crystals. The crystallisation process in the presented example takes 618.6 moles of sodium sulphate out of solution and increases the Li concentration in the leach liquor from 82.4g/l Li to 133.9g/l Li. The yield of sodium sulphate contained in the Glauber salt as a percentage of the feed that went into the calcining process in this example is 68.2%.
In this example, following separation of the Glauber salt from the Li-enriched leach liquorthe solids from the filtration process are heated to a temperature of 60°C to gently evaporate the water of hydration contained in the Glauber salt. This process may be carried out till all water is evaporated and dehydrated sodium sulphate is left for re-use in the calcining process, mixed in as a powder. Alternatively, if the calcining process is based on a pelletised feed, a small quantity of water may be left behind in the sodium sulphate and Glauber salt mixture to aid binding together of the sodium sulphate/Glauber salt/Li mica/calcium carbonate and/or calcium hydroxide mixture.

Claims

1. A process for recovering Glauber salt from a leach liquor derived from the leaching of calcined lithium mica-material comprising: calcining a lithium mica-material containing feed in the presence of a sulphate salt and at least one of: lime and/or calcium carbonate to provide a calcined lithium mica-material containing feed; aqueous leaching of the calcined lithium mica-material containing feed at a solids percentage in the slurry of between 5% and 40%, operating at atmospheric pressure and at temperatures between 5°C and 95°C to generate leached, calcined lithium mica-material and a leach liquor; cooling the leach liquor to a predetermined temperature to cause Glauber salt to precipitate to generate lithium-enriched leach liquor; and recovery of the Glauber salt.
2. A process for recovering Glauber salt from a leach liquor derived from the leaching of calcined lithium mica-material comprising: calcining a lithium mica-material containing feed in the presence of a sulphate salt and at least one of: lime and/or calcium carbonate to provide a calcined lithium mica-material containing feed; aqueous leaching of the calcined lithium mica-material containing feed at a solids percentage in the slurry of between 5% and 40%, operating at atmospheric pressure and at temperatures between 5°C and 95°C to generate leached, calcined lithium mica-material and a leach liquor; adding one or more hydroxide salt(s) and/or carbonate salt(s) to the leach liquor to cause the precipitation of lithium, which is then removed from the leach liquor; cooling the leach liquor to a predetermined temperature to cause Glauber salt to precipitate; and recovery of the Glauber salt.
3. A process as claimed in claim 2, wherein a carbonate salt such as sodium carbonate is added to the leach liquor to cause the precipitation of lithium as lithium carbonate, which is then removed from the leach liquor.
4. A process as claimed in any preceding claim, in which the recovered Glauber salt is reintroduced into the step of calcining lithium mica-material.
5. A process as claimed in any preceding claim, in which the calcining step(s) comprises heating lithium mica material in the presence of a sulphate salt and/or reintroduced Glauber salt.
6. A process as claimed in claim 5, in which the sulphate salt is sodium sulphate or calcium sulphate.
7. A process as claimed in any preceding claim, in which the Glauber salt is sodium sulphate decahydrate.
8. A process as claimed in any preceding claim, in which the cooling step comprises cooling the leach liquor to a temperature of less than 10 °C.
9. A process as claimed in any preceding claim, in which the precipitation step further comprises the addition of a seeding material to the leach liquor to provide nucleation points.
10. A process as claimed in claim 9, in which the seeding material comprises one or more of: calcium sulphate seed crystals and/or sodium sulphate seed crystals and/or potassium sulphate seed crystals and/or magnesium sulphate seed crystals.
11. A process as claimed in any preceding claim, in which the process further comprises the addition of one or more hydroxide salt(s) and/or carbonate salt(s) to the leach liquor to remove impurities such as iron, titanium, magnesium and/or potassium .
12. A process as claimed in any preceding claim, in which the lithium mica-material containing feed is a milled feed stream.
13. A process as claimed in any preceding claim, in which the lithium mica-material containing feed is provided by or formed from igneous rock.
IB
14. A process as claimed in any preceding claim, in which the lithium mica-material containing feed comprises felsic intrusive rock such as a granite.
15. A process as claimed in claim 14, in which the felsic intrusive rock is formed during the Variscan Orogeny.
16. A process as claimed in claim 15, in which the igneous rockforms part of the Cornubian batholith, the Bohemian Batholiths, the Moldanubian Plutonic Complex or the Central French Massif.
17. A process as claimed in any preceding claim, in which the lithium mica-material containing feed is preferably derived from naturally deposited lithium-mica-bearing sediments or anthropogenically generated waste streams or lithium-mica bearing storage dams derived from naturally deposited lithium-mica-bearing rock or sediments.
18. A Glauber salt obtained according to a process as claimed in claim 1 or claim 2.
PCT/EP2022/068229 2021-07-02 2022-07-01 Processes for the recovery and reuse of sulphate reagents from leach liquors derived from lithium micas WO2023275345A2 (en)

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