Aqueous-organic mixtures for lithium carbonate production

Abstract

Compositions and processes for the conversion of lithium bearing solids to lithium carbonate are disclosed. Preferred embodiments utilize sodium salts with organic solvents to produce product slurries from which lithium products, e.g., lithium carbonate, are isolated.

Description

AQUEOUS-ORGANIC MIXTURES FOR LITHIUM CARBONATE PRODUCTIONRelated Applications

[0001] The present application claims convention priority from Australian provisional patent applications 2024902925 (13 September 2024) and 2024903069 (24 September 2024). The content of AU’925 and AU’ 069 is incorporated herein by reference in its entirety.Field of the Invention

[0002] The present invention relates to compositions and processes for the extraction of lithium using a commixtures of lithium-containing ore, sodium salt, organic solvents in water.Background of the Invention

[0003] Any discussion of the publications throughout the specification should in no way be considered as an admission that such publications are widely known or forms part of common general knowledge in the field.

[0004] At an industrial level, lithium is assuming ever-increasing popularity given its many uses: ceramics, glasses, batteries, electronics, lubricating greases, metallurgy, pyrotechnics, air purification, optics, polymer chemistry, military applications and medicine - to name but a few. One of the principal uses of lithium is in batteries - and demand has grown significantly as all-electric vehicles assumed a foothold in the market. Lithium is especially amenable to use in batteries owing to its high electrode potential; and because of its low atomic mass, lithium batteries have high charge-to-weight and power-to-weight ratios. Depending on the design, lithium batteries can produce from 1.5 V (comparable to a zinc-carbon or alkaline battery) to about 3.7 V.

[0005] Lithium carbonate is an important commodity chemical notably useful for the production of lithium-ion batteries. Standard grades for lithium carbonate include: “Industrial Grade” which comprises <99% Li2CO3 on a molar basis; “Technical Grade” which comprises 99% Li2CO3; “Battery Grade” which comprises 99.5% Li2CO3 and accounts for about 75% of the global battery market (2022); “EV Grade” which comprises 99.9% Li2CO3 and accounts for 15% of the worldwide battery market; and finally, “EV-Plus Grade” lithium carbonate which is 99.99% pure and accounts for the remaining 10% of themarket. Notably, the battery grade (battery, EV, and EV+) specifications continue to evolve and become more stringent, not just in purity but in allowable concentrations of specific impurities and in crystal size, shape, and morphology.

[0006] Naturally, lithium occurs in a number of pegmatites, in ocean water, brine wells, and phyllosilicates. It is from the pegmatites and brine waters that lithium is obtained on a commercial basis.

[0007] Of the pegmatites, spodumene is the most common commercially-exploited lithium mineral. It is a pyroxene mineral comprising lithium aluminosilicate, LiAl(SiO3)2. The normal low-temperature form, a-spodumene, is monoclinic whereas the high- temperature forms, y- and P-spodumene are hexagonal and tetragonal system, respectively. The thermal activation of a-spodumene produces a mixture of y- and P-spodumene at temperatures above 900 °C.

[0008] Methods of extracting lithium from spodumene can be classified according to three broad categories: acidic, caustic, and “green”. Typically, all extraction methods require calcination of the a-spodumene (thermal conversion to the P-form), as less than 1% of the lithium contained in a-spodumene is extractable due to the monoclinic crystal structure being largely impenetrable to extraction media and ion mobility being extremely low.

[0009] Acid leaching of lithium from P-spodumene is typically characterised by harsh conditions. In general, a first step is mixing the P-spodumene with concentrated sulfuric acid (96%) at about 250 °C in a sulfating kiln. Therein, the lithium aluminosilicates react to form lithium sulfate which is highly soluble in water. Hydrometallurgical steps follow this acid roasting and leaching, and after crystallisation with soda ash, a Li2CO3 product with a purity of about 98-99 % is precipitated in excellent yields.

[0010] It will be appreciated that the industrial-scale use of strong, concentrated acids, soda ash and other reagents in relation to spodumene extraction can be expensive, inconvenient and environmentally-damaging. Further, the sequence of extraction steps before a commercially saleable technical grade lithium carbonate is obtained can be somewhat labour-intensive.

[0011] International Patent Publication WO 2018 / 157203, now assigned to the present Applicant, proposed for the first time a “green” method for the extraction of lithium carbonate from spodumene using relatively mild conditions (temperature, pressure, time) and most significantly, using carbonic acid as the extraction medium. Commercialisation of this technology is ongoing.

[0012] Other methods of extracting lithium from its constituent ores involve the use of caustic sodium. For instance, when sodium carbonate and an excess of water are applied under specific conditions, the sodium displaces the lithium, and the resultant lithium carbonate then leaches into the aqueous solvent. The lithium carbonate is then removed from the aqueous solution using CO2 to acidify the solution and facilitate precipitation. An example of such a process is US Patent No. 3,112,172, dated 5 December 1960, and assigned to the Department of Natural Resources of the Province of Quebec, Canada.

[0013] Previous publications include: Grasso, M.L. et al., “Lithium extraction from P-LiAlSi20e using Na2COs through thermal reaction” Minerals Engineering 176 (2022) 107349; Xiong Lu et al., “Extraction of Lithium and Synthesis of Kaolinite from a- Spodumene via Alkali Calcination” Chemistry Select 4 January 2024, 9, e202304480; Chen, Y. et al., “Preparation of lithium carbonate from spodumene by a sodium carbonate autoclave process”, 2011, Hydrometallurgy, vol 109, no. 1, pp 43-46; US 2015 / 0044124; US 3,112,171; US 4,124,684; US 2020 / 0071794; WO 2024 / 078460; WO 2016 / 087716 and US 2024 / 0102126.

[0014] Other representative publications include US Patent Nos. 11,292,725; and 9,255,012 to Outotec (Metso); and US Pat. Nos. 4,124,684; 3,380,802; 3,310,368;3,131,022; 3,112,171; 3,112,170; and 3,017,243 to Quebec, commonly known as the Quebec Process.

[0015] It is an object of the present invention to overcome or ameliorate at least one of the disadvantages of the prior art, or to provide a useful alternative.

[0016] It is an object of an especially preferred form of the present invention to provide for an improved process and composition for the extraction and production of lithium carbonate from lithium-containing ores. Traditional extraction methods often rely on harsh acids, caustic reagents, or energy -intensive conditions, which can be costly, environmentally damaging, and operationally complex.Summary of the Invention

[0017] The present invention provides a novel approach to lithium extraction by employing aqueous-organic mixtures that combine sodium salts with organic solvents and water. This unique combination facilitates the efficient conversion of lithium -bearing solids — particularly those containing P-spodumene and other lithium aluminosilicates — into lithium carbonate under relatively mild thermal conditions. The process achieves high yields of lithium carbonate while minimising the use of harsh chemicals and extreme processingconditions. The process is designed to be robust, accommodating both high-grade and lower-grade lithium ores, and is particularly suited to industrial-scale operations where efficiency, safety, and environmental considerations are paramount. The use of miscible organic solvents, such as ethylene glycol or glycerol, not only enhances lithium extraction but also allows for the recycling and reuse of process fluids, further reducing waste and operational costs. The process enables the selective precipitation and isolation of high -purity lithium carbonate, suitable for demanding applications including battery manufacturing.

[0018] The invention addresses several limitations of conventional lithium extraction methods, such as the reliance on concentrated acids or caustic reagents, by providing a more sustainable and less hazardous alternative. The invention provides a flexible and scalable solution that can accommodate a range of lithium -bearing materials, including but not limited to spodumene and other lithium aluminosilicates. The invention is adaptable to various lithium-containing feedstocks and able to operate across a range of particle sizes and lithium concentrations. The invention facilitates the recycling of solvents and reagents, thereby enhancing sustainability and reducing waste generation in industrial lithium carbonate production. By integrating innovative chemistry with practical engineering, the invention represents a significant advancement in the field of lithium resource processing, offering both economic and environmental benefits.

[0019] According to a first aspect of the present invention there is provided a process comprising:

[0020] heating a reaction slurry to a reaction temperature of about 150 °C to about 300 °C; whereby the reaction slurry is converted to a product slurry; thereafter

[0021] extracting a lithium bicarbonate solution from the product slurry; and then

[0022] separating lithium carbonate and a filtrate from the lithium bicarbonate solution;

[0023] wherein the reaction slurry includes: a carrier fluid that includes a sodium salt and an organic solvent; and a particulate having an average particle size of about 1 pm to about 1000 pm and a lithium concentration of about 0.5 wt.% to about 5 wt.%; the reaction slurry further includes a molar ratio of sodium to lithium of about 1 : 1 to about 4: 1.

[0024] In an embodiment, the particulate includes P-spodumene.

[0025] In an embodiment, the carrier fluid includes water.

[0026] In an embodiment, the water and the organic solvent are miscible.

[0027] In an embodiment, the sodium salt is soluble in an admixture of the organic solvent and water.

[0028] In an embodiment, the sodium salt is dissolved in the admixture of the organic solvent and water.

[0029] In an embodiment, the carrier fluid includes a molar ratio of water to the organic solvent of about 1 :1 to about 100: 1.

[0030] In an embodiment, the molar ratio of water to the organic solvent is about 3:2 to about 10: 1.

[0031] In an embodiment, the sodium salt includes sodium carbonate.

[0032] In an embodiment, the sodium salt consists essentially of sodium carbonate.

[0033] In an embodiment, the carrier fluid consists essentially of the sodium salt, water, and the organic solvent.

[0034] In an embodiment, the process further comprises a molar ratio of sodium to the organic solvent of about 1 : 1 to about 10: 1.

[0035] In an embodiment, the organic solvent includes ethylene glycol, propylene glycol, methoxyethanol, ethoxyethanol, methoxypropanol, ethoxypropanol, diethylene glycol, dipropylene glycol, glycerol, 3 -m ethoxy- 1,2-propane diol, 2-methyl-l,3- propanediol, trimethylolmethane, or a mixture thereof.

[0036] In an embodiment, the organic solvent includes ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerol, trimethylolmethane, or a mixture thereof.

[0037] In an embodiment, the organic solvent has a boiling point greater than about 150 °C.

[0038] In an embodiment, the reaction slurry consists essentially of the carrier fluid and the lithium particulate.

[0039] In an embodiment, the lithium bicarbonate solution includes the organic solvent.

[0040] In an embodiment, the lithium bicarbonate solution includes the sodium salt.

[0041] In an embodiment, the filtrate includes the organic solvent.

[0042] In an embodiment, the organic solvent from the filtrate is reused in the process.

[0043] In an embodiment, separating lithium carbonate and a filtrate from the lithium bicarbonate solution includes heating the lithium bicarbonate solution, removing carbon dioxide from the solution, precipitating lithium carbonate crystals from the solution, and then isolating the lithium carbonate crystals.

[0044] In an embodiment, the product slurry includes: a carrier fluid that includessodium carbonate and an organic solvent; a particulate having an average particle size of about 0.1 pm to about 1000 pm, a lithium concentration of about 0.001 wt.% to about 0.5 wt.%, and a sodium concentration of about 1.5 wt.% to about 20 wt.%; and lithium carbonate; the product slurry further includes a molar ratio of sodium to lithium of about 1 : 1 to about 4: 1.

[0045] In an embodiment, the lithium carbonate includes crystalline lithium carbonate.

[0046] In one embodiment, the invention provides a product or reaction slurry that results from the extraction process described.

[0047] In a further aspect, the present invention provides a slurry comprising:

[0048] a carrier fluid that includes a sodium salt and an organic solvent; and

[0049] a particulate having an average particle size of about 1 pm to about 1000 pm and a lithium concentration of about 0.5 wt.% to about 5 wt.%;

[0050] the slurry further comprising a molar ratio of sodium to lithium of about 1 : 1 to about 4: 1.

[0051] In an embodiment, the particulate includes P-spodumene.

[0052] In an embodiment, the particulate is a calcined spodumene concentrate.

[0053] In an embodiment, the carrier fluid includes water.

[0054] In an embodiment, the water and the organic solvent are miscible.

[0055] In an embodiment, the sodium salt is soluble in an admixture of the organic solvent and water.

[0056] In an embodiment, the sodium salt is dissolved in the admixture of the organic solvent and water.

[0057] In an embodiment, the carrier fluid includes a molar ratio of water to the organic solvent of about 1 :1 to about 100: 1.

[0058] In an embodiment, the molar ratio of water to the organic solvent is about 3:2 to about 10: 1.

[0059] In an embodiment, the sodium salt includes sodium carbonate.

[0060] In an embodiment, the sodium salt consists essentially of sodium carbonate.

[0061] In an embodiment, the carrier fluid consists essentially of the sodium salt, water, and the organic solvent.

[0062] In an embodiment, the slurry further comprises a molar ratio of sodium to the organic solvent of about 1 :1 to about 10: 1.

[0063] In an embodiment, the organic solvent includes ethylene glycol, propyleneglycol, methoxyethanol, ethoxyethanol, methoxypropanol, ethoxypropanol, diethylene glycol, dipropylene glycol, glycerol, 3 -m ethoxy- 1,2-propane diol, 2-methyl-l,3- propanediol, trimethylolmethane, or a mixture thereof.

[0064] In an embodiment, the organic solvent includes ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerol, trimethylolmethane, or a mixture thereof.

[0065] In a further aspect, the present invention provides a product slurry comprising:

[0066] a carrier fluid that includes sodium carbonate and an organic solvent;

[0067] a particulate having an average particle size of about 0.1 pm to about 1000 pm, a lithium concentration of about 0.001 wt.% to about 0.5 wt.%, and a sodium concentration of about 1.5 wt.% to about 20 wt.%; and

[0068] lithium carbonate;

[0069] the slurry further comprising a molar ratio of sodium to lithium of about 1 : 1 to about 4: 1.

[0070] In an embodiment, the lithium carbonate includes crystalline lithium carbonate.

[0071] In an embodiment, a portion of the crystalline lithium carbonate is adhered to the particulates.

[0072] In an embodiment, the carrier fluid further includes water.

[0073] In a further aspect, the present invention provides a process comprising:

[0074] heating, to a reaction temperature of about 150 °C to about 300 °C, a reaction slurry that includes of an admixture of a carrier fluid and a lithium particulate, where the carrier fluid includes a sodium salt, water, and an organic solvent, and where the lithium particulate has an average particle size of about 1 pm to about 1000 pm and a lithium concentration of about 0.5 wt.% to about 5 wt.%, the slurry further comprising a molar ratio of sodium to lithium of about 1 : 1 to about 4: 1; whereby the slurry is converted to a product slurry; thereafter

[0075] extracting a lithium bicarbonate solution from the product slurry; and then

[0076] separating lithium carbonate and a filtrate from the lithium bicarbonate solution.

[0077] In an embodiment, the reaction slurry consists essentially of the carrier fluid and the lithium particulate.

[0078] In an embodiment, the organic solvent has a boiling point greater than about150 °C.

[0079] In an embodiment, the he lithium bicarbonate solution includes the organic solvent.

[0080] In an embodiment, the lithium bicarbonate solution includes the sodium salt.

[0081] In an embodiment, the filtrate includes the organic solvent.

[0082] In an embodiment, the organic solvent from the filtrate is reused in the process.

[0083] In an embodiment, separating lithium carbonate and a filtrate from the lithium bicarbonate solution includes heating the lithium bicarbonate solution, removing carbon dioxide from the solution, precipitating lithium carbonate crystals from the solution, and then isolating the lithium carbonate crystals.

[0084] Although the invention will be described with reference to specific examples it will be appreciated by those skilled in the art that the invention may be embodied in many other forms.Definitions and Nomenclature

[0085] Objects, features, and advantages of the present invention will become apparent from the following detailed description. It should be understood, however, that the detailed description and the specific examples, while indicating specific embodiments of the invention, are given by way of illustration only, since various changes and modifications within the spirit and scope of the invention will become apparent to those skilled in the art from this detailed description.

[0086] Herein, the use of the word “a” or “an” when used in conjunction with the term “comprising” in the claims and / or the specification may mean “one,” but it is also consistent with the meaning of “one or more,” “at least one,” and “one or more than one.”

[0087] The term “about” means, in general, the stated value plus or minus 5%.

[0088] The use of the term “or” in the claims is used to mean “and / or” unless explicitly indicated to refer to alternatives only or the alternative are mutually exclusive, although the disclosure supports a definition that refers to only alternatives and “and / or.”

[0089] Unless the context clearly requires otherwise, the words “comprise”, “comprising”, “include”, “including” and the like are to be construed in an inclusive sense as opposed to an exclusive or exhaustive sense; that is to say, in the sense of “including, but not limited to”.

[0090] As used herein, the phrase “consisting of’ excludes any element, step, oringredient not expressly presented. When the phrase “consists of’ (or variations thereof) appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole. As used herein, the phrase “consisting essentially of’ limits the scope of a claim to the specified elements or method steps, plus those that do not materially affect the basis and novel character stic(s) of the claimed subject matter.

[0091] The transitional phrase “consisting of’ excludes any element, step, or ingredient not specified. If in the claim, such would close the claim to the inclusion of materials other than those recited except for impurities ordinarily associated therewith. When the phrase “consisting of’ appears in a clause of the body of a claim, rather than immediately following the preamble, it limits only the element set forth in that clause; other elements are not excluded from the claim as a whole.

[0092] The transitional phrase “consisting essentially of’ is used to define a composition, process or method that includes materials, steps, features, components, or elements, in addition to those literally disclosed, provided that these additional materials, steps, features, components, or elements do not materially affect the basic and novel character! stic(s) of the claimed invention. The term “consisting essentially of’ occupies a middle ground between "comprising" and “consisting of’.

[0093] The recitation of a numerical range using endpoints includes all numbers subsumed within that range (e.g., 1 to 5 includes 1, 1.5, 2, 2.75, 3, 3.80, 4, 5, etc.).

[0094] The terms “preferred” and “preferably” refer to embodiments of the invention that may afford certain benefits, under certain circumstances. However, other embodiments may also be preferred, under the same or other circumstances. Furthermore, the recitation of one or more preferred embodiments does not imply that other embodiments are not useful and is not intended to exclude other embodiments from the scope of the invention.

[0095] Percentages in general are on a weight / weight basis (i.e., % w / w; wt.%).

[0096] This specification is prepared having regard to the principles of general application. As such, where the specification discloses a principle of general application, the claims may be drafted in correspondingly general terms (Biogen vMedeva

[1997] RPC 1 at 48). A “principle of general application” is a general principle that can be practically applied in making a class of products, or in working a process, including where the claims define the products or processes in terms of the result to be achieved.Detailed Description

[0097] A first embodiment is a slurry that includes a carrier fluid and a particulate, i.e., a plurality of particulates. Herewith, the carrier fluid includes a sodium salt and an organic solvent. Preferably, the carrier fluid is a homogeneous solution of the sodium salt in the organic solvent.

[0098] The particulate, preferably a lithium containing particulate, can have an average particle size of about 1 pm to about 1000 pm and a lithium concentration of about 0.5 wt.% to about 5 wt.%. Notably, the slurry including a sodium containing carrier fluid and a lithium containing particulate can have a molar ratio of sodium to lithium of about 1 : 1 to about 4: 1, about 1 : 1 to about 3 : 1, or about 1 : 1 to about 2: 1. In certain instances that Na:Li ratio can be 0.8:l, 0.9: 1, 1 : 1, 1.1 : 1, 1.2: 1, 1.3: 1, 1.4: 1, 1.5: 1, 1.6: 1, 1.8: 1, 1.9: 1, or 2: l. Preferably, the Na:Li ratio is greater than 1..

[0099] The particulate includes, consists essentially of, or consists of a lithium aluminosilicates, for example a phyllosilicate clay, a hectorite clays, lepidolite, petalite, spodumene, and / or amblygonite. In one instance, the particulate includes a spodumene; preferably the particulate includes P-spodumene. In still another instance, the particulate includes a lithium aluminosilicate that consists essentially of or consists of P-spodumene. Notably, the particulate preferably includes P-spodumene but due to the nature of the available raw materials, the P-spodumene is rarely pure and often presents as a mixture with other materials including silicates. Preferably, the first particulate includes at least about 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.%, or 90 wt.% P-spodumene. In another preferable instance, the particulate is a calcined spodumene concentrate.

[0100] The average particle size of the particulate can be less than one micron to greater than 1 mm, preferably, the average particle size is about 1 pm to about 1000 pm , about 2 pm to about 750 pm, about 5 pm to about 500 pm, about 5 pm to about 400 pm, or about 10 pm to about 450 pm. Preferably, the particulate average particle size is above about 1 pm, 2 pm, 3 pm, 4 pm, 5 pm, 7 pm, 10 pm, 15 pm, 20 pm, 25 pm, 50 pm, or 100 pm and below about 2 mm, 1.5 mm, 1000 pm, 900 pm, 800 pm, 700 pm, 600 pm, 500 pm, or 450 pm . In one example, the particulate average particle size is about 100 pm, 200 pm, 300 pm, 400 pm, 500 pm, 600 pm, 700 pm, 800 pm, 900 pm, or 1000 pm. Notably, preference for the particulate average particle size may be driven by material handling concerns (e.g., avoiding inhalation hazards), separation concerns (e.g., process filtration), and cost (e.g., comminution expenses).

[0101] The particulate lithium concentration can be about 0.5 wt.% to about 5 wt.%,about 0.5 wt.% to about 4 wt.%, about 1 wt.% to about 4 wt.%, or about 1.5 wt.% to about 3.5 wt.%. Preferably, the particulate lithium concentration is as high as possible, but the source and beneficiation of the particulate may limit the total lithium concentration.

[0102] The carrier fluid includes the sodium salt and the organic solvent; while the carrier fluid can include, consists essentially of, or consist of the sodium salt and the organic solvent, the carrier fluid, preferably, includes water. In a preferable instance, the carrier fluid includes, consists essentially of, or consists of the sodium salt, the organic solvent, and water; more preferably, the carrier fluid is a homogeneous solution of the sodium salt, organic solvent, and water. In one instance, the water and the organic solvent are miscible. In another instance, the sodium salt is soluble in an admixture of the organic solvent and water. In still another instance, the sodium salt is dissolved in the admixture of the organic solvent and water. Notably, sodium salt hydrates mixed with / dis solved in the organic solvent creates a carrier fluid that includes the sodium salt, the organic solvent, and the water (from the hydrate).

[0103] The carrier fluid further includes a molar ratio of sodium to the organic solvent of about 1 : 10 to about 100:1, about 1 :2 to about 50: 1, about 1 :2 to about 25: 1, about 1 :2 to about 20: 1, about 1 :2 to about 15: 1; about 1 :2 to about 10: 1, or about 1 : 1 to about 10: 1. In one instance, the sodium to organic solvent molar ratio is about 1 : 1 to about 5: 1, about 1 : 1 to about 3 : 1, or about 1 : 1 to about 2: 1.

[0104] The organic solvent is selected, preferably, for those organic solvents that are miscible with water. In one instance, the organic solvent includes ethylene glycol, propylene glycol, methoxyethanol, ethoxyethanol, methoxypropanol, ethoxypropanol, diethylene glycol, dipropylene glycol, glycerol, 3 -m ethoxy- 1,2-propane diol, 2-methyl-l,3- propanediol, trimethylolmethane, or a mixture thereof. In a preferable instance, the organic solvent includes ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerol, trimethylolmethane, or a mixture thereof. In particular instances, the organic solvent includes ethylene glycol, propylene glycol, diethylene glycol, and / or glycerol. In another instance, the organic solvent includes, consists essentially of, or consist of ethylene glycol. In another instance, the organic solvent includes, consists essentially of, or consist of propylene glycol. In another instance, the organic solvent includes, consists essentially of, or consist of glycerol. In another instance, the organic solvent includes, consists essentially of, or consists of trimethylolmethane.

[0105] A carrier fluid that includes water, further includes a molar ratio of water to the organic solvent. The molar ratio of water to the organic solvent can be about 1 : 1 to about100: 1; preferably, the molar ratio of water to the organic solvent is about 3:2 to about 10:1. In another instance, the molar ratio of water to the organic solvent can be about 1, 1.1, 1.2,I.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4,3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6,5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8,7.9, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10,I I, 12, 13, 14, 15, 16, 17, 18, 19, or 20. In still another instance, the molar ratio of water to the organic solvent can be about, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100.

[0106] The sodium salt is preferably an alkaline sodium salt. In another instance, the sodium salt can be selected from sodium carbonate, sodium bicarbonate, sodium sulfate, sodium bisulfate, sodium sulfide, sodium thiolate, sodium nitrate, sodium chloride, sodium acetate, sodium citrate, sodium formate, sodium hydroxide, or mixtures thereof. In a particularly preferable instance, the sodium salt includes sodium carbonate. In a still more preferable instance, the sodium salt consists essentially of sodium carbonate. In a yet still more preferable instance, the sodium salt consists of sodium carbonate.

[0107] Another embodiment is a product slurry that includes a carrier fluid, a particulate (e.g., a particulate from which lithium has been extracted), and lithium carbonate, preferably crystalline lithium carbonate. Herein, the carrier fluid includes sodium carbonate and an organic solvent; while the carrier fluid can include, consists essentially of, or consist of the sodium carbonate and the organic solvent, the carrier fluid, preferably, includes water. In a preferable instance, the carrier fluid includes, consists essentially of, or consists of the sodium carbonate, the organic solvent, and water; more preferably, the carrier fluid is a homogeneous solution of the sodium carbonate, organic solvent, and water. In one instance, the water and the organic solvent are miscible. In another instance, the sodium carbonate is soluble in an admixture of the organic solvent and water. In still another instance, the sodium carbonate is dissolved in the admixture of the organic solvent and water.

[0108] The particulate is preferable a lithium-containing material from which the lithium has been extracted, for example by sodium for lithium exchange. In one instance, the particulate has an average particle size of about 0.1 pm to about 1000 pm, a lithium concentration of about 0.001 wt.% to about 0.5 wt.%, and a sodium concentration of about 1.5 wt.% to about 20 wt.%.

[0109] Herewith, the product slurry further includes lithium carbonate. In apreferable instance, the lithium carbonate is crystalline or includes crystalline lithium carbonate. In another instance, crystalline lithium carbonate is adhered to, affixed to, or deposited upon the particulate(s).

[0110] Still further, the slurry preferably includes a molar ratio of sodium to lithium of about 1 : 1 to about 4:1. Notably, the molar ratio of sodium to lithium includes the sodium in the carrier fluid and in the particulate(s) and includes the lithium in the particulate(s), the lithium carbonate, and any lithium dissolved in the carrier fluid.

[0111] Still another embodiment is a process for extracting lithium from a lithium containing material and providing a lithium product (i.e., lithium carbonate). The process preferably includes heating a reaction slurry that includes an admixture of a carrier fluid and a lithium particulate to a reaction temperature of about 150 °C to about 300 °C. The carrier fluid includes a sodium salt and an organic solvent, preferably includes the sodium salt, water, and the organic solvent. Herewith, the lithium particulate can have an average particle size of about 1 pm to about 1000 pm and a lithium concentration of about 0.5 wt.% to about 5 wt.%. Moreover, the slurry can further comprise a molar ratio of sodium to lithium of about 1 : 1 to about 4: 1. The heating of the reaction slurry converts the slurry to a product slurry (e.g., the product slurry disclosed above). Thereafter, the process can include extracting a lithium bicarbonate solution from the product slurry; and then separating lithium carbonate and a filtrate from the lithium bicarbonate solution.

[0112] Notably, the reaction slurry includes a carrier fluid and a particulate, i.e., a plurality of particulates. Herewith, the carrier fluid includes a sodium salt and an organic solvent. Preferably, the carrier fluid is a homogeneous solution of the sodium salt in the organic solvent. The particulate, preferably a lithium containing particulate, can have an average particle size of about 1 pm to about 1000 pm and a lithium concentration of about 0.5 wt.% to about 5 wt.%. Notably, the reaction slurry including a sodium containing carrier fluid and a lithium containing particulate can have a molar ratio of sodium to lithium of about 1 : 1 to about 4: 1, about 1 : 1 to about 3 : 1, or about 1 : 1 to about 2: 1. In certain instances that Na:Li ratio can be 0.8: l, 0.9: 1, 1 : 1, 1.1 : 1, 1.2:1, 1.3: 1, 1.4: 1, 1.5: 1, 1.6:1, 1.8: 1, 1.9: 1, or 2: 1. Preferably, the Na:Li ratio is greater than 1..

[0113] The particulate includes, consists essentially of, or consists of a lithium aluminosilicates, for example a phyllosilicate clay, a hectorite clays, lepidolite, petalite, spodumene, and / or amblygonite. In one instance, the particulate includes a spodumene; preferably the particulate includes P-spodumene. In still another instance, the particulate includes a lithium aluminosilicate that consists essentially of or consists of P-spodumene.Notably, the particulate preferably includes P-spodumene but due to the nature of the available raw materials, the P-spodumene is rarely pure and often presents as a mixture with other materials including silicates. Preferably, the first particulate includes at least about 50 wt.%, 60 wt.%, 70 wt.%, 80 wt.%, or 90 wt.% P-spodumene. In another preferable instance, the particulate is a calcined spodumene concentrate.

[0114] The average particle size of the particulate can be less than one micron to greater than 1 mm, preferably, the average particle size is about 1 pm to about 1000 pm, about 2 pm to about 750 pm, about 5 pm to about 500 pm, about 5 pm to about 400 pm, or about 10 pm to about 450 pm. Preferably, the particulate average particle size is above about 1 pm, 2 pm, 3 pm, 4 pm, 5 pm, 7 pm, 10 pm, 15 pm, 20 pm, 25 pm, 50 pm, or 100 pm and below about 2 mm, 1.5 mm, 1000 pm, 900 pm, 800 pm, 700 pm, 600 pm, 500 pm, or 450 pm. In one example, the particulate average particle size is about 100 pm, 200 pm, 300 pm, 400 pm, 500 pm, 600 pm, 700 pm, 800 pm, 900 pm, or 1000 pm. Notably, preference for the particulate average particle size may be driven by material handling concerns (e.g., avoiding inhalation hazards), separation concerns (e.g., process filtration), and cost (e.g., comminution expenses).

[0115] The particulate lithium concentration can be about 0.5 wt.% to about 5 wt.%, about 0.5 wt.% to about 4 wt.%, about 1 wt.% to about 4 wt.%, or about 1.5 wt.% to about 3.5 wt.%. Preferably, the particulate lithium concentration is as high as possible, but the source and beneficiation of the particulate may limit the total lithium concentration.

[0116] The carrier fluid includes the sodium salt and the organic solvent; while the carrier fluid can include, consists essentially of, or consist of the sodium salt and the organic solvent, the carrier fluid, preferably, includes water. In a preferable instance, the carrier fluid includes, consists essentially of, or consists of the sodium salt, the organic solvent, and water; more preferably, the carrier fluid is a homogeneous solution of the sodium salt, organic solvent, and water. In one instance, the water and the organic solvent are miscible. In another instance, the sodium salt is soluble in an admixture of the organic solvent and water. In still another instance, the sodium salt is dissolved in the admixture of the organic solvent and water. Notably, sodium salt hydrates mixed with / dissolved in the organic solvent creates a carrier fluid that includes the sodium salt, the organic solvent, and the water (from the hydrate).

[0117] The carrier fluid further includes a molar ratio of sodium to the organic solvent of about 1 : 10 to about 100: 1, about 1 :2 to about 50: 1, about 1 :2 to about 25: 1, about 1 :2 to about 20: 1, about 1 :2 to about 15: 1; about 1:2 to about 10: 1, or about 1 : 1 to about10: 1. In one instance, the sodium to organic solvent molar ratio is about 1 : 1 to about 5: 1, about 1 : 1 to about 3 : 1, or about 1 : 1 to about 2: 1.

[0118] The organic solvent is selected, preferably, for those organic solvents that are miscible with water. In one instance, the organic solvent includes ethylene glycol, propylene glycol, methoxyethanol, ethoxyethanol, methoxypropanol, ethoxypropanol, diethylene glycol, dipropylene glycol, glycerol, 3 -m ethoxy- 1,2-propane diol, 2-methyl-l,3- propanediol, trimethylolmethane, or a mixture thereof. In a preferable instance, the organic solvent includes ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerol, trimethylolmethane, or a mixture thereof. In particular instances, the organic solvent includes ethylene glycol, propylene glycol, diethylene glycol, and / or glycerol. In another instance, the organic solvent includes, consists essentially of, or consist of ethylene glycol. In another instance, the organic solvent includes, consists essentially of, or consist of propylene glycol. In another instance, the organic solvent includes, consists essentially of, or consist of glycerol. In another instance, the organic solvent includes, consists essentially of, or consist of trimethylolmethane. In still another instance, the organic solvent has a boiling point greater than about 125 °C, about 150 °C, 175 °C, or about 200 °C.

[0119] A carrier fluid that includes water, further includes a molar ratio of water to the organic solvent. The molar ratio of water to the organic solvent can be about 1 : 1 to about 100: 1; preferably, the molar ratio of water to the organic solvent is about 3:2 to about 10: 1. In another instance, the molar ratio of water to the organic solvent can be about 1, 1.1, 1.2,I.3, 1.4, 1.5, 1.6, 1.7, 1.8, 1.9, 2, 2.1, 2.2, 2.3, 2.4, 2.5, 2.6, 2.7, 2.8, 2.9, 3, 3.1, 3.2, 3.3, 3.4,3.5, 3.6, 3.7, 3.8, 3.9, 4, 4.1, 4.2, 4.3, 4.4, 4.5, 4.6, 4.7, 4.8, 4.9, 5, 5.1, 5.2, 5.3, 5.4, 5.5, 5.6,5.7, 5.8, 5.9, 6, 6.1, 6.2, 6.3, 6.4, 6.5, 6.6, 6.7, 6.8, 6.9, 7, 7.1, 7.2, 7.3, 7.4, 7.5, 7.6, 7.7, 7.8,7.9, 8, 8.1, 8.2, 8.3, 8.4, 8.5, 8.6, 8.7, 8.8, 8.9, 9, 9.1, 9.2, 9.3, 9.4, 9.5, 9.6, 9.7, 9.8, 9.9, 10,I I, 12, 13, 14, 15, 16, 17, 18, 19, or 20. In still another instance, the molar ratio of water to the organic solvent can be about, 1, 5, 10, 15, 20, 25, 30, 35, 40, 45, 50, 55, 60, 65, 70, 75, 80, 85, 90, 95, or 100.

[0120] The sodium salt is preferably an alkaline sodium salt. In another instance, the sodium salt can be selected from sodium carbonate, sodium bicarbonate, sodium sulfate, sodium bisulfate, sodium sulfide, sodium thiolate, sodium nitrate, sodium chloride, sodium acetate, sodium citrate, sodium formate, sodium hydroxide, or mixtures thereof. In a particularly preferable instance, the sodium salt includes sodium carbonate. In a still more preferable instance, the sodium salt consists essentially of sodium carbonate. In a yet still more preferable instance, the sodium salt consists of sodium carbonate.

[0121] As described above, the process includes extracting a lithium bicarbonate solution from the product slurry; and then separating lithium carbonate and a filtrate from the lithium bicarbonate solution. The process of extracting the lithium bicarbonate can include admixing the product slurry with water and CO2. Notably, the product slurry can be admixed with water and then carbon dioxide added, alternatively, the product slurry can be admixed with a carbonated water. Still further, the process can include diluting the product slurry with carbonated water and then continuing to add carbon dioxide to the lithium bicarbonate solution, preferably until the pH of the solution stabilises, more preferably wherein the pH stabilises at a value of about 6.5, 6.8, 7, 7.2, 7.4, 7.6, 7.8, 8, 8.2, 8.4, or 8.5; or at a pH between the values of about 6.5 and about 8.5, or about 6.7 and about 8.2. The lithium bicarbonate solution prepared by admixing the product slurry with water and carbon dioxide can include the organic solvent. Still further, the lithium bicarbonate solution prepared by admixing the product slurry with water and carbon dioxide can include the sodium salt, specifically excess of the sodium salt that was not utilised in the extraction of the lithium from the lithium particulate.

[0122] The process can include precipitating lithium carbonate from the lithium bicarbonate solution. In one example, the lithium carbonate can be precipitated (crystallised) from the lithium bicarbonate solution by heating the solution thereby driving off carbon dioxide and decreasing the solubility of the lithium carbonate in the solvent(s). Thereafter, the, preferably, crystalline lithium carbonate is recovered by separating the solids from a filtrate. The separation can utilise a filter, a filter press, a centrifuge, or other such solids separation systems as available to the industry. Herein, the filtrate, separated from the lithium carbonate solids, preferably includes the organic solvent. Thereafter the organic solvent from the filtrate can be recycled and / or reused in the process. Even more preferably, the organic solvent is not retained on the lithium carbonate solids or can be washed off of the lithium carbonate solids. That is, the process of separating lithium carbonate and a filtrate from the lithium bicarbonate solution includes heating the lithium bicarbonate solution, removing carbon dioxide from the solution, precipitating lithium carbonate crystals from the solution, and then isolating the lithium carbonate crystals.

[0123] In a further embodiment, the lithium extraction process is implemented as a fully integrated, continuous system designed for industrial-scale operation, with advanced recycling of both the organic solvent and sodium salt. The process begins with the preparation of a reaction slurry, which consists essentially of a lithium-containing particulate — such as P-spodumene, lepidolite, or petalite — combined with a carrier fluidformulated from sodium carbonate, water, and an organic solvent like ethylene glycol, propylene glycol, or glycerol. The particulate is milled or classified to an optimal size range, typically between 10 pm and 1000 pm, to maximise surface area and extraction efficiency.

[0124] The reaction slurry is continuously fed into a heated reactor, where it is maintained at a temperature between 150 °C and 300 °C under controlled agitation. Automated sensors monitor and adjust key parameters, including the molar ratios of sodium to lithium and water to organic solvent, ensuring consistent process conditions. As the slurry reacts, lithium ions are exchanged and solubilised, forming a product slurry rich in lithium carbonate. This product slurry is then transferred to an extraction vessel, where it is treated with water and carbon dioxide, either as a gas or in carbonated water, to convert the lithium carbonate to lithium bicarbonate.

[0125] Following extraction, the lithium bicarbonate solution is separated from the residual solids using filtration or centrifugation. The solution is then heated in a crystallisation unit, where carbon dioxide is removed, causing lithium carbonate to precipitate as high-purity crystals. These crystals are isolated by solid-liquid separation techniques, such as pressure filtration or decantation, and washed to remove any adhering solvent or salt residues.

[0126] The remaining filtrate, which contains the organic solvent and residual sodium carbonate, is collected and subjected to a multi-stage purification process. This may include membrane filtration to remove fine particulates, ion exchange to eliminate trace impurities, and evaporation or distillation to concentrate the solvent and salt. The purified organic solvent and sodium carbonate are then reconstituted to the desired concentrations and ratios, and combined with recycled or fresh water to reformulate the carrier fluid for the next extraction cycle.

[0127] Throughout the process, advanced process control systems continuously monitor reagent concentrations, temperature, pH, and flow rates, allowing for real-time optimisation and rapid response to changes in feedstock quality or operational demands. Energy recovery systems, such as heat exchangers, are integrated to capture and reuse thermal energy from the heating and crystallisation steps, further improving process efficiency.

[0128] This embodiment enables the process to operate with minimal input of fresh reagents, significantly reducing operational costs and environmental impact. The closed- loop recycling of both the organic solvent and sodium salt supports sustainable production practices and regulatory compliance, while the automated controls ensure consistent productquality and high recovery rates. The system is scalable and adaptable, making it suitable for deployment in large-scale lithium processing facilities seeking to maximize resource efficiency and minimise waste.

[0129] In another embodiment, the lithium extraction process is implemented as a modular batch system, designed for flexibility and high recovery from a variety of lithium- bearing feedstocks. The process begins with the preparation of a batch reaction slurry, where a lithium-containing particulate — such as finely milled P-spodumene, lepidolite, or petalite, with a particle size distribution typically between 20 pm and 500 pm — is combined with a carrier fluid comprising sodium carbonate, water, and an organic solvent such as propylene glycol or a mixture of ethylene glycol and glycerol. The batch reactor is equipped with precise temperature and agitation controls, allowing the slurry to be heated to a target range of 175 °C to 250 °C for a defined residence time, ensuring optimal lithium extraction kinetics.

[0130] After the initial heating phase, the batch is transferred to a secondary extraction vessel, where additional water and carbon dioxide are introduced in a controlled manner. This staged addition of water and CO2 promotes the selective conversion of lithium carbonate to lithium bicarbonate, while minimising the dissolution of unwanted impurities. The resulting mixture is then subjected to advanced solid-liquid separation using a combination of cross-flow filtration and decanter centrifugation, which efficiently isolates the lithium bicarbonate-rich solution from the residual solids and unreacted ore.

[0131] The clarified lithium bicarbonate solution is directed to a crystallisation module, where it is gradually heated under reduced pressure to drive off carbon dioxide and induce the precipitation of lithium carbonate. The crystalliser is designed for precise control of temperature ramp rates and agitation, promoting the formation of uniform, high-purity lithium carbonate crystals. These crystals are collected via vacuum filtration, washed with a minimal volume of cold water or organic solvent to remove surface impurities, and then dried under controlled conditions.

[0132] Meanwhile, the filtrate — containing the organic solvent, residual sodium carbonate, and trace impurities — is processed through a multi-stage purification train. This includes activated carbon treatment to remove organic by-products, ion exchange columns for selective removal of dissolved metals, and membrane filtration to concentrate and recover the organic solvent and sodium salt. The purified streams are then recombined and adjusted to the desired concentrations for reuse in subsequent batch cycles, minimising the need for fresh reagent input.

[0133] Throughout the process, modular automation and real-time analytics are employed to monitor key variables such as lithium concentration, sodium-to-lithium ratio, solvent purity, and particle size distribution. This enables rapid adjustment of process parameters to accommodate variations in feedstock quality or production demand. The modular batch design also allows for easy scaling, maintenance, and integration with upstream ore beneficiation or downstream lithium carbonate refining units, making the process highly adaptable for both new and existing lithium processing facilities.Industrial Applicability

[0134] The invention is highly applicable to industrial-scale lithium extraction and processing operations, particularly those involved in the production of lithium carbonate for use in batteries and other advanced materials. Its flexible process design allows for the efficient treatment of a wide range of lithium-containing ores, including both high- and low- grade feedstocks. The use of aqueous-organic mixtures and recyclable solvents not only enhances extraction efficiency and product purity but also reduces environmental impact and operational costs. These advantages make the invention well-suited for integration into existing lithium processing facilities or for deployment in new plants seeking to meet the growing global demand for high-purity lithium carbonate in a sustainable and economically viable manner.Economic and Environmental Considerations

[0135] From both economic and environmental perspectives, the present invention offers significant economic and environmental advantages over conventional lithium extraction methods. By utilising recyclable organic solvents and minimising the use of harsh chemicals, the process reduces both reagent costs and the environmental footprint associated with waste disposal and emissions. The ability to recycle key reagent streams lowers operational expenses and conserves valuable resources. Additionally, the process operates under milder thermal conditions compared to traditional acid or caustic leaching, resulting in lower energy consumption. These features make the invention not only cost-effective for large-scale industrial deployment but also aligned with modern sustainability goals and regulatory requirements for environmentally responsible mineral processing.

[0136] While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the compositions and / or methods in the steps or in the sequence of stepsof the method described herein without departing from the concept, spirit and scope of the invention. More specifically, it will be apparent that certain agents that are both chemically and physically related may be substituted for the agents described herein while the same or similar results would be achieved. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as defined by the appended claims.

Claims

THE CLAIMS DEFINING THE INVENTION ARE AS FOLLOWS:-1. A process comprising: heating a reaction slurry to a reaction temperature of about 150 °C to about 300 °C; whereby the reaction slurry is converted to a product slurry; thereafter extracting a lithium bicarbonate solution from the product slurry; and then separating lithium carbonate and a filtrate from the lithium bicarbonate solution; wherein the reaction slurry includes: a carrier fluid that includes a sodium salt and an organic solvent; and a particulate having an average particle size of about 1 pm to about 1000 pm and a lithium concentration of about 0.5 wt.% to about 5 wt.%; the reaction slurry further includes a molar ratio of sodium to lithium of about 1 : 1 to about 4: 1.

2. A process according to claim 1, wherein the particulate includes P-spodumene.

3. A process according to claim 1 or claim 2, wherein the carrier fluid includes water.

4. A process according to claim 3, wherein the water and the organic solvent are miscible.

5. A process according to claim 4, wherein the sodium salt is soluble in an admixture of the organic solvent and water.

6. A process according to claim 5, wherein the sodium salt is dissolved in the admixture of the organic solvent and water.

7. A process according to claim 3, wherein the carrier fluid includes a molar ratio of water to the organic solvent of about 1 : 1 to about 100: 1.

8. A process according to claim 7, wherein the molar ratio of water to the organic solvent is about 3 :2 to about 10: 1.

9. A process according to any one of claims 3 to 8, wherein the sodium salt includes sodium carbonate.

10. A process according to claim 9, wherein the sodium salt consists essentially of sodium carbonate.

11. A process according to any one of claims 3 to 10, wherein the carrier fluid consists essentially of the sodium salt, water, and the organic solvent.

12. A process according to any one of the preceding claims, further comprising a molar ratio of sodium to the organic solvent of about 1 : 1 to about 10: 1.

13. A process according to any one of the preceding claims, wherein the organic solvent includes ethylene glycol, propylene glycol, methoxyethanol, ethoxyethanol, methoxypropanol, ethoxypropanol, diethylene glycol, dipropylene glycol, glycerol, 3 -m ethoxy- 1,2-propane diol, 2-methyl-l,3-propanediol, trimethylolmethane, or a mixture thereof.

14. A process according to claim 13, wherein the organic solvent includes ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerol, trimethylolmethane, or a mixture thereof.

15. A process according to any one of the preceding claims, wherein the organic solvent has a boiling point greater than about 150 °C.

16. A process according to claim 1, wherein the reaction slurry consists essentially of the carrier fluid and the lithium particulate.

17. A process according to any one of the preceding claims, wherein the lithium bicarbonate solution includes the organic solvent.

18. A process according to claim 17, wherein the lithium bicarbonate solution includes the sodium salt.

19. A process according to claim 17 or claim 18, wherein the filtrate includes the organic solvent.

20. A process according to claim 19, wherein the organic solvent from the filtrate is reused in the process.

21. A process according to any one of the preceding claims, wherein separating lithium carbonate and a filtrate from the lithium bicarbonate solution includes heating the lithium bicarbonate solution, removing carbon dioxide from the solution, precipitating lithium carbonate crystals from the solution, and then isolating the lithium carbonate crystals.

22. A process according to any one of the preceding claims, wherein the product slurry includes: a carrier fluid that includes sodium carbonate and an organic solvent; a particulate having an average particle size of about 0.1 pm to about 1000 pm, a lithium concentration of about 0.001 wt.% to about 0.5 wt.%, and a sodium concentration of about 1.5 wt.% to about 20 wt.%; and lithium carbonate; the product slurry further includes a molar ratio of sodium to lithium of about 1 : 1 to about 4: 1.

23. A process according to claim 22, wherein the lithium carbonate includes crystalline lithium carbonate.

24. The product slurry of claim 22.

25. The reaction slurry of claim 1.

26. A slurry comprising: a carrier fluid that includes a sodium salt and an organic solvent; and a particulate having an average particle size of about 1 pm to about 1000 pm and a lithium concentration of about 0.5 wt.% to about 5 wt.%; the slurry further comprising a molar ratio of sodium to lithium of about1 : 1 to about 4: 1.

27. The slurry of claim 26, wherein the particulate includes P-spodumene.

28. The slurry of claim 26 or 27, wherein the particulate is a calcined spodumene concentrate.

29. The slurry of any one of claims 26 to 28, wherein the carrier fluid includes water.

30. The slurry of claim 29, wherein the water and the organic solvent are miscible.

31. The slurry of claim 30, wherein the sodium salt is soluble in an admixture of the organic solvent and water.

32. The slurry of claim 31, wherein the sodium salt is dissolved in the admixture of the organic solvent and water.

33. The slurry of claim 29, wherein the carrier fluid includes a molar ratio of water to the organic solvent of about 1 : 1 to about 100: 1.

34. The slurry of claim 33, wherein the molar ratio of water to the organic solvent is about 3 :2 to about 10: 1.

35. The slurry of claim 29, wherein the sodium salt includes sodium carbonate.

36. The slurry of claim 36, wherein the sodium salt consists essentially of sodium carbonate.

37. The slurry of claim 29, wherein the carrier fluid consists essentially of the sodium salt, water, and the organic solvent.

38. The slurry of any one of claims 29 to 37, further comprising a molar ratio of sodium to the organic solvent of about 1 : 1 to about 10: 1.

39. The slurry of any one of claims 29 to 38, wherein the organic solvent includes ethylene glycol, propylene glycol, methoxyethanol, ethoxyethanol, methoxypropanol, ethoxy propanol, diethylene glycol, dipropylene glycol, glycerol, 3 -m ethoxy- 1,2-propane diol, 2-methyl-l,3-propanediol, trimethylolmethane, or a mixture thereof.

40. The slurry of claim 39, wherein the organic solvent includes ethylene glycol, propylene glycol, diethylene glycol, dipropylene glycol, glycerol, trimethylolmethane, or a mixture thereof.

41. A product slurry comprising: a carrier fluid that includes sodium carbonate and an organic solvent; a particulate having an average particle size of about 0.1 pm to about 1000 pm, a lithium concentration of about 0.001 wt.% to about 0.5 wt.%, and a sodium concentration of about 1.5 wt.% to about 20 wt.%; and lithium carbonate; the slurry further comprising a molar ratio of sodium to lithium of about 1 : 1 to about 4: 1.

42. The product slurry of claim 41, wherein the lithium carbonate includes crystalline lithium carbonate.

43. The product slurry of claim 41 or claim 42, wherein a portion of the crystalline lithium carbonate is adhered to the particulates.

44. The product slurry of claim 43, wherein the carrier fluid further includes water.

45. A process comprising: heating, to a reaction temperature of about 150 °C to about 300 °C, a reaction slurry that includes of an admixture of a carrier fluid and a lithium particulate, where the carrier fluid includes a sodium salt, water, and an organic solvent, and where the lithium particulate has an average particle size of about 1 pm to about 1000 pm and a lithium concentration of about 0.5 wt.% to about 5 wt.%, the slurry further comprising a molar ratio of sodium to lithium of about1 : 1 to about 4: 1; whereby the slurry is converted to a product slurry; thereafter extracting a lithium bicarbonate solution from the product slurry; and then separating lithium carbonate and a filtrate from the lithium bicarbonate solution.

46. The process of claim 45, wherein the reaction slurry consists essentially of the carrier fluid and the lithium particulate.

47. The process of claim 45 or 46, wherein the organic solvent has a boiling point greater than about 150 °C.

48. The process of any one of claims 45 to 47, wherein the lithium bicarbonate solution includes the organic solvent.

49. The process of any one of claims 45 to 48, wherein the lithium bicarbonate solution includes the sodium salt.

50. The process of any one of claims 45 to 49, wherein the filtrate includes the organic solvent.

51. The process of claim 50, wherein the organic solvent from the filtrate is reused in the process.

52. The process of any one of claims 45 to 52, wherein separating lithium carbonate and a filtrate from the lithium bicarbonate solution includes heating the lithium bicarbonate solution, removing carbon dioxide from the solution, precipitating lithium carbonate crystals from the solution, and then isolating the lithium carbonate crystals.