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WO2025141295A1 - Enrichissement de minerai contenant du lithium - Google Patents

Enrichissement de minerai contenant du lithium Download PDF

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Publication number
WO2025141295A1
WO2025141295A1 PCT/IB2023/000715 IB2023000715W WO2025141295A1 WO 2025141295 A1 WO2025141295 A1 WO 2025141295A1 IB 2023000715 W IB2023000715 W IB 2023000715W WO 2025141295 A1 WO2025141295 A1 WO 2025141295A1
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Prior art keywords
component
formula
units
lithium
ether carboxylic
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English (en)
Inventor
Oriol PORCAR TOST
Thomas Myrdek
Joan Antoni RIAZA MARTÍNEZ
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Kao Corp SA
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Kao Corp SA
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Priority to PCT/IB2023/000715 priority Critical patent/WO2025141295A1/fr
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/0043—Organic compounds modified so as to contain a polyether group
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D1/00—Flotation
    • B03D1/001—Flotation agents
    • B03D1/004—Organic compounds
    • B03D1/008—Organic compounds containing oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2201/00—Specified effects produced by the flotation agents
    • B03D2201/02—Collectors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B03—SEPARATION OF SOLID MATERIALS USING LIQUIDS OR USING PNEUMATIC TABLES OR JIGS; MAGNETIC OR ELECTROSTATIC SEPARATION OF SOLID MATERIALS FROM SOLID MATERIALS OR FLUIDS; SEPARATION BY HIGH-VOLTAGE ELECTRIC FIELDS
    • B03D—FLOTATION; DIFFERENTIAL SEDIMENTATION
    • B03D2203/00—Specified materials treated by the flotation agents; Specified applications
    • B03D2203/02—Ores
    • B03D2203/04—Non-sulfide ores

Definitions

  • the present invention relates to a collector composition for the beneficiation of lithium–containing minerals, from an ore, their use in flotation processes and the process for beneficiation of lithium containing minerals using said collector composition.
  • STATE OF ART Lithium is an important strategic resource substance which is widely applied to emerging fields of batteries, ceramics, glass, lubricants, refrigerants, nuclear industry, photoelectricity and the like, and is an indispensable important raw material of modern high-tech products.
  • the continuous development of high and new technologies growth of lithium battery electric vehicles and lithium battery mobile electronic products, lithium and lithium salt products are more and more widely applied, and the demand of the international market for the lithium products is continuously increasing.
  • Lithium does not occur in elemental form in nature because of its reactivity. However, there are more than 100 known minerals that may contain lithium, although only a few of these are currently economic to extract. The most common lithium-bearing minerals found in economic deposits are Spodumene, Lepidolite, Petalite, Eucryptite, Amblygonite, Hectorite, Bikitaite, Zinnwaldite, and Jadarite. Among them, due to its high lithium content, spodumene is considered the most important lithium ore mineral. A typical run of mine ore can contain 0,5-2% LiO, while a typical Spodumene concentrate suitable for lithium carbonate production contains 5,5-7% LiO (68% - 87% spodumene).
  • Lithium produced from brines is generally of a low grade and, while the capital input for brine production is high, operating costs are low.
  • conventional mining and beneficiation techniques are used to produce high grade spodumene concentrate or other mineral concentrates in which the grade is greater than that of the parent are. It is possible to obtain lithium chemicals of technical, battery grade (99.5%) from various acid-roasting and lime-roasting processes.
  • the mineral which can be dry ground, but preferably wet-ground, is previously crumbled and suspended in water for the flotation.
  • Anionic surfactants are used as collectors in known processes for the beneficiation lithium containing minerals, such as fatty acids.
  • Known anionic collectors are, for example, saturated and unsaturated fatty acids, oleic acid fatty acids, linoleic acids, linolenic acids, resin acids, tall oil fatty acids, phosphoric esters, especially optionally alkoxylated phosphoric esters derived from fatty alcohols or from fatty alcohol mixtures, alkyl sulfates, especially alkyl sulfates derived from fatty alcohols or from fatty alcohol mixtures, alkylaryl sulfonates, alkyl sulfosuccinates, alkylsulfosuccinimates and acyl lactylates.
  • WO2021038017 describes a collector composition, comprising at least one component a) selected from N-oleoyl sarcosine; and at least one component b) selected from the group consisting of di(isononyl)phthalate, di(2-ethylhexyl)phthalate, di(2- propylheptyl) phthalate, di(isononyl)adipate, di(2- ethylhexyl)adipate, di(2-propylheptyl)adipate and isotridecanol for the beneficiation of lithium silicates and magnesium silicates from an ore comprising different silicate minerals, their use in flotation processes and a method for the beneficiation of lithium silicates- and magnesium silicates- containing minerals using said collector composition.
  • component (b) is preferably a C-C fatty acid or a mixture of C-C fatty acids; more preferably a C -C fatty acid or a mixture of C -C fatty
  • component (b) is a C -C fatty acid or a mixture of acids, preferably obtained from tall oil fatty acid, oleic acid or their mixtures.
  • component (b) is a C12-C18 fatty acid or mixture of fatty acids, preferably oleic acid.
  • a:b is 1:99 to 99:1, preferably from 3:97 to 60:40, more preferably from 5:95 to 50:50.
  • the weight ratio between component (a) and component (b), i.e. a:b is from is from 35:65 to 15:85 and/or from 33:67 to 25:75.
  • the amount of fatty acid of Formula (II) or fatty acid mixtures, i.e. component (b), in the collector composition of the invention is from 0.05 to 99.5 wt%, preferably from 40 to 97 wt%, more preferably from 50 to 95 wt%.
  • the collector composition according to the present invention further may comprises a component (c), which is an ether carboxylic acid or a salt thereof as defined below.
  • R in the ether carboxylic acids or salts thereof of component (a) represents a linear or branched alkyl or alkenyl chain as previously defined, but having from 10 to 30 carbon atoms, preferably from 10 to 22, more preferably from 12 to 18, even more preferably from 12 to 16, still more preferably from 12 to 14.
  • P, X, n, m and q in the ether carboxylic acids or salts thereof of component (a) are as previously defined.
  • n, m and q in the ether carboxylic acids or salts thereof of component (a) are each independently a number from 0 to 15, preferably from 0 to 10, more preferably from 0 to 6, and the sum of n+m+q is from 1 to 15, preferably from 1 to 10, more preferably from 1 to 6.
  • the collector composition according to the present invention (wherein R in the ether carboxylic acids or salts thereof of component (a) represents a linear or branched alkyl or alkenyl chain as previously defined, but having from 10 to 30 carbon atoms, preferably from 10 to 22, more preferably from 12 to 18, even more preferably from 12 to 16, still more preferably from 12 to 14) may further comprise a component (c), said component being ether carboxylic acids or salts thereof of formula (III): R-O-A-CH-COOX (III) wherein, R is a linear or branched alkyl or alkenyl chain having from 4 to 8 carbon atoms; preferably from 6 to 8 carbon atoms, more preferably 8 carbon atoms; A consists of r units of –(CHCHO)-, and/or s units of –(CHCHRO)- or –(CHRCHO)-, and/or p units of –(CHCHRO)- or –(CHRCHO)-, wherein
  • alkyl refers to a straight or branched hydrocarbon chain containing the indicated number of carbon atoms, such as from 4 to 8 carbon atoms.
  • alkenyl refers to a linear hydrocarbon chain containing the indicated number of carbon atoms, such as from 4 to 8 carbon atoms, and from 1 to 3 double bonds.
  • alkali metal refers to any of lithium (Li), sodium (Na), potassium (K), rubidium (Rb) and cesium (Cs), preferably any of sodium and potassium.
  • alkaline earth metal refers to any of beryllium (Be), magnesium (Mg), calcium (Ca), strontium (Sr) and barium (Ba), preferably any of magnesium and calcium.
  • ammonium refers to NH .
  • alkyl ammonium refers to a quaternary ammonium substituted by 1, 2 or 3 alkyl groups as defined herein. In particular, each alkyl group has from 1 to 30 carbon atoms.
  • alkylammonium examples include dimethyloctylammonium, dimethyldecylammonium, dimethyllauryl- ammonium, dimethylmyristylammonium, dimethylpalmitylammonium, dimethylcetylammonium, dimethylstearylammonium, dimethylbehenyl- ammonium, or mixtures thereof.
  • alkylammonium examples include methyldioctylammonium, methyldidecylammonium, methyldilauryl- ammonium, methyldimyristylammonium, methyldipalmitylammonium, methyldicetylammonium, methyldistearylammonium, methyldibehenyl- ammonium, or mixtures thereof.
  • salt refers to the carboxylate anion of the compound of formula (III) as defined herein (i.e.
  • R-O-A- CHCOO and a suitable cation selected from the groups of an alkali metal (such as Na and K), an alkaline earth metal (such as Ca and Mg , ammonium, or alkylammonium.
  • salts of ether carboxylic acid represented by formula (III) are sodium salt or potassium salt of the ether carboxylic acid of the compound of formula (III), i.e. wherein X is Na or K.
  • R is a linear or branched alkyl or a linear alkenyl derived from natural fats and oils, as well as of synthetic origin.
  • Preferred fats and oils include palm oil, coconut oil, sunflower oil, rapeseed oil, castor oil, olive oil, soybean oil; animal fat such as tallow, bone oil, fish oil, hardened oils and semi-hardened oils thereof, and mixtures thereof.
  • the fats and oils may contain a great variety of alkyl and/or alkenyl groups, said groups being linear or branched, saturated or unsaturated.
  • R is a linear or branched alkyl chain having from 4 to 8 carbon atoms, preferably from 6 to 8 carbon atoms, more preferably 8 carbon atoms
  • R is a linear alkyl chain having from 4 to 8 carbon atoms, preferably from 6 to 8 carbon atoms, more preferably 8carbon atoms.
  • the ether carboxylic acid or salts thereof according to Formula (III) can be ethoxylated and/or propoxylated and/or butoxylated, i.e. A is an ethoxy and/or propoxy and/or butoxy group.
  • A consists of r units of –(CHCHO)-, and/or s units of –(CHCHRO)- or – (CHRCHO)-, and/or p units of –(CHCHRO)- or –(CHRCHO)-, wherein r represents a number within the range of 0 to 20, preferably 0 to 18, more preferably from 0 to 8; s represents a number within the range of 0 to 20, preferably 0 to 18, more preferably from 0 to 8; p represents a number within the range of 0 to 20, preferably 0 to 18, more preferably from 0 to 8.
  • r represents a number within the range of 0 to 20, preferably 0 to 18, more preferably from 0 to 8.
  • the alkoxylation degree is represented by the sum of moles of ethylene oxide and/or propylene oxide and /or butylene oxide that are present in the ether carboxylic acids or salt thereof of formula (III), i.e., the sum of r+s+p, and which is each independently a number is from 1 to 20, preferably from 1 to 18, more preferably from 1 to 8.
  • the ether carboxylic acid of formula or salts thereof according to Formula (III) are ethoxylated and/or propoxylated and/or butoxylated, i.e. A is an ethoxy and/or propoxy and/or butoxy group.
  • both the ether carboxylic acids or salts thereof and the sum of r+s+p represents the average alkoxylation degree which corresponds to a number from 1 to 20, preferably from 1 to 18, more preferably from 1 to 8.
  • the ether carboxylic acids or salts thereof of formula (III) can be ethoxylated and/or propoxylated and/ or butoxylated.
  • Both the ether carboxylic acid according to formula (III) comprising ethylene oxide groups and/or propylene oxide groups and/or butylene oxide groups in separate blocks and the ether carboxylic acid according to formula (III) comprising ethylene oxide and/or propylene oxide and/or butylene oxide groups randomly distributed can be used in the compositions according to the invention.
  • A consists of r units of –(CHCHO)- wherein s represents a number within the range of 1 to 20, preferably 1 to 18, more preferably from 1 to 8; s and p represent 0, and the sum of r+s+q represents a number from 1 to 20, preferably from 1 to 18, more preferably from 1 to 8.
  • A consists of s units of –(CHCHRO)- or –(CHRCHO)- wherein s represents a number within the range of 1 to 20, preferably 1 to 18, more preferably from 1 to 8; and r and p represents 0, and the sum of r+s+p represents a number from 1 to 20, preferably from 1 to 18, more preferably from 1 to 8.
  • A consists of p units of –(CHCHRO)- or –(CHRCHO)-, wherein p represents a number within the range of 1 to 20, preferably 1 to 18, more preferably from 1 to 8; and r and s represents 0, and the sum of r+s+p represents a number from 1 to 20, preferably from 1 to 18, more preferably from 1 to 8.
  • A consists of r units of –(CHCHO)- and an average of s units of –(CHCHRO)- or –(CHRCHO)-, wherein r represents a number within the range of 0 to 20, preferably 0 to 18, more preferably from 0 to 8; s represents a number within the range of 0 to 20, preferably 0 to 18, more preferably from 0 to 8; p represents 0, and the sum of r+s+p represents a number from 1 to 20, preferably from 1 to 18, more preferably from 1 to 8.
  • the ether carboxylic acid or salts thereof of formula (III) comprises ethylene oxide and propylene oxide groups.
  • the ether carboxylic acid or salts thereof of formula (III) is free from propylene oxide and butylene oxide, i.e. it only contains ethylene oxide units.
  • the ether carboxylic acid or salts thereof are those of formula (IIIa): R-O-(CHCHO)-CH-COOX (IIIa) wherein R is a linear or branched alkyl or alkenyl chain having from 4 to 8 carbon atoms; r is an integer number from 1 to 8, and X is H or a cation selected from the group consisting of an alkali metal, an alkaline earth metal, ammonium and alkylammonium.
  • R is a linear alkyl chain having from 6 to 8 carbon atoms and r is an integer number from 1 to 6.
  • the process for obtaining the ether carboxylic acids or salts thereof according to Formula (III) is the same as previously described for obtaining the of compound of Formula (I).
  • Examples of commercially available ether carboxylates of Formula (III) are AKYPO LF 1, AKYPO LF 2, AKYPO LF 4, and AKYPO LF 6, all marketed by Kao Chemicals Europe.
  • the collector composition according to the present invention may further comprise a component (d), said component being a fatty alcohol or a mixture of fatty alcohols containing from 4 to 30 carbon atoms.
  • C4-C30 fatty alcohols are aliphatic alcohols that can be derived from natural fats and oils.
  • Preferred fats and oils include palm oil, coconut oil, sunflower oil, rapeseed oil, castor oil, olive oil, soybean oil; animal fat such as tallow, fish oil, hardened oils and semihardened oils thereof, and mixtures thereof.
  • the alcohols that are alkoxylated may contain a great variety of alkyl and alkenyl groups, said groups being linear or branched, saturated or unsaturated.
  • fatty alcohols (d) are derived from natural fats and oils, as well as of synthetic origin.
  • Preferred fats and oils include palm oil, coconut oil, sunflower oil, rapeseed oil, castor oil, olive oil, soybean oil; animal fat such as tallow, bone oil, fish oil, hardened oils and semihardened oils thereof, and mixtures thereof.
  • the fats and oils may contain a great variety of alkyl and/or alkenyl groups, said groups being linear or branched, saturated or unsaturated.
  • the fatty alcohol (d) is represented by formula (IV): R-O-D-H (IV) wherein R and D are as previously defined.
  • R is a linear or branched alkyl group containing 10 to 30 carbon atoms or a linear alkenyl group containing 10 to 30 carbon atoms and from 1 to 3 double bonds, preferably from 10 to 22 carbon atoms, more preferably from 12 to 18 carbon atoms, still more preferably from 12 to 16 carbon atoms, even more preferably from 12 to 14 carbon atoms.
  • D consists of t units of –(CHCHO)-, and/or u units of –(CHCHRO)- or – (CHRCHO)-, and/or v units of –(CHCHRO)- or –(CHRCHO)-, wherein t represents a number within the range of 0 to 15 preferably 0 to 10, more preferably from 0 to 6, even more preferably from 0 to 3.; u represents a number within the range of 0 to 15, preferably 0 to 10, more preferably from 0 to 6, even more preferably from 0 to 3; v represents a number within the range of 0 to 15, preferably 0 to 10, more preferably from 0 to 6,even more preferably from 0 to 3.
  • ethylene oxide units, propylene oxide units and butylene oxide units can be present in separate blocks or randomly distributed.
  • R is a linear or branched alkyl group containing 4 to 8 carbon atoms or a linear alkenyl group containing 4 to 8 carbon atoms and from 1 to 3 double bounds; preferably from 6 to 8 carbon atoms, more preferably 8 carbon atoms.
  • the alkoxylation degree of the fatty alcohol of formula (Iva) is represented by the sum of x+y+z are each independently a number from 0 to 20, preferably from 0 to 18, more preferably from 0 to 8.
  • the fatty alcohol of formula (IVa) comprises ethylene oxide and propylene oxide groups.
  • the fatty alcohol (IVa) comprising ethylene oxide and propylene oxide groups in separate blocks, and the fatty alcohol of formula (IVa) comprising ethylene oxide and propylene oxide groups randomly distributed can be used in the compositions according to the invention.
  • the fatty alcohol of formula (IV) can be ethoxylated and propoxylated.
  • component (c) of formula (IVa) corresponds to the mixture of alkoxylated fatty alcohols and non-alkoxylated fatty alcohols of formula (Iva) which may be obtained as side products from the carboxymethylation preparation of the ether carboxylic acid (c) of Formula (III).
  • component (d) comprising one or more fatty alcohols of Formula (IVa) is intentionally added to the composition as a blend or mixture.
  • Alkoxylated fatty alcohols according to formulas (IV) and (IVa) may be produced by procedures well-known in the art by reacting the appropriate starting fatty alcohol with ethylene oxide and/or propylene oxide and/or butylene oxide, in the presence of a suitable catalyst, e.g. a conventional basic catalyst, such as KOH, or so-called, narrow range catalyst (see e.g. Nonionic Surfactants: Organic Chemistry in Surfactant Science Series volume 72, 1998, pp 1-37 and 87-107, edited by Nico M. van Os; Marcel Dekker, Inc). If propylene oxide, ethylene oxide and/or butylene oxide are used, the alkoxides may be added as blocks in either order, or may be added randomly.
  • a suitable catalyst e.g. a conventional basic catalyst, such as KOH, or so-called, narrow range catalyst (see e.g. Nonionic Surfactants: Organic Chemistry in Surfactant Science Series volume 72, 1998, pp 1-37 and 87-107, edited
  • the fatty alcohol (d) comprises a mixture of a fatty alcohol of formula (IV) and fatty alcohol of formula (IVa) as defined above.
  • the fatty alcohol of formula (IV) and/or formula (IVa) comprises the corresponding non-alkoxylated fatty alcohols to those of formula (IV) and/or formula (IVa) (i.e. wherein t, u, v, x, y and z are all 0).
  • component (d) corresponds to a mixture of alkoxylated fatty alcohols and non-alkoxylated fatty alcohols of formula (IV) and (IVa).
  • the amount of fatty alcohol (d) in the collector composition of the invention is not more than 50 wt% based on the total weight of the composition, preferably from 0, to 25 wt%, more preferably from 0 to 10 wt% based on the total weight of the composition. Each of the indicated amounts being expressed as percentage by weight of the mentioned component with respect to the total weight of the composition.
  • the collector composition of the present invention may further comprise a component (e), said component being fatty acid ester or mixture of fatty acid esters, wherein the fatty acid ester is having the formula (V): R-COO-R (V) wherein R is selected from the group consisting of R-O-P-CH-, wherein R and P are as defined in Formula (I), R-O-A-CH-, wherein R and A are as defined in formula (III), and R which is as defined in formula (II); R is selected from the group consisting of -D-R, wherein R and D are as defined above for component (d) of formula (IV), and -E- R, wherein R and E are as defined above for component (d) of formula (IVa).
  • V R-COO-R
  • R is selected from the group consisting of R-O-P-CH-, wherein R and P are as defined in Formula (I), R-O-A-CH-, wherein R and A are as defined in formula (III), and R which is
  • the fatty acid ester or a mixture of fatty acid esters (e) is represented by general formula (V-II): R-O-P-CH-COO-E-R (V-II) wherein R, R, P and E are as previously defined.
  • the component (e) the fatty acid ester or a mixture of fatty acid esters of formula (V- II) may be obtained as a by-product from the reaction of the ether carboxylic acid (a) of formula (I) and the free fatty alcohol (d) of formula (IVa), wherein component (d) of formula (IVa) corresponds to the non-alkoxylated fatty alcohols those of formula (IVa) (i.e.
  • the component (e) the fatty acid ester or a mixture of fatty acid esters of formula (V- II) may be obtained as a by-product from the reaction of the ether carboxylic acid (a) of formula (I) and the free fatty alcohol (d) of formula (IVa), wherein component (d) of formula (IVa) corresponds to a mixture of alkoxylated and non-alkoxylated fatty alcohols of general formula (IVa) species from the preparation of the ether carboxylic acid (a) of Formula (I).
  • the fatty acid ester or mixture of fatty acid esters (e) may be obtained as a by- product from the reaction of the ether carboxylic acid (c) of formula (III) and the free fatty alcohol (d) of formula (IV).
  • component (d) of formula (V) R represents R-O-A-CH-, wherein R and A are as defined in Formula (III) and R is -D-R, wherein R and D are as defined above for component (d) of formula (IV).
  • the fatty acid ester or a mixture of fatty acid esters (e) according to the present embodiment is represented by general formula (V-IV): R-O-A-CH-COO-E-R (V-IV) wherein R, A and E are as previously defined.
  • the fatty acid ester or a mixture of fatty acid esters (e)of formula (V-IV) may be obtained as a by-product from the reaction of the ether carboxylic acid (c) of formula (III) and the free fatty alcohol (d) of formula (IVa), wherein component (d) of formula (IVa) corresponds to the non-alkoxylated fatty alcohols those of formula (IVa) (i.e.
  • the fatty acid ester or a mixture of fatty acid esters(e) of formula (V-IV) may be obtained as a by-product from the reaction of the ether carboxylic acid (c) of formula (III) and the free fatty alcohol (d) of formula (IVa), wherein component (d) of formula (IV) corresponds to a mixture of alkoxylated and non-alkoxylated fatty alcohols of general form (IVa) species from the preparation of the ether carboxylic acid (c) of Formula (III).
  • the fatty acid ester or a mixture of fatty acid esters (e) may be obtained by the reaction of Fatty acid or mixture of fatty acids (b) of Formula (II) and the free fatty alcohol (d) of formula (IV).
  • component (d) of formula (V) represents R as defined in Formula (II) and R is -D-R, wherein R and D are as defined above for component (d) of formula (IV).
  • the fatty acid ester or a mixture of fatty acid esters according to the present embodiment is represented by general formula (V-V): R COO-D-R (V-V) wherein R, R and D are as previously defined.
  • the fatty acid ester or mixture of fatty acid esters (e) is obtained by the reaction from the fatty acid or mixture of fatty acids (b) of formula (II) and the of formula (III) and the free fatty alcohol(d) of formula (IVa).
  • component (d) of formula (V) represents R-, wherein R is as defined in Formula (II) and R is -E-R, wherein R and E are as defined above for component (d) of formula (IVa).
  • the fatty acid ester or a mixture of fatty acid esters (e) according to the present embodiment is represented by general formula (V-VI): R-COO-E-R (V-VI) wherein R, R and E are as previously defined.
  • the fatty acid ester or mixture of fatty acids ester (d) of formula (V-VI) is obtained by the reaction of the fatty acid or mixture of fatty acids(b) of formula (II) and the fatty alcohol (d) of Formula (IVa), wherein component (d) of formula (IVa) corresponds to non-alkoxylated fatty alcohols of general form (IVa) species from the preparation of the ether carboxylic acid (c) of Formula (III).
  • the amount of the fatty acid ester (e) is from 0% wt to 50% wt; preferably from 0% wt to 25% wt; more preferably from 0% wt to 10% wt, based on the total weight of the composition.
  • Each of the indicated amounts being expressed as percentage by weight of the mentioned component with respect to the total weight of the composition.
  • the present invention is directed to the use of the collector composition for the beneficiation of lithium- containing minerals contained in an ore comprising lithium- containing minerals and gangue minerals, wherein the composition comprises: (a) at least an ether carboxylic acid or salts thereof of Formula (I) as described above, and (b) a fatty acid or mixture of fatty acids according to Formula (II) as described above; characterized in that the weight ratio between component a) and component b) is comprised between 99:1 and 1:99, preferably between 3:97 and 60:40, more preferably between 5:95 and 50:50. In another embodiment according to the present invention the weight ratio between component (a) and component (b), i.e.
  • a particular embodiment according to the present invention is directed to the use of the collector composition for the beneficiation of lithium-containing minerals contained in an ore, such as lithium silicates, preferably spodumene.
  • the collector composition used in the invention comprises an ether carboxylic acid or salts thereof of formula (I) (component(a)) and a fatty acid or mixtures of fatty acids of Formula (II)(component (b)).
  • the collector composition used in the invention comprises one or more ether carboxylic acid or salts thereof of Formula (I) (component (a)), a fatty acid or mixture thereof of Formula (II) (component (b)), and at least an ether carboxylic acid or salts thereof of Formula (III) (component (c)),.
  • the weight content of the sum of (a) and (c) in the collector composition of the invention is not greater than 95 wt% the indicated amount being expressed as percentage per weight with respect to the total weight of the composition preferably from 3 to 60 wt%, more preferably from 5 to 50 wt%, content of fatty acid (b) is between 0.05 to 99.5 wt%, preferably between 40 to 97 wt%, more preferably between 50 to 95 wt% based on the total weight of the composition.
  • the collector composition used in the invention comprises at least the ether carboxylic acid of formula (I) (component (a)), the fatty acid of formula (II) (component (b)) and the fatty alcohol of formula (IV) (component(d)) wherein component (d) corresponds to the alkoxylated fatty alcohol and non-alkoxylated fatty alcohol from the preparation of the ether carboxylic acid (a), wherein said components are as previously defined.
  • the weight content of the ether carboxylic acids of formula (I) in the collector composition used in the invention is not greater than 99.5 wt%; the weight content of the fatty acid (b) is from 0.05 to 99.5 wt% and the weight content of fatty alcohol (d) in the collector composition is from 0.05 to 50 wt%, wherein the weight percentages are based on the total weight of the composition.
  • the weight content of ether carboxylic acids of formula (I) in the collector composition used in the invention is from 3 to 60 wt%; the weight content of fatty acid (b) is from 40 to 97 wt% and the weight content of fatty alcohol (d) in the collector composition is from 0.05 to 25 wt%, wherein the weight percentages are based on the total weight of the composition.
  • the weight ratio between ether carboxylic acid or salts thereof (a) of formula (I) and the fatty alcohol (d) formula (III), i.e a:d is from 99:1 to 1:50, preferably from 99:1 to 25:25, more preferably from 99:1 to 50:10.
  • the collector composition used in the invention comprises at least the ether carboxylic acid or salts thereof of formula (I) (component (a)), the fatty acid or mixtures thereof of formula (II) (component (b)) and the fatty acid ester or a mixture of fatty acid esters of formula (V) (component (e)), wherein said components are as previously defined.
  • the weight content of the at least the ethercarboxylic acid or salts thereof of formula (I) in the collector composition is not greater than 99.5 wt%; the weight content of fatty acid (b) is from 0.05 to 99.5 wt% and the weight content of fatty acid ester (e) is from 0% wt to 50% wt; preferably from 0 wt% to 25 wt%; more preferably from 0 wt% to 10 wt%, wherein the weight percentages are based on the total weight of the composition.
  • the collector composition used in the invention comprises at least the ethercarboxylic acid or salts thereof of formula (I) (component (a)), the fatty acid or mixture of fatty acids of formula (II) (component (b)), at least the ether carboxylic acid or salts thereof of formula (III) (component (c)) and the fatty acid ester or a mixture of fatty acid esters of formula (V)(e), as previously defined, where component (a) and (c) are different the sum of the weight content of the ether carboxylic acids or salts thereof of formula (I) and formula (III) the indicated amount being expressed as percentage per weight with respect to the total weight of collector composition, the sum of weight of (a) and (c) in the collector composition is not greater than 99.5%wt based on the total weight of the composition; wherein the weight content of the fatty acid or mixture of fatty acids in the collector is from 0.05 to 99.5 wt% and wherein the weight content of fatty acid ester (e) in
  • the components are mixed, preferably under constant stirring, in particular from 10 minutes to 1 hour (preferably for during 10 to 20 min, more preferably for 15 min), more preferably at a temperature between 20oC to 25 oC.
  • the collector composition used in the invention is obtained by mixing the at least an ethercarboxylic acid or salts thereof of formula (I) (component (a)), the fatty acid or mixture of fatty acids of formula (II) (component (b)), the fatty alcohol of formula (IV) (component (d)), wherein component(d) corresponds to a mixture of the non- carboxymethylated species (alkoxylated fatty alcohol and/or non- alkoxylated fatty alcohol) from the preparation of the ether carboxylic acid (a), and the fatty acid ester (component e).
  • the components are mixed, preferably under constant stirring, in particular from 10 minutes to 1 hour (preferably for during 10 to 20 min, more preferably for 15 min), more preferably at a temperature between 20oC to 25 oC.
  • the collector composition used in the invention in obtained by mixing the at least an ethercarboxylic acid or salts thereof of formula (I) (component (a)), the fatty acid or mixture of fatty acids of formula (II) (component (b)), the at least an ether carboxylic acid or salts thereof of formula (III) (component (c)), the fatty alcohol of formula (d) (IV and Iva), wherein component (d) corresponds to a mixture of the non-carboxymethylated species (alkoxylated fatty alcohol and/or non-alkoxylated fatty alcohol) from the preparation of the ether carboxylic acid (a) and (c), and a fatty acid ester of formula (V)(component e), according to formulas V-VI to V-
  • the components are mixed, preferably under constant stirring, in particular from 10 minutes to 1 hour (preferably for during 10 to 20 min, more preferably for 15 min), more preferably at a temperature between 20oC to 25 oC.
  • Process of flotation Another object of the invention is the process for the beneficiation of lithium-containing minerals from an ore, comprising lithium-containing minerals and gangue minerals, wherein collector compositions as previously defined are used.
  • the lithium-containing minerals are lithium silicates, preferably but not limited to spodumene.
  • Step a) and a1) is mixing the ore comprising lithium-containing minerals and gangue minerals, with water to form an aqueous mixture.
  • the lithium-containing mineral is spodumene (LiAlSiO).
  • the main constituents of the ore comprising lithium- containing minerals are as previously defined, in particular, spodumene, quartz, plagioclase, feldspars, muscovite and other silicate minerals.
  • the pH is adjusted with a pH regulating substance such as NaOH, NaCO, KOH, KCO, HCl, HSO, HPO or HNO.
  • component (a), component (b) and component (d), wherein component (d) corresponds to a mixture of the non-carboxymethylated species (alkoxylated fatty alcohol and non-alkoxylated fatty alcohol) from the preparation of the ether carboxylic acid (a) are charged as a blend in step b) and d1) or alternatively component (a), component (b) and component (d) of collector composition are charged separately.
  • component (a), component (b) and component (e) are charged as a blend in step b) and d1) or alternatively component (a), component (b) and component (e) of collector composition are charged separately.
  • component (a), component (b), component (d) and component (e), wherein component (d) corresponds to a mixture of the non- carboxymethylated species (alkoxylated fatty alcohol and non- alkoxylated fatty alcohol) from the preparation of the ether carboxylic acid (a), are charged as a blend in step b) and d1) or alternatively component (a), component (b), component (d) and component (e) of collector composition are charged separately.
  • component (a), component (b), component (c) and component (d), wherein component (d) corresponds to a mixture of the non- carboxymethylated species (alkoxylated fatty alcohol and non- alkoxylated fatty alcohol) from the preparation of the ether carboxylic acid (a), are charged as a blend in step b) and d1) or alternatively component (a), component (b), component (c) and component (e) of collector composition are charged separately.
  • component (a), component (b), component (c) and component (e) are charged as a blend in step b) and d1) or alternatively component (a), component (b), component (c), component (d) and component (e) of collector composition are charged separately.
  • modifier refers to reagents that are used to modify the action of the collector on mineral surfaces so that the interaction between mineral and collector is modified. In some cases, by promoting the interaction, in other cases by not allowing it.
  • modifiers are sodium silicate, sodium metaphosphate, polyhydric organic acids, starch, sodium fluorosilicate, quebracho and tannin.
  • Step d) and f1) is agitating the mixture obtained in step d) with air injection to generate a froth. This can be done by injection of air into the aqueous mixture in the form of bubbles.
  • Step e) and g1) is collecting the lithium silicates in the froth. This can be done in flotation cells.
  • the flotation process can be undertaken in one cycle, or alternatively in several cycles to maximize the recovery of the lithium concentrate.
  • the flotation process could further include a second cycle comprising the steps of: i) mixing the floated mineral obtained during step e) or g1) with water to form a aqueous mixture, ii) agitating the aqueous suspension obtained in step i) under air injection to generate a froth, and iii) collecting the lithium-containing minerals in the froth.
  • process of flotation is a one cycle process, according to steps a) to e) or a1) to g1) as previously defined, for high LiO recovery.
  • process of flotation is performed in two cycles including steps from a) to e) and i) to iii) or a1) to g1) and i) to iii) aiming at high purities.
  • the amount of collector composition which is added in step b) and d1) is in the range of 5 to 5000 g per ton of ore provided in step a) or a1), preferably from 10 to 3000 g per ton of ore, more preferably from 40 to 2000 g per ton of ore.
  • collector composition 2 Preparation of collector composition 2 (according to the invention): 16.5 g C12-14 alkyl ether carboxylic acid (component a)) having an average ethoxylation degree of 3 ethylene oxide units, 67 g of oleic fatty acid (component b)) and 16.5 g of C8 alkyl ether carboxylic acid (component c)) having an average ethoxylation degree of 5 are mixed during 10 minutes at 25 oC.
  • Example 2 Flotation tests and collectors evaluation Flotation tests An ore containing spodumene (LiAlSiO) as lithium containing mineral and other silicate minerals as gangue minerals was used in all examples.
  • the main constituents of this ore are: spodumene, quartz, plagioclase, feldspars, muscovite and other silicate minerals.
  • the ore containing spodumene and other silicates (gangue minerals) has a content of 1.2% of LiO analyzed by ICP-OES.
  • the particle size distribution of spodumene ore was characterized at 22oC by laser diffraction using a Malvern Mastersizer 2000 with 2-propanol as solvent.
  • the tests were carried out in a 1.2 L flotation cell at 1000 rpm and at room temperature. It was used tap water with hardness range between 10 – 20 oHF. The tests consisted in 2 flotation steps, a rougher flotation and a cleaner flotation. In the rougher flotation, the mineral was conditioned for 5 minutes at pH 8 using NaOH as pH modifier. Afterwards, the collector composition was added at the desired dosage. The floated ore of the rougher flotation was used as feed material of the cleaner flotation. The floated ore of the cleaner flotation is the final concentrate ore. Target figures are LiO content as high as possible, preferably LiO content (%) > 5.5%. Collectors’ evaluation The collector dosages were from 400 to 2000 g/ton added as such.

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Abstract

La présente invention concerne l'utilisation d'une composition de collecteur pour l'enrichissement de minéraux contenant du lithium présents dans un minerai, ainsi que le procédé d'enrichissement de minéraux contenant du lithium à l'aide de ladite composition de collecteur.
PCT/IB2023/000715 2023-12-27 2023-12-27 Enrichissement de minerai contenant du lithium Pending WO2025141295A1 (fr)

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Application Number Priority Date Filing Date Title
PCT/IB2023/000715 WO2025141295A1 (fr) 2023-12-27 2023-12-27 Enrichissement de minerai contenant du lithium

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4171261A (en) * 1975-11-11 1979-10-16 Chem-Y, Fabriek Van Chemische Produkten B.V. Process for the flotation of ores and collector for use in this process
CN105013620A (zh) * 2015-06-25 2015-11-04 西南科技大学 一种锂辉石高效组合捕收剂及其制备方法和应用
WO2021038017A1 (fr) 2019-08-29 2021-03-04 Basf Se Composition de collecteur pour la flottation de minerai de lithium ou de minerai de magnésium
WO2024112416A1 (fr) * 2022-11-21 2024-05-30 Hexion Inc. Procédé et composition de traitement d'un minerai

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4171261A (en) * 1975-11-11 1979-10-16 Chem-Y, Fabriek Van Chemische Produkten B.V. Process for the flotation of ores and collector for use in this process
CN105013620A (zh) * 2015-06-25 2015-11-04 西南科技大学 一种锂辉石高效组合捕收剂及其制备方法和应用
WO2021038017A1 (fr) 2019-08-29 2021-03-04 Basf Se Composition de collecteur pour la flottation de minerai de lithium ou de minerai de magnésium
WO2024112416A1 (fr) * 2022-11-21 2024-05-30 Hexion Inc. Procédé et composition de traitement d'un minerai

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
MEIJERSMID: "Polyether Carboxylates; Anionic Surfactants; Surfactant Science Series", vol. 72, 1998, MARCEL DEKKER, INC, pages: 313 - 361

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